# Patent

## Title
Multilayer propylene resin sheet and heat-treatable packaging material using same

## Abstract

The invention provides a multilayer sheet and a heat-treatable packaging material which have excellent flexibility, transparency, impact resistance, heat resistance, heat-sealability and cleanliness, which are endowed with a good formability without readily incurring drawbacks such as external defects and thickness fluctuations when subjected to multilayer formation, and which, even at a reduced thickness, have an excellent sheet substrate strength decrease-inhibiting effect.
The multilayer sheet is a multilayer propylene resin sheet composed of at least two layers of an inner layer (1) and an outer layer (2), wherein the inner layer (1) is made of a resin composition (X) containing from 60 to 90 wt % of (A) a propylene resin composition which includes from 30 to 70 wt % of (A1) a specific propylene-α-olefin random copolymer component and from 70 to 30 wt % of (A2) a propylene-ethylene random copolymer component, from 40 to 10 wt % of (B) an ethylene-α-olefin copolymer, and from 1 to 25 wt % of (C) a propylene resin, and the outer layer (2) is made of a specific propylene resin composition Y. The heat-treatable packaging material can be obtained from the multilayer propylene resin sheet.

## Background
TECHNICAL FIELD
The present invention relates to a multilayer sheet and to a heat-treatable packaging material which uses the same. More specifically, the invention relates both to a multilayer propylene resin sheet which, even when subjected to heat treatment under applied pressure such as pressurized steam treatment or pressurized hot-water treatment, has an excellent heat resistance and thus does not readily incur deformation or internal fusion, yet is endowed with a good transparency, flexibility and impact resistance; and also to a heat-treatable packaging material which uses the same.
BACKGROUND ART
The performance characteristics desired in retortable packaging materials and in packaging bags that must be sterilized under pressurized treatment, such as intravenous bags (IV bags), include transparency to allow the contents to be checked, flexibility to enable liquid discharge without forming an air vent, low-temperature impact resistance so that the bag does not rupture during low-temperature storage and low-temperature transport to preserve the quality of the contents, heat resistance so that deformation and fusion do not occur even when sterilization at 121° C. is carried out, and fabricability such as heat-sealability to facilitate bag-making.
With regard to IV bags in particular, vinyl chloride resins were formerly used as a material that satisfies the above performance characteristics. However, owing to the leaching out of plasticizers and waste disposal problems, and also to recent concerns over the global environment, such resins have been replaced with polyolefin resins.
IV bags composed primarily of polyethylene, though endowed with an excellent flexibility and impact resistance, have a poor heat resistance and thus give rise to appearance defects such as deformation at a sterilization temperature of 121° C. (overkill conditions), making them incapable of functioning satisfactorily as IV bags (see, for example, Patent Document 1). On the other hand, IV bags composed primarily of polypropylene have a good heat resistance, but are hard as an IV bag material and have an inadequate impact resistance at low temperatures, as a result of which these too are unable to satisfy the above performance characteristics (see, for example, Patent Document 2).
Art has thus been disclosed in which flexibility and impact resistance are conferred by the addition of an elastomeric component to polypropylene (see, for example, Patent Document 3). However, problems with this approach are that the heat resistance of polypropylene is sacrificed, low-molecular-weight ingredients bleed out following sterilization, and the transparency worsens. Art involving the addition of a styrene-based elastomer as the elastomeric component has also been disclosed (see, for example, Patent Document 4), but blocking tends to arise and the productivity leaves much to be desired. Moreover, styrene-based elastomers are more expensive than olefinic elastomers, leading to cost-related issues as well.
Unrelated to the above, polypropylene block copolymers in which an elastomeric component is added by continuous polymerization using a Ziegler-Natta catalyst have been developed (see, for example, Patent Document 5). Unsurprisingly, however, bleedout arises following sterilization, and the transparency is poor. Water-cooled blown films composed of a propylene-ethylene block copolymer having an elastomeric component added thereto and obtained by continuous polymerization using a metallocene catalyst have also been disclosed (see, for example Patent Document 6). However, these do not yet have a sufficient low-temperature impact resistance. In addition, films for medical use which contain a heterogeneous blend of resins have been disclosed (see, for example, Patent Document 7), but these too have lacked an adequate impact resistance at low temperature.
Hence, although there exists a need for IV bag materials which strike a good balance among the properties of heat resistance, transparency, flexibility and impact resistance, and which moreover are low-cost, materials satisfying such a need have not previously been found.
Moreover, the IV bag-making process includes the steps of welding injection-molded parts such as a spout, a discharge port and an injection port to the bag, which requires melting of the film for sufficient fusion to take place. For this purpose, heat sealing is carried out under very harsh conditions (e.g., high temperature, high pressure, long duration). In a fully melted state, the molten resin ends up sticking to the sealing bar, inevitably worsening productivity. To address this problem, technology has been disclosed wherein the outer layer and the inner layer of a laminated film are provided with different melting points, enabling the inner layer to be melted while the outer layer remains solid (see, for example, Patent Document 7). The inner layer is made of a polyethylene resin and can thus withstand a sterilization temperature of 115° C.; however, at 121° C. sterilization, the inner faces of the film end up sticking to each other (“internal fusion”). Hence, the heat resistance is inadequate.
CITATION LIST
Patent Literature


