# Patent

## Title
Resin film and manufacturing method for the same, and resin laminated metal sheet using said resin film and manufacturing method for the same

## Abstract

[Problem] The object is to provide a resin film for metal sheet laminate which endures severe forming owing to excellent formability and impact resistance, and also to excellent adhesion after forming and heating, further gives stable performance independent of forming conditions, and also provides a laminated metal sheet, and a method for manufacturing the same.
[Means for Resolution] The resin film for metal sheet laminate has a mixed resin in which a granular resin mainly existing in a state of grains having 0.1 to 5 μm in diameter is dispersed in a polyester resin having a main basic skeleton of polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate, in a range from 3 to 30% by weight in entire resin. The granular resin is a modified polyolefin resin containing a functional group derived from carboxylic acid in a range from 2 to 20% by weight as carboxylic acid.

## Background
This application is a continuation application of International Application PCT/JP02/12222 filed Nov. 22, 2002.


TECHNICAL FIELD
The present invention relates to a resin film for a resin laminated metal sheet, more particularly, a resin film having high formability, impact resistance, adhesion, flavor property, and retort resistance, and a manufacturing method for the same, and a resin laminated metal sheet using the resin film and a manufacturing method for the same.
BACKGROUND ART
Conventionally, as a metallic can that is subjected to severe forming, such as a thin-wall deep drawn can or a drawn and ironed can (DI can), a can provided with a resin layer on the internal surface thereof is generally used to prevent a decrease in taste and flavor and hence a change in property of the content due to dissolution of metal from a metal sheet. As such a can that is provided with a resin layer on the internal surface thereof and a resin-coated metal sheet capable of forming such a can, a metal sheet to which polyester resin is laminated is used as a substitute for epoxy coating layer of which danger of endocrine disrupter has recently been pointed out.
The polyester resin used in such an application is required to provide the following performance: The adhesion to a metal sheet is good, so that deformation such as elongation and compression of film caused by forming at the can manufacturing time and deterioration of film and decrease in adhesion due to friction do not occur; a polyester resin film is not crystallized or deteriorated after heat treatment such as drying, printing, and retorting, and hence separation and shrinkage of film, cracks, pinholes, etc. do not occur; a polyester film is not cracked or separated by a impact to a can; corrosion or peeling does not occur when polyester resin comes into contact with various kinds of contents; a film is not whitened; and so on. Furthermore, it is required that flavor components of content in a can be not adsorbed or absorbed to a polyester film, or the flavor of content be not impaired by the dissolved components of polyester film and smell (hereinafter referred to as flavor property).
For example, in Unexamined Japanese Patent Publication No. 59-232852, a metal sheet coated with polyethylene terephthalate resin is proposed from a viewpoint of formability, heat resistance, corrosion resistance, flavor property, etc. Also, in Unexamined Japanese Patent Publication No. 1-180336, a metal sheet coated with polybutylene terephthalate resin is proposed. Furthermore, excellent formability that withstands drawing and ironing is required, and also excellent adhesion such that a resin film does not separate from a steel sheet and impact resistance such as to withstand shocks at the can manufacturing time, the canning time, and transportation time are required. To meet the requirements, Unexamined Japanese Patent Publication Nos. 5-269920 and 6-320669 have disclosed a manufacturing method in which excellent formability, adhesion, and impact resistance can be obtained in addition to food sanitation property and flavor property, which a polyethylene terephthalate resin film inherently has, by controlling the crystalline orientation of film by means of laminating technology or the like. Such a technology can be applied to the present requirement level for formability, adhesion, and impact resistance.
However, in the concerned field, the decrease in sheet thickness is progressing year by year, and this tendency is thought to continue in the future as well. In the above-described manufacturing method for polyethylene terephthalate resin, it is difficult to achieve both formability and impact resistance when the resin film is subjected to severer forming. The reason for this is that formability and impact resistance depend greatly on the crystalline orientation (plane orientation), and have a mutually contradictory tendency. Specifically, if a crystalline orientation component increases in a resin layer, plastic deformation is hindered by a crystalline portion, and hence formability is deteriorated. Therefore, from the viewpoint of formability, the smaller amount of oriented crystals is, the better formability is. However, since this crystalline portion acts as a portion for stopping the progress of crack, from the viewpoint of impact resistance, the larger amount of oriented crystals is, the higher impact resistance is. Thus, formability and impact resistance are designed by regulating the amount of oriented crystals so that both properties are in the allowable region. However, the region in which both properties are compatible is the present limit of required performance, so that it has been expected that a new highly formable film that can respond to an increase in the degree of forming in the future, and a resin laminated metal sheet coated with this film will be developed.
In order to satisfy such a need, studies have been conducted earnestly on a technology in which both high formability and impact resistance are achieved by mixing polyolefin resin with polyester resin. Unexamined Japanese Patent Publication Nos. 7-195617 and 7-195618 have disclosed a technology in which a film consisting of a composition of saturated polyester resin and ionomer resin is laminated to a metal sheet. Although these publications indicate that impact resistance can be kept even in an amorphous state, the impact resistance obtained merely by addition of ionomer is insufficient, and inversely, the orientation of polyester resin is actually hindered by the addition of ionomer, which poses a problem in that the mechanical strength that polyester resin inherently has decreases, and resin is broken at the forming time. Also, the adhesion to a substrate metal after forming or after heating is also inferior.
Furthermore, Japanese Patent Publication Nos. 7-290643 and 7-290644 have disclosed that impact resistance can be improved by laminating a ternary composition of polyester resin, polyester elastomer, and ionomer resin to a metal sheet. However, the mixture of this composition also has low capability for relaxing impact stress of polyester elastomer, so that the effect of improving impact resistance of polyester resin is very little. Also, as in the case where elastomer is not added, the adhesion to a substrate metal after forming or after heating is also inferior.
On the other hand, WO 99/27026 Publication has disclosed a technology in which an elastomer resin encapsulated by a vinyl polymer having a polar group is finely dispersed in polyester resin. Such fine dispersion of elastomer resin improves impact resistance, so that the level of formability and impact resistance is high. However, the control of process for manufacturing such a capsule state is difficult to carry out, and the dispersed state of elastomer resin changes greatly depending on the resin forming conditions, and is unstable. Therefore, there arises a problem in that the performance of the resultantly obtained resin film is not always constant. It is found that if such a dispersed state deviates from the optimum conditions, the performance decreases greatly. Even if a resin of such a composition is actually manufactured, a portion where the resin performance is low is produced partially, so that the obtained performance such as formability and impact resistance is insufficient as a whole. Furthermore, there arise problems of decreased adhesion to a substrate metal due to forming or impact and decreased adhesion after heating.
Furthermore, Unexamined Japanese Patent Publication No. 2001-172481 has disclosed a technology in which the decomposition of vinyl polymer is restrained by adding an appropriate amount of an oxidation inhibitor (free radical inhibitor) to a mixed resin in which a vinyl polymer having a polar group is finely dispersed in polyester resin. However, in a particular mixture of vinyl polymer and polyester resin, when a polymerization catalyst of polyester resin and an oxidation inhibitor coexist, resin is liable to be deteriorated. In particular, polyester resin is deteriorated, and performance such as impact resistance and flavor property is decreased.
Still further, Unexamined Japanese Patent Publication No. 2001-353814 has disclosed a technology in which a resin layer in which fine ionomer resin exists in polyester resin as a dispersion phase is coated, by which the impact resistance and adhesion are enhanced. However, the compositions of dispersed modified polyolefin resin and polyester resin are improper, so that the performance is insufficient.
Also, a can using a metal sheet to which such a resin film is laminated has a problem in that the film is whitened after retorting and thereby the appearance is deteriorated. In particular, a can lid and a can bottom, which come into direct contact with retort steam, remarkably is whitened, and such a phenomenon cannot be prevented by means of the above-described prior art.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide a resin film having high formability, impact resistance, adhesion, flavor property, and retort resistance, and a manufacturing method for the same, and a resin laminated metal sheet using the resin film and a manufacturing method for the same.
The inventors carried out studies on the construction of resin layer that withstands severer forming and keeps performance such as impact resistance and adhesion without losing advantages of high formability and flavor property that polyester resin inherently has. Further, we pursued a resin composition by which that construction can be obtained stably regardless of the forming conditions. As a result, we found that a metal sheet coated with a resin film consisting of a mixed resin in which granular modified polyolefin resin having a specific composition is dispersed in polyester resin provides dramatically high formability, impact resistance, and flavor property, and also has adhesion after forming and after heating. Moreover, this resin construction can be obtained stably regardless of the forming conditions. Further, it was verified that in this resin composition, necessary characteristics such as corrosion resistance are also sufficient.
The optimum resin construction of mixed resin layer can be obtained when granular modified polyolefin resin containing a specific amount of a functional group derived from carboxylic acid is dispersed in polyester resin. The modified polyolefin resin having such a functional group composition is dispersed in polyester resin most stably, and moreover the mechanical properties of the modified polyolefin resin itself are optimal, so that high formability and impact resistance can be provided.
As the reason that both formability and impact resistance can be achieved, the following mechanism is presumed. When a destructive force acts on resin by means of severe forming or impact, a craze or crack is generated in polyester resin, and grows, resulting in breakage. However, if granular modified polyolefin resin having a proper composition and grain size is dispersed in polyester resin, the progress of such a craze or crack is restrained by stress relaxation of modified polyolefin resin, so that final occurrence of breakage can be prevented. Further, there appears an effect that the plastic deformation of polyester resin is accelerated in the surroundings in which modified polyolefin resin is in contact with polyester resin, and hence stress concentration that results in breakage is relaxed, and the resin is less liable to be broken.
A resin film obtained by mixing modified polyolefin resin containing carboxylic acid with polyester resin has higher adhesion to a substrate metal than the ordinary polyester resin, but may have insufficient adhesion when being subjected to severer forming. Also, a film having such a resin composition exhibits high formability and impact resistance, and also exhibits flavor property high enough to ordinary use. However, it is true that many persons are very sensitive to a change in flavor depending on the recent applications, and impose very rigid requirements. Contrary to such requirements, polyester resin in which modified olefin is dispersed may have an insufficient flavor property because it contains an olefin compound.
Thereupon, as the result of earnest studies, it was found that a layer of modified polyolefin resin containing carboxylic acid is made a layer that is in contact with a metal sheet, by which adhesion after forming and after heating is improved dramatically. Further, this modified polyolefin resin layer has high adhesion to mixed resin layer, so that there occurs no separation between layers, and thus high adhesion can be kept as a whole. Also, it was found that by lapping a polyester resin layer containing no polyolefin resin on a modified olefin dispersed polyester resin, the flavor property can be enhanced to a level higher than the required one.
The present invention has been made based on the above-described knowledge, and the gist thereof is as described below.
(1) A resin film consisting of a mixed resin in which a granular resin mainly existing in a granular state in which the grain diameter is 0.1 to 5 μm is dispersed in thermoplastic polyester resin in the range of 3 to 30% by weight in weight fraction in entire resin, characterized in that the granular resin is modified polyolefin resin containing 2 to 20% by weight of a functional group derived from carboxylic acid in terms of carboxylic acid.
(2) The resin film described in item (1), characterized in that the amount of the modified polyolefin resin existing in a film in a granular state in which the grain diameter is 0.1 to 5 μm is in the range of 3 to 25% by volume in volume fraction in entire resin.
(3) The resin film described in item (1) or (2), characterized in that the thermoplastic polyester resin is polyester containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton.
(4) The resin film described in any one of items (1) to (3), characterized in that the ratio of terephthalic acid to isophthalic acid, which are dicarboxylic acid components constituting the thermoplastic polyester resin, is 97:3 to 85:15 in molar ratio.
(5) The resin film described in any one of items (1) to (4), characterized in that in a monomer component mainly constituting the thermoplastic polyester resin, dicarboxylic acid is terephthalic acid, and diol components are ethylene glycol and 1,4-butanediol, the ratio thereof being 20:80 to 80:20 in molar ratio.
(6) The resin film described in any one of items (1) to (5), characterized in that the ratio X/Y of the amount X of polyester polymerization catalyst to the amount Y of oxidation inhibitor in the mixed resin is 0.2 or higher in weight ratio.
(7) The resin film described in any one of items (1) to (6), characterized in that the content of oxidation inhibitor in the mixed resin is 500 ppm or lower.
(8) The resin film described in any one of items (1) to (7), characterized in that the resin film contains 5 to 40% by weight of pigment.
(9) The resin film described in any one of items (1) to (7), characterized in that the resin film has a thickness of 10 to 50 μm.
(10) A resin film having a construction in which a resin layer of R1 layer consisting of the mixed resin described in any one of items (1) to (8) and a polyester resin layer of R0 layer containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton are laminated, characterized in that the film is designed so that when it is laminated to a metal sheet, the R0 layer is the outermost layer.
(11) The resin film described in item (10), characterized in that the film thickness of the R1 layer is 10 to 50 μm, the film thickness of the R0 layer is 1 to 10 μm, and the thickness ratio R1/R0 of the R1 layer to the R0 layer is 2/1 to 10/1.
(12) A resin film having a construction in which a resin layer of R1 layer consisting of the mixed resin described in any one of items (1) to (8) and a resin layer of R2 layer consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid are laminated, characterized in that the film is designed so that when it is laminated to a metal sheet, the R2 layer is in contact with the metal sheet.
(13) The resin film described in item (12), characterized in that the film thickness of the R1 layer is 10 to 50 μm, the film thickness of the R2 layer is 1 to 10 μm, and the thickness ratio R1/R2 of the R1 layer to the R2 layer is 1/1 to 20/1.
(14) A resin film having a three-layer construction of R0 layer/R1 layer/R2 layer in which a polyester resin layer of R0 layer containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is laminated on one surface of a resin layer of R1 layer consisting of the mixed resin described in any one of items (1) to (8), and a resin layer of R2 layer consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid is laminated on the other surface of the R1 layer, characterized in that the film is designed so that when it is laminated to a metal sheet, the R0 layer is the outermost layer.
(15) The resin film described in item (14), characterized in that the film thickness of the R1 layer is 10 to 50 μm, the film thickness of the R0 layer is 1 to 10 μm, the film thickness of the R2 layer is 1 to 10 μm, the thickness ratio R1/R0 of the R1 layer to the R0 layer is 2/1 to 10/1, and the thickness ratio R1/R2 of the R1 layer to the R2 layer is 1/1 to 20/1.
(16) The resin film described in any one of items (12) to (15), characterized in that the modified polyolefin resin of the R2 layer contains 2 to 20% by weight of a functional group derived from carboxylic acid in terms of carboxylic acid.
(17) The resin film described in any one of items (10) to (16), characterized in that the resin film contains 5 to 40% by weight of pigment.
(18) A manufacturing method for a resin film, characterized in that in manufacturing the resin film described in any one of items (1) to (9), the mixed resin in which a granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin described in any one of items (1) to (8) is inserted in an extruding machine as a raw material resin and is melted, and a film is formed by extruding the molten resin from a T die.
(19) A manufacturing method for a resin film, characterized in that in manufacturing the resin film described in item (10), (11) or (17), the mixed resin in which a granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin described in any one of items (1) to (8) is inserted in an extruding machine as a raw material resin for the R1 layer and is melted; at the same time, polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is inserted in a separate extruding machine as a raw material resin for the R0 layer and is melted; and a film of two-layer construction of R1 layer/R0 layer is formed by extruding the molten resins from one T die.
(20) A manufacturing method for a resin film, characterized in that in manufacturing the resin film described in item (12), (13), (16) or (17), the mixed resin in which a granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin described in any one of items (1) to (8) is inserted in an extruding machine as a raw material resin for the R1 layer and is melted; at the same time, a resin consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid is inserted in a separate extruding machine as a raw material resin for the R2 layer and is melted; and a film of two-layer construction of R1 layer/R2 layer is formed by extruding the molten resins from one T die.
(21) A manufacturing method for a resin film, characterized in that in manufacturing the resin film described in items (14) to (17), the mixed resin in which a granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin described in any one of items (1) to (8) is inserted in an extruding machine as a raw material resin for the R1 layer and is melted; at the same time, polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is inserted in a separate extruding machine as a raw material resin for the R0 layer and is melted, and also a resin consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid is inserted in another separate extruding machine as a raw material resin for the R2 layer and is melted; and a film of three-layer construction of R0 layer/R1 layer/R2 layer is formed by extruding the molten resins from one T die.
(22) A resin laminated metal sheet characterized in that at least one surface of a metal sheet is coated with the resin film described in any one of items (1) to (17) or the resin film manufactured by the method described in any one of items (18) to (21).
(23) The resin laminated metal sheet described in item (22), characterized in that the metal sheet is a steel sheet subjected to electrolytic chromate treatment, having a metallic chromium layer of 50 to 200 mg/m2 and a chromium oxide layer of 3 to 30 mg/m2 in terms of metallic chromium on the surface thereof.
(24) The resin laminated metal sheet described in item (22) or (23), characterized in that a plane orientation coefficient in the direction parallel to the film surface of the resin film is lower than 0.010.
(25) The resin laminated metal sheet described in any one of items (22) to (24), characterized in that the surface of metal sheet is coated with the resin film by an extrusion laminating method in which the mixed resin described in any one of items (1) to (8) is extruded from a T die directly on the surface of metal sheet.
(26) The resin laminated metal sheet described in any one of items (22) to (24), characterized in that the surface of metal sheet is coated with the resin film by a two-layer extrusion laminating method in which two types of resins consisting of a resin layer (R1 layer) consisting of the mixed resin described in any one of items (1) to (8) and a resin layer (R0 layer) consisting of polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton are extruded simultaneously from one T die directly on the surface of metal sheet.
(27) The resin laminated metal sheet described in any one of items (22) to (24), characterized in that the surface of metal sheet is coated with the resin film by a two-layer extrusion laminating method in which two types of resins consisting of a resin layer (R1 layer) consisting of the mixed resin described in any one of items (1) to (8) and a resin layer of R2 layer consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid are extruded simultaneously from one T die directly on the surface of metal sheet.
(28) The resin laminated metal sheet described in any one of items (22) to (24), characterized in that the surface of metal sheet is coated with the resin film by a three-layer extrusion laminating method in which three types of resins consisting of a resin layer (R0 layer) consisting of polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton, a resin layer (R1 layer) consisting of the mixed resin described in any one of items (1) to (8), and a resin layer of R2 layer consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid are extruded simultaneously from one T die directly on the surface of metal sheet.
(29) A manufacturing method for a resin laminated metal sheet, characterized in that in manufacturing the resin laminated metal sheet described in any one of items (22) to (28), a resin film is laminated to a metal sheet heated to a temperature in the range of the melting point of polyester resin in the mixed resin described in any one of items (1) to (8) minus 70° C. to the melting point thereof plus 30° C.
(30) A manufacturing method for a resin laminated metal sheet, characterized in that in manufacturing the resin laminated metal sheet described in item (25), after the mixed resin is heated to a temperature in the range of the melting point of polyester resin in the mixed resin plus 10° C. to the melting point thereof plus 50° C. and is melted, the molten resin is extruded directly on the surface of metal sheet and is laminated thereon.
(31) The manufacturing method for a resin laminated metal sheet described in item (30), characterized in that after the mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin described in any one of items (1) to (8) is inserted in an extruding machine as a raw material resin and is melted, the molten resin is extruded directly on the surface of metal sheet and is laminated thereon.
(32) A manufacturing method for a resin laminated metal sheet, characterized in that in manufacturing the resin laminated metal sheet described in item (26), after the R1 and R0 layers are heated to a temperature in the range of the melting point of polyester resin in the R1 layer plus 10° C. to the melting point thereof plus 50° C. and are melted, the molten resins are extruded in two layers on the surface of metal sheet and are laminated thereon.
(33) The manufacturing method for a resin laminated metal sheet described in item (32), characterized in that the mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin described in any one of items (1) to (8) is inserted in an extruding machine as a raw material resin for the R1 layer; at the same time, a resin consisting of polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is inserted in a separate extruding machine as a raw material resin for the R0 layer; and then, after these resins are melted, the molten resins are extruded on the surface of metal sheet and are laminated thereon.
(34) A manufacturing method for a resin laminated metal sheet, characterized in that in manufacturing the resin laminated metal sheet described in item (27), after the R1 and R2 layers are heated to a temperature in the range of the melting point of polyester resin in the R1 layer plus 10° C. to the melting point thereof plus 50° C. and are melted, the molten resins are extruded in two layers on the surface of metal sheet and are laminated thereon.
(35) The manufacturing method for a resin laminated metal sheet described in item (34), characterized in that the mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin described in any one of items (1) to (8) is inserted in an extruding machine as a raw material resin for the R1 layer; at the same time, a resin consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid is inserted in a separate extruding machine as a raw material resin for the R2 layer; and then, after these resins are melted, the molten resins are extruded on the surface of metal sheet and are laminated thereon.
(36) A manufacturing method for a resin laminated metal sheet, characterized in that in manufacturing the resin laminated metal sheet described in item (28), after the R1, R2 and R0 layers are heated to a temperature in the range of the melting point of polyester resin in the R1 layer plus 10° C. to the melting point thereof plus 50° C. and are melted, the molten resins are extrusion laminated in three layers on the surface of metal sheet.
(37) The manufacturing method for a resin laminated metal sheet described in item (36), characterized in that the mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin described in any one of items (1) to (8) is inserted in an extruding machine as a raw material resin for the R1 layer; at the same time, polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is inserted in a separate extruding machine as a raw material resin for the R0 layer, and also a resin consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid is inserted in another separate extruding machine as a raw material resin for the R2 layer; and then, after these resins are melted, the molten resins are extruded on the surface of metal sheet and are laminated thereon.


BEST MODE FOR CARRYING OUT THE INVENTION
A resin film in accordance with the present invention and a manufacturing method for the same, and a resin laminated metal sheet using the resin film and a manufacturing method for the same are described below.
The resin film in accordance with the present invention consists of a mixed resin in which a granular resin mainly existing in a state of grain with a diameter of 0.1 to 5 μm is dispersed in thermoplastic polyester resin in the range of 3 to 30% by weight of entire resin, the granular resin being modified polyolefin resin having a functional group derived from carboxylic acid.
Specifically, the resin film in accordance with the present invention is formed mainly of thermoplastic polyester resin. The used thermoplastic polyester resin is such that as the acid component, various kinds of aromatic dicarboxylic acids and aliphatic dicarboxylic acids are copolymerized arbitrarily, and as the glycol component, various kinds of aliphatic diols and aromatic diols are copolymerized arbitrarily.
As the acid component, concretely, terephthalic acid, phthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, diphenic acid, diphenyl ether carboxylic acid, 5-sulfoisophthalic acid, diphenoxy ethane dicarboxylic acid, adipic acid, oxalic acid, malonic acid, succinic acid, malic acid, citric acid, glutaric acid, dimer acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecadion acid, trans-1,4-cyclohexane dicarboxylic acid, or the like is used. In particular, the acid component that is formed mainly of tereophthalic acid and/or isophthalic acid is suitable in terms of the balance of mechanical properties, flavor property, etc.
On the other hand, as the glycol component, concretely, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, trans-1,4-cyclohexanedimethanol, bisphenols, p-xylene glycol, cis-1,4-cyclohexanedimethanol, hydroquinone, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, hydrogenated bisphenol A, or the like is used. In particular, the glycol component that is formed mainly of ethylene glycol and/or 1,4-butanediol is suitable in terms of the balance of mechanical properties, flavor property, etc.
That is to say, thermoplastic polyester resin formed mainly of tereophthalic acid and ethylene glycol, and/or one formed mainly of tereophthalic acid and isophthalic acid and ethylene glycol, and/or one formed mainly of tereophthalic acid and ethylene glycol and 1,4-butanediol are especially suitable in terms of the balance of mechanical properties and flavor property in a mixed resin state.
As thermoplastic polyester resin, polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is suitable. The polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton means polyester resin in which the sum of a portion in which only ethylene glycol and tereophthalic acid in the polyester resin skeleton are a unit and/or a portion in which ethylene glycol and tereophthalic acid and isophthalic acid are a unit accounts for 90% or more by weight. In other portions, as the acid component, various kinds of aromatic dicarboxylic acids and aliphatic dicarboxylic acids may be copolymerized arbitrarily.
Furthermore, in the scope in which the object of the present invention is not impaired, a unit derived from a polyfunctional compound such as trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol may be contained in a small amount, for example, 2% or less by weight.
For the polyester resin in accordance with the present invention, the content of diethylene glycol is preferably 1.5% or lower by weight, further preferably 0.9% or lower by weight. If the content of diethylene glycol is high, deterioration of polymer progresses due to heating treatment such as drying and printing at the forming time, and hence cracks or pinholes are produced, so that the impact resistance and flavor property are sometimes deteriorated.
Also, the content of acetaldehyde in resin is preferably 10 ppm or lower, further preferably 7 ppm or lower, from the viewpoint of flavor property. If the content of acetaldehyde exceeds this range, especially 10 ppm, the flavor property is sometimes deteriorated. The method for limiting the content of acetaldehyde to 10 ppm or lower is not subject to any special restriction. For example, a method can be cited in which polyester resin is formed into a film, the polyester resin being obtained by a method in which resin is heat-treated at a temperature below the melting point of polyester under a reduced pressure or in an inert gas atmosphere to remove acetaldehyde produced by thermal decomposition at the time when polyester resin is manufactured by condensation polymerization etc. Preferably, a method should be used in which polyester resin that is obtained by solid-phase polymerizing resin at a temperature higher than 150° C. and lower than the melting point under a reduced pressure or in an inert gas atmosphere.
Also, the polyester resin in accordance with the present invention preferably has less oligomer consisting of a cyclic trimer etc. in resin from the viewpoint of flavor property. In particular, the content of cyclic trimer is preferably 0.9% or less by weight, further preferably 0.7% or less by weight. If the content of oligomer in resin exceeds this range, especially 0.9% by weight, the flavor property is sometimes deteriorated. The method for limiting the content of oligomer to 0.9% or less by weight is not subject to any special restriction, and this content of oligomer can be achieved by using the same method as the above-described method for reducing the content of acetaldehyde.
The intrinsic viscosity of polyester resin used in the present invention is preferably 0.3 to 2.0 dl/g, further preferably 0.3 to 1.5 dl/g, still further preferably 0.5 to 1.0 dl/g. If the intrinsic viscosity exceeds 2.0 dl/g, the mixing with modified polyolefin resin is remarkably difficult to do because of very high viscosity. As the result of nonuniform dispersion of modified polyolefin resin, the mechanical strength and impact resistance of polyester resin may be decreased. On the other hand, if the intrinsic viscosity is lower than 0.3 dl/g, the formability is poor because of low viscosity, so that it may become difficult to manufacture a uniform film. The intrinsic viscosity is measured by the method specified in JIS K7367-5. It is measured in o-chlorophenol at 25° C. in a concentration of 0.005 g/ml, and is determined by the formula of intrinsic viscosity=(T−T0)/(T0×c). In this formula, c expresses resin concentration per 100 ml of solution in gram, and T and T0 express drop time in a capillary viscometer of solvent and resin solution, respectively.
Further, the glass-transition temperature (Tg) of the polyester resin used in the present invention is preferably 50 to 120° C., further preferably 60 to 100° C. If the glass-transition temperature is lower than 50° C., a flaw etc. are liable to be produced by a temperature rise at the forming time because of deteriorated heat resistance of polyester resin. On the other hand, if the glass-transition temperature exceeds 120° C. inversely the formability is sometimes deteriorated. Also, the low-temperature crystallization temperature (Tc) is usually 130 to 210° C., preferably 140 to 200° C. The melting point (Tm) is usually 210 to 265° C., preferably 220 to 260° C. If the low-temperature crystallization temperature is lower than 130° C., crystallization is liable to occur, so that crystallization occurs at the time of retorting (high-temperature high-humidity treatment at about 120° C. In this description, referred also to as “retorting”), by which the film is easily cracked or separated. On the other hand, if the low-temperature crystallization temperature exceeds 210° C., the formability and mechanical strength such as impact resistance of polyester may be deteriorated. If the melting point is lower than 210° C., resin is deteriorated by heat at the forming time, so that cracks or pinholes are liable to be produced. On the other hand, if the melting point exceeds 265° C., crystallization progresses due to heating treatment such as drying and printing at the forming time, and hence cracks or pinholes are also liable to be produced. The above-described glass-transition temperature, low-temperature crystallization temperature, and crystal melting point are obtained by measuring endothermic peak temperature at the time of temperature rise using a differential scanning calorimeter (DSC). The measurement is made under conditions of a sample amount of 10 mg and a temperature rise rate of 10° C./min.
In the present invention, in a dicarboxylic acid component constituting polyester resin, the ratio of total amount of terephthalic acid to the total amount of isophthalic acid is specified so as to be 97:3 to 85:15 in molar ratio. In the mixed resin in the present invention, modified polyolefin in resin hinders crystallization of polyester resin, so that the decrease in adhesion and corrosion resistance caused by forming, heating, etc. is less liable to occur. Therefore, the optimum ratio spreads toward the terephthalic acid rich side as compared with the case where modified polyolefin resin is not contained. Thus, even if homo-ethylene terephthalate resin that does not contain isophthalic acid at all is used as polyester resin, when the polyester resin contains modified polyolefin resin of the present invention, it can be used as an ordinary can material. Further, if 3 mol % of isophthalic acid is copolymerized, the adhesion after forming and heating increases dramatically. If the amount of isophthalic acid increases as compared with the ratio of total amount of terephthalic acid to the total amount of isophthalic acid of 85:15, the melting point is lowered and hence the heat resistance at the forming time may be deteriorated.
Also, in applications in which retorting is especially performed, in a monomer component mainly constituting thermoplastic polyester resin, dicarboxylic acid is terephthalic acid, and the diol component is ethylene glycol and 1,4-butanediol, and the ratio thereof (in the diol component, the ratio of the amount of ethylene glycol to the amount of 1,4-butanediol) specified so as to be 20:80 to 80:20 in molar ratio is most suitable. Further, the range of 60:40 to 30:70 is most suitable. In the above-described polyester resin containing polyolefin resin, since modified polyolefin resin in resin hinders crystallization of polyester resin, there arises a problem in that the strength of polyester resin is insufficient especially in retorting and thus cohesive failure is liable to occur. To solve this problem, polybutylene terephthalate, which has especially high crystallization rate, is mixed with polyethylene terephthalate in a predetermined ratio. Thereby, the crystallization of polyester resin is accelerated, and cohesive failure is less liable to occur even in retorting. Such an effect is especially remarkable in preventing a phenomenon that in lid material to which a film is laminated, the film is subjected to cohesive failure by water vapor intruding into the film at the retorting time and the film is whitened. By using polyester resin of the above-described composition, such a problem can be solved. If the amount of polyethylene terephthalate is high as compared with the ratio of polyethylene terephthalate to polybutylene terephthalate of 80:20 in molar ratio, the crystallization rate is not accelerated sufficiently, so that the above-described effect cannot be anticipated. On the other hand, if the amount of polybutylene terephthalate is high as compared with the ratio of 20:80, the melting point lowers, and hence the heat resistance is deteriorated.
The modified polyolefin resin having a functional group derived from carboxylic acid mixed in polyester resin must exist mainly in a granular state in which the grain diameter is 0.1 to 5 μm in terms of equivalent sphere to improve the impact resistance and also prevent adverse influence on the properties such as formability and heat resistance. In this case, the phrase “exist mainly ” means that at least 30% or more by weight of the whole modified polyolefin resin exists in a state in which the grain diameter is 0.1 to 5 μm in terms of equivalent sphere. Also, the weight ratio of the modified polyolefin resin to the entire resin must be in the range of 3 to 30% by weight.
If modified polyolefin resin is dispersed in polyester resin, wide dispersion occurs from very fine grains with a diameter not larger than 0.1 μm to large grains with a diameter exceeding 5 μm. The grains with a diameter smaller than 0.1 μm exert no influence on the physical properties of mixed resin. On the other hand, the grains with a diameter exceeding 5 μm also do not improve the physical properties such as formability of mixed resin but rather decreases them. Therefore, at least 30% or more by weight of the whole modified polyolefin resin must have a diameter in the range of 0.1 to 5 μm in terms of equivalent sphere. From the viewpoint of restraining the decrease in physical properties, the ratio of grains with a diameter exceeding 5 μm should preferably be 1% or less by weight. Also, if the ratio of mixed modified polyolefin resin to the entire resin is lower than 3% by weight, the improvement in impact resistance is insufficient. If the ratio exceeds 30% by weight, performance such as formability and heat resistance is decreased.
The glass-transition temperature of modified polyolefin resin is preferably 0° C. or lower by the same measuring method as that for polyester resin. The temperature is further preferably −30° C. If the glass-transition temperature exceeds 0° C., the impact resistance is slightly low, and is low especially at low temperatures. Also, it is preferable that the Young's modulus be 250 MPa or lower and the breaking elongation be 200% or more at room temperature, and further preferable that the Young's modulus be 100 MPa or lower and the breaking elongation be 500% or more. The molecular weight is not subject to any special restriction, but it is preferably not lower than 2×103 and not higher than 1×106 in number-average molecular weight. If the molecular weight is lower than 2×103 or exceeds 1×106, the mechanical properties may be deteriorated and the impact resistance may be decreased, and additionally, forming may become difficult to do.
The functional group derived from carboxylic acid is contained in an amount of 2 to 20%, preferably 3 to 12%, by weight in carboxylic acid conversion. In this composition range, the affinity with polyester resin and the dispersibility are enhanced to the maximum. As the affinity of modified polyolefin resin with polyester resin increases, the effect of relaxing interlayer fracture between different resins is enhanced at the time of shock. As a result, the impact resistance is increased, and as the result that the cohesion of modified polyester grains is restrained at the forming time, variations in performance due to forming conditions are decreased. Such an effect can be obtained when the ratio of functional group is 2% or higher by weight in carboxylic acid conversion. On the other hand, if the ratio exceeds 20% by weight, the affinity with polyester resin decreases inversely, and resultantly the impact resistance is deteriorated.
In the present invention, it is specified that the amount of modified polyolefin resin existing in mixed resin in a granular state in which the grain diameter is 0.1 to 5 μm is in the range of 3 to 25 vol % in volume fraction. As described above, the grains with a diameter smaller than 0.1 μm exert no influence on the physical properties of mixed resin. On the other hand, the grains with a diameter exceeding 5 μm also do not improve the physical properties such as formability of mixed resin but rather decreases them. Therefore, only granular modified polyester resin with a diameter of 0.1 to 5 μm in terms of equivalent sphere contributes to the improvement in impact resistance. Since the physical properties of film having grains of this size can be rearranged by the absolute value of volume in the whole film, the amount of modified polyolefin resin is specified in the range of 3 to 25 vol %. If the volume ratio of modified polyolefin resin is lower than 3 vol %, the improvement in impact resistance is insufficient, and if it exceeds 25 vol %, the performance such as formability is decreased.
Furthermore, the number of modified polyolefin resin grains existing in the mixed resin layer in a state in which the grain diameter is 0.1 to 5 μm in a cube with one side of 10 μm (volume: 1000 μm3) in mixed resin is preferably 5 to 105, further preferably 50 to 104. If the number is smaller than 5, the improvement in impact resistance is insufficient, and if the number exceeds 105, the performance such as formability is decreased.
The thickness of resin film consisting of the above-described mixed resin is preferably in the range of 10 to 50 μm. The upper limit value is determined from the economical viewpoint, and the lower limit value is determined from the viewpoints of impact resistance and formability. Specifically, if the thickness is not lower than 10 μm, the impact resistance and formability become higher, but if the thickness exceeds 50 μm, the cost of resin film increases, and the effect of improving impact resistance and formability is saturated.
The following is a description of a manufacturing method for modified polyolefin resin. As a functional group derived from carboxylic acid, carboxylic acid group, carboxylic acid ester group, metal salt of carboxylic acid ion, and the like can be cited. Carboxylic acid modified polyolefin can be obtained by copolymerization, graft polymerization, or block polymerization of monomer containing these functional groups in polyolefin resin.
As a monomer containing a functional group derived from carboxylic acid, concretely, acrylic acid, methacrylic acid, vinyl acetate, vinyl propionate, maleic acid, maleic anhydride, itaconic acid, unsaturated carboxylic acid with the number of carbons of 3 to 8 such as monomethylester maleate, and metal salt in which the whole or some of these acids is neutralized by metal cation of 1 or 2 valences such as sodium, potassium, lithium, zinc, magnesium, and calcium can be cited. The degree of neutralization is preferably 20 to 80%, further preferably 30 to 70%. A composition formed from modified polyolefin resin with such a degree of neutralization has a high melt extrusion property.
Also, as carboxylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-hydroxyethyl carboxylate, 2-hydroxyethyl methacrylate, monometylester maleate, glycidyl acrylate, glycidyl methacrylate, vinyl acetate, acrylamine, acrylamide, and the like can be cited.
Modified polyolefin resin containing a functional group derived from carboxylic acid can be obtained by copolymerization, block polymerization, or graft polymerization of monomer containing a functional group derived from carboxylic acid with olefin monomer containing no functional group derived from carboxylic acid, such as ethylene, propylene, 1-butane, 1-pentene, isobutene, isobutylene, butadiene, styrene, and acrylonitrile. Among these, in particular, the modified polyolefin resin obtained by graft polymerization or copolymerization of carboxylic acid group in polyolefin resin exhibits high performance. As such a modified polyolefin resin, Modiper A (manufactured by NOF Corp.), Nucrel (manufactured by Mitsui-DuPont Polychemical Co., Ltd.), Bondine (manufactured by Sumitomo Chemical Co., Ltd.), Admer (manufactured by Mitsui Chemicals, Inc.), and Tuftec (manufactured by Asahi Chemical Industry Co., Ltd.), and the like can be cited.
Also, the modified polyolefin resin in which some of carboxylic acid is neutralized by metal salt can be used. For such a resin, though the formability is slightly low, the impact resistance is higher. As a commercially available resin, Himilan (manufactured by Mitsui-DuPont Polychemical Co., Ltd.) and the like can be cited. Further, if zinc oxide or calcium hydroxide is added when carboxylic acid modified polyolefin resin is melted and dispersed in polyester resin, carboxyl group in modified polyolefin resin is neutralized by metal ions thereof, and resultantly, a structure in which the carboxylic acid modified polyolefin resin in which some of carboxylic acid is neutralized by metal salt is dispersed in polyester resin.
By dispersing modified polyolefin resin in polyester resin, a mixed resin, which is used as a raw material, is obtained. As a method for dispersion, there is available, for example, a method in which two resins are melted and mixed, and after the mixture is kept at a temperature at which one phase is formed, it is cooled to a temperature at which it is separated into two phases, by which a modified polyolefin resin phase is dispersed in a polyester resin phase by utilizing phase separation; a method in which after two resins are melted in a common solvent, the solvent is evaporated; a method in which the modified polyolefin resin in which the primary grain diameter has been made fine in advance to 1 μm or finer is melted and dispersed at a temperature at which the resin does not cohere; a method in which polyester resin is manufactured by copolymerizing monomer in a solution containing modified polyolefin resin in which the primary grain diameter has been made fine in advance to 1 μm or finer and polyester resin forming monomer, and a state in which modified polyolefin resin is dispersed in polyester is established; or a method in which two resins are melted and mixed, and modified polyolefin resin is made fine by a mechanical shearing force.
As an apparatus for mixing and melting, a mixing apparatus such as a tumbler blender, a Henschel mixer, and V-type blender, or a melting/mixing apparatus such as an extruder of one axis or two axes, a kneader, and a Banbury type mixer can be used. When these apparatuses are used, the temperature control such as temperature control of mixing apparatus and temperature change is carried out more strictly than in the ordinary mixing method, the mixing time is prolonged, for example, about three to ten times as compared with the ordinary mixing time, the mechanical shearing speed at the mixing time is increased, for example, about two to five times as compared with the ordinary speed, these methods are combined, or, after the resins are mixed mechanically by using, for example, a tumbler blender, they are melted and mixed by an extruder, by which a mixed resin with high dispersibility, in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm has been dispersed in advance in thermoplastic polyester resin can be obtained. By film-forming a mixed resin with high dispersibility, which is obtained by melting and mixing using an extruder, a resin film in which the grain diameter of modified polyolefin resin is more uniform can be obtained. As the result, the performance such as impact resistance is enhanced. By forming a film by inserting such a mixed resin with high dispersibility and uniform grain diameter in an extruder and melting it, the grain diameter distribution of granular resin is narrowed remarkably as compared with the case where modified polyolefin resin is dispersed while a film is formed, and resultantly a film that achieves high grade in various performances can be obtained.
On the other hand, unless the effects of the present invention are hindered, an additive, such as a light stabilizer, impact resistance improving agent, compatibilizing agent, lubricant, plasticizer, antistatic agent, reaction catalyst, color preventing agent, free radical inhibitor, plasticizer, oxidation inhibitor, terminal closing agent, heat stabilizer, mold releasing agent, flame retarder, antibacterial agent, and fungistat, may be added to the mixed resin. The content of these additives is preferably not lower than 0.005 weight part and not higher than 15 weight part, further preferably not lower than 0.01 weight part and not higher than 2 weight part, especially preferable not lower than 0.05 weight part and not higher than 0.5 weight part, with respect to 100 weight part of mixed resin in the present invention. If the content is lower than 0.005 weight part, the effect is insufficient. On the other hand, if the content exceeds 15 weight part, the additive is excessive, so that the mechanical properties of mixed resin layer are decreased.
As inorganic particles having the effect of improving lubricity, formability, and impact resistance, silica manufactured by the dry method or wet method, porous silica, colloidal silica, titanium oxide, zirconium oxide, aluminum oxide, calcium carbonate, talc, calcium sulfate, barium sulfate, spinel, iron oxide, calcium phosphate, and the like can be cited. Also, as organic particles or polymeric organic particles, vinyl resin particles such as polystyrene particles, crosslinking polystyrene particles, styrene-acrylic crosslinking particles, acrylic crosslinking particles, styrene-methacrylate resin crosslinking particles, and methacrylate resin crosslinking particles, and polymeric organic particles consisting of silicone, benzoguanamin-formaldehyde, polytetrafluoroethylene, polyphenolester, phenolic resin, and the like can be cited. The particle diameter and content of these particles are not subject to any special restriction. However, in order to achieve the performance to the utmost, the particle diameter is preferably in the range of 0.01 to 5 μm, further preferably in the range of 0.1 to 2.5 μm. Also, the particle diameter distribution is preferably sharp, and the standard deviation thereof is preferably 0.5 or less. Further, the shape of particle is preferably truly spherical, and the ratio of larger diameter to shorter diameter is preferably 1.0 to 1.2.
As a reaction catalyst, for example, an alkali metal compound, alkali earth metal compound, zinc compound, lead compound, manganese compound, cobalt compound, and aluminum compound can be cited, and as a color preventing agent, for example, a phosphorus compound can be cited.
As a free radical inhibitor, one or two kinds selected from a phenol base free radical inhibitor, phosphorus base free radial inhibitor, sulfide base free radical inhibitor, and nitrogen base free radical inhibitor can be cited.
As a plasticizer, a plasticizer consisting of polyester obtained by terminal esterifying a material obtained by condensation polymerization of aliphatic polybasic acid with the number of carbons of 2 to 20 or aromatic polybasic acid with the number of carbons of 8 to 20 with respect to ester derivative or polybasic acid component with the molar ratio of the ester derivative of 0 to 2.0 with aliphatic alcohol with the number of carbons of 2 to 20 by monobasic acid with the number of carbons of 2 to 20 or its ester derivative and/or monohydroxy alcohol with the number of carbons of 1 to 18 can be cited.
As an antistatic agent, a method of kneading an antistatic agent disclosed in Unexamined Japanese Patent Publication No. 5-222357 in resin composition, a method of applying an antistatic agent disclosed in Unexamined Japanese Patent Publication No. 5-1164 on film surface, and the like method can be used as necessary in order to prevent electrostatic failure such as winding of film on a roll in the film forming process or contamination adhering to film surface.
As an antibacterial agent, a conventionally known antibacterial agent disclosed in Unexamined Japanese Patent Publication Nos. 11-48431 and 11-138702 can be used as necessary. A polymerization catalyst of polyester resin is added to the mixed resin. As a polymerization catalyst, an element of at least one kind selected from germanium, antimony, and titanium is contained in an amount preferably not smaller than 1 ppm and not larger than 500 ppm, further preferably not smaller than 3 ppm, still further preferably not smaller than 10 ppm. If the amount of element of at least one kind selected from germanium, antimony, and titanium is smaller than 1 ppm, the effect of improving flavor property is sometimes insufficient. If the amount exceeds 500 ppm, foreign matters are produced in polyester and serve as a crystalline nucleus, so that crystallization is liable to occur. In some cases, therefore, the impact resistance is deteriorated or heat resistance is decreased. Among these elements, germanium is especially favorable in terms of flavor property.
A compound used for adding an element of at least one kind selected from germanium, antimony, and titanium to the polyester resin of the present invention are as follows: As a germanium compound, for example, germanium oxide such as germanium dioxide and crystallization water containing germanium hydroxide, hydroxide, or a germanium alkoxide compound such as germanium tetramethoxide, germanium tetraethoxide, germanium tetrabutoxide, and germanium ethyleneglycoxide, a germanium phenoxide compound such as germanium phenolate and germanium β-naphtholate, a phosphorus containing germanium compound such as germanium phosphate and germanium phosphite, and germanium acetate can be cited.
As an antimony compound, diantimony trioxide, antimony trifluoride, antimony acetate, antimony borate, antimony formate, antimonious acid, and the like can be cited.
As a titanium compound, oxide such as titanium dioxide, hydroxide such as titanium hydroxide, an alcoxide compound such as tetramethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, tetraisopropoxy titanate, and tetrabutoxy titanate, a glycoside compound such as tetrahydroxyethyl titanate, a phenoxide compound, and a compound such as acetate etc. can be cited.
As a method for adding the above-described element to polyester rein, arbitrary one of conventionally known methods can be used, and the method is not subject to any special restriction. It is preferable that the element be added as a polymerization catalyst usually at an arbitrary stage before the manufacture of polyester is finished. As such a method, in the case of germanium as an example, a method in which germanium compound powder is added as it is, a method in which a germanium compound is melted in a glycol compound, which is a starting material for polyester, and is added as described in Japanese Patent Publication No. 54-22234, and the like method can be cited.
When modified polyolefin resin containing carboxylic acid specified in the present invention is mixed with polyester resin, usually, if the polymerization catalyst mixed in polyester resin and the oxidation inhibitor generally used for stabilization of vinyl polymer coexist, the resin is deteriorated, and hence the performance is decreased. The mechanism for deteriorating the resin and decreasing the performance is not necessarily clear, but it is presumed that the oxidation inhibitor acts on the polymerization catalyst and the effect of polymerization catalyst is decreased, and in particular, a compound that deteriorates polyester resin is produced. In the present invention, therefore, the ratio of the amount X of polymerization catalyst added to the mixed resin to the amount Y of oxidation inhibitor, i.e., X/Y (weight ratio) must be 0.2 or higher. Further, the amount of oxidation inhibitor is preferably 500 ppm or smaller. As such an oxidation inhibitor, one or two kinds selected from phenol base oxidation inhibitor, phosphorus base oxidation inhibitor, sulfide base oxidation inhibitor, and nitrogen base oxidation inhibitor can be cited.
Regarding the mechanical properties of resin film consisting of a mixed resin that withstand severe forming, the breakage elongation is preferably 20% or more, further preferably 50% or more, and the breakage strength is preferably 20 N/mm2 or higher. Herein, the breakage elongation and breakage strength of resin film is determined by using an ordinary tensile testing machine. As a tensile testing method, a resin coated layer measuring 5 mm×60 mm is set at a distance between chucks of 30 mm, and a tensile test is conducted at a tensile speed of 20 mm/min at a constant temperature of 25° C. When tensile properties at low temperature is determined, the same tensile test can be conducted at a constant temperature of 0 to −5° C. A resin sample for testing may be taken from either of film, resin laminated metal sheet, and formed body.
In the present invention, it is specified that 5 to 40 wt % of pigment is contained in resin film. In the polyester resin in which modified polyolefin resin is dispersed, the dispersibility of pigment is improved, and the objective color tone can be obtained by the addition of a small amount of pigment. If the content of pigment is lower than 5 wt %, a desired color tone cannot be obtained, and if it exceeds 40 wt %, the formability is decreased. The kind of pigment is not subject to any special restriction. However, unless the effects of the present invention are hindered, calcium carbonate, barium sulfate, barium carbonate, aerosil, titanium dioxide, zinc white, gloss white, alumina white, magnesium carbonate, carbon black, magnetite, cobalt blue, iron oxide red, or the like is used appropriately, by which a metal laminated sheet or a metal can can be finished so as to have a favorable color tone.
The resin film consisting of the above-described mixed resin has high adhesion to a substrate metal, excellent formability and impact resistance, and flavor property enough for ordinary use as compared with the ordinary polyester resin, so that it is suitable for use as resin film for resin laminated metal sheet.
However, the resin film consisting of the above-described mixed resin may have insufficient adhesion to a substrate metal when being subjected to severe forming. Also, many persons are very sensitive to a change in flavor depending on the recent applications, and impose very rigid requirements. Contrary to such requirements, the resin film consisting of the above-described mixed resin may have an insufficient flavor property because it contains an olefin compound.
The above-described problem is solved by using a film in which a modified polyolefin resin layer containing carboxylic acid is laminated on the resin film consisting of the above-described mixed resin or a film in which a polyester resin layer containing no olefin resin is laminated. The above-described resin film of a multilayer construction will be explained below.
(1) Design is made so that the resin film is a film having a construction such that a resin layer (in this description, also referred to as R2 layer) consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid is laminated on a resin layer (in this description, also referred to as R1 layer or mixed resin layer) consisting of the above-described mixed resin, and when the film is laminated to a metal sheet, the R2 layer serves as an adhesion layer to a substrate metal.
By the film having the above-described construction, the adhesion after forming or after heating can be improved dramatically. Further, since the modified polyolefin resin layer (R2 layer) has high adhesion to the mixed resin layer (R1 layer), separation between layers does not occur, and high adhesion can be kept as a whole. This mechanism is presumed as follows: Polyester resin is originally a resin having few functional groups such as to have chemical bonding to the substrate metal, so that it does not have so high metal adhesion. On the other hand, modified polyolefin resin having a group derived from carboxylic acid is characterized in that the carboxylic acid deriving group contained in the resin has a strong interaction with the substrate metal, so that it has very high adhesion. However, it has inferior heat resistance and flavor property, so that it cannot be used as a film for the internal surface of can. Thereupon, it is expected that if the modified polyolefin resin layer is used as an adhesion layer to the substrate metal and a polyester resin layer is laminated thereon, a film in which both of the adhesion and other performance such as heat resistance and flavor property are achieved can be obtained. However, since the melting viscosity and melting point differ greatly between these resins, the adhesion between layers at the time of laminating these resins is very poor, and such a double-layer film cannot be manufactured actually. The present invention can achieve two effects at the same time. Specifically, modified polyolefin resin of the same composition as that of the modified polyolefin resin layer (R2 layer), which is an adhesion layer, is mixed in the mixed resin layer (R1 layer), by which the adhesion between layers is enhanced to a level at which there is no problem in terms of manufacture and practical use, and also the modified polyolefin resin mixed in the polyester resin is formed into a granular shape, by which the formability and impact resistance can be improved.
The film in which the mixed resin layer (R1 layer) and the modified polyolefin resin layer (R2 layer) are laminated can be obtained by the ordinary double-layer resin extruding method. Specifically, by using two extruding machines, mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in thermoplastic polyester resin and resin consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid are inserted in separate extruding machines, respectively, as raw material resins of R1 and R2 layers, and the resins are melted to a temperature above the respective melting point and are extruded from one T die in a state of being laminated by the feed block method or the multi-manifold method to form a film as a double-layer film by being cooled with a cooling roll etc. and then the film is laminated to a metal sheet. Alternatively, the molten resin is extruded directly on the metal sheet, and then is laminated by being held between the cooling rolls. Thereby, a resin layer of double layers can be manufactured. As the T die method, it is especially preferable that the resin layer be manufactured by the multi-manifold method in which the melting temperatures of a plurality of resins can be controlled precisely.
Also, as another manufacturing method, since the surface tension of modified polyolefin resin is lower than that of polyester resin, by utilizing a property such that modified polyolefin resin is concentrated on the surface of mixed resin during the time when molten mixed resin is cooled, both resins are inserted into one extruding machine, and the cooling rate is decreased when the resins are melted and mixed and extruded from a T die, by which the modified polyolefin resin is concentrated on the surface of mixed resin. By this method as well, a laminated film of both resins can be manufactured.
The thickness ratio R1/R2 of R1 layer to R2 layer is preferably R1/R2=1/1 to 20/1, further preferably R1/R2=5/1 to 10/1, in a composition such that the mechanical properties such as formability and impact resistance and adhesion are at the maximum. If the R1 layer is thinner than this, the mechanical properties are deteriorated greatly. On the other hand, if the R2 layer is thinner than this, the adhesion is deteriorated. Further, the optimum thickness of modified polyolefin resin of R2 layer is preferably 1 to 10 μm, further preferably 1 to 5 μm. If the thickness is smaller than 1 μm, the adhesion is insufficient. On the other hand, if the thickness exceeds 10 μm, high impact resistance and formability of olefin dispersing polyester resin of R1 layer are lost. Similarly, the optimum thickness of modified polyolefin dispersing polyester resin of R1 layer is preferably 10 to 50 μm, further preferably 15 to 25 μm. If the thickness is smaller than 10 μm, the impact resistance and formability are insufficient. On the other hand, if the thickness exceeds 50 μm, these properties are not enhanced, being disadvantageous in terms of cost.
Furthermore, the optimum composition of modified polyolefin resin of R2 layer is, as in the case of modified polyolefin in mixed resin of R1 layer, a composition that contains preferably 2 to 20 wt %, further preferably 3 to 12 wt %, of a functional group derived from carboxylic acid, by weight percentage in carboxylic acid conversion. The reason for this is that regarding adhesion after severe forming or shock, not only the adhesion of resin to a substrate metal but also the adhesion of mixed resin of R1 layer to modified polyolefin resin of R2 layer is important, and the adhesion of these two layers depends basically on the interaction between modified polyolefin resins, so that resin composition closer to each other is advantageous. Herein, weight percentage in carboxylic acid conversion means that all functional groups derived from carboxylic acid contained in modified polyolefin resin are converted into carboxylic acid by hydrolysis or neutralization using acid, and the amount of carboxylic acid group (—COOH) in the original modified polyolefin resin is expressed by weight percentage.
(2) Design is made so that the resin film is a film having a construction such that a polyester resin layer (in this description, also referred to as R0 layer) containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is laminated on the mixed resin layer (R1 layer), and when the film is laminated to a metal sheet, the R0 layer serves as an outermost layer.
The polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton means polyester resin in which the sum of a portion in which only ethylene glycol and tereophthalic acid in the polyester resin skeleton are a unit and/or a portion in which ethylene glycol and tereophthalic acid and isophthalic acid are a unit accounts for 90% or more by weight. In other portions, as the acid component, various kinds of aromatic dicarboxylic acids and aliphatic dicarboxylic acids may be copolymerized arbitrarily.
Since the R1 layer is soft, in copolymerized polyester resin, the heat resistance and flavor property are sometimes inferior. A two-layer construction is provided in which the resin layer (R1 layer) consisting of mixed resin in which modified polyolefin resin is dispersed is made a lower layer, and the polyester resin (R0 layer) containing no olefin is made an upper layer, and the R0 layer is made a layer that comes into contact with the content, by which the flavor property of film is dramatically enhanced. Thereby, the flavor property can be enhanced to a level that meets the above-described rigid requirements. A slight olefin portion contained in polyester resin provides greater sorption of terpene hydrocarbon such as d-limonene, which is a flavor component, than the polyester portion, so that the sorption of flavor is great as a whole as compared with polyester resin containing no olefin. Therefore, when the flavor-containing content comes into contact with the film, a larger amount of flavor component transfers from the content to the film. To restrain such a phenomenon, it is effective to provide a polyester resin layer containing no olefin component on a polyester resin layer containing olefin component. Also, the mechanical properties such as formability and impact resistance can be improved.
The optimum thickness of the upper layer (R0 layer) is preferably 1 to 10 μm, further preferably 3 to 5 μm. If the thickness is smaller than 1 μm, the effect of restraining sorption of flavor component can scarcely be expected. On the other hand, if the thickness exceeds 10 μm, high impact resistance and formability of olefin dispersed polyester resin of the lower layer is lost. The optimum thickness of the lower layer (R1 layer) is preferably 10 to 50 μm, further preferably 15 to 25 μm. If the thickness is smaller than 10 μm, the impact resistance and formability are insufficient. On the other hand, even if the thickness exceeds 50 μm, these properties are not enhanced, being disadvantageous in terms of cost.
The total film thickness of R1 layer and R0 layer is preferably in the range of 10 to 50 μm. The upper limit value is determined from the economical viewpoint, and the lower limit value is determined from the viewpoints of impact resistance and formability. Specifically, if the total thickness is not smaller than 10 μm, the impact resistance and formability becomes higher, but if the total thickness exceeds 50 μm, the cost of resin film increases, and the effect of improving impact resistance and formability is saturated.
The thickness ratio R1/R0 of the lower layer (R1 layer) to the upper layer (R0 layer) is preferably R1/R2=2/1 to 10/1, further preferably 5/1 to 10/1, in a composition such that the mechanical properties such as formability and impact resistance and flavor property are at the maximum. If the R0 layer is thicker than this, the mechanical properties are deteriorated greatly. On the other hand, if the R0 layer is thinner than this, the R0 and R1 layers do not have uniform film thickness in the line direction and the width direction, so that the performance varies and becomes poor.
For the polyester resin of R0 layer, the content of diethylene glycol is preferably 1.5% or lower by weight, further preferably 0.9% or lower by weight. If the content of diethylene glycol is high, deterioration of polymer progresses due to heating treatment such as drying and printing at the forming time, and hence cracks or pinholes are produced, so that the impact resistance and flavor property are sometimes deteriorated.
The intrinsic viscosity of polyester resin of R0 layer is preferably 0.3 to 2.0 dl/g, further preferably 0.3 to 1.5 dl/g, still further preferably 0.5 to 1.0 dl/g. If the intrinsic viscosity is lower than 0.3 dl/g, the mixing with modified polyolefin resin is remarkably difficult. As the result of nonuniform dispersion of modified polyolefin resin, the mechanical strength and impact resistance of polyester resin may be decreased. On the other hand, if the intrinsic viscosity exceeds 2.0 dl/g, the formability is poor because of low viscosity, so that it may become difficult to manufacture a uniform film. The intrinsic viscosity is measured by the method specified in JIS K7367-5. It is measured in o-chlorophenol at 25° C. in a concentration of 0.005 g/ml, and is determined by the formula of intrinsic viscosity=(T−T0)/(T0×c). In this formula, c expresses resin concentration per 100 ml of solution in gram, and T0 and T express drop time in a capillary viscometer of solvent and resin solution, respectively.
The glass-transition temperature (Tg) of the polyester resin of R0 layer is preferably 30 to 100° C., further preferably 50 to 80° C. If the glass-transition temperature is lower than 30° C., a flaw etc. are liable to be produced by a temperature rise at the forming time because of deteriorated heat resistance of polyester resin. On the other hand, if the glass-transition temperature exceeds 100° C., inversely the formability is sometimes deteriorated. Also, the low-temperature crystallization temperature (Tc) is usually 70 to 21° C., preferably 80 to 200° C. The melting point (Tm) is usually 210 to 265° C., preferably 220 to 260° C. If the low-temperature crystallization temperature is lower than 70° C., crystallization is liable to occur, so that crystallization occurs at the time of retorting, by which the film is easily cracked or separated. On the other hand, if the low-temperature crystallization temperature exceeds 210° C., the mechanical strength is deteriorated. If the melting point is lower than 210° C., resin is deteriorated by heat at the forming time, so that cracks or pinholes are liable to be produced. On the other hand, if the melting point exceeds 265° C., crystallization progresses due to heating treatment such as drying and printing at the forming time, and hence cracks or pinholes are also liable to be produced. The above-described glass-transition temperature, low-temperature crystallization temperature, and crystal melting point are obtained by measuring endothermic peak temperature at the time of temperature rise using a differential scanning calorimeter (DSC). The measurement is made under conditions of sample amount of 10 mg and temperature rise rate of 10° C./min.
The film in which the mixed resin layer (R1 layer) and the polyester resin layer (R0 layer) containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton are laminated can be obtained by the ordinary double-layer resin extruding method. Specifically, by using two extruding machines, mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin as described in any one of claims 1 to 8 and polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton are inserted in separate extruding machines, respectively, as raw material resins of R1 and R0 layers, and the resins are melted to a temperature above the respective melting point and are extruded from one T die in a state of being laminated by the feed block method or the multi-manifold method to form a film as a double-layer film by being cooled with a cooling roll etc. and then the film is laminated to a metal sheet. Alternatively, the molten resin is extruded directly on the metal sheet, and then is laminated by being held between the cooling rolls. Thereby, a resin layer of double layers can be manufactured. As the T die method, it is especially preferable that the resin layer be manufactured by the multi-manifold method in which the melting temperatures of a plurality of resins can be controlled precisely.
Also, unless the effects of the present invention are hindered, an additive, such as a light stabilizer, impact resistance improving agent, compatibilizing agent, lubricant, plasticizer, antistatic agent, reaction catalyst, color preventing agent, free radical inhibitor, plasticizer, antistatic agent, terminal closing agent, oxidation inhibitor, heat stabilizer, mold releasing agent, flame retarder, antibacterial agent, and fungistat, may be added to the polyester resin of R0 layer. The content of these additives is preferably not lower than 0.005 weight part and not higher than 15 weight part, further preferably not lower than 0.01 weight part and not higher than 2 weight part, especially preferable not lower than 0.05 weight part and not higher than 0.5 weight part, with respect to 100 weight part of polyester resin of R0 layer. If the content is lower than 0.005 weight part, the effect is insufficient. On the other hand, the content exceeds 15 weight part, the additive is excessive, so that the component contained in the polyester resin phase decreases the mechanical properties.
As inorganic particles having the effect of improving lubricity, formability, and impact resistance, silica manufactured by the dry method or wet method, porous silica, colloidal silica, titanium oxide, zirconium oxide, aluminum oxide, calcium carbonate, talc, calcium sulfate, barium sulfate, spinel, iron oxide, calcium phosphate, and the like are cited. Also, as organic particles or polymeric organic particles, vinyl resin particles such as polystyrene particles, crosslinking polystyrene particles, styrene-acrylic crosslinking particles, acrylic crosslinking particles, styrene-methacrylate resin crosslinking particles, and methacrylate resin crosslinking particles, and particles consisting of silicone, benzoguanamin-formaldehyde, polytetrafluoroethylene, polyphenolester, phenolic resin, and the like can be cited. The particle diameter and content of these particles are not subject to any special restriction. However, in order to achieve the performance to the utmost, the particle diameter is preferably in the range of 0.01 to 5 μm, further preferably in the range of 0.1 to 2.5 μm. Also, the particle diameter distribution is preferably sharp, and the standard deviation thereof is preferably 0.5 or less. Further, the shape of particle is preferably truly spherical, and the ratio of larger diameter to shorter diameter is preferably 1.0 to 1.2.
As a reaction catalyst, for example, an alkali metal compound, alkali earth metal compound, zinc compound, lead compound, manganese compound, cobalt compound, and aluminum compound can be cited, and as a color preventing agent, for example, a phosphorus compound can be cited.
As a free radical inhibitor, one or two kinds selected from a phenol base free radical inhibitor, phosphorus base free radical inhibitor, sulfide base free radical inhibitor, and nitrogen base free radical inhibitor can be cited.
As a plasticizer, a plasticizer consisting of polyester obtained by terminal esterifying a material obtained by condensation polymerization of aliphatic polybasic acid with the number of carbons of 2 to 20 or aromatic polybasic acid with the number of carbons of 8 to 20 with respect to ester derivative or polybasic acid component with the molar ratio of the ester derivative of 0 to 2.0 with aliphatic alcohol with the number of carbons of 2 to 20 by monobasic acid with the number of carbons of 2 to 20 or its ester derivative and/or monohydroxy alcohol with the number of carbons of 1 to 18 can be cited.
As an antistatic agent, a method of kneading an antistatic agent disclosed in Unexamined Japanese Patent Publication No. 5-222357 in resin composition, a method of applying an antistatic agent disclosed in Unexamined Japanese Patent Publication No. 5-1164 on film surface, and the like method can be used as necessary in order to prevent electrostatic failure such as winding of film on a roll in the film forming process or contamination adhering to film surface.
As an antibacterial agent, a conventionally known antibacterial agent disclosed in Unexamined Japanese Patent Publication Nos. 11-48431 and 11-138702 can be used as necessary.
The polyester resin of R0 layer preferably contains 1 to 500 ppm; further preferably 3 to 300 ppm, of an element of at least one kind selected from germanium, antimony, and titanium as a polymerization catalyst. If the amount of element of at least one kind selected from germanium, antimony, and titanium is smaller than 1 ppm, the effect of improving flavor property is sometimes insufficient. If the amount exceeds 500 ppm, foreign matters are produced in polyester and serve as a crystalline nucleus, so that crystallization is liable to occur. In some cases, therefore, the impact resistance is deteriorated or heat resistance is decreased. Among these elements, germanium is especially favorable in terms of flavor property.
A compound used for adding an element of at least one kind selected from germanium, antimony, and titanium to the resin of the present invention are as follows: As a germanium compound, for example, germanium oxide such as germanium dioxide and crystallization water containing germanium hydroxide, hydroxide, or a germanium alkoxide compound such as germanium tetramethoxide, germanium tetraethoxide, germanium tetrabutoxide, and germanium ethyleneglycoxide, a germanium phenoxide compound such as germanium phenolate and germanium β-naphtholate, a phosphorus containing germanium compound such as germanium phosphate and germanium phosphite, and germanium acetate can be cited.
As an antimony compound, diantimony trioxide, antimony trifluoride, antimony acetate, antimony borate, antimony formate, antimonious acid, and the like can be cited.
As a titanium compound, oxide such as titanium dioxide, hydroxide such as titanium hydroxide, an alcoxide compound such as tetramethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, tetraisopropoxy titanate, and tetrabutoxy titanate, a glycoside compound such as tetrahydroxyethyl titanate, a phenoxide compound, and a compound such as acetate etc. can be cited.
As a method for adding the above-described element to polyester, arbitrary one of conventionally known methods can be used, and the method is not subject to any special restriction. It is preferable that the element be added as a polymerization catalyst usually at an arbitrary stage before the manufacture of polyester is finished. As such a method, in the case of germanium as an example, a method in which germanium compound powder is added as it is, a method in which a germanium compound is melted in a glycol compound, which is a starting material for polyester, and is added as described in Japanese Patent Publication No. 54-22234, and the like method can be cited.
For the polyester resin of R0 layer of the present invention, the content of acetaldehyde in the resin is preferably not higher than 10 ppm, further preferably not higher than 7 ppm from the viewpoint of flavor property. If the content of acetaldehyde exceeds this range, especially 10 ppm, the flavor property is sometimes deteriorated. The method for limiting the content of acetaldehyde to 10 ppm or lower is not subject to any special restriction. For example, a method can be cited in which polyester resin is formed into a film, the polyester resin being obtained by a method in which resin is heat-treated at a temperature below the melting point of polyester under a reduced pressure or in an inert gas atmosphere to remove acetaldehyde produced by thermal decomposition at the time when polyester resin is manufactured by condensation polymerization etc. Preferably, a method should be used in which polyester resin that is obtained by solid-phase polymerizing resin at a temperature higher than 150° C. and lower than the melting point under a reduced pressure or in an inert gas atmosphere.
Also, the polyester resin in accordance with the present invention preferably has less oligomer consisting of a cyclic trimer etc. in resin from the viewpoint of flavor property. In particular, the content of cyclic trimer is preferably 0.9% or lower by weight, further preferably 0.7% or lower by weight. If the content of oligomer in resin exceeds this range, especially 0.9% by weight, the flavor property is sometimes deteriorated. The method for limiting the content of oligomer to 0.9% or lower by weight is not subject to any special restriction, and this content of oligomer can be achieved by using the same method as the above-described method for reducing the content of acetaldehyde.
When an oxidation inhibitor is added to the R0 layer, the added amount should preferably be the same as the added amount to the R1 layer to minimize the influence on the R1 layer.
(3) Design is made so that the resin film is a film having a three-layer construction of R0 layer/R1 layer/R2 layer such that the polyester resin layer (R0 layer) containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is laminated on one surface of the resin layer (R1 layer) consisting of mixed resin, and the resin layer (R2 layer) consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid is laminated on the other surface of the R1 layer; and when the film is laminated to a metal sheet, the R0 layer serves as an outermost layer.
This film is formed by laminating the R0 layer described in the above item (1) on the R1 layer of the resin film of a two-layer construction consisting of R1 layer and R2 layer described in the above item (2). This film having a three-layer construction has high adhesion to the substrate metal and high flavor property. The construction and operation/effect of the R1 layer, R0 layer, and R2 layer are the same as those described in the above items (1) and (2). Further, such a three-layer construction enhances adhesion and a stress relaxing effect, so that defects are less liable to be produced in forming, and thus the formability is enhanced dramatically.
The above-described film having a three-layer construction of R0 layer/R1 layer/R2 layer can be obtained by the ordinary extruding method for a double-layer resin. Specifically, by using three extruding machine, mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin as described in any one of claims 1 to 8 is inserted in the extruding machine as a raw material of R1 layer and is melted, and at the same time, polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton and modified polyolefin resin having a functional group derived from carboxylic acid are inserted in extruding machines separate from the above-described extruding machine, respectively, as raw material resins of R0 and R2 layers, and the resins are melted to a temperature above the respective melting point and are extruded from one T die in a state of being laminated by the feed block method or the multi-manifold method to form a film as a multi-layer film by being cooled with a cooling roll etc. and then the film is laminated to a metal sheet. Alternatively, the molten resin is extruded directly on the metal sheet, and then is laminated by being held between the cooling rolls. Thereby, a resin layer of multiple layers can be manufactured. As the T die method, it is especially preferable that the resin layer be manufactured by the multi-manifold method in which the melting temperatures of a plurality of resins can be controlled precisely.
Furthermore, in any case, the resin film can be formed so as to have a layer construction such that another polyester resin layer is laminated on the mixed resin layer (R1 layer) or the polyester resin layer (R0 layer) containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton. In this case, the polyester resin that is a raw material of the third layer is inserted in a separate extruding machine and is melted, and is poured into a T die simultaneously with other resins and is extruded through one port, by which a resin film is manufactured. When the resin layer (R2 layer) consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid exists, design must be made so that the R2 layer is on the substrate metal side.
In the resin films described in the above items (1) to (3) it is specified that five to 40 wt % of pigment is contained in resin film. In the polyester resin in which modified polyolefin resin is dispersed, the dispersibility of pigment is improved, and the objective color tone can be obtained by the addition of a small amount of pigment, so that it is preferable to add pigment to the R1 layer. If the content of pigment in the resin film is lower than 5 wt %, a desired color tone cannot be obtained, and if it exceeds 40 wt %, the formability is decreased. The kind of pigment is not subject to any special restriction. However, unless the effects of the present invention are hindered, calcium carbonate, barium sulfate, barium carbonate, aerosil, titanium dioxide, zinc white, gloss white, alumina white, magnesium carbonate, carbon black, magnetite, cobalt blue, iron oxide red, or the like is used appropriately, by which a metal laminated sheet or a metal can can be finished so as to have a favorable color tone.
In the present invention, the metal sheet is not subject to any special restriction. However, a metal sheet formed of iron and aluminum is preferable in terms of formability. In the case of metal sheet formed of iron, in order to improve the resin adhesion and corrosion resistance, an inorganic oxide film layer, for example, a chemical conversion coating layer represented by chromic acid treatment, phosphate treatment, chromic acid/phosphate treatment, electrolytic chromic acid treatment, chromate treatment, chrome chromate treatment, and the like may be provided on the surface of metal sheet. Also, a malleable metal plating layer, for example, a plating layer of nickel, tin, zinc, aluminum, gun metal, brass, or the like may be provided. Also, the plating layer having the amount of plating of 0.5 to 15 g/m2 in the case of tin plating and 1.8 to 20 g/m2 in the case of nickel or aluminum plating is especially preferable in terms of formability and resin adhesion. The thickness of such a metal sheet is usually 0.01 to 5 mm, preferably 0.1 to 2 mm. On one surface or both surfaces of the metal sheet, a resin laminated layer coated with the above-described resin composition layer in accordance with the present invention is formed.
In the case of metal sheet in which iron is used as a raw material, the steel sheet subjected to electrolytic chromate treatment defined in the eighth invention is especially preferable in terms of adhesion to the resin film of the present invention, corrosion resistance, and manufacturing cost. Since the resin in accordance with the present invention has high adhesion after forming or heating, the optimum range of metallic chromium and chromium oxide is wider than that of the conventional resin. However, it has been found that when higher performance is demanded, the range of the present invention is the optimum one. The reason why the lower limit of the amount of metallic chromium in metallic chromium layer is specified so as to be 50 mg/m2 is that if the amount is smaller than 50 mg/m2, the corrosion resistance and adhesion after forming are sometimes insufficient. The reason why the upper limit thereof is specified so as to be 200 mg/m2 is that if the amount exceeds 200 mg/m2, the effect of improving the corrosion resistance and adhesion after forming is saturated, and inversely the manufacturing cost is increased. The reason why the lower limit of metallic chromium conversion amount of the amount of chromium in chromium oxide is specified so as to be 3 mg/m2 is that if the amount is smaller than 3 mg/m2, the adhesion is sometimes deteriorated. The reason why the upper limit thereof is specified so as to be 30 mg/m2 is that if the amount exceeds 30 mg/m2, the color tone is deteriorated, and also the adhesion becomes inferior.
The reason why the plane orientation coefficient in the direction parallel with the film surface of resin film is specified so as to be 0.010 or lower is that the resin film in this range especially has high formability. As the plane orientation coefficient increases, the formability becomes inferior. This is because oriented crystals hinder plastic deformation as described above. The range of plane orientation coefficient in accordance with the present invention is at a level at which adverse influence is not substantially exerted on the formability. Also, even in the range of plane orientation coefficient of the 24th invention, sufficiently high impact resistance is provided as compared with the prior art. However, considering the required formability and impact resistance, the plane orientation coefficient can also be increased intentionally to 0.010 or higher to obtain still higher impact resistance. The above-described film orientation can be obtained by laminating a stretched film to the metal sheet. Specifically, a film is stretched in the one-axis or two-axis direction by the publicly known method at the time of film manufacture to provide stretch orientation, and the stretched film is thermally laminated by being controlled so that the orientation remains at the laminating time, by which the film orientation can be obtained. Regarding the stretching of film, two-axis stretching is especially superior from the viewpoint of mechanical properties.
As the method for manufacturing a resin laminated metal sheet, the publicly known method can be used. An especially preferable method is one in which a resin film is pushed, by using a rotating roll, on a metal sheet heated to a temperature in the range of the melting point of polyester resin in mixed resin of R1 layer minus 70° C. to the melting point thereof plus 30° C. to laminate the resin film to the metal sheet. If the heating temperature is lower than the melting point of polyester resin minus 70° C., the adhesion to metal sheet is insufficient, and if it exceeds the melting point of polyester resin plus 30° C., the film layer fuses to the laminate roll. Since the resin of the present invention has high formability and adhesion after heating, the optimum range of manufacturing conditions in film laminating becomes wider than that in the case of the conventional resin, so that labor saving and stabilization in terms of manufacture control and quality control can be provided advantageously.
As the laminating film, both a stretch oriented film and a non-stretched film can be used. In particular, when the stretched film is used, control is needed so that the degree of orientation is made a target value by temperature control at the thermal laminating time as described above.
When a resin laminated metal sheet is manufactured, a direct laminating method in which molten resin is extruded directly on a metal sheet, and then is laminated by being held between cooling rolls as described below is preferable.
When a resin film consisting of mixed resin is laminated to a metal sheet, a mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin as described in any one of claims 1 to 8 is inserted in an extruding machine as a resin used for raw material, the above-described resin used for raw material is heated to a temperature in the range of the melting point of polyester resin in that resin plus 10 to the melting point plus 50° C. and is melted, and then the molten resin is directly extruded from a T die and is laminated on the surface of metal sheet.
When a resin film consisting of R1 layer and R0 layer is laminated to a metal sheet, a mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin as described in any one of claims 1 to 8 is inserted in an extruding machine as a resin used for raw material of R1 layer, and at the same time, a resin consisting of polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton is inserted in a separate extruding machine as a resin used for raw material of R0 layer. After these resins are heated to a temperature in the range of the melting point of polyester resin in the R1 layer plus 10° C. to the melting point plus 50° C. and are melted, they are directly extruded in two layers from a T die and are laminated on the surface of metal sheet so that the R1 layer is on the metal sheet side in a state in which the R1 layer and the R0 layer are laminated.
When a resin film consisting of R1 layer and R2 layer is laminated to a metal sheet, a mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin as described in any one of claims 1 to 8 is inserted in an extruding machine as a resin used for raw material of R1 layer, and at the same time, a resin consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid is inserted in a separate extruding machine as a resin used for raw material of R2 layer. After these resins are heated to a temperature in the range of the melting point of polyester resin in the R1 layer plus 10° C. to the melting point plus 50° C. and are melted, they are directly extruded in two layers from a T die and are laminated on the surface of metal sheet so that the R2 layer is on the metal sheet side in a state in which the R1 layer and the R2 layer are laminated.
When a resin film of three-layer construction of R0 layer/R1 layer/R2 layer is laminated to a metal sheet, a mixed resin in which granular modified polyolefin resin with a grain diameter of 0.1 to 5 μm is dispersed in advance in the thermoplastic polyester resin as described in any one of claims 1 to 8 is inserted in an extruding machine as a resin used for raw material of R1 layer, and at the same time, a resin consisting of polyester resin containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a main basic skeleton and a resin consisting mainly of modified polyolefin resin having a functional group derived from carboxylic acid are inserted in extruding machines separate from the above-described extruding machine, respectively, as resins used for raw materials of R0 and R2 layers. After these resins are heated to a temperature in the range of the melting point of polyester resin in the R1 layer plus 10° C. to the melting point plus 50° C. and are melted, they are directly extruded in three layers from a T die and are laminated on the surface of metal sheet so that the R2 layer is on the metal sheet side, the R1 layer is an intermediate layer, and the R0 layer is an outermost layer in a state in which the R0 layer, the R1 layer, and the R2 layer are laminated.
If the temperature at which resin is melted is lower than the melting point of polyester resin plus 10° C., the viscosity of resin is remarkably inferior, so that the quality stability and productivity are deteriorated. If the temperature exceeds the melting point of polyester resin plus 50° C., there arise problems of adhesion to laminate roll, intrusion of air bubble, and deteriorated resin. The temperature is preferably not higher than the melting point of polyester resin plus 40° C. Also, the temperature of metal sheet is preferably in the range of the melting point of polyester resin in mixed resin of R1 layer minus 70° C. to the melting point plus 30° C.
The resin in accordance with the present invention need not be controlled strictly even under the manufacturing conditions in extrusion laminating. Therefore, labor saving and stabilization in terms of manufacture control and quality control can be provided advantageously. Also, such a mixed resin having uniform grain diameter and high dispersibility is inserted in the extruding machine to form a film. Therefore, the grain diameter distribution of granular resin is narrowed remarkably as compared with the case where modified polyolefin resin is dispersed while a film is formed, and resultantly a film that achieves high grade in various performances can be obtained.
The reason why the resin film is limited to one that is coated by the extrusion laminating method is that the extrusion laminating method is superior to the ordinary film laminating method from the viewpoint of inclusion of air bubbles at the laminating time. In the general film laminating method, in particular, as the laminating speed increases, air bubbles are liable to be included. The included air bubbles not only decrease adhesion to a substrate metal sheet but also exert an adverse influence on impact resistance. The inventors found out that since stresses concentrate in the edge portion of air bubble at the time of shock, this portion is brittle and serves as a starting point of film fracture. Further, a difference in manufacturing cost between the process in which resin is formed into a film and laminated and the process in which resin is directly extruded and laminated is also an advantage of the extrusion laminating method.
The resin in accordance with the present invention can be manufactured by the extrusion laminating method that cannot be used for the conventional polyester resin because the resin of the present invention can provide sufficient performance substantially even in a non-oriented state. The conventional polyester resin requires strict control of orientation amount, so that it cannot be manufactured by direct extrusion that cannot be controlled strictly. As compared with this, the resin of the present invention also has a great advantage in terms of manufacture.
For the resin laminated metal sheet in accordance with the present invention, a metal sheet has only to be coated with the resin film of the present invention. The publicly known resin film may be laminated as necessary to the lower layer and/or the upper layer of resin film of the present invention, and a metal sheet may be coated with the laminated film.
In the present invention, unless the effects of the present invention are hindered, a primer layer may be provided as an adhesion layer to metal sheet. Although the laminated metal sheet of the present invention has high primary adhesion between resin layer and metal sheet and high adhesion after forming, in a severer corrosive environment or in an environment in which higher adhesion is required, a primer layer can be provided to provide characteristics that meet the requirement. For example, when the laminated metal sheet is used as a metallic can, if more corrosive content is put into the can, the content intrudes an interface with metal sheet through the resin layer, by which the metal sheet may be corroded, and the adhesion to film may be deteriorated. In such a case, a proper primer layer is provided to prevent the resin layer from being separated. When the R2 layer is absent, it is effective to provide the primer layer as an adhesion layer.
The kind of primer is not subject to any special restriction, and the publicly known primer layer can also be used. For example, a water-base dispersing agent of polyester resin base disclosed in Japanese Patent Publication No.60-12233, an epoxy-base primer disclosed in Japanese Patent Publication No. 63-13829, and a polymer having various functional groups disclosed in Unexamined Japanese Patent Publication No. 61-149341 can be cited. Also, a method for forming a primer layer is not subject to any special restriction. A primer paint may be applied on the metal sheet and dried, or a primer paint may be applied on the film of the present invention and dried. Alternatively, a primer film may be laminated to the metal sheet, or a film formed by affixing a primer layer to the film of the present invention may be laminated.
The resin film in accordance with the present invention can be used suitably to coat the internal surface of a two-piece metallic can manufactured by drawing or ironing. Also, since the film in accordance with the present invention has good metal adhesion and formability as a coating film for a lid portion of two-piece can or a sidewall, lid, and bottom of three-piece can, it can be favorably used in this application. Also, the resin laminated metal sheet coated with the film has high formability, impact resistance, and adhesion, it is suitable as a material used for a thin-wall deep drawn can in which a decrease in material thickness progresses and especially severe forming is forced.
Also, since the resin laminated metal sheet coated with the film can prevent the film from being whitened at the retorting time, it can suitably be used as a can member used for a can lid or a can bottom that is required to prevent the film from being whitened, for example, a lid member of two-piece can or a lid member or a sidewall member of three-piece can.
EXAMPLE 1
Modified polyolefin resin with group derived from carboxylic acid having a primary grain diameter of 0.3 μm, which was a starting raw material, was cold blended with polyester resin in a blending ratio given in Tables 1 and 2 by using a tumbler blender, and then the blended resin was melted and kneaded at 260° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. The obtained raw material resin pellet was extruded from a T die by using a one-axis extruding machine, by which a resin film with a thickness of 5 to 55 μm was manufactured.
The used polyester resin and modified polyolefin resin with group derived from carboxylic acid were as follows:
1. Polyester Resin
(1) PET/I(18): Ethylenephthalate-ethyleneisophthalate copolymerized resin with a ratio of terephthalic acid to isophthalic acid of 82:18 (manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.6 dl/g, Tg: 58° C., Tc: 210° C., Tm: 215° C., Ge content: 10 ppm
(2) PET/I(10): Ethylenephthalate-ethyleneisophthalate copolymerized resin with a ratio of terephthalic acid to isophthalic acid of 90:10 (IP121B manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.6 dl/g, Tg: 70° C., Tc: 170° C., Tm: 230° C., Ge content: 10 ppm
(3) PET/I(5): Ethylenephthalate-ethyleneisophthalate copolymerized resin with a ratio of terephthalic acid to isophthalic acid of 95:5 (manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.62 dl/g, Tg: 720° C., Tc: 156° C., Tm: 255° C., Ge content: 20 ppm
(4) PET/I(2): Ethylenephthalate-ethyleneisophthalate copolymerized resin with a ratio of terephthalic acid to isophthalic acid of 98:2 (manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.6 dl/g, Tg: 68° C., Tc: 150° C., Tm: 250° C., Ge content: 10 ppm
(5) PET: Homopolyethylene phthalate resin (EFG10 manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.62 dl/g, Tg: 72° C., Tc: 150° C., Tm: 255° C., Ge content: 20 ppm
2. Modified Polyolefin Resin with Group Derived from Carboxylic Acid
(1) EM1: Polymethyl methacrylate-ethylene-ethyl acrylate copolymer) graft copolymer (Modiper A5200 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 21 wt %, glass-transition temperature: −30° C. or lower
(2) EM2: Polymethyl methacrylate-(ethylene-ethyl acrylate-maleic anhydride copolymer) graft copolymer (Modiper A8200 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 18 wt %, glass-transition temperature: −30° C. or lower
(3) EM3: Ethylene-ethyl acrylate-maleic anhydride copolymer (Bondine HX8290 manufactured by Sumitomo Chemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 11 wt %, glass-transition temperature: −30° C. or lower
(4) EM4: Ethylene-methacrylic acid copolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 8 wt %, glass-transition temperature: −30° C. or lower
(5) EM5: 50% Zn neutralized substance of ethylene-methacrylic acid copolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co., Ltd. neutralized partially by Zn), weight ratio of functional group derived from carboxylic acid: 7 wt %, glass-transition temperature: −30° C. or lower
(6) EM6: 70% Zn neutralized substance of ethylene-methacrylic acid copolymer (Nucrel N1035 manufactured by Mitsui-DuPont Polychemical Co., Ltd. neutralized partially by Zn), weight ratio of functional group derived from carboxylic acid: 5 wt %, glass-transition temperature: −30° C. or lower
(7) EM7: Ethylene-methacrylic acid copolymer (Nucrel N0200H manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 1 wt %, glass-transition temperature: −30° C. or lower
(8) EM8: Polystyrene-(ethylene-ethyl acrylate copolymer) graft copolymer (Modiper A5100 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 6 wt %, glass-transition temperature: 20° C.
(9) EPR: Ethylene-propylene rubber (EP07P manufactured by JSR Corp.), weight ratio of functional group derived from carboxylic acid: 0 wt %, glass-transition temperature: −30° C. or lower
Pelletized modified polyolefin resin with group derived from carboxylic acid, which was a starting raw material, was mixed with polyester resin in a blending ratio given in comparative example 14 in Table 1, the mixed resin was melted and kneaded at 260° C. by using a one-axis extruding machine, and the mixed resin of modified polyolefin resin and polyester resin was extruded from a T die, by which a resin film with a thickness of 25 μm was manufactured.
For the grain diameter of modified polyolefin resin dispersed in resin film, polyester resin in the surface layer was etched by alkaline aqueous solution and modified polyolefin grains were caused to remain, the larger diameter and shorter diameter thereof were measured one by one, and the grain diameter (in terms of equivalent sphere) was calculated, by which the volume ratio, i.e., the number of grains in the film with one side of 10 μm was determined. Also, various temperatures in the tables were measured by a method using the aforementioned DSC.
As a metal sheet, a tin-free steel (hereinafter abbreviated to TFS) with a thickness of 0.18 mm for thin-wall deep drawn can and 0.23 mm for DI can, which had a degree of temper of DR9, metallic chromium layer of 80 mg/m2, and chromium oxide layer of 15 mg/m2 (metallic chromium conversion), was used, by which a resin laminated metal sheet was obtained by a thermo-compression bonding method in which the resin film obtained as described above was hot-pressed on both surfaces of the metal sheet heated by an induction heating system, and then the laminated metal sheet was rapidly cooled in water. The metal sheet temperature at the laminating time (laminating temperature) is given in Tables 3 and 4.
For the plane orientation coefficient of resin laminated metal sheet, the refractive index was measured by using Abbe's refractometer. In measuring, the light source was a sodium/D ray, the intermediate solution was methylene iodide, and the temperature was 25° C. Then, the refractive index Nx in the lengthwise direction of metal sheet on the film surface, the refractive index Ny in the widthwise direction of metal sheet on the film surface, and the refractive index Nz in the film thickness direction were determined, and the plane orientation coefficient Ns was calculated by the following equation.