    Patent Literature 1: JP-A-H9-308682
    Patent Literature 2: JP-A-H9-99036
    Patent Literature 3: JP-A-H9-75444
    Patent Literature 4: JP-A-H9-324022
    Patent Literature 5: JP-A-2006-307072
    Patent Literature 6: JP-A-2008-524391
    Patent Literature 7: JP-A-2007-245490


SUMMARY OF THE INVENTION
Technical Problem
To provide a good balance of the performance characteristics such as transparency, heat resistance and flexibility required of heat-treatable packaging bags, it is effective to use a combination of a propylene-α-olefin random copolymer exhibiting heat resistance with a propylene-ethylene random copolymer which has a specific amount of ethylene added thereto, is obtained using a metallocene catalyst, and is capable of having a flexibilizing effect without a loss of transparency. Also, because polyolefins obtained using a metallocene catalyst have extremely low levels of low-molecular-weight components and low-crystallinity components, they have an excellent cleanliness, and can thus be regarded as highly suitable for food and medical-related applications.
On the other hand, there is a possibility that, in this state, such polyolefins will have an inadequate low-temperature impact resistance.
Accordingly, the present invention provides multilayer sheets which are endowed with excellent flexibility, transparency, impact resistance, heat resistance and cleanliness, and are also capable of withstanding harsh heat-sealing conditions during bag-making. The invention also provides heat-treatable packaging bags which use such multilayer sheets.
Solution to Problem
The inventors have conducted various investigations and analyses with the aim of arriving at a solution to the above problems. As a result, they have discovered that these problems can be satisfactorily resolved by compounding in an outer layer a propylene resin having a specific melting peak temperature, and by blending in an inner layer a specific amount of a mixture of a propylene-α-olefin copolymer component having a specific melting peak temperature and a propylene-ethylene random copolymer component having a specific ethylene content (the mixture having a single tan δ peak at or below 0° C.) with a specific amount of an ethylene-α-olefin copolymer having a specific density and a specific melt flow rate. The inventors ultimately arrived at the present invention upon learning that the above resin formulations and layer compositions enable the performance characteristics required in a heat-treatable packaging bag to be obtained in a good balance and at a high level.
That is, in a first aspect, the invention provides a multilayer propylene resin sheet of at least two layers composed of an inner layer and an outer layer, wherein the respective layers satisfy the following conditions:

    (1) the inner layer is made of (X) a propylene resin composition including:
    from 60 to 90 wt % of (A) a propylene resin composition which satisfies the conditions of