Plane orientation coefficient (Ns)=(Nx+Ny)/2−Nz

Furthermore, the resin laminated metal sheet obtained as described above was formed into a can, and subjected to straightening heat treatment to manufacture a sample can. The formability, impact resistance, adhesion after forming, and adhesion after heating of film of manufactured can body were investigated.
The following is a detailed description of the investigation method.
1. Evaluation by Thickness-decreasing Deep Drawing
For a resin laminated metal sheet using a TFS with a thickness of 0.18 mm, a thin-wall deep drawn can was manufactured by the method described below, and the propriety of thin-wall deep drawn can was investigated.
Can Manufacturing
A resin laminated metal sheet was subjected to first-stage drawing and redrawing under the following conditions, by which a thin-wall deep drawn can was obtained.

    
    
        First-stage drawing
    
    


















Blank diameter
150 to 160 mm



First-stage drawing
drawing ratio: 1.65










    
    
        Redrawing
    
    















Primary redrawing
drawing ratio: 1.25


Secondary redrawing
drawing ratio: 1.25


Radius of curvature of die corner in redrawing
0.4 mm


process


Load for pressing wrinkle at the time of redrawing
39227 N (4000 kg)









    
    
        Average Thickness Decreasing Percentage of Can Sidewall
        40 to 55% with respect to thickness of resin laminated metal sheet before forming

1-2 Straightening Heat Treatment

    
    


Forming strain of film caused by can manufacturing was removed by keeping the can in a thermal environment of film melting point minus 15° C. for 30 seconds and then by rapidly cooling it.
1-3 Evaluation of Propriety of Thin-wall Deep Drawn Can
(1) Formability
Evaluation was made as described below by the limit of capability for manufacturing can without film failure. Grades not lower than ◯ marked grade are acceptable.

    Limit of forming (thickness decreasing percentage): Grade
    Incapable of forming at thickness decreasing percentage of 40%: (Inferior)
    Capable of forming up to thickness decreasing percentage of 40%
    Capable of forming up to thickness decreasing percentage of 45%
    Capable of forming up to thickness decreasing percentage of 50%
    Capable of forming up to thickness decreasing percentage of 55%: (Superior)

(2) Evaluation of Room-temperature and Low-temperature Impact Resistance



A can body (thickness decreasing percentage: 50%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, an iron ball of 0.5 kg was dropped from a height of 30 cm to give a shock to the can bottom. Thereafter, the lid was opened, and 1% salt water was poured in the can so that a portion that had suffered shock was immersed. After immersion for five minutes, a load of 6 V was applied across a platinum electrode immersed in the liquid and a can metal portion, and the current value after five minutes was read, by which evaluation was made as described below. The same tests were conducted at room temperature of 20° C. and at a temperature of 0° C. The former test was for evaluating room-temperature impact resistance, and the latter test was for evaluating low-temperature impact resistance. Grades not lower than ◯ marked grade are acceptable.
(Evaluation of Room-temperature Impact Resistance)


    Test result: Grade
    Current value not lower than 30 mA: (Inferior)
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(Evaluation of Low-temperature Impact Resistance)

    Test result: Grade
    Current value not lower than 30 mA: (Inferior)
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(3) Adhesion After Forming



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was immersed in aqueous solution containing 1.5 wt % citric acid and 1.5 wt % sodium chloride for 24 hours. Thereafter, the peeling length of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling length longer than 10 mm: (Inferior)
    Peeling length longer than 5 mm and not longer than 10 mm
    Peeling length longer than 2 mm and not longer than 5 mm
    Peeling length not longer than 2 mm
    No peeling: (Superior)

(4) Adhesion After Heating



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was heated without content therein at 210° C. for 10 minutes in an oven. Thereafter, the degree of peeling of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling percentage higher than 10%: (Inferior)
    Peeling percentage higher than 5% and not higher than 10%
    Peeling percentage higher than 2% and not higher than 5%
    Peeling percentage not higher than 2%
    No peeling: (Superior)

2. Evaluation by Drawing and Ironing (DI Forming)



For a resin laminated metal sheet using a TFS with a thickness of 0.23 mm, a DI can was manufactured by the method described below, and the propriety of DI can was investigated.
2-1 Can Manufacturing
A resin laminated metal sheet was drawn and ironed under the following conditions, by which a DI can was obtained.

    
    
        First-stage drawing
        
            Blank diameter: 150 mm
            Drawing ratio: 1.6
        
        
        Second-stage Drawing
        
            Drawing ratio: 1.25
        
        
        Ironing
        
            Ironing punch diameter: 3-stage ironing 65.8 mm dia
        
        
        Total ironing percentage of can sidewall
        
            55 to 70% with respect to thickness of resin laminated metal sheet before forming

2-2 Straightening Heat Treatment

        
        
    
    


Forming strain of film caused by can manufacturing was removed by keeping the can in a thermal environment of film melting point minus 15° C. for 30 seconds and then by rapidly cooling it.
2-3 Evaluation of Propriety of DI Can
(1) Formability
Evaluation was made as described below by the limit of capability for manufacturing can without film failure. Grades not lower than ◯ marked grade are acceptable.

    Limit of forming (total ironing percentage): Grade
    Incapable of forming at total ironing percentage of 55%: (Inferior)
    Capable of forming up to total ironing percentage of 55%
    Capable of forming up to total ironing percentage of 60%
    Capable of forming up to total ironing percentage of 65%
    Capable of forming up to total ironing percentage of 70%: (Superior)

(2) Evaluation of Room-temperature and Low-temperature Impact Resistance



A can body (total ironing percentage: 65%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, an iron ball of 0.5 kg was dropped from a height of 25 cm to give a shock to the can bottom. Thereafter, the lid was opened, and 1% salt water was poured in the can so that a portion that had suffered shock was immersed. After immersion for five minutes, a load of 6 V was applied across a platinum electrode immersed in the liquid and a can metal portion, and the current value after five minutes was read, by which evaluation was made as described below. The same tests were conducted at room temperature of 20° C. and at a temperature of 0° C. The former test was for evaluating room-temperature impact resistance, and the latter test was for evaluating low-temperature impact resistance. Grades not lower than ◯ marked grade are acceptable.
(Evaluation of Room-temperature Impact Resistance)


    Test result: Grade
    Current value not lower than 30 mA: (Inferior)
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(Evaluation of Low-temperature Impact Resistance)

    Test result: Grade
    Current value not lower than 30 mA: (Inferior)
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(3) Adhesion After Forming



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was immersed in aqueous solution containing 1.5 wt % citric acid and 1.5 wt % sodium chloride for five hours. Thereafter, the peeling length of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling length longer than 10 mm: (Inferior)
    Peeling length longer than 5 mm and not longer than 10 mm
    Peeling length longer than 2 mm and not longer than 5 mm
    Peeling length not longer than 2 mm
    No peeling: (Superior)

(4) Adhesion After Heating



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was heated without content therein at 210° C. for 10 minutes in an oven. Thereafter, the degree of peeling of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling percentage higher than 10%: (Inferior)
    Peeling percentage higher than 5% and not higher than 10%
    Peeling percentage higher than 2% and not higher than 5%
    Peeling percentage not higher than 2%
    No peeling: (Superior)

The investigation results are given in Tables 3 and 4.



From Tables 1 to 4, the following facts are found for either can type.
Invention examples 1 to 5 are films in which modified polyolefin resin specified in the present invention is dispersed in polyester resin in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate is changed variously, and invention examples 35 to 39 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, and adhesion. Also, invention example 38 in which the film of invention example 4 using polyester resin containing a small amount of isophthalic acid is laminated and invention example 39 in which the film of invention example 5 using homopolyethylene terephthalate is laminated have a tendency toward deteriorated formability and adhesion, but provide high performance as a whole. Also, invention example 35 in which the film of invention example 1 using polyester resin containing a high amount of isophthalic acid is laminated has a tendency toward deteriorated adhesion after heating because of a slightly low melting point, but provides high performance as a whole. Further, invention examples 33 and 34 are films in which polyester resins with different copolymerization ratio of two types are mixed in the range of the present invention, and invention examples 67 and 68 in which the films are laminated under the laminating conditions of the present invention have a tendency toward slightly deteriorated formability, but exhibit high formability, impact resistance, and adhesion. On the other hand, comparative examples 1 to 6 are examples of films in which polyolefin resin is not contained in polyester resin in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate is changed variously. Comparative examples 15 to 20 in which these films are laminated especially have a low level of impact resistance.
Invention examples 6 to 10 are mixed resins in which various polyolefin resins are dispersed in polyester resin, and invention examples 40 to 44 in which the mixed resins are laminated exhibit high formability, impact resistance, and adhesion. However, invention example 40 in which the film of invention example 6 using polyolefin resin with a slightly high percentage of functional group derived from carboxylic acid is laminated and invention example 44 in which the film of invention example 10 using polyolefin resin having a slightly high glass-transition temperature is laminated have a tendency toward slightly deteriorated low-temperature impact resistance. On the other hand, comparative examples 11 to 13 are mixed resins in which polyolefin resin containing a functional group derived from carboxylic acid whose percentage deviates from the range of the present invention is dispersed in polyester resin, and comparative examples 25 to 27 in which these mixed resins are laminated have inferior formability and impact resistance.
Comparative example 14 is a film in which modified polyolefin resin with group derived from carboxylic acid and polyester resin are simply mixed with each other, and comparative example 28 in which this film is laminated has greatly deteriorated formability and impact resistance because modified polyolefin resin is not dispersed in polyester resin in a fine granular form.
Invention examples 11 to 18 are films in which the blending ratio and dispersion state of modified polyolefin resin in polyester resin are changed variously in the range of the present invention, and invention examples 45 to 52 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, and adhesion. However, invention example 45 in which the film of invention example 11 containing a small amount of dispersed modified polyolefin resin is laminated and invention example 51 in which the film of invention example 17 having a very large number of grains of modified polyolefin resin is laminated have a tendency toward slightly deteriorated low-temperature impact resistance.
On the other hand, comparative examples 7 to 10 are films in which the blending ratio of modified polyolefin resin in polyester resin does not meet the requirement of the present invention, and comparative examples 21 to 24 in which the films are laminated under the laminating conditions of the present invention have greatly deteriorated formability and impact resistance. Comparative examples 21 and 22 in which the films of comparative examples 7 and 8 containing a small amount of dispersed modified polyolefin resin are laminated have greatly deteriorated room-temperature impact resistance, and comparative examples 23 and 24 in which the films of comparative examples 9 and 10 containing a large amount of modified polyolefin resin are laminated have greatly deteriorated formability.
Invention examples 19 to 23 are films in which titanium dioxide pigment is mixed with a mixed resin of modified polyolefin resin and polyester resin, and invention examples 53 to 57 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, and adhesion, and also provide a white uniform color tone. However, invention example 53 in which the film of invention example 19 in which the added amount of pigment is smaller than a desired range is laminated has slightly insufficient opacifying property of color tone. On the other hand, invention example 57 in which the film of invention example 23 in which the added amount of pigment is larger than a desired range is laminated has slightly deteriorated formability.
Invention examples 24 to 28 are films in which the thickness thereof is changed in the range of the present invention, and invention examples 58 to 62 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, and adhesion. Invention examples 24 and 28 are films in which the thickness thereof exceeds the desired range of the present invention, and invention examples 58 and 62 in which the films are laminated have slightly lower formability and impact resistance than the case of desired film thickness.
Invention examples 36 and 69 to 72 are films obtained by changing the laminating conditions of the film of invention example 2 in the range of the present invention. If the conditions are within the range of the present invention, high formability, impact resistance, and adhesion are exhibited regardless of the laminating temperature. On the other hand, in comparative example 30, the film of invention example 2 was laminated under conditions lower than the lower limit of laminating temperature range of the present invention, so that the film did not adhere to a steel sheet, and therefore evaluation could not be made. On the other hand, in comparative example 29, the film of invention example 2 was laminated under conditions exceeding the upper limit of laminating temperature range of the present invention, so that the film fused to a laminate roll, and therefore evaluation could not be made.
Invention examples 29 to 31 are films in which a lubricant, free radical inhibitor, and compatibilizing agent are mixed, respectively, in a mixed resin of modified polyolefin resin and polyester resin of the present invention, and invention examples 63 to 65 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, and adhesion. Further, invention examples 63 to 65 also have lubricity, free radical deterioration resistance, and compatibility depending on the function of added additive, and in particular, invention example 65 exhibits excellent low-temperature impact resistance.
Invention example 32 is a film of the present invention that is manufactured by the two-axis stretching method, and invention examples 66 and 73 in which the film is laminated exhibit high performance. Invention example 73, which has a plane orientation coefficient of 0.015, exhibits a slightly deteriorated formability. However, in the low-temperature impact resistance test, it was verified that the formability is slightly higher than the case of low plane orientation coefficient. Invention example 66, which has a plane orientation coefficient in the range of the present invention, exhibits very high formability and impact resistance.










TABLE 1









Polyolefin resin



















Number of




Weight


Volume
grains with



percentage


percentage
diameter of



of functional

Blending
of grains
0.1 to 5 μm



group derived

ratio in
with
in cube with


















Film
Polyester resin
Pigment

from

entire
diameter
one side of




















Sample
thickness
Resin


Content
Resin
carboxylic
Tg
resin
of 0.1 to
10 μm



film
(μm)
type
Additive
Kind
*1)
type
acid (wt %)
(° C.)
(wt %)
5 μm (vol %)
(grains)
Stretching






















Invention
25
PET/I (18)
None
None
0
EM4
8
<−30
15
12
2000
Non-


example 1











stretched


Invention
25
PET/I (10)
None
None
0
EM4
8
<−30
15
12
2000
Non-


example 2











stretched


Invention
25
PET/I (5)
None
None
0
EM4
8
<−30
15
12
2000
Non-


example 3











stretched


Invention
25
PET/I (2)
None
None
0
EM4
8
<−30
15
12
2000
Non-


example 4











stretched


Invention
25
PET
None
None
0
EM4
8
<−30
15
12
2000
Non-


example 5











stretched


Invention
25
PET/I (10)
None
None
0
EM2
18
<−30
15
13
500
Non-


example 6











stretched


Invention
25
PET/I (10)
None
None
0
EM4
8
<−30
15
12
2000
Non-


example 7











stretched


Invention
25
PET/I (10)
None
None
0
EM5
7
<−30
15
12
2000
Non-


example 8











stretched


Invention
25
PET/I (10)
None
None
0
EM6
5
<−30
15
12
2000
Non-


example 9











stretched


Invention
25
PET/I (10)
None
None
0
EM8
6
 20
15
12
2000
Non-


example 10











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
5
3
3
Non-


example 11











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
5
5
70
Non-


example 12











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
10
8
30
Non-


example 13











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
10
10
250
Non-


example 14











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
15
15
500
Non-


example 15











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
15
18
20000
Non-


example 16











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
20
22
200000
Non-


example 17











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
25
20
8000
Non-


example 18











stretched


Invention
25
PET/I (10)
None
TiO2
3
EM5
7
<−30
15
12
2000
Non-


example 19











stretched


Invention
25
PET/I (10)
None
TiO2
7
EM5
7
<−30
15
12
2000
Non-


example 20











stretched


Invention
25
PET/I (10)
None
TiO2
15
EM5
7
<−30
15
12
2000
Non-


example 21











stretched


Invention
25
PET/I (10)
None
TiO2
30
EM5
7
<−30
15
12
2000
Non-


example 22











stretched


Invention
25
PET/I (10)
None
TiO2
50
EM5
7
<−30
15
12
2000
Non-


example 23











stretched


Invention
 5
PET/I (10)
None
None
0
EM6
5
<−30
15
12
2000
Non-


example 24











stretched





*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment.
















TABLE 2









Polyolefin resin



















Weight


Volume
Number of






percentage


percentage
grains with





of


of grains
diameter of





functional

Blending
with
0.1 to 5 μm



Film

group

ratio in
diameter
in cube with


















thick-
Polyester resin
Pigment

derived from

entire
of 0.1 to
one side of




















Sample
ness
Resin


Content
Resin
carboxylic
Tg
resin
5 μm 0.2
10 μm



film
(μm)
type
Additive
Kind
*1)
type
acid (wt %)
(° C.)
(wt %)
(vol %)
(grains)
Stretching






















Invention
15
PET/I (10)
None
None
0
EM6
5
<−30
15
12
2000
Non-


example 25











stretched


Invention
20
PET/I (10)
None
None
0
EM6
5
<−30
15
12
2000
Non-


example 26











stretched


Invention
40
PET/I (10)
None
None
0
EM6
5
<−30
15
12
2000
Non-


example 27











stretched


Invention
55
PET/I (10)
*2) 0.3 wt %
None
0
EM6
5
<−30
15
12
2000
Non-


example 28











stretched


Invention
25
PET/I (10)
*3) 0.1 wt %
None
0
EM3
11
<−30
15
12
2000
Non-


example 29











stretched


Invention
25
PET/I (10)
*4) 3 wt %
None
0
EM3
11
<−30
15
13
2000
Non-


example 30











stretched


Invention
25
PET/I (10)
None
None
0
EM3
11
<−30
15
12
2000
Non-


example 31











stretched


Invention
25
PET/I (10)
None
None
0
EM4
8
<−30
15
12
2000
Two-axis


example 32











stretched


Invention
25
PET70 % +
None
None
0
EM4
8
<−30
15
12
2000
Non-


example 33

PET/I (10) 30%









stretched


Invention
25
PET40 % +
None
None
0
EM4
8
<−30
15
12
2000
Non-


example 34

PET/I (18) 60%









stretched


Comparative
25
PET/I (18)
None
None
0
None
—
—
0
0
0
Non-


example 1











stretched


Comparative
25
PET/I (10)
None
None
0
None
—
—
0
0
0
Non-


example 2











stretched


Comparative
25
PET/I (10)
None
None
0
None
—
—
0
0
0
Two-axis


example 3











stretched


Comparative
25
PET/I (5)
None
None
0
None
—
—
0
0
0
Non-


example 4











stretched


Comparative
25
PET/I (2)
None
None
0
None
—
—
0
0
0
Non-


example 5











stretched


Comparative
25
PET
None
None
0
None
—
—
0
0
0
Non-


example 6











stretched


Comparative
25
PET/I (10)
None
None
0
EM3
11
<−30
2
2
3
Non-


example 7











stretched


Comparative
25
PET/I (10)
None
None
0
EM3
11
<−30
2
2
45
Non-


example 8











stretched


Comparative
25
PET/I (10)
None
None
0
EM3
11
<−30
35
28
15000
Non-


example 9











stretched


Comparative
25
PET/I (10)
None
None
0
EM3
11
<−30
35
28
120000
Non-


example 10











stretched


Comparative
25
PET/I (10)
None
None
0
EM1
21
<−30
15
14
40
Non-


example 11











stretched


Comparative
25
PET/I (10)
None
None
0
EM7
1
<−30
15
3
20
Non-


example 12











stretched


Comparative
25
PET/I (10)
None
None
0
EPR
0
<−30
15
1
5
Non-


example 13











stretched


Comparative
25
PET/I (10)
None
None
0
EM5
7
<−30
15
Not
Not
Non-


example 14









dispersed
dispersed
stretched












in fine
in fine












grains
grains





*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment.


*2) Silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.


*3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radical inhibitor is added by 0.1 weight part to 100 weight part of mixed resin.


*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin.

















TABLE 3









Melting

Thin-wall deep drawn can


















point of



Impact





Laminated

polyester

Plane

resistance
Impact
Adhesion
Adhesion


metal
Sample
resin
Laminating
orientation
Form-
(room
resistance
after
after


sheet
film
(° C.)
temp. (° C.)
coefficient
ability
temp.)
(low temp.)
forming
heating





Invention
Invention
215
200
0
⊚
⊚
⊚⊚
⊚
⊚


example 35
example 1


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 36
example 2


Invention
Invention
255
230
0
⊚
⊚
⊚⊚
⊚
⊚


example 37
example 3


Invention
Invention
250
225
0
⊚
⊚
⊚⊚
⊚
⊚


example 38
example 4


Invention
Invention
255
230
0
⊚
⊚
⊚⊚
⊚
⊚


example 39
example 5


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 40
example 6


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 41
example 7


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 42
example 8


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 43
example 9


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 44
example 10


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 45
example 11


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 46
example 12


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 47
example 13


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 48
example 14


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 49
example 15


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 50
example 16


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 51
example 17


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 52
example 18


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 53
example 19


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 54
example 20


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 55
example 21


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 56
example 22


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 57
example 23


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚
⊚


example 58
example 24













Drawn and ironed can (DI can)

















Impact






Laminated

resistance
Impact
Adhesion
Adhesion



metal
Form-
(room
resistance
after
after



sheet
ability
temp.)
(low temp.)
forming
heating







Invention
⊚
⊚
⊚⊚
⊚
◯



example 35



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 36



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 37



Invention
◯
⊚
⊚⊚
◯
◯



example 38



Invention
◯
⊚
⊚⊚
◯
◯



example 39



Invention
⊚
◯
◯
⊚
⊚



example 40



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 41



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 42



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 43



Invention
⊚
◯
◯
⊚
⊚



example 44



Invention
◯
◯
◯
◯
⊚



example 45



Invention
⊚
◯
⊚
⊚
⊚



example 46



Invention
⊚
◯
⊚
⊚
⊚



example 47



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 48



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 49



Invention
⊚
◯
⊚
⊚
⊚



example 50



Invention
⊚
◯
◯
⊚
⊚



example 51



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 52



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 53



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 54



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 55



Invention
⊚
⊚
⊚⊚
⊚
⊚



example 56



Invention
◯
⊚
⊚⊚
◯
⊚



example 57



Invention
◯
⊚
⊚
⊚
⊚



example 58



















TABLE 4









Thin-wall deep drawn can

















Melting



Impact
Impact



Laminated

point of

Plane

resistance
resistance
Adhesion


metal
Sample
polyester
Laminating
orientation
Forma-
(room
(low
after


sheet
film
resin (° C.)
temp. (° C.)
coefficient
bility
temp.)
temp.)
forming





Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚


example 59
example 25


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚


example 60
example 26


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚


example 61
example 27


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚


example 62
example 28


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚


example 63
example 29


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚


example 64
example 30


Invention
Invention
230
210
0
⊚
⊚
⊚⊚
⊚


example 65
example 31


Invention
Invention
230
210
0.005
⊚
⊚
⊚⊚
⊚


example 66
example 32


Invention
Invention
255
230
0
⊚
⊚
⊚⊚
⊚


example 67
example 33


Invention
Invention
255
230
0
⊚
⊚
⊚⊚
⊚


example 68
example 34


Invention
Invention
230
255
0
⊚
⊚
⊚⊚
⊚


example 69
example 2


Invention
Invention
230
230
0
⊚
⊚
⊚⊚
⊚


example 70
example 2


Invention
Invention
230
190
0
⊚
⊚
⊚⊚
⊚


example 71
example 2


Invention
Invention
230
170
0
⊚
⊚
⊚⊚
⊚


example 72
example 2


Invention
Invention
230
200
0.015
⊚
⊚
⊚⊚
⊚


example 73
example 32


Comparative
Comparative
215
200
0
⊚
⊚
⊚⊚
⊚


example 15
example 1


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 16
example 2


Comparative
Comparative
255
225
0
⊚
⊚
⊚⊚
⊚


example 17
example 3


Comparative
Comparative
250
230
0
⊚
⊚
⊚⊚
⊚


example 18
example 4


Comparative
Comparative
255
210
0
⊚
⊚
⊚⊚
⊚


example 19
example 5


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 20
example 6


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 21
example 7


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 22
example 8


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 23
example 9


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 24
example 10


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 25
example 11


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 26
example 12


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 27
example 13


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚
⊚


example 28
example 14


Comparative
Invention
230
265
—
—
—
—
—


example 29
example 2


Comparative
Invention
230
150
—
—
—
—
—


example 30
example 2













Drawn and ironed can (DI can)

















Thin-wall deep drawn can

Impact
Impact





Laminated
Adhesion

resistance
resistance
Adhesion
Adhesion



metal
after
Form-
(room
(low
after
after



sheet
heating
ability
temp.)
temp.)
forming
heating







Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 59



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 60



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 61



Invention
⊚
◯
⊚
⊚
⊚
⊚



example 62



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 63



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 64



Invention
⊚
⊚
⊚
⊚⊚⊚
⊚
⊚



example 65



Invention
⊚
⊚
⊚
⊚⊚⊚
⊚
⊚



example 66



Invention
⊚
◯
⊚
⊚⊚
⊚
⊚



example 67



Invention
⊚
◯
⊚
⊚⊚
⊚
◯



example 68



Invention
⊚
◯
⊚
⊚⊚
⊚
⊚



example 69



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 70



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 71



Invention
⊚
⊚
⊚
⊚⊚
◯
◯



example 72



Invention
⊚
◯
⊚
⊚⊚⊚
⊚
⊚



example 73



Comparative
⊚
Δ
XX
Δ
Δ
Δ



example 15



Comparative
⊚
Δ
XX
Δ
Δ
◯



example 16



Comparative
⊚
X
XX
Δ
Δ
◯



example 17



Comparative
⊚
Δ
XX
Δ
Δ
◯



example 18



Comparative
⊚
X
X X
Δ
X
◯



example 19



Comparative
⊚
XX
XX
Δ
XX
Δ



example 20



Comparative
⊚
◯
XX
Δ
Δ
◯



example 21



Comparative
⊚
◯
X
Δ
◯
⊚



example 22



Comparative
⊚
X
◯
Δ
X
◯



example 23



Comparative
⊚
XX
◯
Δ
XX
◯



example 24



Comparative
⊚
X
◯
Δ
◯
◯



example 25



Comparative
⊚
Δ
X
Δ
◯
Δ



example 26



Comparative
⊚
X
X X
Δ
X
X



example 27



Comparative
⊚
XX
X X
Δ
X X
Δ



example 28



Comparative
—
—
—
—
—
—



example 29



Comparative
—
—
—
—
—
—



example 30










EXAMPLE 2
Modified polyolefin resin with group derived from carboxylic acid having a primary grain diameter of 0.3 μm, which was a starting raw material, was cold blended with polyester resin in a blending ratio given in Tables 5 and 6 by using a tumbler blender, and then the blended resin was melted and kneaded at 260° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. In the tables, the resin type corresponding to the symbol of resin type of polyester resin and resin type of polyolefin resin is the same as that described in Example 1.
As a metal sheet, as in Example 1, a tin-free steel (hereinafter abbreviated to TFS) with a thickness of 0.18 mm for thin-wall deep drawn can and 0.23 mm for DI can, which had a degree of temper of DR9, metallic chromium layer of 80 mg/m2, and chromium oxide layer of 15 mg/m2 (metallic chromium conversion), was used, by which a both-side resin laminated metal sheet was obtained by a method in which the raw material resin pellet was inserted in a one-axis extruding machine, molten resin was extruded directly from a T die onto one surface of the metal sheet, the extruded resin was once cooled while being held adherently between two rolls, and immediately after the resin was laminated on the opposite surface in the same manner, the resin laminated metal sheet was cooled rapidly in water. The temperature of metal sheet at the laminating time was 50° C. The lip opening width of T die was adjusted so that the thickness of resin film was 6 to 55 μm. The type of sample resin and the resin melting temperature at the laminating time are given in Tables 7 and 8. The used polyester resin and modified polyolefin resin with group derived from carboxylic acid are the same as those used in Example 1.
Pelletized modified polyolefin resin with group derived from carboxylic acid, which was a starting raw material, was mixed with polyester resin in a blending ratio given in comparative example 43 in Table 6, the mixed resin was melted and kneaded at 260° C. by using a one-axis extruding machine, and the obtained mixed resin of modified polyolefin resin and polyester resin was extruded from a T die, by which the resin that had been directly extruded to a thickness of 25 μm was laminated to the TFS.
All of the grain diameter of modified polyolefin resin dispersed in resin film, various temperatures in the table, and the method for measuring the plane orientation coefficient of laminated metal sheet are the same as those in Example 1. As in Example 1, a thin-wall deep drawn can or a DI can was manufactured from the laminated metal sheet obtained as described above, and the can was subjected to straightening heat treatment to manufacture a sample can. The formability, impact resistance, and adhesion of film of the manufactured can body were investigated as in Example 1.
The investigation results are given in Tables 7 and 8.
From Tables 5 to 8, the following facts are found for either can type.
Invention examples 74 to 82 are films which are formed by dispersing modified polyolefin resin specified in the present invention in polyester resin in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate is changed variously, and exhibit high formability, impact resistance, and adhesion. Also, invention example 81 using polyester resin containing a small amount of isophthalic acid and invention example 82 using homopolyethylene terephthalate have a tendency toward deteriorated formability and adhesion, but provide high performance as a whole. Also, invention example 74 using polyester resin containing a large amount of isophthalic acid has a tendency toward deteriorated adhesion after heating because of slightly low melting point, but provide high performance as a whole. Further, invention examples 109 and 110 are resins in which polyester resins with different copolymerization ratio of two types are mixed in the range of the present invention, and have a tendency toward slightly deteriorated formability, but exhibit high formability, impact resistance, and adhesion. On the other hand, comparative examples 31 to 35 are examples of resins in which polyolefin resin is not contained in polyester resin in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate is changed variously, and especially have a low level of impact resistance.
Invention examples 83 to 87 are examples of mixed resins in which various polyolefin resins are dispersed in polyester resin, and exhibit high formability, impact resistance, and adhesion. However, invention example 83 using polyolefin resin with a slightly high percentage of functional group derived from carboxylic acid and invention example 87 using polyolefin resin with a slightly high glass-transition temperature have a tendency toward slightly deteriorated low-temperature impact resistance. On the other hand, comparative examples 40 to 42 are mixed resins in which polyolefin resin containing a functional group derived from carboxylic acid whose percentage deviates from the range of the present invention is dispersed in polyester resin, and have inferior formability and impact resistance.
Comparative example 43 is a resin in which modified polyolefin resin with group derived from carboxylic acid and polyester resin are simply mixed with each other, and has greatly deteriorated formability and impact resistance because modified polyolefin resin is not dispersed in polyester resin in a fine granular form.
Invention examples 88 to 95 are resins in which the blending ratio and dispersion state of modified polyolefin resin in polyester resin are changed variously in the range of the present invention, and exhibit high formability, impact resistance, and adhesion. However, the resin of invention example 88 containing a small amount of dispersed modified polyolefin resin and the resin of invention example 94 having a very large number of grains of modified polyolefin resin have a tendency toward slightly deteriorated low-temperature impact resistance.
On the other hand, comparative examples 36 to 39 are resins in which the blending ratio of modified polyolefin resin in polyester resin does not meet requirement of the present invention, and have greatly deteriorated formability and impact resistance. Comparative examples 36 and 37 containing a small amount of dispersed modified polyolefin resin have greatly deteriorated room-temperature impact resistance, and comparative examples 38 and 39 containing a large amount of modified polyolefin resin have greatly deteriorated formability.
Invention examples 96 to 100 are resins in which titanium dioxide pigment is mixed with a mixed resin of modified polyolefin resin and polyester resin, and exhibit high formability, impact resistance, and adhesion, and also provide a white uniform color tone. However, invention example 96 in which the added amount of pigment is smaller than a desired range has slightly insufficient opacifying property of color tone. On the other hand, invention example 100 in which the added amount of pigment is larger than a desired range has slightly deteriorated formability.
Invention examples 101 to 105 are resins in which the thickness thereof is changed in the range of the present invention, and exhibit high formability, impact resistance, and adhesion. Invention examples 101 and 105 are resins in which the thickness thereof exceeds the desired range of the present invention, and have slightly lower formability and impact resistance than the case of desired film thickness.
Invention examples 75 to 79 are resins obtained by changing the extrusion laminating conditions in the range of the present invention. If the conditions are within the range of the present invention, high formability, impact resistance, and adhesion are exhibited regardless of the laminating temperature. Invention example 75 was laminated under conditions lower than the desired lower limit of laminating temperature range, and invention example 79 was laminated under conditions exceeding the desired upper limit of laminating temperature range, so that these invention examples have slightly deteriorated formability and low-temperature impact resistance.
Invention examples 106 to 108 are resins in which a lubricant, free radical inhibitor, and compatibilizing agent are mixed, respectively, in a mixed resin of modified polyolefin resin and polyester resin of the present invention, and exhibit high formability, impact resistance, and adhesion. Further, invention examples 106 to 108 also have lubricity, free radical deterioration resistance, and compatibility depending on the function of added additive, and in particular, invention example 108 exhibits excellent low-temperature impact resistance.









TABLE 5









Polyolefin resin
















Volume
Number of grains



Weight percentage

Blending
percentage
with diameter



of functional

ratio in
of grains
of 0.1 to 5 μm















Laminated
Polyester resin
Pigment

group derived

entire
with diameter
in cube with one

















metal
Resin


Content
Resin
from carboxylic
Tg
resin
of 0.1 to
side of 10 μm


sheet
type
Additive
Kind
*1)
type
acid (wt %)
(° C.)
(wt %)
5 μm (vol %)
(grains)




















Invention
PET/I (18)
None
None
0
EM4
8
<−30
15
14
2500


example 74


Invention
PET/I (10)
None
None
0
EM4
8
<−30
15
14
2500


example 75


Invention
PET/I (10)
None
None
0
EM4
8
<−30
15
14
2500


example 76


Invention
PET/I (10)
None
None
0
EM4
8
<−30
15
14
2500


example 77


Invention
PET/I (10)
None
None
0
EM4
8
<−30
15
14
2500


example 78


Invention
PET/I (10)
None
None
0
EM4
8
<−30
15
14
2500


example 79


Invention
PET/I (5)
None
None
0
EM4
8
<−30
15
14
2500


example 80


Invention
PET/I (2)
None
None
0
EM4
8
<−30
15
14
2500


example 81


Invention
PET
None
None
0
EM4
8
<−30
15
14
2500


example 82


Invention
PET/I (10)
None
None
0
EM2
18
<−30
15
15
1000


example 83


Invention
PET/I (10)
None
None
0
EM4
8
<−30
15
14
2500


example 84


Invention
PET/I (10)
None
None
0
EM5
7
<−30
15
14
2500


example 85


Invention
PET/I (10)
None
None
0
EM6
5
<−30
15
14
2500


example 86


Invention
PET/I (10)
None
None
0
EM8
6
 20
15
14
2500


example 87


Invention
PET/I (10)
None
None
0
EM3
11
<−30
5
4
4


example 88


Invention
PET/I (10)
None
None
0
EM3
11
<−30
5
8
100


example 89


Invention
PET/I (10)
None
None
0
EM3
11
<−30
10
10
50


example 90


Invention
PET/I (10)
None
None
0
EM3
11
<−30
10
12
500


example 91


Invention
PET/I (10)
None
None
0
EM3
11
<−30
15
18
800


example 92


Invention
PET/I (10)
None
None
0
EM3
11
<−30
15
20
22000


example 93


Invention
PET/I (10)
None
None
0
EM3
11
<−30
20
24
250000


example 94


Invention
PET/I (10)
None
None
0
EM3
11
<−30
25
22
10000


example 95


Invention
PET/I (10)
None
TiO2
3
EM5
7
<−30
15
14
2500


example 96


Invention
PET/I (10)
None
TiO2
7
EM5
7
<−30
15
14
2500


example 97


Invention
PET/I (10)
None
TiO2
15
EM5
7
<−30
15
14
2500


example 98


Invention
PET/I (10)
None
TiO2
30
EM5
7
<−30
15
14
2500


example 99


Invention
PET/I (10)
None
TiO2
50
EM5
7
<−30
15
14
2500


example 100





*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment.















TABLE 6









Polyolefin resin
















Volume







percentage
Number of grains



Weight percentage

Blending
of grains
with diameter



of functional

ratio in
with diameter
of 0.1 to 5 μm















Laminated
Polyester resin
Pigment

group derived

entire
of 0.1 to
in cube with one

















metal
Resin


Content
Resin
from carboxylic
Tg
resin
5 μm
side of 10 μm


sheet
type
Additive
Kind
*1)
type
acid (wt %)
(° C.)
(wt %)
(vol %)
(grains)




















Invention
PET/I (10)
None
None
0
EM6
5
<−30
15
14
2500


example 101


Invention
PET/I (10)
None
None
0
EM6
5
<−30
15
14
2500


example 102


Invention
PET/I (10)
None
None
0
EM6
5
<−30
15
14
2500


example 103


Invention
PET/I (10)
None
None
0
EM6
5
<−30
15
14
2500


example 104


Invention
PET/I (10)
None
None
0
EM6
5
<−30
15
14
2500


example 105


Invention
PET/I (10)
*2) 0.3 wt %
None
0
EM3
11
<−30
15
14
2500


example 106


Invention
PET/I (10)
*3) 0.1 wt %
None
0
EM3
11
<−30
15
14
2500


example 107


Invention
PET/I (10)
*4) 3 wt %
None
0
EM3
11
<−30
15
14
2500


example 108


Invention
PET70 % +
None
None
0
EM4
8
<−30
15
14
2500


example 109
PET/I (10) 30%


Invention
PET40 % +
None
None
0
EM4
8
<−30
15
14
2500


example 110
PET/I (18) 60%


Comparative
PET/I (18)
None
None
0
None
—
—
0
0
0


example 31


Comparative
PET/I (10)
None
None
0
None
—
—
0
0
0


example 32


Comparative
PET/I (5)
None
None
0
None
—
—
0
0
0


example 33


Comparative
PET/I (2)
None
None
0
None
—
—
0
0
0


example 34


Comparative
PET
None
None
0
None
—
—
0
0
0


example 35


Comparative
PET/I (10)
None
None
0
EM3
11
<−30
2
3
5


example 36


Comparative
PET/I (10)
None
None
0
EM3
11
<−30
2
3
50


example 37


Comparative
PET/I (10)
None
None
0
EM3
11
<−30
35
30
20000


example 38


Comparative
PET/I (10)
None
None
0
EM3
11
<−30
35
30
130000


example 39


Comparative
PET/I (10)
None
None
0
EM1
21
<−30
15
16
50


example 40


Comparative
PET/I (10)
None
None
0
EM7
1
<−30
15
4
40


example 41


Comparative
PET/I (10)
None
None
0
EPR
0
<−30
15
1
4


example 42


Comparative
PET/I (10)
None
TiO2
3
EM5
7
<−30
15
Not dispersed
Not dispersed


example 43








in fine grains
in fine grains





*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment.


*2) Silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.


*3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydroclnnamate)] methane of free radical inhibitor is added by 0.1 weight part to 100 weight part of mixed resin.


*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin.


















TABLE 7









Melting
Melting





point of mixed
temp. of

Thin-wall deep drawn can














Laminated
resin (melting
mixed
Resin

Impact
Impact
Adhesion


metal
point of polyester
resin
thickness

resistance
resistance
after


sheet
resin) (° C.)
(° C.)
(μm)
Formability
(room temp.)
(low temp.)
forming





Invention
215
235
25
⊚
⊚
⊚⊚
⊚


example 74


Invention
230
235
25
⊚
⊚
⊚⊚
⊚


example 75


Invention
230
240
25
⊚
⊚
⊚⊚
⊚


example 76


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 77


Invention
230
265
25
⊚
⊚
⊚⊚
⊚


example 78


Invention
230
275
25
⊚
⊚
⊚⊚
⊚


example 79


Invention
255
275
25
⊚
⊚
⊚⊚
⊚


example 80


Invention
250
270
25
⊚
⊚
⊚⊚
⊚


example 81


Invention
255
275
25
⊚
⊚
⊚⊚
⊚


example 82


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 83


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 84


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 85


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 86


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 87


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 88


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 89


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 90


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 91


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 92


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 93


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 94


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 95


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 96


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 97


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 98


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 99


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


sxample 100













Thin-wall deep drawn can
Drawn and ironed can (DI can)













Laminated
Adhesion

Impact
Impact
Adhesion
Adhesion


metal
after

resistance
resistance
after
after


sheet
heating
Formability
(room temp.)
(low temp.)
forming
heating





Invention
⊚
⊚
⊚
⊚⊚
⊚
◯


example 74


Invention
⊚
◯
⊚
⊚
◯
⊚


example 75


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 76


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 77


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 78


Invention
⊚
◯
◯
◯
◯
⊚


example 79


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 80


Invention
⊚
◯
⊚
⊚⊚
◯
◯


example 81


Invention
⊚
◯
⊚
⊚⊚
◯
◯


example 82


Invention
⊚
⊚
◯
◯
⊚
⊚


example 83


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 84


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 85


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 86


Invention
⊚
⊚
◯
◯
⊚
⊚


example 87


Invention
⊚
◯
◯
◯
◯
⊚


example 88


Invention
⊚
⊚
⊚
⊚
⊚
⊚


example 89


Invention
⊚
⊚
◯
⊚
⊚
⊚


example 90


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 91


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 92


Invention
⊚
⊚
◯
⊚
⊚
⊚


example 93


Invention
⊚
⊚
◯
◯
⊚
⊚


example 94


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 95


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 96


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 97


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 98


Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚


example 99


Invention
⊚
◯
⊚
⊚⊚
◯
⊚


sxample 100





*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment.


















TABLE 8









Melting
Melting





point of mixed
temp. of

Thin-wall deep drawn can














Laminated
resin (melting
mixed
Resin

Impact
Impact
Adhesion


metal
point of polyester
resin
thickness

resistance
resistance
after


sheet
resin) (° C.)
(° C.)
(μm)
Formability
(room temp.)
(low temp.)
forming





Invention
230
250
 6
⊚
⊚
⊚⊚
⊚


example 101


Invention
230
250
15
⊚
⊚
⊚⊚
⊚


example 102


Invention
230
250
20
⊚
⊚
⊚⊚
⊚


example 103


Invention
230
250
40
⊚
⊚
⊚⊚
⊚


example 104


Invention
230
250
55
⊚
⊚
⊚⊚
⊚


example 105


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 106


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 107


Invention
230
250
25
⊚
⊚
⊚⊚
⊚


example 108


Invention
255
275
25
⊚
⊚
⊚⊚
⊚


example 109


Invention
255
275
25
⊚
⊚
⊚⊚
⊚


example 110


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 31


Comparative
255
275
25
⊚
⊚
⊚⊚
⊚


example 32


Comparative
250
270
25
⊚
⊚
⊚⊚
⊚


example 33


Comparative
255
275
25
⊚
⊚
⊚⊚
⊚


example 34


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 35


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 36


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 37


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 38


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 39


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 40


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 41


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 42


Comparative
230
250
25
⊚
⊚
⊚⊚
⊚


example 43













Drawn and ironed can (DI can)

















Thin-wall deep drawn can

Impact






Laminated
Adhesion

resistance
Impact
Adhesion
Adhesion



metal
after
Form-
(room
resistance
after
after



sheet
heating
ability
temp.)
(low temp.)
forming
heating







Invention
⊚
◯
⊚
⊚
⊚
⊚



example 101



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 102



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 103



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 104



Invention
⊚
◯
⊚
⊚
⊚
⊚



example 105



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 106



Invention
⊚
⊚
⊚
⊚⊚
⊚
⊚



example 107



Invention
⊚
⊚
⊚
⊚⊚⊚
⊚
⊚



example 108



Invention
⊚
◯
⊚
⊚⊚
⊚
⊚



example 109



Invention
⊚
◯
⊚
⊚⊚
⊚
◯



example 110



Comparative
⊚
Δ
XX
Δ
Δ
Δ



example 31



Comparative
⊚
Δ
XX
Δ
Δ
◯



example 32



Comparative
⊚
Δ
XX
Δ
Δ
◯



example 33



Comparative
⊚
X
XX
Δ
X
◯



example 34



Comparative
⊚
XX
XX
Δ
XX
Δ



example 35



Comparative
⊚
◯
XX
Δ
Δ
◯



example 36



Comparative
⊚
◯
X
Δ
◯
⊚



example 37



Comparative
⊚
X
Δ
Δ
X
◯



example 38



Comparative
⊚
XX
Δ
Δ
XX
◯



example 39



Comparative
⊚
X
Δ
Δ
◯
◯



example 40



Comparative
⊚
Δ
X
Δ
◯
Δ



example 41



Comparative
⊚
X
XX
Δ
X
X



example 42



Comparative
⊚
XX
XX
Δ
XX
Δ



example 43







*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment.



*2) Silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.



*3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radical inhibitor is added by 0.1 weight part to 100 weight part of mixed resin.



*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin.






EXAMPLE 3
As a resin raw material, modified polyolefin resin with group derived from carboxylic acid was cold blended with polyester resin in a blending ratio given in Tables 9 to 12 by using a tumbler blender, and then the blended resin was melted and kneaded at 270° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. The obtained raw material resin pellet was inserted in a one-axis extruding machine, and was extruded from a multi-manifold type T die while being controlled by the discharge amount of molten resin from the extruding machine, by which a resin film with a total thickness of 10 to 50 μm was manufactured continuously while being cooled by the surface of a rotating metallic roll.
On the other hand, in the case of film of two-layer construction, modified polyolefin resin with group derived from carboxylic acid, which was a resin raw material for R1 layer, was cold blended with polyester resin in a blending ratio given in Tables 9 to 12 by using a tumbler blender, and then the blended resin was melted and kneaded at 270° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. The obtained raw material resin pellet was inserted in a one-axis extruding machine, and on the other hand, polyester resin containing no modified polyolefin resin, which was a resin raw material for R0 layer, was inserted in a separate one-axis extruding machine, and each of molten resins was introduced into a multi-manifold type T die and extruded in two layers while being controlled by the discharge amount of molten resin from the extruding machine, by which a resin film was manufactured continuously while being cooled by the surface of a rotating metallic roll.
The used polyester resin and modified polyolefin resin with group derived from carboxylic acid were as follows:
1. Polyester Resin
(1) PET: Polyethylene terephthalate resin, intrinsic viscosity: 0.62 dl/g
(2) PET/I (10): Isophthalic acid copolymerized resin with a ratio of terephthalic acid to isophthalic acid of 90:10, intrinsic viscosity: 0.6 dl/g
(3) PET/PBT(60): mixed resin with a ratio of polyethylene terephthalate to polybutylene terephthalate of 40:60, intrinsic viscosity: 0.6 dl/g
(4) PET/AD(20): Adipic acid copolymerized polyethylene terephthalate copolymerized resin with a ratio of terephthalic acid to adipic acid of 80:20, intrinsic viscosity: 0.6 dl/g
2. Modified Polyolefin Resin with Group Derived from Carboxylic Acid
(1) EM1: Polymethyl methacrylate-(ethylene-ethyl acrylate copolymer) graft copolymer (Modiper A5200 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 21 wt %, glass-transition temperature: −30° C. or lower
(2) EM2: Polymethyl methacrylate-(ethylene-ethyl acrylate-maleic anhydride copolymer) graft copolymer (Modiper A8200 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 18 wt %, glass-transition temperature: −30° C. or lower
(3) EM3: Ethylene-ethyl acrylate-maleic anhydride copolymer (Bondine HX8290 manufactured by Sumitomo Chemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 11 wt %, glass-transition temperature: −30° C. or lower
(4) EM4: Ethylene-methacrylic acid copolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 8 wt %, glass-transition temperature: −30° C. or lower
(5) EM5: 50% Zn neutralized substance of ethylene-methacrylic acid copolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co., Ltd. neutralized partially by Zn), weight ratio of functional group derived from carboxylic acid: 7 wt %, glass-transition temperature: −30° C. or lower
(6) EM6: 60% Zn neutralized substance of ethylene-methacrylic acid copolymer (Himilan 1557 manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 5 wt %, glass-transition temperature: −30° C. or lower
(7) EM7: Ethylene-methacrylic acid copolymer (Nucrel N0200H manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 1 wt %, glass-transition temperature: −30° C. or lower
(8) EM8: Polystyrene-(ethylene-ethyl acrylate copolymer) graft copolymer (Modiper A5100 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 6 wt %, glass-transition temperature: 20° C.
(9) EPR: Ethylene-propylene rubber (EP07P manufactured by JSR Corp.), weight ratio of functional group derived from carboxylic acid: 0 wt %, glass-transition temperature: −30° C. or lower
Furthermore, a commercially available resin (Sealer PT4274 manufactured by Mitsui-DuPont Polychemical Co., Ltd.) that had been pelletized in advance in a state in which modified polyolefin resin with group derived from carboxylic acid was dispersed in polyester resin, which was used as a resin raw material, was inserted in a one-axis extruding machine in blending ratios shown in invention examples 32 and 36 in Table 11, and was extruded from a multi-manifold type T die while being controlled by the discharge amount of molten resin from the extruding machine, by which resin films of single layer and two layers were manufactured continuously while being cooled by the surface of a rotating metallic roll.
A resin laminated metal sheet was obtained by a thermo-compression bonding method in which the resin film obtained as described above was hot-pressed on both surfaces of a tin-free steel (hereinafter abbreviated to TFS, thickness: 0.18 mm for thin-wall deep drawn can and 0.23 mm for DI can, degree of temper: DR9, metallic chromium layer: 80 mg/m2, chromium oxide layer: 15 mg/m2 (metallic chromium conversion)) heated by an induction heating system, and then the laminated metal sheet was rapidly cooled in water. The metal sheet temperature at the laminating time (laminating temperature) is given in Tables 13 and 14.
The grain diameter of modified polyolefin resin dispersed in R1 layer of resin film, various temperatures in the table, and the plane orientation coefficient of resin laminated metal sheet were measured by the same method as that in Example 1.
A thin-wall deep drawn can or a DI can was manufactured from the laminated metal sheet obtained as described above, and the can was subjected to straightening heat treatment to manufacture a sample can. The formability, impact resistance (room temperature, low temperature), adhesion after forming, adhesion after heating, and flavor property of film of the manufactured can body were investigated.
The following is a detailed description of the investigation method.
1. Evaluation by Thickness-decreasing Deep Drawing
1-1 Can Manufacturing
A resin laminated metal sheet was subjected to first-stage drawing and redrawing under the following conditions, by which a thin-wall deep drawn can was obtained.

    
    
        First-stage drawing
    
    


















Blank diameter
150 to 160 mm



First-stage drawing
drawing ratio: 1.65










    
    
        Redrawing
    
    















Primary redrawing
drawing ratio: 1.25


Secondary redrawing
drawing ratio: 1.25


Radius of curvature of die corner in redrawing
0.4 mm


process


Load for pressing wrinkle at the time of redrawing
39227 N (4000 kg)









    
    
        Average thickness decreasing percentage of can sidewall
        
            40 to 55% with respect to thickness of resin laminated metal sheet before forming

1-2 Straightening Heat Treatment

        
        
    
    


Forming strain of film caused by can manufacturing was removed by keeping the can in a thermal environment of film melting point minus 15° C. for 30 seconds and then by rapidly cooling it.
(1) Formability
Evaluation was made as described below by the limit of capability for manufacturing can without film failure. Grades not lower than ◯ marked grade are acceptable.

    Limit of forming (thickness decreasing percentage): Grade
    Incapable of forming at thickness decreasing percentage of 40%: (Inferior)
    Capable of forming up to thickness decreasing percentage of 40%
    Capable of forming up to thickness decreasing percentage of 45%
    Capable of forming up to thickness decreasing percentage of 50%
    Capable of forming up to thickness decreasing percentage of 55%: (Superior)

(2) Evaluation of Room-temperature and Low-temperature Impact Resistance



A can body (thickness decreasing percentage: 50%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, an iron ball of 0.5 kg was dropped from a height of 30 cm to give a shock to the can bottom. Thereafter, the lid was opened, and 1% salt water was poured in the can so that a portion that had suffered shock was immersed. After immersion for five minutes, a load of 6 V was applied across a platinum electrode immersed in the liquid and a can metal portion, and the current value after five minutes was read, by which evaluation was made as described below. The same tests were conducted at room temperature of 20° C. and at a temperature of 0° C. The former test was for evaluating room-temperature impact resistance, and the latter test was for evaluating low-temperature impact resistance. Grades not lower than ◯ marked grade are acceptable.
(Evaluation of Room-temperature Impact Resistance)


    Test result: Grade
    Current value not lower than 30 mA: (Inferior)
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(Evaluation of Low-temperature Impact Resistance)

    Test result: Grade
    Current value not lower than 50 mA: (Inferior)
    Current value not lower than 30 mA and lower than 50 mA
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(3) Adhesion After Forming



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was immersed in aqueous solution containing 1.5 wt % citric acid and 1.5 wt % sodium chloride for 24 hours. Thereafter, the peeling length of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling length longer than 10 mm: (Inferior)
    Peeling length longer than 5 mm and not longer than 10 mm
    Peeling length longer than 2 mm and not longer than 5 mm
    Peeling length not longer than 2 mm
    No peeling: (Superior)

(4) Adhesion After Heating



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was heated without content therein at 210° C. for 10 minutes in an oven. Thereafter, the degree of peeling of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling percentage higher than 10%: (Inferior)
    Peeling percentage higher than 5% and not higher than 10%
    Peeling percentage higher than 2% and not higher than 5%
    Peeling percentage higher than 0.5% and not higher than 2%
    Peeling percentage not higher than 0.5%
    No peeling: (Superior)

(5) Flavor Property



The internal surface of can body subjected to straightening heat treatment was cleaned, and flavor aqueous solution (d-limonene 20 ppm aqueous solution) was put in the can and left at ordinary temperature for 20 days after sealing. Thereafter, the can was unsealed, and a portion expelled by ether immersion was determined by gas chromatography as adsorption of d-limonene per can, by which flavor property was evaluated. Grades not lower than ◯ marked grade are acceptable.

    Test result: grade
    Adsorption larger than 200 μg/can: (Inferior)
    Adsorption larger than 100 μg/can and not larger than 200 μg/can
    Adsorption larger than 30 μg/can and not larger than 100 μg/can
    Adsorption larger than 10 μg/can and not larger than 30 μg/can
    Adsorption not larger than 10 μg/can: (Superior)

2. Evaluation by Drawing and Ironing (DI Forming)

2-1 Can Manufacturing



A resin laminated metal sheet was drawn and ironed under the following conditions, by which a DI can was obtained.

    
    
        First-stage Drawing
        
            Blank diameter: 150 mm
            Drawing ratio: 1.6
        
        
        Second-stage Drawing
        
            Drawing ratio: 1.25
        
        
        Ironing
        
            Ironing punch diameter: 3-stage ironing 65.8 mm dia
        
        
        Total ironing percentage of can sidewall
        
            55 to 70% with respect to thickness of resin laminated metal sheet before forming

2-2 Straightening Heat Treatment

        
        
    
    


Forming strain of film caused by can manufacturing was removed by keeping the can in a thermal environment of film melting point minus 15° C. for 30 seconds and then by rapidly cooling it.
(1) Formability
Evaluation was made as described below by the limit of capability for manufacturing can without film failure. Grades not lower than ◯ marked grade are acceptable.

    Limit of forming (total ironing percentage): Grade
    Incapable of forming at total ironing percentage of 55%: (Inferior)
    Capable of forming up to total ironing percentage of 55%
    Capable of forming up to total ironing percentage of 60%
    Capable of forming up to total ironing percentage of 65%
    Capable of forming up to total ironing percentage of 70%: (Superior)

(2) Evaluation of Room-temperature and Low-temperature Impact Resistance



A can body (total ironing percentage: 65%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, an iron ball of 0.5 kg was dropped from a height of 25 cm to give a shock to the can bottom. Thereafter, the lid was opened, and 1% salt water was poured in the can so that a portion that had suffered shock was immersed. After immersion for five minutes, a load of 6 V was applied across a platinum electrode immersed in the liquid and a can metal portion, and the current value after five minutes was read, by which evaluation was made as described below. The same tests were conducted at room temperature of 20° C. and at a temperature of 0° C. The former test was for evaluating room-temperature impact resistance, and the latter test was for evaluating low-temperature impact resistance. Grades not lower than ◯ marked grade are acceptable.
(Evaluation of Room-temperature Impact Resistance)


    Test result: Grade
    Current value not lower than 30 mA: (Inferior)
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(Evaluation of Low-temperature Impact Resistance)

    Test result: Grade
    Current value not lower than 50 mA: (Inferior)
    Current value not lower than 30 mA and lower than 50 mA
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(3) Adhesion After Forming



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was immersed in aqueous solution containing 1.5 wt % citric acid and 1.5 wt % sodium chloride for five hours. Thereafter, the peeling length of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling length longer than 10 mm: (Inferior)
    Peeling length longer than 5 mm and not longer than 10 mm


Peeling length longer than 2 mm and not longer than 5 mm

    Peeling length not longer than 2 mm
    No peeling: (Superior)

(4) Adhesion After Heating



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was heated without content therein at 210° C. for 10 minutes in an oven. Thereafter, the degree of peeling of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling percentage higher than 10%: (Inferior)
    Peeling percentage higher than 5% and not higher than 10%
    Peeling percentage higher than 2% and not higher than 5%
    Peeling percentage higher than 0.5% and not higher than 2%
    Peeling percentage not higher than 0.5%
    No peeling: (Superior)

(5) Flavor Property



The internal surface of can body subjected to straightening heat treatment was cleaned, and flavor aqueous solution (d-limonene 20 ppm aqueous solution) was put in the can and left at ordinary temperature for 20 days after sealing. Thereafter, the can was unsealed, and a portion expelled by ether immersion was determined by gas chromatography as adsorption of d-limonene per can, by which flavor property was evaluated. Grades not lower than ◯ marked grade are acceptable.

    Test result: grade
    Adsorption larger than 200 μg/can: (Inferior)
    Adsorption larger than 100 μg/can and not larger than 200 μg/can
    Adsorption larger than 30 μg/can and not larger than 100 μg/can
    Adsorption larger than 10 μg/can and not larger than 30 μg/can
    Adsorption not larger than 10 μg/can: (Superior)


The investigation results are given in Tables 13 and 14.
From Tables 9 to 14, the following facts are found for either can type.
Invention examples 1 to 3 and 5 are films in which modified polyolefin resin specified in the present invention is dispersed in polyester resin in which polyester type of mixed resin is change variously in a single layer, and invention examples 37 to 39 and 41 in which the films are laminated under the laminating conditions of the present invention exhibit very high formability, impact resistance, adhesion, and flavor property. Among these, invention example 39 in which the film of invention example 3 using adipic acid copolymerized polyethylene terephthalate resin is laminated has a high performance as a whole, but has a tendency toward deteriorated adhesion after heating and flavor property because of slightly low melting point of polyester resin and slightly low barrier property. Also, invention examples 68 and 72 in which invention examples 32 and 36 of films manufactured from a commercially available resin in which modified polyolefin resin is dispersed in polyester resin are laminated under the laminating conditions of the present invention similarly exhibit high performance. On the other hand, comparative examples 1 to 5 are examples of films in which polyolefin resin is not contained in polyester resin in which polyester type is changed variously. Comparative examples 15 to 19 in which these films are laminated have especially low levels of formability and impact resistance.
Invention examples 4 to 8 are films using mixed resin in which various polyolefin resins of the present invention are dispersed in polyester resin, and invention examples 40 to 44 in which these films are laminated exhibit high formability, impact resistance, adhesion, and flavor property. However, invention example 44 in which the film of invention example 8 using polyolefin resin having a slightly high glass-transition temperature is laminated has a has a tendency toward slightly deteriorated formability and impact resistance. On the other hand, comparative examples 10 to 12 are mixed resins in which polyolefin resin containing a functional group derived from carboxylic acid whose percentage deviates from the range of the present invention is dispersed in polyester resin, and comparative examples 24 to 26 in which these mixed resins are laminated have inferior formability and impact resistance.
Invention examples 9 to 16 are films in which the blending ratio and dispersion state of modified polyolefin resin in polyester resin are changed variously in the range of the present invention, and invention examples 45 to 52 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and flavor property. However, invention example 45 in which the film of invention example 9 containing a small amount of dispersed modified polyolefin resin is laminated and invention example 51 in which the film of invention example 15 having a very large number of grains of modified polyolefin resin is laminated have a tendency toward slightly deteriorated impact resistance.
On the other hand, comparative examples 6 to 9 are films in which the blending ratio of modified polyolefin resin in polyester resin does not meet the requirement of the present invention, and comparative examples 20 to 23 in which the films are laminated under the laminating conditions of the present invention have greatly deteriorated formability and impact resistance. Comparative example 20 in which the film of comparative example 6 containing a small amount of dispersed modified polyolefin resin is laminated has greatly deteriorated room-temperature impact resistance, and comparative example 23 in which the film of comparative example 9 containing a large amount of modified polyolefin resin is laminated has greatly deteriorated formability.
Invention examples 27 to 31 are films in which titanium dioxide pigment is mixed with a mixed resin of modified polyolefin resin and polyester resin, and invention examples 63 to 67 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and flavor property, and also provide a white uniform color tone. However, invention example 63 in which the film of invention example 27 in which the added amount of pigment is smaller than a desired range is laminated has slightly insufficient opacifying property of color tone. On the other hand, invention example 67 in which the film of invention example 31 in which the added amount of pigment is larger than a desired range is laminated has slightly deteriorated formability.
Invention examples 17 to 21 are films in which the blending ratio of polymerization catalyst and oxidation inhibitor in mixed resin is changed variously in the range of the present invention, and invention examples 53 to 57 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and flavor property. However, invention example 53 containing a large amount of oxidation inhibitor has slightly deteriorated formability and impact resistance. On the other hand, comparative examples 27 and 28 in which the films of comparative examples 13 and 14 in which the blending ratio of polymerization catalyst and oxidation inhibitor in mixed resin deviates from the range of the present invention are laminated under the laminating conditions of the present invention have deteriorated formability, impact resistance, and adhesion.
Invention examples 22 and 23 are films in which the thickness of each layer of film is changed, and invention examples 58 and 59 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and flavor property. Since the film of invention example 22 is slightly thin, invention example 58 in which this film is laminated has slightly deteriorated impact resistance.
Invention examples 41 and 73 to 76 are films obtained by changing the laminating conditions for the film of invention example 5 in the range of the present invention. If the conditions are within the range of the present invention, high formability, impact resistance, adhesion, and flavor property are exhibited regardless of the laminating temperature.
Invention examples 24 and 25 are films in which a lubricant, free radical inhibitor, and compatibilizing agent are mixed, respectively, in a mixed resin of modified polyolefin resin and polyester resin of the present invention, and invention examples 60 and 61 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and flavor property. Further, invention examples 60 and 61 also have lubricity, free radical deterioration resistance, and compatibility depending on the function of added additive, and in particular, invention example 61 containing a compatibilizing agent exhibits excellent low-temperature impact resistance.
Invention example 26 is a film of the present invention that is manufactured by the two-axis stretching method, and invention examples 62 and 77 in which the film is laminated exhibit high performance. Invention example 77, which has a plane orientation coefficient of 0.015, exhibits a slightly deteriorated formability. Invention example 62, which has a plane orientation coefficient in the range of the present invention, exhibits very high formability and impact resistance.
Invention examples 33 to 36 are two-layer films in which a polyester resin layer containing no olefin is provided as an upper layer, and invention examples 69 to 72 in which the two-layer films are laminated have high low-temperature impact resistance and flavor property as compared with the single-layer film. However, invention example 71 in which the film of invention example 35 using a film containing polybutylene terephthalate as an upper layer is laminated has a slightly deteriorated flavor property.









TABLE 9









R1 layer










Polyester resin

















*1)







Polymerization
Oxidation


Polyolefin resin


Sample
Resin
catalyst (ppm)
inhibitor


Resin


film
type
(X)
(ppm) (Y)
X/Y
Additive
type

















Invention
PET
GeO2 100 ppm
400
ppm
0.25
None
EM4


example 1


Invention
PET/PBT (60)
GeO2 100 ppm
400
ppm
0.25
None
EM4


example 2


Invention
PET/AD (20)
GeO2 100 ppm
400
ppm
0.25
None
EM4


example 3


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM2


example 4


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM4


example 5


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM5


example 6


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM6


example 7


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM8


example 8


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM3


example 9


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM3


example 10


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM3


example 11


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM3


example 12


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM3


example 13


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM3


example 14


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM3


example 15


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM3


example 16


Invention
PET/1 (10)
GeO2 120 ppm
600
ppm
0.20
None
EM6


example 17


Invention
PET/I (10)
GeO2 100 ppm
100
ppm
1.0
None
EM6


example 18


Invention
PET/I (10)
GeO2 100 ppm
10
ppm
10
None
EM6


example 19


Invention
PET/I (10)
GeO2  50 ppm
0.5
ppm
100
None
EM6


example 20


Invention
PET/I (10)
GeO2  50 ppm
0.05
ppm
1000
None
EM6


example 21


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM6


example 22


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM6


example 23


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
*3) 3 wt %
EM3


example 24


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
*4) 3 wt %
EM3


example 25


Invention
PET/I (10)
GeO2 100 ppm
400
ppm
0.25
None
EM4


example 26













R1 layer











Polyolefin resin















Weight


Volume
Number of




percentage

Blending
percentage
grains with



of functional

ratio in
of grains
diameter of 0.1



group derived

entire
with diameter
to 5 μm in cube
Film


Sample
from carboxylic
Tg
resin
of 0.1 to
with one side of
thickness


film
acid (wt %)
(° C.)
(wt %)
5 μm (vol %)
10 μm (grains)
(μm)





Invention
8
<−30
15
12
2000
22


example 1


Invention
8
<−30
15
12
2000
22


example 2


Invention
8
<−30
15
12
2000
22


example 3


Invention
18
<−30
15
13
500
22


example 4


Invention
8
<−30
15
12
2000
22


example 5


Invention
7
<−30
15
12
2000
22


example 6


Invention
5
<−30
15
12
2000
22


example 7


Invention
6
 20
15
12
2000
22


example 8


Invention
11
<−30
5
3
3
22


example 9


Invention
11
<−30
5
5
70
22


example 10


Invention
11
<−30
10
8
30
22


example 11


Invention
11
<−30
10
10
250
22


example 12


Invention
11
<−30
15
15
500
22


example 13


Invention
11
<−30
15
18
20000
22


example 14


Invention
11
<−30
20
22
200000
22


example 15


Invention
11
<−30
28
20
8000
22


example 16


Invention
5
<−30
15
12
2000
22


example 17


Invention
5
<−30
15
12
2000
22


example 18


Invention
5
<−30
15
12
2000
22


example 19


Invention
5
<−30
15
12
2000
22


example 20


Invention
5
<−30
15
12
2000
22


example 21


Invention
5
<−30
15
12
2000
10


example 22


Invention
5
<−30
15
12
2000
50


example 23


Invention
11
<−30
15
12
2000
22


example 24


Invention
11
<−30
15
12
2000
22


example 25


Invention
8
<−30
15
12
2000
22


example 26





*1) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane is used as oxidation inhibitor.