(A-i) containing from 30 to 70 wt % of a (A1) propylene-α-olefin random copolymer component having a melting peak temperature (Tm (A1)) of from 125 to 145° C., and from 70 to 30 wt % of (A2) a propylene-ethylene random copolymer component having an ethylene content (E [A2]) of from 7 to 17 wt % and obtained using a metallocene catalyst,
(A-ii) having a melt flow rate (MFR (A), at 230° C. and 2.16 kg) in a range of from 0.5 to 20 g/10 min, and
(A-iii) having, in a temperature-loss tangent (tan δ) curve obtained by dynamic mechanical analysis (DMA), a single peak at or below 0° C. on the tan δ curve representing a glass transition observed in a range of from −60 to 20° C., and from 40 to 10 wt % of (B) an ethylene-α-olefin copolymer which satisfies the conditions of
(B-i) having a density in a range of from 0.860 to 0.910 g/cm3, and
(B-ii) having a melt flow rate (MFR (B), at 190° C. and 2.16 kg) in a range of from 0.1 to 20 g/10 min; and

    (2) the outer layer is made of (Y) a propylene resin composition including (D) a propylene resin having a melting peak temperature (Tm (D)) in a range of from 135 to 170° C.


In a second aspect, the invention provides the multilayer propylene resin sheet according to the first aspect of the invention, wherein the respective layers satisfy the following conditions:

    (1) The inner layer is made of (X) a propylene resin composition including:
    from 45 to 89 wt % of (A) a propylene resin composition which satisfies the conditions of


(A-i) containing from 30 to 70 wt % of (A1) a propylene-α-olefin random copolymer component having a melting peak temperature (Tm (A1)) of from 125 to 145° C., and from 70 to 30 wt % of (A2) a propylene-ethylene random copolymer component having an ethylene content (E [A2]) of from 7 to 17 wt % and obtained using a metallocene catalyst,
(A-ii) having a melt flow rate (MFR (A), at 230° C. and 2.16 kg) in a range of from 0.5 to 20 g/10 min, and
(A-iii) having, in a temperature-loss tangent (tan δ) curve obtained by dynamic mechanical analysis, a single peak at or below 0° C. on the tan δ curve representing a glass transition observed in a range of from −60 to 20° C., from 10 to 30 wt % of (B) an ethylene-α-olefin copolymer which satisfies the conditions of
(B-i) having a density in a range of from 0.860 to 0.910 g/cm3, and
(B-ii) having a melt flow rate (MFR (B), at 190° C. and 2.16 kg) in a range of from 0.1 to 20 g/10 min, and from 1 to 25 wt % of (C) a propylene resin which satisfies the conditions of
(C-i) having a melting peak temperature (Tm (C)) which is at least 6° C. higher than the melting peak temperature (Tm (A1)) of the propylene-α-olefin random copolymer component (A1), and
(C-ii) having a melt flow rate (MFR(C), at 230° C. and 2.16 kg) in a range of from 0.5 to 30 g/10 min.

    (2) The outer layer is made of (Y) a propylene resin composition including (D) a propylene resin having a melting peak temperature (Tm (D)) in a range of from 135 to 170° C.


In a third aspect, the invention provides the multilayer propylene resin sheet according to the first or second aspect of the invention, wherein the propylene-α-olefin random copolymer component (A1) in the propylene resin composition (A) is obtained using a metallocene catalyst.
In a fourth aspect, the invention provides the multilayer propylene resin sheet according to the first to third aspects of the invention, wherein the propylene-α-olefin random copolymer component (A1) and the propylene-ethylene random copolymer component (A2) of the propylene resin composition (A) are obtained by successive polymerization using a metallocene catalyst, the successive polymerization including:

    (1) a first step of polymerizing from 50 to 60 wt % of the propylene-α-olefin random copolymer component (A1), and
    (2) a second step of polymerizing from 50 to 40 wt % of the propylene-ethylene random copolymer component (A2) having an ethylene content (E [A2]) of from 8 to 14 wt %.