*3) Silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.


*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin.
















TABLE 10









Entire film












R0 layer
Film













Film
thick-
Pigment















Polyester
thick-
ness

Content



Sample
resin
ness
(R1 + R0)

(wt %)


film
Resin type
(μm)
(μm)
Type
*2)
Stretching





Invention


22
None
0
Non-


example 1





stretched


Invention


22
None
0
Non-


example 2





stretched


Invention


22
None
0
Non-


example 3





stretched


Invention


22
None
0
Non-


example 4





stretched


Invention


22
None
0
Non-


example 5





stretched


Invention


22
None
0
Non-


example 6





stretched


Invention


22
None
0
Non-


example 7





stretched


Invention


22
None
0
Non-


example 8





stretched


Invention


22
None
0
Non-


example 9





stretched


Invention


22
None
0
Non-


example 10





stretched


Invention


22
None
0
Non-


example 11





stretched


Invention


22
None
0
Non-


example 12





stretched


Invention


22
None
0
Non-


example 13





stretched


Invention


22
None
0
Non-


example 14





stretched


Invention


22
None
0
Non-


example 15





stretched


Invention


22
None
0
Non-


example 16





stretched


Invention


22
None
0
Non-


example 17





stretched


Invention


22
None
0
Non-


example 18





stretched


Invention


22
None
0
Non-


example 19





stretched


Invention


22
None
0
Non-


example 20





stretched


Invention


22
None
0
Non-


example 21





stretched


Invention


10
None
0
Non-


example 22





stretched


Invention


50
None
0
Non-


example 23





stretched


Invention


22
None
0
Non-


example 24





stretched


Invention


22
None
0
Non-


example 25





stretched


Invention


22
None
0
Two-axis


example 26





stretched





*2) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment.















TABLE 11









R1 layer









Polyolefin resin









Weight











Polyester resin

percentage

















*1)



of functional




Polymerization
Oxidation



group derived


Sample
Resin
catalyst (ppm)
inhibitor


Resin
from carboxylic


film
type
(X)
(ppm) (Y)
X/Y
Additive
type
acid (wt %)


















Invention
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM5
7


example 27


Invention
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM5
7


example 28


Invention
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM5
7


example 29


Invention
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM5
7


example 30


Invention
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM5
7


example 31


Invention
PT4274
Sb2O3
250 ppm
500 ppm
0.50
None
EM5
10


example 32


Invention
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM5
7


example 33


Invention
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM5
7


example 34


Invention
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM5
7


example 35


Invention
PT4274
Sb2O3
250 ppm
500 ppm
0.50
None
EM5
10


example 36


Invention
PET
GeO2
100 ppm
400 ppm
0.25
None
None
—


example 1


Comparative
PET/PBT(60)
GeO2
100 ppm
400 ppm
0.25
None
None
—


example 2


Comparative
PET/AD(20)
GeO2
100 ppm
400 ppm
0.25
None
None
—


example 3


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
None
—


example 4


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
None
—


example 5


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM3
11


example 6


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM3
11


example 7


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM3
11


example 8


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM3
11


example 9


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM1
21


example 10


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EM7
1


example 11


Comparative
PET/I(10)
GeO2
100 ppm
400 ppm
0.25
None
EPR
0


example 12


Comparative
PET/I(10)
GeO2
 40 ppm
400 ppm
0.10
None
EM6
5


example 13


Comparative
PET/I(10)
GeO2
 40 ppm
400 ppm
0.10
None
EM6
5


example 14













R1 layer











Polyolefin resin


















Volume
Number of






Blending
percentage
grains with





ratio in
of grains
diameter of 0.1





entire
with diameter
to 5 μm in cube
Film



Sample
Tg
resin
of 0.1 to
with one side of
thickness



film
(° C.)
(wt %)
5 μm (vol %)
10 μm (grains)
(μm)







Invention
<−30
15
12
2000
22



example 27



Invention
<−30
15
12
2000
22



example 28



Invention
<−30
15
12
2000
22



example 29



Invention
<−30
15
12
2000
22



example 30



Invention
<−30
15
12
2000
22



example 31



Invention
<−30
15
12
2000
20



example 32



Invention
<−30
15
12
2000
20



example 33



Invention
<−30
15
12
2000
20



example 34



Invention
<−30
15
12
2000
20



example 35



Invention
<−30
15
12
2000
20



example 36



Invention
—
0
0
0
22



example 1



Comparative
—
0
0
0
22



example 2



Comparative
—
0
0
0
22



example 3



Comparative
—
0
0
0
22



example 4



Comparative
—
0
0
0
22



example 5



Comparative
<−30
2
2
3
22



example 6



Comparative
<−30
2
2
45
22



example 7



Comparative
<−30
35
28
15000
22



example 8



Comparative
<−30
35
28
120000
22



example 9



Comparative
<−30
15
14
40
22



example 10



Comparative
<−30
15
3
20
22



example 11



Comparative
<−30
15
1
5
22



example 12



Comparative
<−30
15
12
2000
22



example 13



Comparative
<−30
15
12
2000
20



example 14







*1) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane is used as oxidation inhibitor.

















TABLE 12









R0 layer
Entire film














Polyester
Film
Film
Pigment















resin
thick-
thickness

Content



Sample
Resin
ness
(R1 + R0)

(wt %)


film
type
(μm)
(μm)
Type
*2)
Stretching
















Invention


22
TiO2
3
Non-


example 27





stretched


Invention


22
TiO2
7
Non-


example 28





stretched


Invention


22
TiO2
15
Non-


example 29





stretched


Invention


22
TiO2
30
Non-


example 30





stretched


Invention


22
TiO2
50
Non-


example 31





stretched


Invention


20
None
0
Non-


example 32





stretched


Invention
PET
5
20
None
0
Non-


example 33





stretched


Invention
PET/
5
20
None
0
Non-


example 34
I(10)




stretched


Invention
PET/
5
20
None
0
Non-


example 35
PBT(60)




stretched


Invention
PET
5
20
None
0
Non-


example 36





stretched


Comparative


22
None
0
Non-


example 1





stretched


Comparative


22
None
0
Non-


example 2





stretched


Comparative


22
None
0
Non-


example 3





stretched


Comparative


22
None
0
Non-


example 4





stretched


Comparative


22
None
0
Two-axis


example 5





stretched


Comparative


22
None
0
Non-


example 6





stretched


Comparative


22
None
0
Non-


example 7





stretched


Comparative


22
None
0
Non-


example 8





stretched


Comparative


22
None
0
Non-


example 9





stretched


Comparative


22
None
0
Non-


example 10





stretched


Comparative


22
None
0
Non-


example 11





stretched


Comparative


22
None
0
Non-


example 12





stretched


Comparative


22
None
0
Non-


example 13





stretched


Comparative
PET
5
20
None
0
Non-


example 14





stretched





*2) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment.
















TABLE 13









Melting




point



of R1



layer












poly-
Laminat-

Thin-wall deep drawn can

















Laminated

ester
ing
Plane

Impact
Impact
Adhesion
Adhesion



metal
Sample
resin
temp.
orientation
Form-
resistance
resistance
after
after
Flavor


sheet
film
(° C.)
(° C.)
coefficient
ability
(room temp.)
(low temp.)
forming
heating
property





Invention
Invention
255
240
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 37
example 1


Invention
Invention
235
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 38
example 2


Invention
Invention
220
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 39
example 3


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 40
example 4


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 41
example 5


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 42
example 6


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 43
example 7


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 44
example 8


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 45
example 9


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 46
example 10


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 47
example 11


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 48
example 12


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 49
example 13


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 50
example 14


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 51
example 15


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 52
example 16


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 53
example 17


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 54
example 18


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 55
example 19


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 56
example 20


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 57
example 21


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 58
example 22


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 59
example 23


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 60
example 24


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 61
example 25


Invention
Invention
230
215
0.005
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 62
example 26













Drawn and ironed can (DI can)
















Laminated

Impact
Impact
Adhesion
Adhesion




metal
Form-
resistance
resistance
after
after
Flavor



sheet
ability
(room temp.)
(low temp.)
forming
heating
property







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 37



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 38



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 39



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 40



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 41



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 42



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 43



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 44



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 45



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 46



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 47



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 48



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 49



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 50



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 51



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 52



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 53



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 54



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 55



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 56



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 57



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 58



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 59



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 60



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 61



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 62




















TABLE 14









Melting




point



of R1



layer












poly-
Laminat-

Thin-wall deep drawn can

















Laminated

ester
ing
Plane

Impact
Impact
Adhesion
Adhesion



metal
Sample
resin
temp.
orientation
Form-
resistance
resistance
after
after
Flavor


sheet
film
(° C.)
(° C.)
coefficient
ability
(room temp.)
(low temp.)
forming
heating
property





Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 63
example 27


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 64
example 28


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 65
example 29


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 66
example 30


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 67
example 31


Invention
Invention
255
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 68
example 32


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 69
example 33


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 70
example 34


Invention
Invention
230
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 71
example 35


Invention
Invention
255
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 72
example 36


Invention
Invention
230
260
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 73
example 5


Invention
Invention
230
230
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 74
example 5


Invention
Invention
230
190
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 75
example 5


Invention
Invention
230
170
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 76
example 5


Invention
Invention
230
200
0.015
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 77
example 26


Comparative
Comparative
215
200
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 15
example 1


Comparative
Comparative
220
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 16
example 2


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 17
example 3


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 18
example 4


Comparative
Comparative
240
220
0.015
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 19
example 5


Comparative
Comparative
245
225
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 20
example 6


Comparative
Comparative
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 21
example 7


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 22
example 8


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 23
example 9


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 24
example 10


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 25
example 11


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 26
example 12


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 27
example 13


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 28
example 14













Drawn and ironed can (DI can)
















Laminated

Impact
Impact
Adhesion
Adhesion




metal
Form-
resistance
resistance
after
after
Flavor



sheet
ability
(room temp.)
(low temp.)
forming
heating
property







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 63



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 64



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 65



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 66



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 67



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 68



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 69



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 70



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 71



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 72



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 73



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 74



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 75



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 76



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 77



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 15



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 16



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 17



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 18



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 19



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 20



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 21



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 22



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 23



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 24



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 25



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 26



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 27



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 28










EXAMPLE 4
As a resin raw material, modified polyolefin resin with group derived from carboxylic acid was cold blended with polyester resin in a blending ratio given in Tables 15 and 16 by using a tumbler blender, and then the blended resin was melted and kneaded at 270° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. Partially, a commercially available resin (Sealer PT4274 manufactured by Mitsui-DuPont Polychemical Co., Ltd.) that had been pelletized in advance in a state in which modified polyolefin resin with group derived from carboxylic acid was dispersed in polyester resin, which was used as a resin raw material, was used as it was. In the tables, the resin type corresponding to the symbol of resin type of polyester resin and resin type of polyolefin resin is the same as that described in Example 3.
As a metal sheet, as in Example 3, a tin-free steel (hereinafter abbreviated to TFS) with a thickness of 0.18 mm for thin-wall deep drawn can and 0.23 mm for DI can, which had a degree of temper of DR9, metallic chromium layer of 80 mg/m2, and chromium oxide layer of 15 mg/m2 (metallic chromium conversion), was used, by which a both-side resin laminated metal sheet was obtained by a method in which the raw material resin pellet was inserted in a one-axis extruding machine, a resin for R0 layer was inserted in a separate extruding machine in the case of two layers and simultaneously melted and extruded, molten resin was extruded directly onto one surface of the metal sheet, the extruded resin was once cooled while being held adherently between two rolls, and immediately after the resin was laminated on the opposite surface in the same manner, the resin laminated metal sheet was cooled rapidly in water. The temperature of metal sheet at the laminating time was 230° C. The lip opening width of T die was adjusted so that the thickness of resin film was 10 to 50 μm. The type of sample resin and the resin melting temperature at the laminating time are given in Tables 15 to 18. The used polyester resin and modified polyolefin resin with group derived from carboxylic acid are the same as those used in Example 3.
All of the grain diameter of modified polyolefin resin dispersed in resin film, various temperatures in the table, and the method for measuring the plane orientation coefficient of resin laminated metal sheet are the same as those in Example 3. As in Example 3, a thin-wall deep drawn can or a DI can was manufactured from the resin laminated metal sheet obtained as described above, and the can was subjected to straightening heat treatment to manufacture a sample can. The formability, impact resistance, adhesion, and flavor property of film of the manufactured can body were investigated as in Example 3.
The investigation results are given in Tables 17 and 18.
From Tables 15 to 18, the following facts are found for either can type.
Invention examples 78 to 80 and 81 are resin layers formed in a single layer, in which modified polyolefin resin specified in the present invention is dispersed in polyester resin in which polyester type of mixed resin is changed variously, and exhibit high formability, impact resistance, adhesion, and flavor property. Among these, invention example 80 using adipic acid copolymerized polyethylene terephthalate resin has high performance as a whole, but has a tendency toward deteriorated adhesion after heating and flavor property because of slightly low melting point of polyester resin and slightly low barrier property. Also, invention examples 108 and 112 manufactured from a commercially available resin in which modified polyolefin resin is dispersed in polyester resin similarly exhibit high performance. On the other hand, comparative examples 29 to 32 are examples of resins in which polyolefin resin is not contained in polyester resin in which polyester type is changed variously. These resins especially have low levels of formability and impact resistance.
Invention examples 81 to 85 use mixed resin in which various polyolefin resins of the present invention are dispersed in polyester resin, and exhibit high formability, impact resistance, adhesion, and flavor property. However, invention example 85 using polyolefin resin having a slightly high glass-transition temperature has a tendency toward slightly deteriorated formability and impact resistance. On the other hand, comparative examples 37 to 39 are mixed resins in which polyolefin resin containing a functional group derived from carboxylic acid whose percentage deviates from the range of the present invention is dispersed in polyester resin, and have inferior formability and impact resistance.
Invention examples 86 to 93 are resin layers obtained by laminating, under the laminating conditions of the present invention, mixed resins in which the blending ratio and dispersion state of modified polyolefin resin in polyester resin are changed variously in the range of the present invention, and exhibit high formability, impact resistance, adhesion, and flavor property. However, invention example 86 containing a small amount of dispersed modified polyolefin resin and invention example 92 (93) having a very large number of grains of modified polyolefin resin have a tendency toward slightly deteriorated impact resistance.
On the other hand, comparative examples 33 to 36 are resin layers in which the blending ratio of modified polyolefin resin in polyester resin does not meet the requirement of the present invention, and have greatly deteriorated formability and impact resistance. Comparative example 33 containing a small amount of dispersed modified polyolefin resin has greatly deteriorated room-temperature impact resistance, and comparative example 36 containing a large amount of modified polyolefin resin has greatly deteriorated formability. Comparative examples 35 and 36 containing a large amount of modified polyolefin resin also have a problem with flavor.
Invention examples 103 to 107 are mixed resin layers in which titanium dioxide pigment is mixed with a mixed resin of modified polyolefin resin and polyester resin, and exhibit high formability, impact resistance, adhesion, and flavor property, and also provide a white uniform color tone. However, invention example 103 in which the added amount of pigment is smaller than a desired range has slightly insufficient opacifying property of color tone. On the other hand, invention example 107 in which the added amount of pigment is larger than a desired range has slightly deteriorated formability.
Invention examples 94 to 98 are resin layers in which the blending ratio of polymerization catalyst and oxidation inhibitor in mixed resin is changed variously in the range of the present invention, and exhibit high formability, impact resistance, adhesion, and flavor property. However, invention example 94 containing a large amount of oxidation inhibitor has slightly deteriorated formability and impact resistance. On the other hand, comparative examples 40 and 41 in which the blending ratio of polymerization catalyst and oxidation inhibitor in mixed resin deviates from the range of the present invention have deteriorated formability, impact resistance, and adhesion.
Invention examples 99 and 100 are resin layers in which the thickness of each layer is changed, and exhibit high formability, impact resistance, adhesion, and flavor property. Since the resin layer of invention example 99 is slightly thin, the impact resistance is slightly deteriorated.
Invention examples 101 and 102 are resin layers in which a lubricant, free radical inhibitor, and compatibilizing agent are mixed, respectively, in a mixed resin of modified polyolefin resin and polyester resin of the present invention, and exhibit high formability, impact resistance, adhesion, and flavor property. Further, invention examples 101 and 102 also have lubricity, free radical deterioration resistance, and compatibility depending on the function of added additive, and in particular, invention example 102 containing a compatibilizing agent exhibits excellent low-temperature impact resistance.
Invention examples 109 to 112 are two-layer resins in which a polyester resin layer containing no olefin is provided as an upper layer, and have high low-temperature impact resistance and flavor property as compared with the single-layer resin. However, invention example 111 using a resin containing polybutylene terephthalate as an upper layer has a slightly deteriorated flavor property.









TABLE 15









R1 layer









Polyester resin









Weight











Polyester resin

percentage


















*1)


Polyester

of functional




Polymerization
Oxidation


meloting

group derived


Sample
Resin
catalyst (ppm)
inhibitor


point
Polyolefin
from carboxylic


film
type
(X)
(ppm) (Y)
X/Y
Additive
(° C.)
resin
acid (wt %)



















Invention
PET
GeO2 100 ppm
400
ppm
0.25
None
255
EM4
8


example 78


Invention
PET/PBT(60)
GeO2 100 ppm
400
ppm
0.25
None
235
EM4
8


example 79


Invention
PET/AD(20)
GeO2 100 ppm
400
ppm
0.25
None
220
EM4
8


example 80


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM2
18


example 81


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM4
8


example 82


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM5
7


example 83


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM6
5


example 84


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM8
6


example 85


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM3
11


example 86


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM3
11


example 87


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM3
11


example 88


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM3
11


example 89


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM3
11


example 90


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM3
11


example 91


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM3
11


example 92


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM3
11


example 93


Invention
PET/I(10)
GeO2 120 ppm
600
ppm
0.2
None
230
EM6
5


example 94


Invention
PET/I(10)
GeO2 100 ppm
100
ppm
1
None
230
EM6
5


example 95


Invention
PET/I(10)
GeO2 100 ppm
10
ppm
10
None
230
EM6
5


example 96


Invention
PET/I(10)
 GeO2 50 ppm
0.5
ppm
100
None
230
EM6
5


example 97


Invention
PET/I(10)
GeO2 100 ppm
0.05
ppm
1000
None
230
EM6
5


example 98


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM6
5


example 99


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
None
230
EM6
5


example 100


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
*3) 3 wt %
230
EM3
11


example 101


Invention
PET/I(10)
GeO2 100 ppm
400
ppm
0.25
*4) 3 wt %
230
EM3
11


example 102













R1 layer











Polyester resin



















Number of








grains with







diameter of





Blending
Volume
0.1 to 5 μm





ratio in
percentage of
in cube with





entire
grains with
one side of
Film



Sample
Tg
resin
diameter of 0.1
10 μm
thickness



film
(° C.)
(wt %)
to 5 μm (vol %)
(grains)
(μm)







Invention
<−30
15
14
2500
25



example 78



Invention
<−30
15
14
2500
25



example 79



Invention
<−30
15
14
2500
25



example 80



Invention
<−30
15
14
1000
25



example 81



Invention
<−30
15
14
2500
25



example 82



Invention
<−30
15
14
2500
25



example 83



Invention
<−30
15
14
2500
25



example 84



Invention
20
15
14
2500
25



example 85



Invention
<−30
5
4
4
25



example 86



Invention
<−30
5
8
100
25



example 87



Invention
<−30
10
10
50
25



example 88



Invention
<−30
10
12
500
25



example 89



Invention
<−30
15
18
800
25



example 90



Invention
<−30
15
20
22000
25



example 91



Invention
<−30
20
24
250000
25



example 92



Invention
<−30
28
22
10000
25



example 93



Invention
<−30
15
14
2500
25



example 94



Invention
<−30
15
14
2500
25



example 95



Invention
<−30
15
14
2500
25



example 96



Invention
<−30
15
14
2500
25



example 97



Invention
<−30
15
14
2500
25



example 98



Invention
<−30
15
14
2500
10



example 99



Invention
<−30
15
14
2500
50



example 100



Invention
<−30
15
14
2500
25



example 101



Invention
<−30
15
14
2500
25



example 102







*1) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane is used as oxidation inhibitor.



*3) Silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.



*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin. Table 15















TABLE 16









R1 layer









Polyester resin









Weight











Polyester resin

percentage


















*1)


Polyester

of functional




Polymerization
Oxidation


meloting

group derived


Sample
Resin
catalyst (ppm)
inhibitor


point
Polyolefin
from carboxylic


film
type
(X)
(ppm) (Y)
X/Y
Additive
(° C.)
resin
acid (wt %)



















Invention
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM5
7


example 103


Invention
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM5
7


example 104


Invention
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM5
7


example 105


Invention
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM5
7


example 106


Invention
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM5
7


example 107


Invention
PT4274
Sb2O3 250
ppm
500 ppm
0.5
None
255
EM5
10


example 108


Invention
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM5
7


example 109


Invention
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM5
7


example 110


Invention
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM5
7


example 111


Invention
PT4274
Sb2O3 250
ppm
500 ppm
0.5
None
255
EM5
10


example 112


Comparative
PET
GeO2 100
ppm
400 ppm
0.25
None
255
None
—


example 29


Comparative
PET/PBT(60)
GeO2 100
ppm
400 ppm
0.25
None
235
None
—


example 30


Comparative
PET/AD(20)
GeO2 100
ppm
400 ppm
0.25
None
220
None
—


example 31


Comparative
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
None
—


example 32


Comparative
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM3
11


example 33


Comparative
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM3
11


example 34


Comparative
PET/I(10)
GeO2 120
ppm
400 ppm
0.25
None
230
EM3
11


example 35


Comparative
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM3
11


example 36


Comparative
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM1
21


example 37


Comparative
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EM7
1


example 38


Comparative
PET/I(10)
GeO2 100
ppm
400 ppm
0.25
None
230
EPR
0


example 39


Comparative
PET/I(10)
GeO2 40
ppm
400 ppm
0.1
None
230
EM6
5


example 40


Comparative
PET/I(10)
GeO2 40
ppm
400 ppm
0.1
None
230
EM6
5


example 41













R1 layer











Polyester resin



















Number of








grains with





Blending
Volume
diameter of





ratio in
percentage of
0.1 to 5 μm





entire
grains with
in cube with
Film



Sample
Tg
resin
dilameter of 0.1
one side of
thickness



film
(° C.)
(wt %)
to 5 μm (vol %)
10 μm (grains)
(μm)







Invention
<−30
15
14
2500
25



example 103



Invention
<−30
15
14
2500
25



example 104



Invention
<−30
15
14
2500
25



example 105



Invention
<−30
15
14
2500
25



example 106



Invention
<−30
15
14
2500
25



example 107



Invention
<−30
15
14
2500
22



example 108



Invention
<−30
15
14
2500
20



example 109



Invention
20
15
14
2500
20



example 110



Invention
<−30
15
14
2500
20



example 111



Invention
<−30
15
14
2500
20



example 112



Comparative
—
0
0
0
25



example 29



Comparative
—
0
0
0
25



example 30



Comparative
—
0
0
0
25



example 31



Comparative
—
0
0
0
25



example 32



Comparative
<−30
2
3
5
25



example 33



Comparative
<−30
2
3
50
25



example 34



Comparative
<−30
35
30
20000
25



example 35



Comparative
<−30
35
30
135000
25



example 36



Comparative
<−30
15
16
50
25



example 37



Comparative
<−30
15
4
40
25



example 38



Comparative
<−30
15
1
4
25



example 39



Comparative
<−30
15
14
2500
25



example 40



Comparative
<−30
15
14
2500
20



example 41







*1) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane is used as oxidation inhibitor.


















TABLE 17









R0 layer
Entire film
Melting temp. of
Investigation result













Poly-
Film

R1 layer
Thin-wall deep drawn can

















ester
Film
thick-

resin at

Impact
Impact




resin
thick-
ness
Pigment
extrusion

resistance
resistance
Adhesion

















Sample
Resin
ness
(R1 + R0)

Content
laminating
Form-
(room
(low
after


film
type
(μm)
(μm)
Type
(wt %) *2)
time (° C.)
ability
temp.)
temp.)
forming





Invention


25
None
0
285
⊚
⊚
⊚⊚⊚
⊚


example 78


Invention


25
None
0
265
⊚
⊚
⊚⊚⊚
⊚


example 79


Invention


25
None
0
250
⊚
⊚
⊚⊚⊚
⊚


example 80


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 81


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 82


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 83


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 84


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 85


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 86


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 87


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 88


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 89


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 90


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 91


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 92


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 93


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 94


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 95


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 96


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 97


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 98


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 99


Invention


10
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 100


Invention


50
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 101


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 101


Invention


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 102













Investigation result












Thin-wall deep drawn can
Drawn and ironed can (DI can)



















Adhesion


Impact
Impact
Adhesion
Adhesion




Sample
after
Flavor
Form-
resistance
resistance
after
after
Flavor



film
heating
property
ability
(room temp.)
(low temp.)
forming
heating
property







Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 78



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 79



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 80



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 81



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 82



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 83



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 84



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 85



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 86



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 87



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 88



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 89



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 90



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 91



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 92



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 93



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 94



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 95



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 96



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 97



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 98



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 99



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 100



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 101



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 101



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 102







*2) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.

















TABLE 18









Entire film

Investigation result













R0 layer
Film

Melting temp. of
Thin-wall deep drawn can
















Poly-
thick-

R1 layer

Impact
Impact


















ester
Film
ness
Pigment
resin at

resis-
resis-



















resin
thick-
(R1 +

Content
extrusion

tance
tance
Adhesion


Sample
Resin
ness
R0)

(wt %)
laminating
Form-
(room
(low
after


film
type
(μm)
(μm)
Type
*2)
time (° C.)
ability
temp.)
temp.)
forming





Invention


25
TiO2
3
260
⊚
⊚
⊚⊚⊚
⊚


example 103


Invention


25
TiO2
7
260
⊚
⊚
⊚⊚⊚
⊚


example 104


Invention


25
TiO2
15
260
⊚
⊚
⊚⊚⊚
⊚


example 105


Invention


25
TiO2
30
260
⊚
⊚
⊚⊚⊚
⊚


example 106


Invention


25
TiO2
50
260
⊚
⊚
⊚⊚⊚
⊚


example 107


Invention


25
None
0
285
⊚
⊚
⊚⊚⊚
⊚


example 108


Invention
PET
5
25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 109


Invention
PET/I
5
25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 110
(10)


Invention
PET/PBT
5
25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 111
(60)


Invention
PET
5
25
None
0
285
⊚
⊚
⊚⊚⊚
⊚


example 112


Comparative


25
None
0
285
⊚
⊚
⊚⊚⊚
⊚


example 29


Comparative


25
None
0
265
⊚
⊚
⊚⊚⊚
⊚


example 30


Comparative


25
None
0
250
⊚
⊚
⊚⊚⊚
⊚


example 31


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 32


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 33


Comparati34


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 34


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 35


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 36


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 37


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 38


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 39


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 40


Comparative


25
None
0
260
⊚
⊚
⊚⊚⊚
⊚


example 41













Investigation result











Drawn and ironed can (DI can)












Impact
Impact














Thin-wall deep drawn can

resis-
resis-



















Adhesion


tance
tance
Adhesion
Adhesion




Sample
after
Flavor
Form-
(room
(low
after
after
Flavor



film
heating
property
ability
temp.)
temp.)
forming
heating
property







Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 103



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 104



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 105



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 106



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 107



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 108



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 109



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 110



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 111



Invention
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 112



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 29



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 30



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 31



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 32



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 33



Comparati34
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 34



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 35



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 36



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 37



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 38



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 39



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 40



Comparative
⊚⊚
⊚⊚
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 41







*2) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.






EXAMPLE 5
As a resin raw material for R1 layer, modified polyolefin resin with group derived from carboxylic acid having a primary grain diameter of 0.3 μm was cold blended with polyester resin in a blending ratio given in Tables 19 and 20 by using a tumbler blender, and then the blended resin was melted and kneaded at 270° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. On the other hand, polyester resin containing no modified polyolefin resin, which was a resin raw material for R0 layer, was inserted in a separate one-axis extruding machine, and each of molten resins was introduced into a multi-manifold type T die and extruded in two layers while the film thickness of R1 and R0 layers was controlled by the discharge amount of molten resin from the extruding machine, by which a resin film with a total thickness of 9.5 to 70 p was manufactured continuously while being cooled by the surface of a rotating metallic roll.
The used polyester resin and modified polyolefin resin with group derived from carboxylic acid were as follows:
1. Polyester Resin
(1) PET/PBT(90): Mixed resin with a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutylene terephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.) of 10:90, intrinsic viscosity: 0.6 dl/g, Tg: 27° C., Tc: 60° C., Tm: 215° C., Ge content: 10 ppm
(2) PET/PBT(80): Mixed resin with a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutylene terephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.) of 20:80, intrinsic viscosity: 0.6 dl/g, Tg: 35° C., Tc: 75° C., Tm: 220° C., Ge content: 10 ppm
(3) PET/PBT(70): Mixed resin with a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutylene terephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.) of 30:70, intrinsic viscosity: 0.62 dl/g, Tg: 45° C., Tc: 90° C., Tm: 230° C., Ge content: 20 ppm
(4) PET/PBT(60): Mixed resin with a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutylene terephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.) of 40:60, intrinsic viscosity: 0.6 dl/g, Tg: 50° C., Tc: 105° C., Tm: 235° C., Ge content: 10 ppm
(5) PET/PBT(40): Mixed resin with a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutylene terephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.) of 60:40, intrinsic viscosity: 0.6 dl/g, Tg: 60° C., Tc: 120° C., Tm: 240° C., Ge content: 10 ppm
(6) PET/PBT(20): Mixed resin with a ratio of polyethylene terephthalate (EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutylene terephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.) of 80:20, intrinsic viscosity: 0.6 dl/g, Tg: 65° C., Tc: 140° C., Tm: 245° C., Ge content: 10 ppm
(7) PET: Polyethylene terephthalate (EFG10 manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.62 dl/g, Tg: 72° C., Tc: 150° C., Tm: 255° C., Ge content: 20 ppm
(8) PET/I(10): Ethylenephthalate-ethyleneisophthalate copolymerized resin with a ratio of terephthalic acid to isophthalic acid of 90:10 (IP121B manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.6 dl/g, Tg: 70° C., Tc: 170° C., Tm: 230° C., Ge content: 10 ppm
2. Modified Polyolefin Resin with Group Derived from Carboxylic Acid
(1) EM1: Polymethyl methacrylate-(ethylene-ethyl acrylate copolymer) graft copolymer (Modiper A5200 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 21 wt %, glass-transition temperature: −30° C. or lower
(2) EM2: Polymethyl methacrylate-(ethylene-ethyl acrylate-maleic anhydride copolymer) graft copolymer (Modiper A8200 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 18 wt %, glass-transition temperature: −30° C. or lower
(3) EM3: Ethylene-ethyl acrylate-maleic anhydride copolymer (Bondine HX8290 manufactured by Sumitomo Chemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 11 wt %, glass-transition temperature: −30° C. or lower
(4) EM4: Ethylene-methacrylic acid copolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 8 wt %, glass-transition temperature: −30° C. or lower
(5) EM5: 50% Zn neutralized substance of ethylene-methacrylic acid copolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co., Ltd. neutralized partially by Zn), weight ratio of functional group derived from carboxylic acid: 7 wt %, glass-transition temperature: −30° C. or lower
(6) EM6: 60% Zn neutralized substance of ethylene-methacrylic acid copolymer (Himilan 1557 manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 5 wt %, glass-transition temperature: −30° C. or lower
(7) EM7: Ethylene-methacrylic acid copolymer (Nucrel N0200H manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functional group derived from carboxylic acid: 1 wt %, glass-transition temperature: −30° C. or lower
(8) EM8: Polystyrene-(ethylene-ethyl acrylate copolymer) graft copolymer (Modiper A5100 manufactured by NOF Corp.), weight ratio of functional group derived from carboxylic acid: 6 wt %, glass-transition temperature: 20° C.
(9) EPR: Ethylene-propylene rubber (EP07P manufactured by JSR Corp.), weight ratio of functional group derived from carboxylic acid: 0 wt %, glass-transition temperature: −30° C. or lower
As a resin raw material for R1 layer, pelletized modified polyolefin resin with group derived form carboxylic acid and polyester resin are inserted in a one-axis extruding machine in the blending ratio shown in comparative example 16 in Table 20. On the other hand, polyester resin containing no modified polyolefin resin, which was a resin raw material for R0 layer, was inserted in a separate one-axis extruding machine, and each of molten resins was introduced into a multi-manifold type T die and extruded in two layers while the film thickness of R1 and R0 layers was controlled by the discharge amount of molten resin from the extruding machine, by which a resin film with a total thickness of 9.5 to 70 μm was manufactured continuously while being cooled by the surface of a rotating metallic roll.
A resin laminated metal sheet was obtained by a thermo-compression bonding method in which the resin film obtained as described above was hot-pressed on both surfaces of a tin-free steel (hereinafter abbreviated to TFS, thickness: 0.18 mm for thin-wall deep drawn can and 0.23 mm for DI can, degree of temper: DR9, metallic chromium layer: 80 mg/m2, chromium oxide layer: 15 mg/m2 (metallic chromium conversion)) heated by an induction heating system, and then the laminated metal sheet was rapidly cooled in water. The metal sheet temperature at the laminating time (laminating temperature) is given in Tables 21 and 22.
The grain diameter of modified polyolefin resin dispersed in R1 layer of resin film, various temperatures in the table, and the plane orientation coefficient of resin laminated metal sheet were measured by the same method as that in Example 1.
A thin-wall deep drawn can or a DI can was manufactured from the laminated metal sheet obtained as described above, and the can was subjected to straightening heat treatment to manufacture a sample can. The formability, impact resistance (room temperature, low temperature), adhesion after forming, adhesion after heating, and retort resistance of film of the manufactured can body were investigated. The retort resistance was evaluated by cloudiness of film at the can bottom after retorting (cloudiness resistance). The lid was obtained by forming the resin laminated metal sheet in the same way as a can lid of a commercially available 250 ml negative-pressure can (three-piece can).
The following is a detailed description of the investigation method.
1. Evaluation by Thickness-decreasing Deep Drawing
1-1 Can Manufacturing
A resin laminated metal sheet was subjected to first-stage drawing and redrawing under the following conditions, by which a thin-wall deep drawn can was obtained.

    
    
        First-stage drawing
    
    


















Blank diameter
150 to 160 mm



First-stage drawing
drawing ratio: 1.65










    
    
        Redrawing
    
    















Primary redrawing
drawing ratio: 1.25


Secondary redrawing
drawing ratio: 1.25


Radius of curvature of die corner in redrawing
0.4 mm


process


Load for pressing wrinkle at the time of redrawing
39227 N (4000 kg)









    
    
        Average thickness decreasing percentage of can sidewall
        
            40 to 55% with respect to thickness of resin laminated metal sheet before forming

1-2 Straightening Heat Treatment

        
        
    
    


Forming strain of film caused by can manufacturing was removed by keeping the can in a thermal environment of film melting point minus 15° C. for 30 seconds and then by rapidly cooling it.
Formability
Evaluation was made as described below by the limit of capability for manufacturing can without film failure. Grades not lower than ◯ marked grade are acceptable.

    Limit of forming (thickness decreasing percentage): Grade
    Incapable of forming at thickness decreasing percentage of 40%: (Inferior)
    Capable of forming up to thickness decreasing percentage of 40%
    Capable of forming up to thickness decreasing percentage of 45%
    Capable of forming up to thickness decreasing percentage of 50%
    Capable of forming up to thickness decreasing percentage of 55%: (Superior)

(2) Evaluation of Room-temperature and Low-temperature Impact Resistance



A can body (thickness decreasing percentage: 50%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, an iron ball of 0.5 kg was dropped from a height of 30 cm to give a shock to the can bottom. Thereafter, the lid was opened, and 1% salt water was poured in the can so that a portion that had suffered shock was immersed. After immersion for five minutes, a load of 6 V was applied across a platinum electrode immersed in the liquid and a can metal portion, and the current value after five minutes was read, by which evaluation was made as described below. The same tests were conducted at room temperature of 20° C. and at a temperature of 0° C. The former test was for evaluating room-temperature impact resistance, and the latter test was for evaluating low-temperature impact resistance. Grades not lower than ◯ marked grade are acceptable.
(Evaluation of Room-temperature Impact Resistance)


    Test result: Grade
    Current value not lower than 30 mA: (Inferior)
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(Evaluation of Low-temperature Impact Resistance)

    Test result: Grade
    Current value not lower than 50 mA: (Inferior)
    Current value not lower than 30 mA and lower than 50 mA
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(3) Adhesion After Forming



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was immersed in aqueous solution containing 1.5 wt % citric acid and 1.5 wt % sodium chloride for 24 hours. Thereafter, the peeling length of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling length longer than 10 mm: (Inferior)
    Peeling length longer than 5 mm and not longer than 10 mm
    Peeling length longer than 2 mm and not longer than 5 mm
    Peeling length not longer than 2 mm
    No peeling: (Superior)

(4) Adhesion After Heating



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was heated without content therein at 210° C. for 10 minutes in an oven. Thereafter, the degree of peeling of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling percentage higher than 10%: (Inferior)
    Peeling percentage higher than 5% and not higher than 10%
    Peeling percentage higher than 2% and not higher than 5%
    Peeling percentage higher than 0.5% and not higher than 2%
    Peeling percentage not higher than 0.5%
    No peeling: (Superior)

(5) Cloudiness of Film After Retorting



A can body (thickness decreasing percentage: 50%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, the can was cooled to 4° C., and thereafter retorting was performed in an atmosphere of 130° C. for one hour. After retorting, the degree of cloudiness of film at the can bottom was observed. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Cloudiness more than 50% of the whole: (Inferior)
    Cloudiness more than 10% of the whole and not more than 50%
    Cloudiness more than 2% of the whole and not more than 10%
    Very slight cloudiness (not more than 2% of the whole)
    No change: (Superior)

2. Evaluation by Drawing and Ironing (DI Forming)

2-1 Can Manufacturing



A resin laminated metal sheet was drawn and ironed under the following conditions, by which a DI can was obtained.

    
    
        First-stage drawing
        
            Blank diameter: 150 mm
            Drawing ratio: 1.6
        
        
        Second-stage drawing
        
            Drawing ratio: 1.25
        
        
        Ironing
        
            Ironing punch diameter: 3-stage ironing 65.8 mm dia
        
        
        Total ironing percentage of can sidewall
        
            55 to 70% with respect to thickness of resin laminated metal sheet before forming

1-2 Straightening Heat Treatment

        
        
    
    


Forming strain of film caused by can manufacturing was removed by keeping the can in a thermal environment of film melting point minus 15° C. for 30 seconds and then by rapidly cooling it.
(1) Formability
Evaluation was made as described below by the limit of capability for manufacturing can without film failure. Grades not lower than ◯ marked grade are acceptable.

    Limit of forming (total ironing percentage): Grade
    Incapable of forming at total ironing percentage of 55%: (Inferior)
    Capable of forming up to total ironing percentage of 55%
    Capable of forming up to total ironing percentage of 60%
    Capable of forming up to total ironing percentage of 65%
    Capable of forming up to total ironing percentage of 70%: (Superior)

(2) Evaluation of Room-temperature and Low-temperature Impact Resistance



A can body (total ironing percentage: 65%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, an iron ball of 0.5 kg was dropped from a height of 25 cm to give a shock to the can bottom. Thereafter, the lid was opened, and 1% salt water was poured in the can so that a portion that had suffered shock was immersed. After immersion for five minutes, a load of 6 V was applied across a platinum electrode immersed in the liquid and a can metal portion, and the current value after five minutes was read, by which evaluation was made as described below. The same tests were conducted at room temperature of 20° C. and at a temperature of 0° C. The former test was for evaluating room-temperature impact resistance, and the latter test was for evaluating low-temperature impact resistance. Grades not lower than ◯ marked grade are acceptable.
(Evaluation of Room-temperature Impact Resistance)


    Test result: Grade
    Current value not lower than 30 mA: (Inferior)
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(Evaluation of Low-temperature Impact Resistance)

    Test result: Grade
    Current value not lower than 50 mA: (Inferior)
    Current value not lower than 30 mA and lower than 50 mA
    Current value not lower than 10 mA and lower than 30 mA
    Current value not lower than 5 mA and lower than 10 mA
    Current value not lower than 1 mA and lower than 5 mA
    Current value lower than 1 mA: (Superior)

(3) Adhesion After Forming



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was immersed in aqueous solution containing 1.5 wt % citric acid and 1.5 wt % sodium chloride for five hours. Thereafter, the peeling length of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling length longer than 10 mm: (Inferior)
    Peeling length longer than 5 mm and not longer than 10 mm
    Peeling length longer than 2 mm and not longer than 5 mm
    Peeling length not longer than 2 mm
    No peeling: (Superior)

(4) Adhesion After Heating



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was heated without content therein at 210° C. for 10 minutes in an oven. Thereafter, the degree of peeling of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling percentage higher than 10%: (Inferior)
    Peeling percentage higher than 5% and not higher than 10%
    Peeling percentage higher than 2% and not higher than 5%
    Peeling percentage higher than 0.5% and not higher than 2%
    Peeling percentage not higher than 0.5%
    No peeling: (Superior)

(5) Cloudiness of Film After Retorting (Cloudiness Resistance)



A can body (total ironing percentage: 65%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, the can was cooled to 4° C., and thereafter retorting was performed in an atmosphere of 130° C. for one hour. After retorting, the degree of cloudiness of film at the can bottom was observed. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Cloudiness more than 50% of the whole: (Inferior)
    Cloudiness more than 10% of the whole and not more than 50%
    Cloudiness more than 2% of the whole and not more than 10%
    Very slight cloudiness (not more than 2% of the whole)
    No change: (Superior) The investigation results are given in Tables 21 and 22.


From Tables 19 to 22, the following facts are found for either can type.
Invention examples 1 to 7 are films in which R1 layer is a resin layer in which modified polyolefin resin specified in the present invention is dispersed in polyester resin in which the mixing ratio of polyethylene terephthalate to polybutylene terephthalate is changed variously and R0 layer is a resin layer of polyethylene terephthalate specified in the present invention, and invention examples 38 to 44 in which these films are laminated under the laminating conditions of the present invention exhibit very high formability, impact resistance, adhesion, and cloudiness resistance. Among these, invention example 43 in which the film of invention example 6 using polyester resin having a low percentage of polybutylene terephthalate is laminatead and invention example 44 in which the film of invention example 7 further using homopolyethylene terephthalate is laminated have a tendency for adhesion after heating and cloudiness resistance after retorting to be deteriorated as the percentage of polybutylene terephthalate becomes low, but still have high performance as a whole. Also, invention example 45 in which the film of invention example 8 using polyethylene terephthalate in which polyester resin is copolymerized by isophthalic acid is laminated has a tendency for adhesion after heating and cloudiness resistance after retorting to be deteriorated slightly, but still have high performance as a whole. On the other hand, invention examples 38 and 39 in which the films of invention examples 1 and 2 having a very high percentage of polybutylene terephthalate are laminated have a tendency toward deteriorated adhesion after heating because the melting point is slightly low, but have high performance as a whole. On the other hand, comparative examples 1 to 8 are examples of films in which polyester resin in which the mixing ratio of polyethylene terephthalate to polybutylene terephthalate is changed variously does not contain polyolefin resin. Comparative examples 23 to 30 in which these films are laminated especially have a low level of impact resistance.
Invention examples 9 to 13 are films using mixed resin in which various types of polyolefin resins are dispersed in polyester resin as R1 layer, and invention examples 46 to 50 in which these films are laminated exhibit high formability, impact resistance, adhesion, and cloudiness resistance. However, invention example 46 in which the film of invention example 9 using polyolefin resin having a slightly high percentage of functional group derived from carboxylic acid is laminated and invention example 50 in which the film of invention example 13 using polyolefin resin having a slightly high glass-transition temperature is laminated have a tendency toward slightly deteriorated low-temperature impact resistance. On the other hand, comparative examples 13 to 15 are mixed resins in which polyolefin resin containing a functional group derived from carboxylic acid whose percentage deviates from the range of the present invention is dispersed in polyester resin, and comparative examples 35 to 37 in which these mixed resins are laminated have deteriorated formability and impact resistance.
Comparative example 16 is a film in which modified polyolefin resin with group derived from carboxylic acid and polyester resin are simply mixed with each other, and comparative example 38 in which this film is laminated has greatly deteriorated formability and impact resistance because modified polyolefin resin is not dispersed in polyester resin in a fine granular form.
Invention examples 14 to 21 are films in which the blending ratio and dispersion state of modified polyolefin resin in polyester resin are changed variously in the range of the present invention, and invention examples 51 to 58 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and cloudiness resistance. However, invention example 51 in which the film of invention example 14 containing a small amount of dispersed modified polyolefin resin is laminated and invention example 57 in which the film of invention example 20 containing a very large amount of modified polyolefin resin is laminated have a tendency toward slightly deteriorated low-temperature impact resistance.
On the other hand, comparative examples 9 to 12 are films in which the blending ratio of modified polyolefin resin in polyester resin does not meet the requirement of the present invention, and comparative examples 31 to 34 in which the films are laminated under the laminating conditions of the present invention have greatly deteriorated formability or impact resistance. Comparative examples 31 and 32 in which the films of comparative examples 9 and 10 containing a small amount of dispersed modified polyolefin resin are laminated have greatly deteriorated room-temperature impact resistance, and comparative examples 33 and 34 in which the films of comparative examples 11 and 12 containing a large amount of modified polyolefin resin are laminated have greatly deteriorated formability.
Invention examples 33 to 37 are films in which titanium dioxide pigment is mixed with a mixed resin of modified polyolefin resin and polyester resin, and invention examples 70 to 74 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and cloudiness resistance, and also provide a white uniform color tone. However, invention example 70 in which the film of invention example 33 in which the added amount of pigment is smaller than a desired range is laminated has slightly insufficient opacifying property of color tone. On the other hand, invention example 74 in which the film of invention example 37 in which the added amount of pigment is larger than a desired range is laminated has slightly deteriorated formability.
Invention examples 22 to 28 are films in which the thickness of each layer of film is changed, and invention examples 59 to 65 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and cloudiness resistance. Since the invention examples 22 and 28 are films in which the total thickness of film exceeds the desired range of the present invention, invention examples 59 and 65 in which the films are laminated have slightly deteriorated formability and impact resistance as compared with the film having a desired thickness. On the other hand, invention examples 17a to 20a are films in which the thickness or thickness ratio of each layer of film deviates from the desired range of the present invention, and invention examples 39a to 42a in which the films are laminated have slightly deteriorated balance of formability and impact resistance as compared with invention examples 22 to 28.
Invention examples 41 and 75 to 78 are films obtained by changing the laminating conditions of the film of invention example 4 in the range of the present invention. If the conditions are within the range of the present invention, high formability, impact resistance, adhesion, and cloudiness resistance are exhibited regardless of the laminating temperature. On the other hand, in comparative example 39, the film of invention example 4 was laminated under conditions lower than the lower limit of laminating temperature range of the present invention, so that the film did not adhere to a steel sheet, and therefore evaluation could not be made. On the other hand, in comparative example 40, the film of invention example 4 was laminated under conditions exceeding the upper limit of laminating temperature range of the present invention, so that the film fused to a laminate roll, and therefore evaluation could not be made.
Invention examples 29 to 31 are films in which a lubricant, free radical inhibitor, and compatibilizing agent are mixed, respectively, in a mixed resin of modified polyolefin resin and polyester resin of the present invention, and invention examples 66 to 68 in which the films are laminated under the laminating conditions of the present invention exhibit high formability, impact resistance, adhesion, and cloudiness resistance. Further, invention examples 66 to 68 also have lubricity, free radical deterioration resistance, and compatibility depending on the function of added additive, and in particular, invention example 68 exhibits excellent low-temperature impact resistance.
Invention example 32 is a film of the present invention that is manufactured by the two-axis stretching method, and invention examples 69 and 79 in which the film is laminated exhibit high performance. Invention example 79, which has a plane orientation coefficient of 0.015, exhibits a slightly deteriorated formability. Invention example 69, which has a plane orientation coefficient in the range of the seventh invention, exhibits very high formability and impact resistance.
Invention examples 21a and 22a are films using polyester resin other than the present invention as R0 layer, and invention examples 43a and 44a in which the films are laminated have slightly deteriorated adhesion after heating.









TABLE 19









R1 layer










Polyolefin resin














Weight percentage

Volume
Number of grains

















Polyester

of functional

Blending
percentage of
with diameter of
Film



resin

group derived

ratio in
grains with
0.1 to 5 μm in
thick-
















Sample
Resin

Resin
from carboxylic
Tg
entire
diameter of 0.1
cube with one side
ness


film
type
Additive
type
acid (wt %)
(° C.)
resin (wt %)
to 5 μm (vol %)
of 10 μm (grains)
(μm)





Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 1
PBT(90)


Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 2
PBT(80)


Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 3
PBT(70)


Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 4
PBT(60)


Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 5
PBT(40)


Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 7
PBT(20)


Invention
PET
None
EM4
8
<−30
15
12
2000
22


example 7


Invention
PET/I
None
EM4
8
<−30
15
12
2000
22


example 8
(10)


Invention
PET/
None
EM2
18
<−30
15
13
500
22


example 9
PBT(60)


Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 10
PBT(60)


Invention
PET/
None
EM5
7
<−30
15
12
2000
22


example 11
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
22


example 12
PBT(60)


Invention
PBT/
None
EM8
6
20
15
12
2000
22


example 13
PBT(60)


Invention
PET/
None
EM3
11
<−30
5
3
3
22


example 14
PBT(60)


Invention
PET/
None
EM3
11
<−30
5
5
70
22


example 15
PBT(60)


Invention
PET/
None
EM3
11
<−30
10
8
30
22


example 16
PBT(60)


Invention
PET/
None
EM3
11
<−30
10
10
250
22


example 17
PBT(60)


Invention
PET/
None
EM3
11
<−30
15
15
500
22


example 18
PBT(60)


Invention
PET/
None
EM3
11
<−30
15
18
20000
22


example 19
PBT(60)


Invention
PET/
None
EM3
11
<−30
20
22
200000
22


example 20
PBT(60)


Invention
PET/
None
EM3
11
<−30
28
20
8000
22


example 21
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
10


example 22
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
15


example 23
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
20


example 24
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
25


example 25
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
30


example 26
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
45


example 27
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
50


example 28
PBT(60)


Invention
PET/
*2)
EM3
11
<−30
15
12
2000
22


example 29
PBT(60)
0.3 wt %


Invention
PET/
*3)
EM3
11
<−30
15
12
2000
22


example 30
PBT(60)
0.1 wt %


Invention
PET/
*4)
EM3
11
<−30
15
12
2000
22


example 31
PBT(60)
3 wt %













Entire film











Thickness













R0 layer
Film
ratio of














Polyester
Film
thick-
R1 layer















resin
thick-
ness
to R0
Pigment

















Sample
Resin
ness
(R1 + R0)
layer

Content




film
type
(μm)
(μm)
R1/R0
Type
(wt %) *1)
Stretching







Invention
PET
4
26
5.5
None
0
Non-



example 1






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 2






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 3






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 4






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 5






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 7






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 7






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 8






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 9






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 10






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 11






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 12






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 13






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 14






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 15






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 16






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 17






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 18






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 19






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 20






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 21






stretched



Invention
PET
1
11
10.0
None
0
Non-



example 22






stretched



Invention
PET
3
18
5.0
None
0
Non-



example 23






stretched



Invention
PET
3
23
6.7
None
0
Non-



example 24






stretched



Invention
PET
5
30
5.0
None
0
Non-



example 25






stretched



Invention
PET
4
34
7.5
None
0
Non-



example 26






stretched



Invention
PET
5
50
9.0
None
0
Non-



example 27






stretched



Invention
PET
10
60
5.0
None
0
Non-



example 28






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 29






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 30






stretched



Invention
PET
4
26
5.5
None
0
Non-



example 31






stretched







*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.



*2) Silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.



*3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radical Inhibitor is added by 0.1 weight part to 100 weight part of mixed resin.



*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin















TABLE 20









R1 layer










Polyolefin resin















Weight


Volume
Number of grains




percentage

Blending
percentage of
with diameter of
















Polyester

of functional

ratio in
grains with
0.1 to 5 μm in
Film



resin

group derived

entire
diameter of
cube with one
thick-
















Sample
Resin

Resin
from carboxylic
Tg
resin
0.1 to 5 μm
side of 10 μm
ness


film
type
Additive
type
acid (wt %)
(° C.)
(wt %)
(vol %)
(grains)
(μm)





Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 32
PBT(60)


Invention
PET/
None
EM5
7
<−30
15
12
2000
22


example 33
PBT(60)


Invention
PET/
None
EM5
7
<−30
15
12
2000
22


example 34
PBT(60)


Invention
PET/
None
EM5
7
<−30
15
12
2000
22


example 35
PBT(60)


Invention
PET/
None
EM5
7
<−30
15
12
2000
22


example 36
PBT(60)


Invention
PET/
None
EM5
7
<−30
15
12
2000
22


example 37
PBT(60)


Comparative
PET/
None
None
—
—
0
0
0
22


example 1
PBT(90)


Comparative
PET/
None
None
—
—
0
0
0
22


example 2
PBT(80)


Comparative
PET/
None
None
—
—
0
0
0
22


example 3
PBT(70)


Comparative
PET/
None
None
—
—
0
0
0
22


example 4
PBT(60)


Comparative
PET/
None
None
—
—
0
0
0
22


example 5
PBT(60)


Comparati34
PET/
None
None
—
—
0
0
0
22


example 6
PBT(40)


Comparative
PET/
None
None
—
—
0
0
0
22


example 7
PBT(20)


Comparative
PET
None
None
—
—
0
0
0
22


example 8


Comparative
PET/
None
EM3
11
<−30
2
2
3
22


example 9
PBT(60)


Comparative
PET/
None
EM3
11
<−30
2
2
45
22


example 10
PBT(60)


Comparative
PET/
None
EM3
11
<−30
35
28
15000
22


example 11
PBT(60)


Comparative
PET/
None
EM3
11
<−30
35
28
120000
22


example 12
PBT(60)


Comparative
PET/
None
EM1
21
<−30
15
14
40
22


example 13
PBT(60)


Comparative
PET/
None
EM7
1
<−30
15
3
20
22


example 14
PBT(60)


Comparative
PET/
None
EPR
0
<−30
15
1
5
22


example 15
PBT(60)


Comparative
PET/
None
EM5
7
<−30
15
Not dispersed
Not dispersed
22


example 16
PBT(60)





in fine grains
in fine grains


Invention
PET/
None
EM6
5
<−30
15
12
2000
7


example 17a
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
60


example 18a
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
20


example 19a
PBT(60)


Invention
PET/
None
EM6
5
<−30
15
12
2000
15


example 20a
PBT(60)


Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 21a
PBT(60)


Invention
PET/
None
EM4
8
<−30
15
12
2000
22


example 22a
PBT(60)













Entire film











Thickness













R0 layer
Film
ratio of















Polyester
Film
thick-
R1 layer
Pigment


















resin
thick-
ness
to R0

Content




Sample
Resin
ness
(R1 + R0)
layer

(wt %)



film
type
(μm)
(μm)
R1/R0
Type
*1)
Stretching







Invention
PET
4
26
5.5
None
0
Two-axis



example 32






stretched



Invention
PET
4
26
5.5
TiO2
3
Non-



example 33






stretched



Invention
PET
4
26
5.5
TiO2
7
Non-



example 34






stretched



Invention
PET
4
26
5.5
TiO2
15
Non-



example 35






stretched



Invention
PET
4
26
5.5
TiO2
30
Non-



example 36






stretched



Invention
PET
4
26
5.5
TiO2
50
Non-



example 37






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 1






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 2






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 3






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 4






stretched



Comparative
PET
4
26
5.5
None
0
Two-axis



example 5






stretched



Comparati34
PET
4
26
5.5
None
0
Non-



example 6






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 7






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 8






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 9






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 10






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 11






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 12






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 13






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 14






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 15






stretched



Comparative
PET
4
26
5.5
None
0
Non-



example 16






stretched



Invention
PET
1
8
7.0
None
0
Non-



example 17a






stretched



Invention
PET
10
70
6.0
None
0
Non-



example 18a






stretched



Invention
PET
1.5
21.5
13.3
None
0
Non-



example 19a






stretched



Invention
PET
8
23
1.9
None
0
Non-



example 20a






stretched



Invention
PET/PBT
4
26
5.5
None
0
Non-



example 21a
(60)





stretched



Invention
PET/I
4
26
5.5
None
0
Non-



example 22a
(10)





stretched







*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.
















TABLE 21









Melting












point of

Thin-wall deep drawn can



















R1 layer







Cloudi-


Laminated

polyester
Laminating
Plane

Impact
Impact
Adhesion
Adhesion
ness of


metal
Sample
resin
temp.
orientation
Form-
resistance
resistance
after
after
retorted


sheet
film
(° C.)
(° C.)
coefficient
ability
(room temp.)
(low temp.)
forming
heating
film





Invention
Invention
215
200
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 38
example 1


Invention
Invention
220
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 39
example 2


Invention
Invention
230
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 40
example 3


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 41
example 4


Invention
Invention
240
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 42
example 5


Invention
Invention
245
225
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 43
example 6


Invention
Invention
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 44
example 7


Invention
Invention
230
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 45
example 8


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 46
example 9


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 47
example 10


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 48
example 11


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 49
example 12


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 50
example 13


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 51
example 14


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 52
example 15


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 53
example 16


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 54
example 17


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 55
example 18


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 56
example 19


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 57
example 20


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 58
example 21


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 59
example 22


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 60
example 23


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 61
example 24


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 62
example 25


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 63
example 26


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 64
example 27


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 65
example 28


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 66
example 29


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 67
example 30


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 68
example 31













Drawn and ironed can (DI can)






















Cloudi-



Laminated

Impact
Impact
Adhesion
Adhesion
ness of



metal

resistance
resistance
after
after
retorted



sheet
Formability
room temp.)
(low temp.)
forming
heating
film







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 38



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 39



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 40



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 41



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 42



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 43



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 44



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 45



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 46



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 47



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 48



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 49



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 50



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 51



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 52



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 53



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 54



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 55



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 56



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 57



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 58



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 59



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 60



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 61



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 62



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 63



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 64



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 65



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 66



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 67



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 68





















TABLE 22









Melting





point of

Thin-wall deep drawn can



















R1 layer







Cloudi-


Laminated

polyester

Plane

Impact
Impact
Adhesion
Adhesion
ness of


metal
Sample
resin
Laminating
orientation
Form-
resistance
resistance
after
after
retorted


sheet
film
(° C.)
temp. (° C.)
coefficient
ability
(room temp.)
(low temp.)
forming
heating
film





Invention
Invention
235
215
0.005
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 69
example 32


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 70
example 33


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 71
example 34


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 72
example 35


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 73
example 36


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 74
example 37


Invention
Invention
235
260
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 75
example 4


Invention
Invention
235
230
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 76
example 4


Invention
Invention
235
190
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 77
example 4


Invention
Invention
235
170
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 78
example 4


Invention
Invention
235
200
0.015
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 79
example 32


Comparative
Comparative
215
200
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 23
example 1


Comparative
Comparative
220
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 24
example 2


Comparative
Comparative
230
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 25
example 3


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 26
example 4


Comparative
Comparative
240
220
0.015
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 27
example 5


Comparative
Comparative
245
225
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 28
example 6


Comparative
Comparative
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 29
example 7


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 30
example 8


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 31
example 9


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 32
example 10


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 33
example 11


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 34
example 12


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 35
example 13


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 36
example 14


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 37
example 15


Comparative
Comparative
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 38
example 16


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 39a
example 17a


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 40a
example 18a


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 41a
example 19a


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 42a
example 20a


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
◯
⊚⊚


example 43a
example 21a


Invention
Invention
235
215
0
⊚
⊚
⊚⊚⊚
⊚
◯
⊚⊚


example 44a
example 22a


Comparative
Invention
235
270
—
—
—
—
—
—
—


example 39
example 4


Comparative
Invention
235
160
—
—
—
—
—
—
—


example 40
example 4













Drawn and ironed can (DI can)






















Cloudi-



Laminated

Impact
Impact
Adhesion
Adhesion
ness of



metal
Form-
resistance
resistance
after
after
retorted



sheet
ability
(room temp.)
(low temp.)
forming
heating
film







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 69



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 70



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 71



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 72



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 73



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 74



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 75



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 76



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 77



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 78



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 79



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 23



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 24



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 25



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 26



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 27



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 28



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 29



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 30



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 31



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 32



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 33



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 34



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 35



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 36



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 37



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 38



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 39a



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 40a



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 41a



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 42a



Invention
⊚
⊚
⊚⊚⊚
⊚
◯
⊚⊚



example 43a



Invention
⊚
⊚
⊚⊚⊚
⊚
◯
⊚⊚



example 44a



Comparative
—
—
—
—
—
—



example 39



Comparative
—
—
—
—
—
—



example 40










EXAMPLE 6
Modified polyolefin resin with group derived from carboxylic acid having a primary grain diameter of 0.3 μm, which was a starting raw material, was cold blended with polyester resin in a blending ratio given in Tables 23 and 24 by using a tumbler blender, and then the blended resin was melted and kneaded at 260° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. In the tables, the resin type corresponding to the symbol of resin type of polyester resin and resin type of polyolefin resin is the same as that described in Example 5.
As a metal sheet, as in Example 5, a tin-free steel (hereinafter abbreviated to TFS) with a thickness of 0.18 mm for thin-wall deep drawn can and 0.23 mm for DI can, which had a degree of temper of DR9, metallic chromium layer of 80 mg/m2, and chromium oxide layer of 15 mg/m2 (metallic chromium conversion), was used, by which a both-side laminated metal sheet was obtained by a method in which the raw material resin pellet was inserted in a one-axis extruding machine as a resin for R1 layer, a resin for R0 layer was inserted in a separate extruding machine and simultaneously melted and extruded, molten resin was put in a T die by a combining adapter, two-layer molten resin was extruded directly onto one surface of the metal sheet, the extruded resin was once cooled while being held adherently between two rolls, and immediately after the resin was laminated on the opposite surface in the same manner, the resin laminated metal sheet was cooled rapidly in water. The temperature of metal sheet at the laminating time was 230° C. The lip opening width of T die was adjusted so that the thickness of resin film was 9.5 to 70 μm. The type of sample resin and the resin melting temperature at the laminating time are given in Tables 23 and 24. The used polyester resin and modified polyolefin resin with group derived from carboxylic acid are the same as those used in Example 5.
Pelletized modified polyolefin resin with group derived from carboxylic acid, which was a starting raw material, was mixed with polyester resin in a blending ratio given in comparative example 61 in Table 25, the mixed resin was melted and kneaded at 265° C. by using a one-axis extruding machine, and the obtained mixed resin of modified polyolefin resin and polyester resin was extruded from a T die as R1 layer, by which the resin that had been directly extruded to a thickness of 26 μm was laminated to the TFS.
All of the grain diameter of modified polyolefin resin dispersed in resin film, various temperatures in the table, and the method for measuring the plane orientation coefficient of resin laminated metal sheet are the same as those in Example 5. As in Example 5, a thin-wall deep drawn can or a DI can was manufactured from the laminated metal sheet obtained as described above, and the can was subjected to straightening heat treatment to manufacture a sample can. The formability, impact resistance, adhesion, and retort resistance of film of the manufactured can body were investigated as in Example 5.
The investigation results are given in Tables 25 and 26.
From Tables 23 to 26, the following facts are found for either can type.
Invention examples 80 to 90 are films using a resin layer in which modified polyolefin resin specified in the present invention is dispersed in polyester resin in which the ratio of polyethylene terephthalate to polybutylene terephthalate is changed variously as R1 layer, and exhibit high formability, impact resistance, adhesion, and cloudiness resistance. Among these, invention example 89 using polyester resin having a low percentage of polybutylene terephthalate and invention example 90 further using homopolyethylene terephthalate have a tendency for adhesion after heating and cloudiness resistance after retorting to be deteriorated as the percentage of polybutylene terephthalate becomes low, but still have high performance as a whole. Also, invention example 91 using polyethylene terephthalate in which polyester resin is copolymerized by isophthalic acid has a tendency for adhesion after heating and cloudiness resistance after retorting to be deteriorated slightly, but still have high performance as a whole. On the other hand, invention examples 80 and 81 having a very high percentage of polybutylene terephthalate have a tendency toward deteriorated adhesion after heating because the melting point is slightly low, but have high performance as a whole. On the other hand, comparative examples 47 to 53 are examples in which polyester resin in which the mixing ratio of polyethylene terephthalate to polybutylene terephthalate is changed variously does not contain polyolefin resin, and especially have a low level of impact resistance.
Invention examples 91 to 96 are films using mixed resin in which various types of polyolefin resins are dispersed in polyester resin as R1 layer, and exhibit high formability, impact resistance, adhesion, and cloudiness resistance. However, invention example 92 using polyolefin resin having a slightly high percentage of functional group derived from carboxylic acid and invention example 96 using polyolefin resin having a slightly high glass-transition temperature have a tendency toward slightly deteriorated low-temperature impact resistance. On the other hand, comparative examples 58 to 60 are mixed resins in which polyolefin resin containing a functional group derived from carboxylic acid whose percentage deviates from the range of the present invention is dispersed in polyester resin, and have deteriorated formability and impact resistance.
Comparative example 61 is a resin in which modified polyolefin resin with group derived from carboxylic acid and polyester resin are simply mixed with each other, and has greatly deteriorated formability and impact resistance because modified polyolefin resin is not dispersed in polyester resin in a fine granular form.
Invention examples 97 to 104 are resins in which the blending ratio and dispersion state of modified polyolefin resin in polyester resin are changed variously in the range of the present invention, and exhibit high formability, impact resistance, adhesion, and cloudiness resistance. However, invention example 97 containing a small amount of dispersed modified polyolefin resin and invention example 103 containing a very large amount of modified polyolefin resin have a tendency toward slightly deteriorated low-temperature impact resistance.
On the other hand, comparative examples 54 to 57 are resins in which the blending ratio of modified polyolefin resin in polyester resin does not meet the requirement of the present invention, and have greatly deteriorated formability or impact resistance. Comparative examples 54 and 55 containing a small amount of dispersed modified polyolefin resin have greatly deteriorated room-temperature impact resistance, and comparative examples 56 and 57 containing a large amount of modified polyolefin resin have greatly deteriorated formability.
Invention examples 115 to 119 are resins in which titanium dioxide pigment is mixed with a mixed resin of modified polyolefin resin and polyester resin, and exhibit high formability, impact resistance, adhesion, and cloudiness resistance, and also provide a white uniform color tone. However, invention example 115 in which the added amount of pigment is smaller than a desired range has slightly insufficient opacifying property of color tone. On the other hand, invention example 119 in which the added amount of pigment is larger than a desired range has slightly deteriorated formability.
Invention examples 105 to 111 are resins in which the thickness of each layer of film is changed, and exhibit high formability, impact resistance, adhesion, and cloudiness resistance. Since the invention examples 105 and 111 are resins in which the total thickness of film exceeds the desired range of the present invention, both formability and impact resistance are slightly deteriorated as compared with the resin having a desired film thickness. On the other hand, invention examples 120 to 123 are resins in which the thickness or thickness ratio of each layer of film deviates from the desired range of the present invention, and have slightly deteriorated balance of formability and impact resistance as compared with invention examples 105 to 111.
Invention examples 112 to 114 are resins in which a lubricant, free radical inhibitor, and compatibilizing agent are mixed, respectively, in a mixed resin of modified polyolefin resin and polyester resin of the present invention, and exhibit high formability, impact resistance, adhesion, and cloudiness resistance. Further, invention examples 112 to 114 also have lubricity, free radical deterioration resistance, and compatibility depending on the function of added additive, and in particular, invention example 114 exhibits excellent low-temperature impact resistance.
Invention examples 124 and 125 are resins using polyester resin other than the present invention as R0 layer, and have slightly deteriorated adhesion after heating.









TABLE 23









R1 layer









Polyolefin resin












Polyester resin

Weight

















Melting


percentage

Blending




point of


of functional

ratio in




polyester


group derived

entire


Sample
Resin
resin

Resin
from carboxylic
Tg
resin


film
type
(° C.)
Additive
type
acid (wt %)
(° C.)
(wt %)





Invention
PET/PBT(90)
215
None
EM4
8
<−30
15


example 80


Invention
PET/PBT(80)
220
None
EM4
8
<−30
15


example 81


Invention
PET/PBT(70)
230
None
EM4
8
<−30
15


example 82


Invention
PET/PBT(60)
235
None
EM4
8
<−30
15


example 83


Invention
PET/PBT(60)
235
None
EM4
8
<−30
15


example 84


Invention
PET/PBT(60)
235
None
EM4
8
<−30
15


example 85


Invention
PET/PBT(60)
235
None
EM4
8
<−30
15


example 86


Invention
PET/PBT(60)
235
None
EM4
8
<−30
15


example 87


Invention
PET/PBT(40)
240
None
EM4
8
<−30
15


example 88


Invention
PET/PBT(20)
245
None
EM4
8
<−30
15


example 89


Invention
PET
255
None
EM4
8
<−30
15


example 90


Invention
PET/I(10)
230
None
EM4
8
<−30
15


example 91


Invention
PET/PBT(60)
235
None
EM2
18
<−30
15


example 92


Invention
PET/PBT(60)
235
None
EM4
8
<−30
15


example 93


Invention
PET/PBT(60)
235
None
EM5
7
<−30
15


example 94


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 95


Invention
PET/PBT(60)
235
None
EM8
6
20
15


example 96


Invention
PET/PBT(60)
235
None
EM3
11
<−30
5


example 97


Invention
PET/PBT(60)
235
None
EM3
11
<−30
5


example 98


Invention
PET/PBT(60)
235
None
EM3
11
<−30
10


example 99


Invention
PET/PBT(60)
235
None
EM3
11
<−30
10


example 100


Invention
PET/PBT(60)
235
None
EM3
11
<−30
15


example 101


Invention
PET/PBT(60)
235
None
EM3
11
<−30
15


example 102


Invention
PET/PBT(60)
235
None
EM3
11
<−30
20


example 103


Invention
PET/PBT(60)
235
None
EM3
11
<−30
28


example 104


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 105


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 106


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 107


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 108


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 109


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 110


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 111
















Melting



R1 layer

temp. of



Polyolefin resin

R1 layer













Volume
Number of grains
R0 layer

resin at



percentage of
with diameter of
Polyester
Pigment
extrusion














grains with
0.1 to 5 μm in
resin

Content
laminating


Sample
diameter of 0.1
cube with one side
Resin

(wt %)
time


film
to 5 μm (vol %)
of 10 μm (grains)
type
Type
*1)
(° C.)





Invention
14
2500
PET
None
0
245


example 80


Invention
14
2500
PET
None
0
250


example 81


Invention
14
2500
PET
None
0
260


example 82


Invention
14
2500
PET
None
0
240


example 83


Invention
14
2500
PET
None
0
250


example 84


Invention
14
2500
PET
None
0
265


example 85


Invention
14
2500
PET
None
0
280


example 86


Invention
14
2500
PET
None
0
290


example 87


Invention
14
2500
PET
None
0
270


example 88


Invention
14
2500
PET
None
0
275


example 89


Invention
14
2500
PET
None
0
285


example 90


Invention
14
2500
PET
None
0
260


example 91


Invention
15
1000
PET
None
0
265


example 92


Invention
14
2500
PET
None
0
265


example 93


Invention
14
2500
PET
None
0
265


example 94


Invention
14
2500
PET
None
0
265


example 95


Invention
14
2500
PET
None
0
265


example 96


Invention
4
4
PET
None
0
265


example 97


Invention
8
100
PET
None
0
265


example 98


Invention
10
50
PET
None
0
265


example 99


Invention
12
500
PET
None
0
265


example 100


Invention
18
800
PET
None
0
265


example 101


Invention
20
22000
PET
None
0
265


example 102


Invention
24
250000
PET
None
0
265


example 103


Invention
22
10000
PET
None
0
265


example 104


Invention
14
2500
PET
None
0
265


example 105


Invention
14
2500
PET
None
0
265


example 106


Invention
14
2500
PET
None
0
265


example 107


Invention
14
2500
PET
None
0
265


example 108


Invention
14
2500
PET
None
0
265


example 109


Invention
14
2500
PET
None
0
265


example 110


Invention
14
2500
PET
None
0
265


example 111





*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.















TABLE 24









R1 layer










Polyester resin
Polyolefin resin
















Melting


Weight percentage

Blending




point of


of functional

ratio in




polyester


group derived from

entire


Sample
Resin
resin

Resin
carboxylic acid
Tg
resin


film
type
(° C.)
Additive
type
(wt %)
(° C.)
(wt %)





Invention
PET/PBT(60)
235
*2)
EM3
11
<−30
15


example 112


0.3 wt %


Invention
PET/PBT(60)
235
*3)
EM3
11
<−30
15


example 113


0.1 wt %


Invention
PET/PBT(60)
235
*4)
EM3
11
<−30
15


example 114


3 wt %


Invention
PET/PBT(60)
235
None
EM5
7
<−30
15


example 115


Invention
PET/PBT(60)
235
None
EM5
7
<−30
15


example 116


Invention
PET/PBT(60)
235
None
EM5
7
<−30
15


example 117


Invention
PET/PBT(60)
235
None
EM5
7
<−30
15


example 118


Invention
PET/PBT(60)
235
None
EM5
7
<−30
15


example 119


Comparative
PET/PBT(90)
215
None
None
—
—
0


example 47


Comparative
PET/PBT(80)
220
None
None
—
—
0


example 48


Comparative
PET/PBT(70)
230
None
None
—
—
0


example 49


Comparative
PET/PBT(60)
235
None
None
—
—
0


example 50


Comparative
PET/PBT(40)
245
None
None
—
—
0


example 51


Comparative
PET/PBT(20)
255
None
None
—
—
0


example 52


Comparative
PET
235
None
None
—
—
0


example 53


Comparative
PET/PBT(60)
235
None
EM3
11
<−30
2


example 54


Comparative
PET/PBT(60)
235
None
EM3
11
<−30
2


example 55


Comparative
PET/PBT(60)
235
None
EM3
11
<−30
35


example 56


Comparative
PET/PBT(60)
235
None
EM3
11
<−30
35


example 57


Comparative
PET/PBT(60)
235
None
EM1
21
<−30
15


example 58


Comparative
PET/PBT(60)
235
None
EM7
1
<−30
15


example 59


Comparative
PET/PBT(60)
235
None
EPR
0
<−30
15


example 60


Comparative
PET/PBT(60)
235
None
EM5
7
<−30
15


example 61


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 120


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 121


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 122


Invention
PET/PBT(60)
235
None
EM6
5
<−30
15


example 123


Invention
PET/PBT(60)
235
None
EM4
8
<−30
15


example 124


Invention
PET/PBT(60)
235
None
EM4
8
<−30
15


example 125














R1 layer

Melting



Polyolefin resin

temp. of












Volume
Number of grains

R1 layer













percentage of
with diameter of
R0 layer
Pigment
resin at














grains with
0.1 to 5 μm in
Polyester

Content
extrusion


Sample
diameter of 0.1
cube with one side
resin

(wt %)
laminating


film
to 5 μm (vol %)
of 10 μm (grains)
Resin type
Type
*1)
time (° C.)