In a fifth aspect, the invention provides the multilayer polypropylene resin sheet according to the first to fourth aspects of the invention which is a multilayer sheet of at least three layers further including an innermost layer, in order of an outer layer, an inner layer and the innermost layer, wherein the innermost layer is made of (Z) a propylene resin composition having a soluble content at or below 0° C. (S0), as measured by temperature rising elution fractionation (TREF), of 15 wt % or less.
In a sixth aspect, the invention provides the multilayer propylene resin sheet according to the fifth aspect of the invention, wherein the propylene resin composition (Z) is (Z1) a propylene resin composition composed of from 80 to 99 wt % of (E) a propylene-α-olefin copolymer having a melting peak temperature (Tm (E)) of from 130 to 145° C., and from 1 to 20 wt % of (F) an ethylene-α-olefin copolymer having a density of from 0.860 to 0.910 g/cm3.
In a seventh aspect, the invention provides the multilayer propylene resin sheet according to the fifth aspect of the invention, wherein the propylene resin composition (Z) is a propylene resin composition (Z2) which includes: from 60 to 90 wt % of (G) a propylene resin composition which satisfies the condition of
(G-i) including from 30 to 70 wt % of (G1) a propylene-α-olefin random copolymer component having a melting peak temperature Tm (G1) in a range of from 125 to 145° C., and from 70 to 30 wt % of (G2) a propylene-ethylene random copolymer component having an ethylene content (E [G2]) of from 7 to 17 wt % and obtained using a metallocene catalyst; and from 40 to 10 wt % of (H) an ethylene-α-olefin copolymer which satisfies the condition of
(H-i) having a density in a range of from 0.860 to 0.910 g/cm3.
In an eight aspect, the invention provides the multiplayer propylene resin sheet according to the fifth aspect of the invention, wherein the propylene resin composition (Z) is (Z2) a propylene resin composition which includes:

    from 45 to 89 wt % of (G) a propylene resin composition which satisfies the condition of


(G-i) including from 30 to 70 wt % of (G1) a propylene-α-olefin random copolymer component having a melting peak temperature Tm (G1) in a range of from 125 to 145° C., and from 70 to 30 wt % of (G2) a propylene-ethylene random copolymer component having an ethylene content (E [G2]) of from 7 to 17 wt % and obtained using a metallocene catalyst;

    from 10 to 30 wt % of (H) an ethylene-α-olefin copolymer which satisfies the condition of


(H-i) having a density in a range of from 0.860 to 0.910 g/cm3; and

    from 1 to 25 wt % of (I) a propylene resin which satisfies the condition of


(I-i) having a melting peak temperature (Tm (I)) which is at least 6° C. higher than the melting peak temperature (Tm (G1)) of the propylene-α-olefin random copolymer component (G1).
In a ninth aspect, the invention provides the multilayer propylene resin sheet according to the seventh or eighth aspect of the invention, wherein the propylene resin composition (G) further satisfies the condition of
(G-ii) having, in a temperature-loss tangent (tan δ) curve obtained by dynamic mechanical analysis (DMA), a single peak at or below 0° C. on the tan δ curve representing a glass transition observed in a range of from −60 to 20° C.
In a tenth aspect, the invention provides the multilayer propylene resin sheet according to any one of the seventh to ninth aspects of the invention, wherein the propylene-α-olefin random copolymer component (G1) is obtained using a metallocene catalyst.
In an eleventh aspect, the invention provides the multilayer propylene resin sheet according to the seventh or eighth aspect of the invention, wherein the propylene-α-olefin random copolymer component (G1) and the propylene-ethylene random copolymer component (G2) of the propylene resin composition (G) are obtained by successive polymerization using a metallocene catalyst, the successive polymerization including:

    (1) a first step of polymerizing from 50 to 60 wt % of the propylene-α-olefin random copolymer (G1), and
    (2) a second step of polymerizing from 50 to 40 wt % of the propylene-ethylene random copolymer component (G2) having an ethylene content (E [G2]) of from 8 to 14 wt %.