Invention
14
2500
PET
None
0
265


example 112


Invention
14
2500
PET
None
0
265


example 113


Invention
14
2500
PET
None
0
265


example 114


Invention
14
2500
PET
TiO2
3
265


example 115


Invention
14
2500
PET
TiO2
7
265


example 116


Invention
14
2500
PET
TiO2
15
265


example 117


Invention
14
2500
PET
TiO2
30
265


example 118


Invention
14
2500
PET
TiO2
50
265


example 119


Comparative
0
0
PET
None
0
245


example 47


Comparative
0
0
PET
None
0
250


example 48


Comparative
0
0
PET
None
0
260


example 49


Comparative
0
0
PET
None
0
265


example 50


Comparative
0
0
PET
None
0
275


example 51


Comparative
0
0
PET
None
0
285


example 52


Comparative
0
0
PET
None
0
265


example 53


Comparative
3
5
PET
None
0
265


example 54


Comparative
3
50
PET
None
0
265


example 55


Comparative
30
20000
PET
None
0
265


example 56


Comparative
30
135000
PET
None
0
265


example 57


Comparative
16
50
PET
None
0
265


example 58


Comparative
4
40
PET
None
0
265


example 59


Comparative
1
4
PET
None
0
265


example 60


Comparative
Not dispersed
Not dispersed
PET
None
0
265


example 61
in fine grains
in fine grains


Invention
14
2500
PET
None
0
265


example 120


Invention
14
2500
PET
None
0
265


example 121


Invention
14
2500
PET
None
0
265


example 122


Invention
14
2500
PET
None
0
265


example 123


Invention
14
2500
PET/PBT(60)
None
0
265


example 124


Invention
14
2500
PET/I(10)
None
0
265


example 125





*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.


*2) silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.


*3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radical inhibitor is added by 0.1 weight part to 100 weight part of mixed resin.


*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin.
















TABLE 25










Investigation result



Resin film thickness
Thin-wall deep drawn can

















Extrusion


Total film
Thickness





Cloudi-


laminated
R1
R0
thickness
ratio of R1

Impact
Impact
Adhesion
Adhesion
ness of


metal
layer
layer
(R1 + R0)
layer to R0
Form-
resistance
resistance
after
after
retorted


sheet
(μm)
(μm)
(μm)
layer R1/R0
ability
(room temp.)
(low temp.)
forming
heating
film





Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 80


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 81


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 82


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 83


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 84


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 85


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 86


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 87


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 88


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 89


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 90


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 91


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 92


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 93


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 94


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 95


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 96


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 97


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 98


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 99


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 100


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 101


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 102


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 103


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 104


Invention
10
1
11
10.0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 105


Invention
15
3
18
5.0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 106


Invention
20
3
23
6.7
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 107


Invention
25
5
30
5.0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 108


Invention
30
4
34
7.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 109


Invention
45
5
50
9.0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 110


Invention
50
10
60
5.0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 111













Investigation result




Drawn and ironed can (DI can)















Extrusion





Cloudi-



laminated

Impact
Impact
Adhesion
Adhesion
ness of



metal

resistance
resistance
after
after
retorted



sheet
Formability
(room temp.)
(low temp.)
forming
heating
film







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 80



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 81



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 82



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 83



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 84



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 85



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 86



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 87



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 88



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 89



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 90



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 91



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 92



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 93



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 94



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 95



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 96



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 97



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 98



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 99



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 100



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 101



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 102



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 103



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 104



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 105



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 106



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 107



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 108



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 109



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 110



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 111




















TABLE 26










Investigation result



Resin film thickness
Thin-wall deep drawn can

















Extrusion


Total film
Thickness





Cloudi-


laminated
R1
R0
thickness
ratio of R1

Impact
Impact
Adhesion
Adhesion
ness of


metal
layer
layer
(R1 + R0)
layer to R0
Form-
resistance
resistance
after
after
retorted


sheet
(μm)
(μm)
(μm)
layer R1/R0
ability
(room temp.)
(low temp.)
forming
heating
film





Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 112


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 113


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 114


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 115


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 116


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 117


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 118


Invention
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 119


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 47


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 48


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 49


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 50


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 51


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 52


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 53


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 54


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 55


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 56


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 57


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 58


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 59


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 60


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 61


Comparative
7
1
8
7.0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 120


Comparative
60
10
70
6.0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 121


Comparative
20
1.5
21.5
13.3
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 122


Comparative
15
8
23
1.9
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 123


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
◯
⊚⊚


example 124


Comparative
22
4
26
5.5
⊚
⊚
⊚⊚⊚
⊚
◯
⊚⊚


example 125













Investigation result




Drawn and ironed can (DI can)















Extrusion





Cloudi-



laminated

Impact
Impact
Adhesion
Adhesion
ness of



metal

resistance
resistance
after
after
retorted



sheet
Formability
(room temp.)
(low temp.)
forming
heating
film







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 112



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 113



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 114



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 115



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 116



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 117



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 118



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 119



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 47



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 48



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 49



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 50



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 51



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 52



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 53



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 54



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 55



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 56



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 57



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 58



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 59



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 60



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 61



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 120



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 121



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 122



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 123



Comparative
⊚
⊚
⊚⊚⊚
⊚
◯
⊚⊚



example 124



Comparative
⊚
⊚
⊚⊚⊚
⊚
◯
⊚⊚



example 125










EXAMPLE 7
As a resin raw material for R1 layer, modified polyolefin resin with group derived from carboxylic acid was cold blended with polyester resin in a blending ratio given in Tables 27 to 29 by using a tumbler blender, and then the blended resin was melted and kneaded at 270° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. The raw material resin pellet was inserted in a one-axis extruding machine, and on the other hand, modified polyolefin resin, which was a resin raw material for R2 layer, was inserted in a separate one-axis extruding machine, and each of molten resins was introduced into a multi-manifold type T die and extruded in two layers while the film thickness of R1 and R2 layers was controlled by the discharge amount of molten resin from the extruding machine, by which a resin film was manufactured continuously while being cooled by the surface of a rotating metallic roll.
Also, in the case of three-layer construction having R0 layer, polyester resin, which was a resin raw material for R0 layer, was inserted in a separate one-axis extruding machine, and each of molten resins was introduced into a multi-manifold type T die and extruded in three layers while the film thickness of R0, R1 and R2 layers was controlled by the discharge amount of molten resin from the extruding machine, by which a resin film was manufactured continuously while being cooled by the surface of a rotating metallic roll.
The used polyester resin and modified polyolefin resin with group derived from carboxylic acid were as follows:
Polyester Resin
(1) PET: Polyethylene terephthalate resin, intrinsic viscosity: 0.62 dl/g
(2) PET/I: Isophthalic acid copolymerized polyethylene terephthalate resin with a ratio of terephthalic acid to isophthalic acid of 90:10, intrinsic viscosity: 0.62 dl/g
(3) PET/PBT: Mixed resin with a ratio of polyethylene terephthalate to polybutylene terephthalate of 40:60, intrinsic viscosity: 0.6 dl/g
(4) PET/AD: Adipic acid copolymerized polyethylene terephthalate resin with a ratio of terephthalic acid to adipic acid of 80:20, intrinsic viscosity: 0.6 dl/g
2. Modified Polyolefin Resin with Group Derived from Carboxylic Acid
(1) EM1: Polymethyl methacrylate-(ethylene-ethyl acrylate copolymer) graft copolymer (Modiper A5200 manufactured by NOF Corp.), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 21 wt %, glass-transition temperature: −30° C. or lower
(2) EM2: Polymethyl methacrylate-(ethylene-ethyl acrylate-maleic anhydride copolymer) graft copolymer (Modiper A8200 manufactured by NOF Corp.), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 18 wt %, glass-transition temperature: −30° C. or lower
(3) EM3: Ethylene-ethyl acrylate-maleic anhydride copolymer (Bondine HX8290 manufactured by Sumitomo Chemical Co., Ltd.), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 11 wt %, glass-transition temperature: −30° C. or lower
(4) EM4: Ethylene-methacrylic acid copolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 8 wt %, glass-transition temperature: −30° C. or lower
(5) EM5: 50% Zn neutralized substance of ethylene-methacrylic acid copolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co., Ltd. neutralized partially by Zn), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 7 wt %, glass-transition temperature: −30° C. or lower
(6) EM6: 60% Zn neutralized substance of ethylene-methacrylic acid copolymer (Himilan 1557 manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 5 wt %, glass-transition temperature: −30° C. or lower
(7) EM7: Ethylene-methacrylic acid copolymer (Nucrel N0200H manufactured by Mitsui-DuPont Polychemical Co., Ltd.), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 1 wt %, glass-transition temperature: −30° C. or lower (8) EM8: Polystyrene-(ethylene-ethyl acrylate copolymer) graft copolymer (Modiper A5100 manufactured by NOF Corp.), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 6 wt %, glass-transition temperature: 20° C.
(9) EPR: Ethylene-propylene rubber (EP07P manufactured by JSR Corp.), weight ratio (carboxylic acid conversion) of functional group derived from carboxylic acid: 0 wt %, glass-transition temperature: −30° C. or lower
Furthermore, as a resin raw material, a commercially available resin (Sealer PT4274 manufactured by Mitsui-DuPont Polychemical Co., Ltd.) that had been pelletized in advance in a state in which modified polyolefin resin with group derived from carboxylic acid was dispersed in polyester resin was inserted in a one-axis extruding machine in the blending ratio shown in invention examples 41 and 46 in Table 28, and on the other hand, modified polyolefin resin, which was a resin raw material for R2 layer, was inserted in a separate one-axis extruding machine, and each of molten resins was introduced into a multi-manifold type T die and extruded in two layers while the film thickness of R1 and R2 layers was controlled by the discharge amount of molten resin from the extruding machine, by which a resin film was manufactured continuously while being cooled by the surface of a rotating metallic roll. In the case of three-layer construction having R0 layer, polyester resin, which was a resin raw material for R0 layer, was inserted in a separate one-axis extruding machine, and each of molten resins was introduced into a multi-manifold type T die and extruded in three layers while the film thickness of R0, R1 and R2 layers was controlled by the discharge amount of molten resin from the extruding machine, by which a resin film was manufactured continuously while being cooled by the surface of a rotating metallic roll.
A resin laminated metal sheet was obtained by a thermo-compression bonding method in which the resin film obtained as described above was hot-pressed on both surfaces of a tin-free steel (hereinafter abbreviated to TFS) heated by an induction heating system, and then the laminated metal sheet was rapidly cooled in water. The metal sheet temperature at the laminating time (laminating temperature) is given in Tables 30 and 31. The thickness of TFS was 0.18 mm for thin-wall deep drawn can and 0.23 mm for DI can, the degree of temperature was DR9 for both cans, and the coating amount of metallic chromium and chromium oxide of surface chrome plating layer were 80 mg/m2 and 15 mg/m2 (metallic chromium conversion), respectively.
The grain diameter of modified polyolefin resin dispersed in R1 layer of resin film, various temperatures in the table, and the plane orientation coefficient of resin laminated metal sheet were measured by the same method as that in Example 1.
Further, a thin-wall deep drawn can or a DI can was manufactured from the laminated metal sheet obtained as described above, and the can was subjected to straightening heat treatment to manufacture a sample can. The formability, impact resistance (room temperature, low temperature), adhesion after forming, adhesion after heating, and flavor property of film of the manufactured can body were investigated.
The following is a detailed description of the investigation method.
1. Evaluation by Thickness-decreasing Deep Drawing
1-1 Can Manufacturing
A resin laminated metal sheet was subjected to first-stage drawing and redrawing under the following conditions, by which a thin-wall deep drawn can was obtained.

    
    
        First-stage Drawing
    
    


















Blank diameter
150 to 160 mm



First-stage drawing
drawing ratio: 1.65










    
    
        Redrawing
    
    















Primary redrawing
drawing ratio: 1.25


Secondary redrawing
drawing ratio: 1.25


Radius of curvature of die corner in redrawing
0.4 mm


process


Load for pressing wrinkle at the time of redrawing
39227 N (4000 kg)









    
    
        Average thickness decreasing percentage of can sidewall
        
            45 to 60% with respect to thickness of resin laminated metal sheet before forming

1-2 Straightening Heat Treatment

        
        
    
    


Forming strain of film caused by can manufacturing was removed by keeping the can in a thermal environment of film melting point minus 15° C. for 30 seconds and then by rapidly cooling it.
(1) Formability
Evaluation was made as described below by the limit of capability for manufacturing can without film failure. Grades not lower than ◯ marked grade are acceptable.

    Limit of forming (thickness decreasing percentage): Grade
    Incapable of forming at thickness decreasing percentage of 45%: (Inferior)
    Capable of forming up to thickness decreasing percentage of 45%
    Capable of forming up to thickness decreasing percentage of 50%
    Capable of forming up to thickness decreasing percentage of 55%
    Capable of forming up to thickness decreasing percentage of 60%: (Superior)

(2) Evaluation of Room-temperature and Low-temperature Impact Resistance



A can body (thickness decreasing percentage: 55%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, an iron ball of 0.5 kg was dropped from a height of 30 cm to give a shock to the can bottom. Thereafter, the lid was opened, and 1% salt water was poured in the can so that a portion that had suffered shock was immersed. After immersion for five minutes, a load of 6 V was applied across a platinum electrode immersed in the liquid and a can metal portion, and the current value after five minutes was read, by which evaluation was made as described below. The same tests were conducted at room temperature of 20° C. and at a temperature of 0° C. The former test was for evaluating room-temperature impact resistance, and the latter test was for evaluating low-temperature impact resistance. Grades not lower than ◯ marked grade are acceptable.
(Evaluation of Room-temperature Impact Resistance)


    Test result: Grade
    Current value not lower than 3 mA: (Inferior)
    Current value not lower than 1 mA and lower than 3 mA
    Current value not lower than 0.5 mA and lower than 1 mA
    Current value not lower than 0.1 mA and lower than 0.5 mA
    Current value lower than 0.1 mA: (Superior)

(Evaluation of Low-temperature Impact Resistance)

    Test result: Grade
    Current value not lower than 5 mA: (Inferior)
    Current value not lower than 3 mA and lower than 5 mA
    Current value not lower than 1 mA and lower than 3 mA
    Current value not lower than 0.5 mA and lower than 1 mA
    Current value not lower than 0.1 mA and lower than 0.5 mA
    Current value lower than 0.1 mA: (Superior)

(3) Adhesion After Forming



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was immersed in aqueous solution containing 1.5 wt % citric acid and 1.5 wt % sodium chloride for 24 hours. Thereafter, the peeling length of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling length longer than 5 mm: (Inferior)
    Peeling length longer than 2 mm and not longer than 5 mm
    Peeling length longer than 1 mm and not longer than 2 mm
    Peeling length not longer than 1 mm
    No peeling: (Superior)

(4) Adhesion After Heating



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was heated without content therein at 210° C. for 10 minutes in an oven. Thereafter, the degree of peeling of resin, in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling percentage higher than 5%: (Inferior)
    Peeling percentage higher than 2% and not higher than 5%
    Peeling percentage higher than 1% and not higher than 2%
    Peeling percentage not higher than 1%
    No peeling: (Superior)

(5) Flavor Property



The internal surface of can body subjected to straightening heat treatment was cleaned, and flavor aqueous solution (d-limonene 20 ppm aqueous solution) was put in the can and left at ordinary temperature for 20 days after sealing. Thereafter, the can was unsealed, and a portion expelled by ether immersion was determined by gas chromatography as adsorption of d-limonene per can, by which flavor property was evaluated. Grades not lower than ◯ marked grade are acceptable.
Test result: grade


    Adsorption larger than 200 μg/can: (Inferior)
    Adsorption larger than 100 μg/can and not larger than 200 μg/can
    Adsorption larger than 30 μg/can and not larger than 100 μg/can
    Adsorption larger than 10 μg/can and not larger than 30 μg/can
    Adsorption not larger than 10 μg/can: (Superior)

2. Evaluation by Drawing and Ironing (DI Forming)

2-1 Can Manufacturing



A resin laminated metal sheet was drawn and ironed under the following conditions, by which a DI can was obtained.

    
    
        First-stage drawing
        
            Blank diameter: 150 mm
            Drawing ratio: 1.6
        
        
        Second-stage drawing
        
            Drawing ratio: 1.25
        
        
        Ironing
        
            Ironing punch diameter: 3-stage ironing 65.8 mm dia
        
        
    
    


Total ironing percentage of can sidewall

    
    
        
        
            60 to 75% with respect to thickness of resin laminated metal sheet before forming

2-2 Straightening Heat Treatment

        
        
    
    


Forming strain of film caused by can manufacturing was removed by keeping the can in a thermal environment of film melting point minus 15° C. for 30 seconds and then by rapidly cooling it.
(1) Formability
Evaluation was made as described below by the limit of capability for manufacturing can without film failure. Grades not lower than ◯ marked grade are acceptable.

    Limit of forming (total ironing percentage): Grade
    Incapable of forming at total ironing percentage of 60%: (Inferior)
    Capable of forming up to total ironing percentage of 60%
    Capable of forming up to total ironing percentage of 65%
    Capable of forming up to total ironing percentage of 70%
    Capable of forming up to total ironing percentage of 75%: (Superior)

(2) Evaluation of Room-temperature and Low-temperature Impact Resistance



A can body (total ironing percentage: 70%) subjected to straightening heat treatment was necked, and the can body was filled with distilled water. After a lid was installed and tightened, an iron ball of 0.5 kg was dropped from a height of 25 cm to give a shock to the can bottom. Thereafter, the lid was opened, and 1% salt water was poured in the can so that a portion that had suffered shock was immersed. After immersion for five minutes, a load of 6 V was applied across a platinum electrode immersed in the liquid and a can metal portion, and the current value after five minutes was read, by which evaluation was made as described below. The same tests were conducted at room temperature of 20° C. and at a temperature of 0° C. The former test was for evaluating room-temperature impact resistance, and the latter test was for evaluating low-temperature impact resistance. Grades not lower than ◯ marked grade are acceptable.
(Evaluation of Room-temperature Impact Resistance)


    Test result: Grade
    Current value not lower than 3 mA: (Inferior)
    Current value not lower than 1 mA and lower than 3 mA
    Current value not lower than 0.5 mA and lower than 1 mA
    Current value not lower than 0.1 mA and lower than 0.5 mA
    Current value lower than 0.1 mA: (Superior)

(Evaluation of Low-temperature Impact Resistance)

    Test result: Grade
    Current value not lower than 5 mA: (Inferior)
    Current value not lower than 3 mA and lower than 5 mA
    Current value not lower than 1 mA and lower than 3 mA
    Current value not lower than 0.5 mA and lower than 1 mA
    Current value not lower than 0.1 mA and lower than 0.5 mA
    Current value lower than 0.1 mA: (Superior)

(3) Adhesion After Forming



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was immersed in aqueous solution containing 1.5 wt % citric acid and 1.5 wt % sodium chloride for five hours. Thereafter, the peeling length of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling length longer than 5 mm: (Inferior)
    Peeling length longer than 2 mm and not longer than 5 mm
    Peeling length longer than 1 mm and not longer than 2 mm
    Peeling length not longer than 1 mm
    No peeling: (Superior)

(4) Adhesion After Heating



The internal surface of can body subjected to straightening heat treatment was cleaned, and the can was heated without content therein at 210° C. for 10 minutes in an oven. Thereafter, the degree of peeling of resin in the can end portion was observed, and evaluation was made as described below. Grades not lower than ◯ marked grade are acceptable.

    Test result: Grade
    Peeling percentage higher than 5%: (Inferior)
    Peeling percentage higher than 2% and not higher than 5%
    Peeling percentage higher than 1% and not higher than 2%
    Peeling percentage not higher than 1%
    No peeling: (Superior)

(5) Flavor Property



The internal surface of can body subjected to straightening heat treatment was cleaned, and flavor aqueous solution (d-limonene 20 ppm aqueous solution) was put in the can and left at ordinary temperature for 20 days after sealing. Thereafter, the can was unsealed, and a portion expelled by ether immersion was determined by gas chromatography as adsorption of d-limonene per can, by which flavor property was evaluated. Grades not lower than ◯ marked grade are acceptable.

    Test result: grade
    Adsorption larger than 200 μg/can: (Inferior)
    Adsorption larger than 100 μg/can and not larger than 200 μg/can
    Adsorption larger than 30 μg/can and not larger than 100 μg/can
    Adsorption larger than 10 μg/can and not larger than 30 μg/can
    Adsorption not larger than 10 μg/can: (Superior)


The investigation results are given in Tables 30 and 31.
From Tables 27 to 31, the following facts are found for either can type.
Invention examples 1 to 4 are films in which R1 layer is a mixed resin layer in which modified polyolefin resin specified in the present invention is dispersed in various types of polyester resins and a modified polyolefin resin layer specified in the present invention is also used in R2 layer, and invention examples 47 to 50 in which these films are laminated on the metal sheet of the present invention exhibit high formability, impact resistance, adhesion, and flavor property. Among these, invention example 49 using adipic acid copolymerized polyethylene terephthalate resin has high performance as a whole, but has a tendency toward low adhesion after heating and flavor property because of slightly low melting point of polyester resin and slightly low barrier property. Also, invention example 87 in which the film of invention example 41 manufactured from a commercially available resin in which modified polyolefin resin is dispersed in polyester resin similarly exhibits high performance. On the other hand, comparative examples 1 to 5 are examples of films in which modified polyolefin resin specified in the present invention is not contained in polyester resin in which polyester type is changed variously. Comparative examples 20 to 24 in which these films are laminated especially have low levels of formability and impact resistance.
Invention examples 4 to 10 are films using a mixed resin in which various types of modified polyolefin resins specified in the present invention are dispersed in polyester resin, and invention examples 50 to 56 in which the films are laminated exhibit high formability, impact resistance, adhesion, and flavor property. In particular, invention examples 50 and 52 to 54 in which the films of invention examples 4 and 6 to 8 using modified polyolefin resin containing a proper amount of functional group derived from carboxylic acid and having a glass-transition temperature of −30° C. or lower are laminated have excellent formability, impact resistance, adhesion, and flavor property. On the other hand, comparative example 6 is a film using, as R1 layer, a mixed resin in which polyolefin resin containing no functional group derived from carboxylic acid is dispersed in polyester resin, and comparative example 25 in which the film is laminated has greatly deteriorated formability and impact resistance.
Invention examples 11 to 18 are films in which the blending ratio and dispersion state of modified polyolefin resin dispersed in polyester resin of R1 mixed resin layer are changed variously in the range of the present invention, and invention examples 57 to 64 in which the films are laminated on a metal sheet exhibit high formability, impact resistance, adhesion, and flavor property. In particular, invention examples 58, 60 and 61 in which the films of invention examples 12, 14 and 15 containing a proper amount of dispersed modified polyolefin resin and having a proper number of grains per a fixed volume are laminated have excellent formability, impact resistance, adhesion, and flavor property.
On the other hand, comparative examples 7 to 10 are films in which the blending ratio of modified polyolefin resin in polyester resin of R1 mixed resin layer does not meet the requirement of the present invention, and comparative examples 26 to 29 in which the films are laminated have greatly deteriorated formability or impact resistance. Comparative example 26 in which the film of comparative example 7 having a small number of grains of dispersed modified polyolefin resin is laminated and comparative example 29 in which the film of comparative example 10 having a large number of grains of modified polyolefin resin is laminated have greatly deteriorated formability and impact resistance.
Invention examples 19 to 25 are films in which the thickness of R1 layer and R2 layer of film is changed in the range specified in the present invention, and invention examples 65 to 71 in which the films are laminated on a metal sheet exhibit high formability, impact resistance, adhesion, and flavor property. Among these, invention examples 66, 67 and 69 in which the films of invention examples 20, 21 and 23 in which the thickness ratio of R1 layer to R2 layer is in the range of 5 to 10 and the thickness of R1 layer is in the range of 15 to 25 μm are laminated have excellent formability, impact resistance, adhesion, and flavor property. Also, invention example 13a is a film in which the thickness ratio R1/R2 of mixed resin layer of R1 to modified polyolefin layer of R2 is lower than the desired range of the present invention, and invention example 32a in which this film is laminated has slightly deteriorated mechanical properties of film and adhesion to a substrate metal sheet as compared with invention examples 65 to 71. On the other hand, invention example 14a is a film in which the ratio R1/R2 is higher than the proper range of the present invention, and invention example 33a in which this film is laminated has slightly deteriorated adhesion to a substrate metal sheet as compared with invention examples 65 to 71.
Invention examples 26 to 31 are films using various types of modified polyolefin resins specified in the present invention as R2 layer, and invention examples 72 to 77 in which the films are laminated exhibit high formability, impact resistance, adhesion, and flavor property. In particular, invention examples 73 to 75 in which the films of invention examples 27 to 29 using modified polyolefin resin containing a proper amount of functional group derived from carboxylic acid and having a glass-transition temperature of −30r, or lower are laminated have excellent formability, impact resistance, adhesion, and flavor property. On the other hand, comparative example 13 is a film using, as R2 layer, polyolefin resin containing no functional group derived from carboxylic acid, and comparative example 32 in which the film is laminated has greatly deteriorated formability and impact resistance.
Invention examples 32 to 34 are films in which a lubricant, free radical inhibitor, and compatibilizing agent are mixed, respectively, in a mixed resin of modified polyolefin resin and polyester resin of the present invention, and invention examples 78 to 80 in which the films are laminated exhibit high formability, impact resistance, adhesion, and flavor property. Further, invention examples 78 to 80 also have lubricity, free radical deterioration resistance, and compatibility depending on the function of added additive, and in particular, invention example 80 containing a compatibilizing agent exhibits excellent low-temperature impact resistance.
Invention example 35 is a film of the present invention that is manufactured by the two-axis stretching method, and invention examples 81 and 97 in which the film is laminated exhibit high performance. Invention example 97, which has a plane orientation coefficient of 0.015, exhibits a slightly deteriorated formability. However, invention example 81, which has a plane orientation coefficient in the range of the present invention, has a high level of impact resistance.
Invention examples 36 to 40 are films in which titanium dioxide pigment is mixed with the film of the present invention, and invention examples 82 to 86 in which the films are laminated exhibit high formability, impact resistance, adhesion, and flavor property, and also provide a white uniform color tone. However, invention example 82 in which the film of invention example 36 in which the added amount of pigment is smaller than a desired range is laminated has slightly insufficient opacifying property of color tone. On the other hand, invention example 86 in which the film of invention example 40 in which the added amount of pigment is larger than a desired range is laminated has slightly deteriorated formability.
Invention examples 93 to 96 are films obtained by changing the laminating conditions for the film of invention example 4 in the range of the present invention. If the conditions are within the range of the present invention, high formability, impact resistance, adhesion, and flavor property are exhibited regardless of the laminating temperature.
Invention examples 42 to 46 are three-layer films in which a polyester resin layer of R0 layer containing no olefin and a mixed resin layer of R1 layer and a modified polyolefin layer of R2 layer are laminated (R0 layer is laminated on R1 layer), and invention examples 88 to 92 in which the three-layer films are laminated have very high formability, impact resistance, adhesion, and flavor property. In particular, invention examples 88, 89 and 92 in which the films using, as R0 layer, a polyester resin layer with a proper thickness that consists of polyethylene terephthalate or isophthalic acid copolymerized polyethylene terephthalate are laminated have excellent low-temperature impact resistance and flavor property.
Invention examples 15a and 16a are three-layer films in which a polyester resin layer of R0 layer containing no olefin and a mixed resin layer of R1 layer and a modified polyolefin layer of R2 layer are laminated (R0 layer is laminated on R1 layer) but R2 layer deviates from the proper range of the present invention, and invention examples 34a and 35a in which the three-layer films are laminated have deteriorated adhesion as compared with invention examples 42 to 46 in which R2 layer is within the proper range of the present invention.









TABLE 27









R1 layer










Polyolefin resin

















Number of







grains





Volume
with



Height

percentage
diameter



percentage

of grains
of 0.1 to
















R0 layer

of group

Blending
with
5 μm in



















Poly-
Film
Polyester

derived

ratio in
diameter
cube with
Film



ester
thick-
resin

from

entire
of 0.1 to
one side
thick-


















Sample
resin
ness
Resin

Resin
carboxylic
Tg
resin
5 μm
of 10 μm
ness


film
type
(μm)
type
Additive
type
acid (wt %)
(° C.)
(wt %)
(vol %)
(grains)
(μm)





Inventive


PET
None
EM4
8
<−30
15
12
2000
22


example 1


Inventive


PET/PBT
None
EM4
8
<−30
15
12
2000
22


example 2


Inventive


PET/AD
None
EM4
8
<−30
15
12
2000
22


example 3


Inventive


PET/I
None
EM4
8
<−30
15
12
2000
22


example 4


Inventive


PET/I
None
EM1
21
<−30
15
14
40
22


example 5


Inventive


PET/I
None
EM2
18
<−30
15
13
500
22


example 6


Inventive


PET/I
None
EM5
7
<−30
15
12
2000
22


example 7


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
22


example 8


Inventive


PET/I
None
EM7
1
<−30
15
3
20
22


example 9


Inventive


PET/I
None
EM8
6
20
15
12
2000
22


example 10


Inventive


PET/I
None
EM3
11
<−30
5
3
3
22


example 11


Inventive


PET/I
None
EM3
11
<−30
5
5
70
22


example 12


Inventive


PET/I
None
EM3
11
<−30
10
8
30
22


example 13


Inventive


PET/I
None
EM3
11
<−30
10
10
250
22


example 14


Inventive


PET/I
None
EM3
11
<−30
15
15
500
22


example 15


Inventive


PET/I
None
EM3
11
<−30
15
18
20000
22


example 16


Inventive


PET/I
None
EM3
11
<−30
20
22
200000
22


example 17


Inventive


PET/I
None
EM3
11
<−30
28
20
8000
22


example 18


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
10


example 19


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
15


example 20


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
20


example 21


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
20


example 22


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
25


example 23


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
35


example 24


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
40


example 25














R2 layer
Entire film













Polyolefin resin

Thick-














Height


ness




percentage


ratio



of group

Film
of R1















derived

Film
thick-
layer
Pigment





















from

thick-
ness
to R0

Content




Sample
Resin
carboxylic
Tg
ness
(R1 + R0)
layer

(wt %)



film
type
acid (wt %)
(° C.)
(μm)
(μm)
R1/R0
Type
*1
Stretching







Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 1








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 2








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 3








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 4








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 5








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 6








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 7








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 8








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 9








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 10








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 11








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 12








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 13








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 14








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 15








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 16








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 17








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 18








stretched



Inventive
EM6
5
<−30
1
11
10.0
None
0
Non-



example 19








stretched



Inventive
EM6
5
<−30
3
18
5.0
None
0
Non-



example 20








stretched



Inventive
EM6
5
<−30
3
23
6.7
None
0
Non-



example 21








stretched



Inventive
EM6
5
<−30
10
30
2.0
None
0
Non-



example 22








stretched



Inventive
EM6
5
<−30
3
28
8.3
None
0
Non-



example 23








stretched



Inventive
EM6
5
<−30
5
40
7.0
None
0
Non-



example 24








stretched



Inventive
EM6
5
<−30
6
46
6.7
None
0
Non-



example 25








stretched







*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer















TABLE 28









R1 layer










Polyolefin resin

















Number of







grains






with



Height

Volume
diameter



percentage

percentage
of 0.1 to
















R0 layer

of group

Blending
of grains
5 μm in



















Poly-
Film
Polyester

derived

ratio in
with
cube with
Film



ester
thick-
resin

from

entire
diameter
one side
thick-


















Sample
resin
ness
Resin

Resin
carboxylic
Tg
resin
of 0.1 to
of 10 μm
ness


film
type
(μm)
type
Additive
type
acid (wt %)
(° C.)
(wt %)
5 μm (vol %)
(grains)
(μm)





Inventive


PET/I
None
EM6
5
<−30
15
12
2000
22


example 26


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
22


example 27


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
22


example 28


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
22


example 29


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
22


example 30


Inventive


PET/I
None
EM6
5
<−30
15
12
2000
22


example 31


Inventive


PET/I
*2)
EM3
11
<−30
15
12
2000
22


example 32



0.3 wt %


Inventive


PET/I
*3)
EM3
11
<−30
15
12
2000
22


example 33



0.1 wt %


Inventive


PET/I
*4)
EM3
11
<−30
15
12
2000
22


example 34



3 wt %


Inventive


PET/I
None
EM4
8
<−30
15
12
2000
22


example 35


Inventive


PET/I
None
EM5
7
<−30
15
12
2000
22


example 36


Inventive


PET/I
None
EM5
7
<−30
15
12
2000
22


example 37


Inventive


PET/I
None
EM5
7
<−30
15
12
2000
22


example 38


Inventive


PET/I
None
EM5
7
<−30
15
12
2000
22


example 39


Inventive


PET/I
None
EM5
7
<−30
15
12
2000
22


example 40


Inventive


PET
None

15
<−30
15
15
2500
25


example 41


(PT4274)


Inventive
PET
8
PET/I
None
EM6
5
<−30
15
12
2000
22


example 42


Inventive
PET/I
4
PET/I
None
EM6
5
<−30
15
12
2000
22


example 43


Inventive
PET/PBT
4
PET/I
None
EM6
5
<−30
15
12
2000
22


example 44


Inventive
PET/AD
4
PET/I
None
EM6
5
<−30
15
12
2000
22


example 45


Inventive
PET
4
PET
None

15
<−30
15
15
2500
25


example 46


(PT4274)














R2 layer
Entire film













Polyolefin resin

Thick-














Height


ness




percentage


ratio



of group

Film
of R1















derived

Film
thick-
layer
Pigment





















from

thick-
ness
to R0

Content




Sample
Resin
carboxylic
Tg
ness
(R1 + R0)
layer

(wt %)



film
type
acid (wt %)
(° C.)
(μm)
(μm)
R1/R0
Type
*1
Stretching







Inventive
EM1
21
<−30
4
26
5.5
None
0
Non-



example 26








stretched



Inventive
EM2
18
<−30
4
26
5.5
None
0
Non-



example 27








stretched



Inventive
EM4
8
<−30
4
26
5.5
None
0
Non-



example 28








stretched



Inventive
EM5
7
<−30
4
26
5.5
None
0
Non-



example 29








stretched



Inventive
EM7
1
<−30
4
26
5.5
None
0
Non-



example 30








stretched



Inventive
EM8
6
20
4
26
5.5
None
0
Non-



example 31








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 32








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 33








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 34








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 35








stretched



Inventive
EM6
5
<−30
4
26
5.5
TiO2
3
Two-axis



example 36








stretched



Inventive
EM6
5
<−30
4
26
5.5
TiO2
7
Non-



example 37








stretched



Inventive
EM6
5
<−30
4
26
5.5
TiO2
15
Non-



example 38








stretched



Inventive
EM6
5
<−30
4
26
5.5
TiO2
30
Non-



example 39








stretched



Inventive
EM6
5
<−30
4
26
5.5
TiO2
50
Non-



example 40








stretched



Inventive
EM6
5
<−30
3
28
8.3
None
0
Non-



example 41








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 42








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 43








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 44








stretched



Inventive
EM6
5
<−30
4
26
5.5
None
0
Non-



example 45








stretched



Inventive
EM6
5
<−30
3
28
8.3
None
0
Non-



example 46








stretched







*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.



*2) silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.



*3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radical inhibitor is added by 0.1 weight part to 100 weight part of mixedresin.



*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin.















TABLE 29









R1 layer










Polyolefin resin

















Number of







grains






with



Weight

Volume
diameter
















R0

percentage


percentage
of 0.1 to




layer

of group

Blending
of grains
5 μm in


















Poly-
Film
Polyester

derived

ratio in
with
cube with
Film



ester
thick-
resin

from

entire
diameter
one side
thick-


















Sample
resin
ness
Resin

Resin
carboxylic
Tg
resin
of 0.1 to
of 10 μm
ness


film
type
(μm)
type
Additive
type
acid (wt %)
(° C.)
(wt %)
5 μm (vol %)
(grains)
(μm)





Comparative


PET
None
None
—
—
0
0
0
22


example 1


Comparative


PET/PBT
None
None
—
—
0
0
0
22


example 2


Comparative


PET/AD
None
None
—
—
0
0
0
22


example 3


Comparative


PET/I
None
None
—
—
0
0
0
22


example 4


Comparative


PET/I
None
None
—
—
0
0
0
22


example 5


Comparative


PET/I
None
EPR
0
<−30
15
1
5
22


example 6


Comparative


PET/I
None
EM3
11
<−30
2
2
3
22


example 7


Comparative


PET/I
None
EM3
11
<−30
2
2
45
22


example 8


Comparative


PET/I
None
EM3
11
<−30
32
28
15000
22


example 9


Comparative


PET/I
None
EM3
11
<−30
32
28
120000
22


example 10


Comparative


PET/I
None
EM4
8
<−30
15
12
2000
22


example 11


Comparative


PET
None

15
<−30
15
15
2500
25


example 12


(PT





4274)


Inventive


PET/I
None
EM4
8
<−30
15
12
2000
10


example 13a


Inventive


PET/I
None
EM4
8
<−30
15
12
2000
32


example 14a


Inventive


PET/I
None
EM4
8
<−30
15
12
2000
22


example 13


Inventive
PET
4
PET/I
None
EM4
8
<−30
15
12
2000
22


example 14


Comparative
PET
4
PET
None

15
<−30
15
15
2500
25


example 15


(PT





4274)


Inventive
PET
4
PET/I
None
EM4
8
<−30
15
12
2000
10


example 15a


Inventive
PET
4
PET/I
None
EM4
8
<−30
15
12
2000
32


example 16a














R2 layer
Entire film













Polyolefin resin

Thick-














Weight


ness




percentage


ratio



of group

Film
of R1















derived

Film
thick-
layer
Pigment





















from

thick-
ness
to R0

Content




Sample
Resin
carboxylic
Tg
ness
(R1 + R0)
layer

(wt %)



film
type
acid (wt %)
(° C.)
(μm)
(μm)
R1/R0
Type
1
Stretching







Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 1








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 2








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 3








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 4








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Two-axis



example 5








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 6








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 7








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 8








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 9








stretched



Comparative
EM6
5
<−30
4
26
5.5
None
0
Non-



example 10








stretched



Comparative
None
—
—
—
—
—
None
0
Non-



example 11








stretched



Comparative
None
—
—
—
—
—
None
0
Non-



example 12








stretched



Inventive
EM6
5
<−30
12
22
0.8
None
0
Non-



example 13a








stretched



Inventive
EM6
5
<−30
3
35
10.7
None
0
Non-



example 14a








stretched



Inventive
EPR
0
<−30
4
26
5.5
None
0
Non-



example 13








stretched



Inventive
None
—
—
—
—
—
None
0
Non-



example 14








stretched



Comparative
None
—
—
—
—
—
None
0
Non-



example 15








stretched



Inventive
EM6
5
<−30
12
22
0.8
None
0
Non-



example 15a








stretched



Inventive
EM6
5
<−30
3
35
10.7
None
0
Non-



example 16a








stretched







*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.
















TABLE 30









Melting












point

Thin-wall deep drawn can

















Laminated

of R1 layer

Plane
Form-
Impact
Impact
Adhesion
Adhesion



metal
Sample
polyester
Laminating
orientation
abil-
resistance
resistance
after
after
Flavor


sheet
film
resin (° C.)
temp. (° C.)
coefficient
ity
(room temp.)
(low temp.)
forming
heating
property





Invention
Invention
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 47
example 1


Invention
Invention
235
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 48
example 2


Invention
Invention
220
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 49
example 3


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 50
example 4


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 51
example 5


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 52
example 6


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 53
example 7


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 54
example 8


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 55
example 9


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 56
example 10


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 57
example 11


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 58
example 12


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 59
example 13


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 60
example 14


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 61
example 15


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 62
example 16


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 63
example 17


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 64
example 18


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 65
example 19


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 66
example 20


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 67
example 21


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 68
example 22


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 69
example 23


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 70
example 24


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 71
example 25


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 72
example 26


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 73
example 27


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 74
example 28


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 75
example 29


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 76
example 30


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 77
example 31


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 78
example 32


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 79
example 33


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 80
example 34


Invention
Invention
230
220
0.005
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 81
example 35













Drawn and ironed can (DI can)
















Laminated

Impact
Impact
Adhesion
Adhesion




metal

resistance
resistance
after
after
Flavor



sheet
Formability
(room temp.)
(low temp.)
forming
heating
property







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 47



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 48



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 49



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 50



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 51



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 52



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 53



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 54



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 55



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 56



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 57



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 58



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 59



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 60



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 61



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 62



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 63



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 64



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 65



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 66



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 67



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 68



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 69



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 70



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 71



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 72



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 73



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 74



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 75



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 76



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 77



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 78



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 79



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 80



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 81






















TABLE 31









Melting

Plane




point

orienta-
Thin-wall deep drawn can

















Laminated

of R1 layer
Laminating
tion

Impact
Impact
Adhesion
Adhesion



metal
Sample
polyester
temp.
coef-
Form-
resistance
resistance
after
after
Flavor


sheet
film
resin (° C.)
(° C.)
ficient
ability
(room temp.)
(low temp.)
forming
heating
property





Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 82
example 36


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 83
example 37


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 84
example 38


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 85
example 39


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 86
example 40


Invention
Invention
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 87
example 41


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 88
example 42


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 89
example 43


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 90
example 44


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 91
example 45


Invention
Invention
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 92
example 46


Invention
Invention
230
260
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 93
example 4


Invention
Invention
230
240
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 94
example 4


Invention
Invention
230
200
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 95
example 4


Invention
Invention
230
170
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 96
example 4


Invention
Invention
235
200
0.015
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 97
example 35


Comparative
Comparative
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 20
example 1


Comparative
Comparative
235
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 21
example 2


Comparative
Comparative
220
210
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 22
example 3


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 23
example 4


Comparative
Comparative
230
220
0.005
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 24
example 5


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 25
example 6


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 26
example 7


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 27
example 8


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 28
example 9


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 29
example 10


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 30
example 11


Comparative
Comparative
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 31
example 12


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 32a
example 13a


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 33a
example 14a


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 32
example 13


Comparative
Comparative
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 33
example 14


Comparative
Comparative
255
235
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 34
example 15


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 34a
example 15a


Invention
Invention
230
220
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 35a
example 16a













Drawn and ironed can (DI can)
















Laminated

Impact
Impact
Adhesion
Adhesion




metal
Form-
resistance
resistance
after
after
Flavor



sheet
ability
(room temp.)
(low temp.)
forming
heating
property







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 82



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 83



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 84



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 85



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 86



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 87



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 88



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 89



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 90



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 91



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 92



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 93



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 94



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 95



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 96



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 97



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 20



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 21



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 22



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 23



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 24



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 25



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 26



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 27



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 28



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 29



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 30



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 31



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 32a



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 33a



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 32



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 33



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 34



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 34a



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 35a










EXAMPLE 8
As a resin raw material for R1 layer, modified polyolefin resin with group derived from carboxylic acid was cold blended with polyester resin in a blending ratio given in Tables 32 to 34 by using a tumbler blender, and then the blended resin was melted and kneaded at 270° C. by using a two-axis extruding machine, by which a raw material pellet of polyester resin in which modified polyolefin resin was dispersed was obtained. In the tables, the resin type corresponding to the symbol of resin type of polyester resin and resin type of polyolefin resin is the same as that described in Example 7. As some resin raw material for R1 layer, a commercially available resin (Sealer PT4274 manufactured by Mitsui-DuPont Polychemical Co., Ltd.) that had been pelletized in advance in a state in which modified polyolefin resin with group derived from carboxylic acid was dispersed in polyester resin was used as it was.
As a metal sheet, as in Example 7, a TFS with a thickness of 0.18 mm for thin-wall deep drawn can and 0.23 mm for DI can, which had a degree of temper of DR9, metallic chromium layer of 80 mg/m2, and chromium oxide layer of 15 mg/m2 (metallic chromium conversion), was used, by which a both-side laminated metal sheet was obtained by a method in which the raw material resin pellet for R1 layer was inserted in a one-axis extruding machine, modified polyolefin, which was a resin raw material for R2 layer, was inserted in a separate extruding machine in the case of two layers, each of molten resins was introduced into a multi-manifold type T die and extruded in two layers while the film thickness of R1 and R2 layers was controlled by the discharge amount of molten resin from the extruding machine, molten resin was directly extruded onto one surface of the metal sheet heated to 230° C. in advance, the extruded resin was once cooled while being held adherently between two rolls, and immediately after the resin was laminated on the opposite surface in the same manner, the resin laminated metal sheet was cooled rapidly in water.
Also, in the case of three-layer construction having R0 layer, a both-side laminated metal sheet was obtained by a method in which polyester resin, which was a resin raw material for R0 layer, was inserted in a separate one-axis extruding machine, each of molten resins was introduced into a multi-manifold type T die and extruded in three layers while the film thickness of R0, R1 and R2 layers was controlled by the discharge amount of molten resin from the extruding machine, molten resin was directly extruded onto one surface of the metal sheet heated to 230° C. in advance, the extruded resin was once cooled while being held adherently between two rolls, and immediately after the resin was laminated on the opposite surface in the same manner, the resin laminated metal sheet was cooled rapidly in water. The lip opening width of T die was adjusted so that the thickness of resin film was as given in Tables 32 to 34. The type of sample resin and the resin melting temperature at the extrusion laminating time are given in Tables 32 and 37. The used polyester resin and modified polyolefin resin with group derived from carboxylic acid are the same as those used in Example 7.
All of the grain diameter of modified polyolefin resin dispersed in resin film, various temperatures in the table, and the method for measuring the plane orientation coefficient of resin laminated metal sheet are the same as those in Example 7. As in Example 7, a thin-wall deep drawn can or a DI can was manufactured from the laminated metal sheet obtained as described above, and the can was subjected to straightening heat treatment to manufacture a sample can. The formability, impact resistance, adhesion, and flavor property of film of the manufactured can body were investigated as in Example 7.
The investigation results are given in Tables 35 and 37.
From Tables 32 to 37, the following facts are found for either can type.
Invention examples 98 to 101 are resin laminated steel sheets in which R1 layer is a mixed resin layer in which modified polyolefin resin specified in the present invention is dispersed in various types of polyester resins and a modified polyolefin resin layer specified in the present invention is also used in R2 layer, and exhibit high formability, impact resistance, adhesion, and flavor property. Among these, invention example 100 using adipic acid copolymerized polyethylene terephthalate resin has high performance as a whole, but has a tendency toward low adhesion after heating and flavor property because of slightly low melting point of polyester resin and slightly low barrier property. Also, invention example 137 of resin laminated steel sheet manufactured from a commercially available resin in which modified polyolefin resin is dispersed in polyester resin similarly exhibits high performance. On the other hand, comparative examples 39 to 42 are examples of resin laminated steel sheets in which modified polyolefin resin specified in the present invention is not contained in polyester resin in which polyester type is changed variously, and especially have low levels of formability and impact resistance.
Invention examples 101 to 107 are examples of resin laminated steel sheets using a mixed resin in which various types of modified polyolefin resins specified in the present invention are dispersed in polyester resin, and exhibit high formability, impact resistance, adhesion, and flavor property. In particular, invention examples 101 and 103 to 105 using modified polyolefin resin containing a proper amount of functional group derived from carboxylic acid and having a glass-transition temperature of −30° C. or lower have excellent formability, impact resistance, and adhesion. On the other hand, comparative example 43 is an example using, as R1 layer, a mixed resin in which polyolefin resin containing no functional group derived from carboxylic acid is dispersed in polyester resin, and has greatly deteriorated formability and impact resistance.
Invention examples 108 to 115 are resin laminated steel sheets in which the blending ratio and dispersion state of modified polyolefin resin dispersed in polyester resin of R1 mixed resin layer are changed variously in the range of the present invention, and exhibit high formability, impact resistance, and adhesion. In particular, invention examples 109, 111 and 112 containing a proper amount of dispersed modified polyolefin resin and having a proper number of grains per a fixed volume have excellent formability, impact resistance, adhesion, and flavor property.
On the other hand, comparative examples 44 to 47 are examples in which the blending ratio of modified polyolefin resin in polyester resin of R1 mixed resin layer does not meet the requirement of the present invention, and have greatly deteriorated formability or impact resistance. Comparative example 44 containing a small amount of dispersed modified polyolefin resin and comparative example 47 containing a large amount of modified polyolefin resin have greatly deteriorated formability and impact resistance.
Invention examples 116 to 122 are examples in which the thickness of R1 layer and R2 layer is changed in the range specified in the present invention, and exhibit high formability, impact resistance, adhesion, and flavor property. Among these, invention examples 117, 118 and 120 in which the thickness ratio R1/R2 of R1 layer to R2 layer is in the range of 5 to 10 and the thickness of R1 layer is in the range of 15 to 25 μm have excellent formability, impact resistance, adhesion, and flavor property. Also, invention example 143 is an example in which the thickness ratio R1/R2 of R1 layer to R2 layer is lower than the proper range of the present invention, and has slightly deteriorated mechanical properties of resin and adhesion to a substrate metal sheet as compared with invention examples 116 to 122. On the other hand, invention example 144 is an example in which the ratio R1/R2 is higher than the proper range of the present invention, and has slightly deteriorated adhesion to a substrate metal sheet as compared with invention examples 116 to 122.
Invention examples 123 to 128 are resin laminated steel sheets using various types of modified polyolefin resins specified in the present invention as R2 layer, and exhibit high formability, impact resistance, adhesion, and flavor property. In particular, invention examples 124 to 126 using modified polyolefin resin containing a proper amount of functional group derived from carboxylic acid and having a glass-transition temperature of −30° C. or lower have excellent formability, impact resistance, adhesion, and flavor property.
Invention examples 129 to 131 are resin laminated steel sheets in which a lubricant, free radical inhibitor, and compatibilizing agent are mixed, respectively, in a mixed resin of modified polyolefin resin and polyester resin of the present invention, and exhibit high formability, impact resistance, adhesion, and flavor property. Further, invention examples 129 to 131 also have lubricity, free radical deterioration resistance, and compatibility depending on the function of added additive, and in particular, invention example 131 containing a compatibilizing agent exhibits excellent low-temperature impact resistance.
Invention examples 132 to 136 are resin laminated steel sheets in which titanium dioxide pigment is mixed with the resin layer of the present invention, and exhibit high formability, impact resistance, adhesion, and flavor property, and also provide a white uniform color tone. However, invention example 132 in which the added amount of pigment is smaller than a desired range has slightly insufficient opacifying property of color tone. On the other hand, invention example 136 in which the added amount of pigment is larger than a desired range has slightly deteriorated formability.
Invention examples 138 to 142 are steel sheets on which three-layer resin in which a polyester resin layer containing no olefin (R0 layer) is further provided on R1 layer is laminated, have very high formability, impact resistance, adhesion, and flavor property. In particular, invention examples 138, 139 and 142 using, as R0 layer, a polyester resin layer with a proper thickness that consists of polyethylene terephthalate or isophthalic acid copolymerized polyethylene terephthalate specified in the present invention have excellent low-temperature impact resistance and flavor property.
Invention examples 145 and 146 are steel sheets on which three-layer resin in which a polyester resin layer containing no olefin (R0 layer) is further provided on R1 layer is laminated, and have deteriorated adhesion as compared with invention examples 138 to 142 because the thickness ratio R1/R2 of R1 layer to R2 layer deviates from the proper range of the present invention.









TABLE 32









R1 layer










Polyolefin resin











Number of
















R0 layer

Weight

Volume
grains with




















Resin
Polyester

percentage


percentage
diameter of




Poly-
layer
resin

of group

Blending
of grains
0.1 to 5 μm in
Film




















ester
thick-

Melting


derived from

ratio in
with diameter
cube with one
thick-


Sample
resin
ness
Resin
point

Resin
carboxylic
Tg
entire
of 0.1 to 5 μm
side of 10 μm
ness


film
type
(μm)
type
(° C.)
Additive
type
acid (wt %)
(° C.)
resin (wt %)
(vol %)
(grains)
(μm)





Inventive


PET
255
None
EM4
8
<−30
15
14
2500
22


example 98


Inventive


PET/
235
None
EM4
8
<−30
15
14
2500
22


example 99


PBT


Inventive


PET/
220
None
EM4
8
<−30
15
14
3000
22


example 100


AD


Inventive


PET/I
230
None
EM4
8
<−30
15
14
2500
22


example 101


Inventive


PET/I
230
None
EM1
21
<−30
15
16
50
22


example 102


Inventive


PET/I
230
None
EM2
18
<−30
15
15
1000
22


example 103


Inventive


PET/I
230
None
EM5
7
<−30
15
14
2500
22


example 104


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 105


Inventive


PET/I
230
None
EM7
1
<−30
15
4
40
22


example 106


Inventive


PET/I
230
None
EM8
6
20
15
14
2500
22


example 107


Inventive


PET/I
230
None
EM3
11
<−30
 5
 4
4
22


example 108


Inventive


PET/I
230
None
EM3
11
<−30
 5
 8
100
22


example 109


Inventive


PET/I
230
None
EM3
11
<−30
10
10
50
22


example 110


Inventive


PET/I
230
None
EM3
11
<−30
10
12
500
22


example 111


Inventive


PET/I
230
None
EM3
11
<−30
15
18
800
22


example 112


Inventive


PET/I
230
None
EM3
11
<−30
15
20
22000
22


example 113


Inventive


PET/I
230
None
EM3
11
<−30
20
24
250000
22


example 114


Inventive


PET/I
230
None
EM3
11
<−30
28
22
10000
22


example 115


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
10


example 116


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
15


example 117


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
20


example 118


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
20


example 119


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
25


example 120


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
35


example 121


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
40


example 122













R2 layer




Polyolefin resin
















Weight


Melting





percentage


temp. of





of group

Resin
R1 layer





derived

layer
resin at





from

thick-
extrusion



Sample
Resin
carboxylic
Tg
ness
laminating



film
type
acid (wt %)
(° C.)
(μm)
time (° C.)







Inventive
EM6
21
<−30
4
285



example 98



Inventive
EM6
18
<−30
4
265



example 99



Inventive
EM6
8
<−30
4
250



example 100



Inventive
EM6
7
<−30
4
260



example 101



Inventive
EM6
1
<−30
4
260



example 102



Inventive
EM6
6
 20
4
260



example 103



Inventive
EM6
5
<−30
4
260



example 104



Inventive
EM6
5
<−30
4
260



example 105



Inventive
EM6
5
<−30
4
260



example 106



Inventive
EM6
5
<−30
4
260



example 107



Inventive
EM6
5
<−30
4
260



example 108



Inventive
EM6
5
<−30
4
260



example 109



Inventive
EM6
5
<−30
4
260



example 110



Inventive
EM6
5
<−30
4
260



example 111



Inventive
EM6
5
<−30
4
260



example 112



Inventive
EM6
5
<−30
4
260



example 113



Inventive
EM6
5
<−30
4
260



example 114



Inventive
EM6
5
<−30
4
260



example 115



Inventive
EM6
5
<−30
1
260



example 116



Inventive
EM6
5
<−30
3
260



example 117



Inventive
EM6
5
<−30
3
260



example 118



Inventive
EM6
5
<−30
10
260



example 119



Inventive
EM6
5
<−30
3
260



example 120



Inventive
EM6
5
<−30
5
260



example 121



Inventive
EM6
5
<−30
6
260



example 122



















TABLE 33









R1 layer










Polyolefin resin











Number of
















R0 layer

Weight

Volume
grains with
















Resin

percentage

percentage
diameter of



















Poly-
layer
Polyester resin

of group

Blending
of grains
0.1 to 5 μm in
Film




















ester
thick-

Melting


derived from

ratio in
with diameter
cube with one
thick-


Sample
resin
ness
Resin
point

Resin
carboxylic
Tg
entire
of 0.1 to 5 μm
side of 10 μm
ness


film
type
(μm)
type
(° C.)
Additive
type
acid (wt %)
(° C.)
resin (wt %)
(vol %)
(grains)
(μm)





Inventive


PET
230
None
EM6
5
<−30
15
14
2500
22


example 123


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 124


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 125


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 126


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 127


Inventive


PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 128


Inventive


PET/I
230
*2) 0.3
EM3
11
<−30
15
14
2500
22


example 129




wt %


Inventive


PET/I
230
*3) 0.1
EM3
11
<−30
15
14
2500
22


example 130




wt %


Inventive


PET/I
230
*4) 3
EM3
11
<−30
15
14
2500
22


example 131




wt %


Inventive


PET/I
230
None
EM5
7
<−30
15
14
2500
22


example 132


Inventive


PET/I
230
None
EM5
7
<−30
15
14
2500
22


example 133


Inventive


PET/I
230
None
EM5
7
<−30
15
14
2500
22


example 134


Inventive


PET/I
230
None
EM5
7
<−30
15
14
2500
22


example 135


Inventive


PET/I
230
None
EM5
7
<−30
15
14
2500
22


example 136


Inventive


PET
255
None

15
<−30
15
17
2500
25


example 137


(PT





4274)


Inventive
PET
8
PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 138


Inventive
PET/I
4
PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 139


Inventive
PET/
4
PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 140
PBT


Inventive
PET/
4
PET/I
230
None
EM6
5
<−30
15
14
2500
22


example 141
AD


Inventive
PET
4
PET
255
None

15
<−30
15
17
2500
25


example 142


(PT





4274)













R2 layer




Polyolefin resin
















Weight


Melting





percentage


temp. of





of group

Resin
R1 layer





derived

layer
resin at





from

thick-
extrusion



Sample
Resin
carboxylic
Tg
ness
laminating



film
type
acid (wt %)
(° C.)
(μm)
time (° C.)







Inventive
EM1
21
<−30
4
260



example 123



Inventive
EM2
18
<−30
4
260



example 124



Inventive
EM4
8
<−30
4
260



example 125



Inventive
EM5
7
<−30
4
260



example 126



Inventive
EM7
1
<−30
4
260



example 127



Inventive
EM8
6
 20
4
260



example 128



Inventive
EM6
5
<−30
4
260



example 129



Inventive
EM6
5
<−30
4
260



example 130



Inventive
EM6
5
<−30
4
260



example 131



Inventive
EM6
5
<−30
4
260



example 132



Inventive
EM6
5
<−30
4
260



example 133



Inventive
EM6
5
<−30
4
260



example 134



Inventive
EM6
5
<−30
4
260



example 135



Inventive
EM6
5
<−30
4
260



example 136



Inventive
EM6
5
<−30
3
285



example 137



Inventive
EM6
5
<−30
4
260



example 138



Inventive
EM6
5
<−30
4
260



example 139



Inventive
EM6
5
<−30
4
260



example 140



Inventive
EM6
5
<−30
4
260



example 141



Inventive
EM6
5
<−30
3
285



example 142







*2) Silicone of lubricant is added by 3 weight part to 100 weight part of mixed resin.



*3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radical inhibitor is added by 0.1 weight part to 100 weight part of mixed resin.



*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) of compatibilizing agent is added by 3 weight part to 100 weight part of mixed resin.















TABLE 34









R1 layer










Polyolefin resin











Number of
















R0 layer

Weight

Volume
grains with

















Resin

percentage

Blending
percentage
diameter of



















Poly-
layer
Polyester resin

of group

ratio in
of grains
0.1 to 5 μm in
Film




















ester
thick-

Melting


derived from

entire
with diameter
cube with one
thick-


Sample
resin
ness
Resin
point

Resin
carboxylic
Tg
resin
of 0.1 to
side of 10 μm
ness


film
type
(μm)
type
(° C.)
Additive
type
acid (wt %)
(° C.)
(wt %)
5 μm (vol %)
(grains)
(μm)





Comparative


PET
255
None
None
—
—
0
0
0
22


example 39


Comparative


PET/
235
None
None
—
—
0
0
0
22


example 40


PBT


Comparative


PET/
220
None
None
—
—
0
0
0
22


example 41


AD


Comparative


PET/I
230
None
None
—
—
0
0
0
22


example 42


Comparative


PET/I
230
None
EPR
0
<−30
15
1
4
22


example 43


Comparative


PET/I
230
None
EM3
11
<−30
2
3
5
22


example 44


Comparative


PET/I
230
None
EM3
11
<−30
2
3
50
22


example 45


Comparative


PET/I
230
None
EM3
11
<−30
35
30
20000
22


example 46


Comparative


PET/I
230
None
EM3
11
<−30
35
30
135000
22


example 47


Comparative


PET/I
230
None
EM4
8
<−30
15
15
2500
22


example 48


Comparative


PET
255
None

15
<−30
15
17
2500
25


example 49


(PT4274)


Comparative


PET/I
230
None
EM4
8
<−30
15
15
2500
10


example 143


Comparative


PET/I
230
None
EM4
8
<−30
15
15
2500
32


example 144


Comparative
PET
4
PET/I
230
None
EM4
8
<−30
15
15
2500
22


example 50


Comparative
PET
4
PET
255
None

15
<−30
15
17
2500
25


example 51


(PT4274)


Inventive
PET
4
PET/I
230
None
EM4
8
<−30
15
15
2500
10


example 145


Inventive
PET
4
PET/I
230
None
EM4
8
<−30
15
15
2500
32


example 146













R2 layer




Polyolefin resin
















Weight


Melting





percentage


temp. of





of group

Resin
R1 layer





derived

layer
resin at





from

thick-
extrusion



Sample
Resin
carboxylic
Tg
ness
laminating



film
type
acid (wt %)
(° C.)
(μm)
time (° C.)







Comparative
EM6
5
<−30
4
285



example 39



Comparative
EM6
5
<−30
4
265



example 40



Comparative
EM6
5
<−30
4
250



example 41



Comparative
EM6
5
<−30
4
260



example 42



Comparative
EM6
5
<−30
4
260



example 43



Comparative
EM6
5
<−30
4
260



example 44



Comparative
EM6
5
<−30
4
260



example 45



Comparative
EM6
5
<−30
4
260



example 46



Comparative
EM6
5
<−30
4
260



example 47



Comparative
None
—
—
—
260



example 48



Comparative
None
—
—
—
285



example 49



Comparative
EM6
5
<−30
12
260



example 143



Comparative
EM6
5
<−30
3
260



example 144



Comparative
None
—
—
—
260



example 50



Comparative
None
—
—
—
285



example 51



Inventive
EM6
5
<−30
12
260



example 145



Inventive
EM6
5
<−30
3
260



example 146




















TABLE 35









Entire resin layer











Thick-




ness














ratio

Investigation result



Total
of R1

Thin-wall deep drawn can















resin
layer
Pigment

Impact
Impact



















thick-
to R2

Content

resistance
resistance
Adhesion
Adhesion



Sample
ness
layer

(wt %)
Form-
(room
(low
after
after
Flavor


film
(μm)
R1/R2
Type
*1)
ability
temp.)
temp.)
forming
heating
property





Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 98


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 99


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 100


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 101


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 102


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 103


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 104


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 105


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 106


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 107


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 108


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 109


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 110


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 111


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 112


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 113


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 114


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 115


Invention
11
10.0
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 116


Invention
18
5.0
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 117


Invention
23
6.7
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 118


Invention
30
2.0
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 119


Invention
28
8.3
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 120


Invention
40
7.0
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 121


Invention
46
6.7
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 122













Investigation result




Drawn and ironed can (DI can)

















Impact









resistance
Impact
Adhesion
Adhesion



Sample
Form-
(room
resistance
after
after
Flavor



film
ability
temp.)
(low temp.)
forming
heating
property







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 98



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 99



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 100



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 101



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 102



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 103



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 104



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 105



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 106



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 107



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 108



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 109



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 110



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 111



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 112



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 113



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 114



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 115



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 116



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 117



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 118



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 119



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 120



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 121



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 122




















TABLE 36









Entire resin layer











Thick-




ness














ratio

Investigation result



Total
of R1

Thin-wall deep drawn can















resin
layer
Pigment

Impact
Impact



















thick-
to R2

Content

resistance
resistance
Adhesion
Adhesion



Sample
ness
layer

(wt %)
Form-
(room
(low
after
after
Flavor


film
(μm)
R1/R2
Type
*1)
ability
temp.)
temp.)
forming
heating
property





Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 123


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 124


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 125


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 126


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 127


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 128


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 129


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 130


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 131


Invention
26
5.5
TiO2
3
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 132


Invention
26
5.5
T1O2
7
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 133


Invention
26
5.5
TiO2
15
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 134


Invention
26
5.5
TiO2
30
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 135


Invention
26
5.5
TiO2
50
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 136


Invention
28
8.3
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 137


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 138


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 139


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 140


Invention
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 141


Invention
28
8.3
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 142













Investigation result




Drawn and ironed can (DI can)

















Impact









resistance
Impact
Adhesion
Adhesion



Sample
Form-
(room
resistance
after
after
Flavor



film
ability
temp.)
(low temp.)
forming
heating
property







Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 123



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 124



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 125



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 126



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 127



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 128



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 129



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 130



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 131



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 132



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 133



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 134



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 135



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 136



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 137



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 138



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 139



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 140



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 141



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 142







*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.
















TABLE 37









Entire resin layer











Thick-




ness














ratio

Investigation result



Total
of R1

Thin-wall deep drawn can















resin
layer
Pigment

Impact
Impact



















thick-
to R2

Content

resistance
resistance
Adhesion
Adhesion



Sample
ness
layer

(wt %)
Form-
(room
(low
after
after
Flavor


film
(μm)
R1/R2
Type
*1)
ability
temp.)
temp.)
forming
heating
property





Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 39


Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 40


Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 41


Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 42


Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 43


Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 44


Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 45


Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 46


Comparative
26
5.5
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 47


Comparative
—
—
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 48


Comparative
—
—
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 49


Invention
22
0.8
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 143


Invention
35
10.7
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 144


Comparative
—
—
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 50


Comparative
—
—
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 51


Invention
22
0.8
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 145


Invention
35
10.7
None
0
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚


example 146













Investigation result




Drawn and ironed can (DI can)

















Impact









resistance
Impact
Adhesion
Adhesion



Sample
Form-
(room
resistance
after
after
Flavor



film
ability
temp.)
(low temp.)
forming
heating
property







Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 39



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 40



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 41



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 42



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 43



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 44



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 45



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 46



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 47



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 48



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 49



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 143



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 144



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 50



Comparative
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 51



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚



example 145



Invention
⊚
⊚
⊚⊚⊚
⊚
⊚⊚
⊚⊚



example 146







*1) Pigment content means weight percentage (wt %) of pigment with respect to total film amount of entire resin and pigment. Pigment is added to R1 layer.

## Claims

1. A non-stretched resin film which consists essentially of a thermoplastic polyester resin containing 3 to 30 percent by weight in a weight fraction in the entire resin of a granular resin with a grain diameter of 0.1 to 5 μm, said granular resin being a modified polyolefin resin containing 2 to 20 percent by weight of a functional group derived from carboxylic acid in terms of carboxylic acid.

2. The resin film according to claim 1, wherein the modified polyolefin resin is contained in an amount of 3 to 25 percent by volume in a volume fraction in the entire resin.

3. The resin film according to claim 1, wherein said thermoplastic polyester resin is a polyester containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a basic skeleton.

4. The resin film according to claim 1, wherein the thermoplastic resin contains terephthalic acid and isophthalic acid, which are dicarboxylic acid components constituting the thermoplastic polyester resin, in a molar ratio of 97/3 to 85/15.

5. The resin film according to claim 1, which further comprises 5 to 40 percent by weight of a pigment.

6. The resin film according to claim 1, wherein the film has a thickness of 10 to 50 μm.

7. A resin film having a two-layer construction comprising a resin layer R1 comprising the resin film set forth in claim 1 and a resin layer R2 comprising a modified polyolefin resin having a functional group derived from carboxylic acid which is laminated to resin layer R1.

8. The resin film according to claim 7, wherein the resin layer R1 has a thickness of 10 to 50 μm, the resin layer R2 has a thickness of 1 to 10 μm, and a thickness ratio of the resin layer R1 to the resin layer R2 is 1 to 20.

9. The resin film according to claim 7, wherein the modified polyolefin of the resin layer R2 contains 2 to 20 percent by weight of the functional group derived from carboxylic acid in terms of carboxylic acid.

10. The resin film according to claim 7, which further comprises 5 to 40 percent by weight of a pigment.

11. A resin laminated metal sheet comprising a metal sheet and a resin film, wherein at least one surface of the metal sheet is coated with the resin film as set forth in claim 7 so that the resin layer R2 is in contact with the metal sheet.

12. The resin laminated metal sheet according to claim 11, wherein a plane orientation coefficient in a direction parallel to a film surface of the resin film is lower than 0.010.

13. The resin laminated metal sheet according to claim 11, wherein the resin film is formed by extruding two types of resins, one of said resins constituting the resin layer R1 which consists essentially of a thermoplastic polyester resin containing 3 to 30 percent by weight in a weight fraction in the entire resin of a granular resin with a grain diameter of 0.1 to 5 μm, said granular resin being a modified polyolefin resin containing 2 to 20 percent by weight of a functional group derived from carboxylic acid in terms of carboxylic acid and a resin constituting the resin layer R2 comprising a modified polyolefin resin having a functional group derived from carboxylic acid, simultaneously from one T die directly on a surface of the metal sheet.

14. A method for manufacturing a resin laminated to a metal sheet comprising heating a metal sheet to a temperature in the range of the melting point of thermoplastic polyester resin constituting the resin layer R1 as set forth in claim 7 minus 70° C. to the melting point thereof plus 30° C. to form a heated metal sheet, and laminating the resin film as set forth in claim 13 to the heated metal sheet.

15. A method for manufacturing a resin laminated to a metal sheet comprising heating a resin constituting the resin layer R1 as set forth in claim 7 and a resin constituting the resin layer R2 as set forth in claim 7 to a temperature in the range of the melting point of thermoplastic polyester resin of the resin layer R1 plus 10° C. to the melting point thereof plus 50° C. to melt resin layer R1 and resin layer R2 to form two melted resins, and extrusion laminating the two melted resins in two layers on a surface of a metal sheet.

16. The method for manufacturing a resin laminated metal sheet according to claim 15, wherein the resin constituting the resin layer R1 which consists essentially of a thermoplastic polyester resin containing 3 to 30 percent by weight in a weight fraction in the entire resin of a granular resin with a grain diameter of 0.1 to 5 μm, said granular resin being a modified polyolefin resin containing 2 to 20 percent by weight of a functional group derived from carboxylic acid in terms of carboxylic acid and the resin constituting the resin layer R2 comprising a modified polyolefin resin having a functional group derived from carboxylic acid are inserted in separate extruding machines and are melted.

17. A resin film having a three-layer construction comprising a polyester resin layer R0 containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a basic skeleton is laminated on one surface of a resin layer R1 comprising of the resin film as set forth in claim 1, and a resin layer R2 comprising modified polyolefin resin having a functional group derived from carboxylic acid is laminated on another surface of the resin layer R1.

18. The resin film according to claim 17, wherein the resin layer R1 has a thickness of 10 to 50 μm, the resin layer R0 has a thickness of 1 to 10 μm, the resin layer R2 has a thickness of 1 to 10 μm, a thickness ratio of the resin layer R1 to the resin layer R0 is 1 to 20, and a thickness ratio of the resin layer R1 to the resin layer R2 is 1 to 20.

19. The resin film according to claim 17, wherein the modified polyolefin resin of the resin layer R2 contains 2 to 20 percent by weight of the functional group derived from carboxylic acid in terms of carboxylic acid.

20. The resin film according to claim 17, which further comprises 5 to 40 percent by weight of pigment is contained.

21. A resin laminated metal sheet comprising a metal sheet and a resin film, wherein at least one surface of the metal sheet is coated with the resin film as set forth in claim 17 so that the resin layer R2 is in contact with the metal sheet.

22. The resin laminated metal sheet according to claim 21, wherein a plane orientation coefficient in a direction parallel to a film surface of the resin film is lower than 0.010.

23. The resin laminated metal sheet according to claim 21, wherein the resin film is formed by extruding three types of resins, one of said resins constituting the resin layer R1 which consists essentially of a thermoplastic polyester resin containing 3 to 30 percent by weight in a weight fraction in the entire resin of a granular resin with a grain diameter of 0.1 to 5 μm, said granular resin being a modified polyolefin resin containing 2 to 20 percent by weight of a functional group derived from carboxylic acid in terms of carboxylic acid, a resin constituting the resin layer R0 containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a basic skeleton, and a resin constituting the resin layer R2 comprising a modified polyolefin resin having a functional group derived from carboxylic acid, simultaneously from one T die directly on the surface of metal sheet.

24. A method for manufacturing a resin laminated to a metal sheet comprising heating a metal sheet to a temperature in the range of the melting point of the thermoplastic polyester resin constituting the resin layer R1 as set forth in claim 17 minus 70° C. to the melting point thereof plus 30° C. to form a heated metal sheet, and laminating the resin film as set forth in claim 17 to the heated metal sheet.

25. A method for manufacturing a resin laminated to a metal sheet comprising heating a resin constituting the resin layer R1 as set forth in claim 17, a resin constituting the resin layer R0 as set forth in claim 17, and a resin constituting the resin layer R2 as set forth in claim 17 to a temperature in the range of the melting point of the thermoplastic polyester resin of the resin layer R1 plus 10° C. to the melting point thereof plus 50° C. to melt resin layer R1, resin layer R0 and resin layer R2 to form three melted resins, and extrusion laminating the three melted resins in three layers on the surface of a metal sheet.

26. The method for manufacturing a resin laminated metal sheet according to claim 25, wherein the resin constituting the resin layer R1 as set forth in claim 17, the resin constituting the resin layer R0 as set forth in claim 17, and the resin constituting the resin layer R2 as set forth in claim 17 are inserted in separate extruding machines and are melted.

27. A method for manufacturing a resin film, comprising inserting the thermoplastic polyester resin containing 3 to 30 percent by weight of a granular resin with a grain diameter of 0.1 to 5 μm as set forth in claim 1 in an extruding machine as a raw material resin to melt the thermoplastic polyester resin and form a molten resin, and forming a film by extruding the molten resin from a T die.

28. A resin laminated metal sheet comprising a metal sheet and a resin film, wherein at least one surface of the metal sheet is coated with the resin film as set forth in claim 1.

29. The resin laminated metal sheet according to claim 28, wherein the metal sheet is a steel sheet subjected to electrolytic chromate treatment, having a metallic chromium layer of 50 to 200 mg/m2 and a chromium oxide layer of 3 to 30 mg/m2 in terms of metallic chromium on the surface thereof.

30. The resin laminated metal sheet according to claim 28, wherein a plane orientation coefficient in a direction parallel to a film surface of the resin film is lower than 0.010.

31. The resin laminated metal sheet according to claim 28, wherein the resin film is formed by extruding the thermoplastic polyester resin containing 3 to 30 percent by weight in a weight fraction of the entire resin of a granular resin with a grain diameter of 0.1 to 5 μm, said granular resin being a modified polyolefin resin containing 2 to 20 percent by weight of a functional group derived from carboxylic acid in terms of carboxylic acid from a T die directly on a surface of the metal sheet.

32. A method for manufacturing a resin laminated metal sheet comprising heating a metal sheet to a temperature in the range of the melting point of the thermoplastic polyester resin containing 3 to 30 percent by weight of a granular resin with a grain diameter of 0.1 to 5 μm as set forth in claim 1 minus 70° C. to the melting point thereof plus 30° C., to form a heated metal sheet, and laminating the resin film as set forth in claim 1 to the heated metal sheet.

33. A method for manufacturing a resin laminated metal sheet comprising heating the thermoplastic polyester resin containing 3 to 30 percent by weight of a granular resin with a grain diameter of 0.1 to 5 μm as set forth in claim 1 to a temperature in the range of the melting point of the thermoplastic polyester resin plus 10° C. to the melting point thereof plus 50° C. to melt the thermoplastic polyester resin, and laminating the melted thermoplastic polyester resin by directly extruding the melted thermoplastic polyester resin on a surface of a metal sheet.

34. A method for manufacturing a resin laminated metal sheet comprising mixing 3 to 30 percent by weight of a granular resin with a grain diameter of 0.1 to 5 μm as set forth in a claim 1 in a thermoplastic polyester resin to form a mixed resin, inserting the mixed resin in an extruding machine to melt the mixed resin and form a molten resin, and laminating the molten resin by directly extruding the molten resin on a surface of a metal sheet.

35. A method for manufacturing resin film comprising inserting a thermoplastic polyester resin containing 3 to 30 percent by weight in a weight fraction in the entire resin of a granular resin with a grain diameter of 0.1 to 5 μm, said granular resin being a modified polyolefin resin containing 2 to 20 percent by weight of a functional group derived from carboxylic acid in terms of carboxylic acid in an extruding machine as a raw material resin to melt the resin and form a molten resin, inserting a layer R2 comprising a modified polyolefin resin having a functional group derived from carboxylic acid in an extruding machine to melt the modified polyolefin resin to form a molten modified polyolefin resin, and forming a film comprising a two-layer construction by extruding the molten resin and the molten modified polyolefin resin from one T die.

36. A method for manufacturing a resin film comprising inserting a thermoplastic polyester resin containing 3 to 30 percent by weight in a weight fraction in the entire resin of a granular resin with a grain diameter of 0.1 to 5 μm, said granular resin being a modified polyolefin resin containing 2 to 20 percent by weight of a functional group derived from carboxylic acid in terms of carboxylic acid in an extruding machine as a raw material resin to melt the resin and form a molten resin, inserting a polyester resin constituting a resin layer R0 containing polyethylene terephthalate and/or isophthalic acid copolymerized polyethylene terephthalate as a basic skeleton in an extruding machine to melt the polyester resin and from a molten polyester resin, inserting a resin layer R2 comprising a modified polyolefin resin having a functional group derived from carboxylic acid in an extruding machine to melt the modified polyolefin resin to form a molten polyolefin resin, and forming a film comprising a three-layer construction by extruding the molten resin, the molten polyester resin and the molten modified polyolefin resin from one T die.