In a twelfth aspect, the invention provides a heat-treatable packaging material, which material is characterized by the use of the multilayer propylene resin sheet according to any one of the first to eleventh aspects of the invention.
Finally, in a thirteenth aspect, the invention provides a heat-treatable packaging material according to the twelfth aspect of the invention, which is an IV bag.
The basic feature of the inventive multilayer sheet and the inventive heat-treatable packaging material using the same are the use in an inner layer (1) of (X) a propylene resin composition containing (A) a specific propylene resin composition and (B) a specific ethylene-α-olefin copolymer, and the use in an outer layer (2) of (Y) a propylene resin composition composed primarily of (D) a specific propylene resin.
Propylene resin composition (A) used in the inner layer (1), because it is a propylene-ethylene copolymer composition which contains (A1) a propylene-α-olefin random copolymer component having a melting peak temperature in a specific range and (A2) a propylene-ethylene random copolymer component obtained using a metallocene catalyst and having a specific ethylene content, because it has a high flexibility and because, in dynamic mechanical analysis, the glass transition temperature observed as a tan δ curve peak in a range of from −60 to 20° C. exhibits a single peak at or below 0° C., is able to impart to the resulting multilayer sheet a good balance of transparency and flexibility.
Ethylene-α-olefin copolymer (B) used in the inner layer (1) is specified in terms of its density and melt flow rate, and is capable of conferring to the resulting multilayer sheet the quality of being flexible without a loss of transparency.
Also, in a preferred embodiment, the inner layer (1) further includes (C) a propylene resin. The propylene resin (C) used in such a case is specified in terms of its melting peak temperature and melt flow rate. By having a melting peak temperature which is at least 6° C. higher than that of propylene resin composition (A), this component is able to confer to the resulting multilayer sheet the ability to prevent appearance defects such as bleedout from arising, to suppress appearance defects such as thickness variation and interfacial roughness, and to suppress a reduction in thickness during heat sealing.
A propylene resin (D) specified in terms of the melting peak temperature is used in propylene resin composition (Y) employed in the outer layer (2) to prevent the multilayer sheet from sticking to the sealing bar during heat sealing and thereby make the multilayer sheet suitable for bag-making.
In a preferred embodiment, the multilayer sheet of the invention may also have an innermost layer (3). That is, the multilayer sheet may be composed of at least three layers which include an innermost layer (3), in order of an outer layer (1), an inner layer (2), and the innermost layer (3). The propylene resin composition (Z) used in the innermost layer (3) preferably has a soluble content at or below 0° C. (S0) of 15 wt % or less, and contains either propylene resin composition (Z1) or propylene resin composition (Z2).
Propylene resin composition (Z1) is specified in terms of the melting peak temperature and density, and preferably is composed primarily of (E) a propylene-α-olefin copolymer obtained with a metallocene catalyst. However, with propylene-α-olefin copolymer (E) alone, the impact resistance is poor. When a blend of (E) is used together with (F) an ethylene-α-olefin copolymer having a specific density, the impact resistance can be conferred. Because the (E) has a sharp molecular weight distribution, both cleanliness owing to the low level of low-molecular-weight components and heat sealability owing to the abrupt rise in the heat sealing strength can be conferred. Because a large amount of crystalline components are also contained, a strong heat seal is possible.
Propylene resin composition (Z2) is composed primarily of (G) a propylene resin composition. Propylene resin composition (G) is a propylene-ethylene copolymer composition containing (G1) a propylene-α-olefin random copolymer composition having a melting peak temperature in a specific range, and (G2) a propylene-ethylene random copolymer component which, owing to its specific ethylene content, has a high flexibility and keeps the transparency from worsening. By using this propylene resin composition (Z2), the resulting multilayer sheet can be conferred with a good balance of transparency and flexibility.
Ethylene-α-olefin copolymer (H) used in propylene resin composition (Z2) is specified in terms of density, and can confer flexibility without a loss of transparency to the resulting multilayer sheet.
In addition, propylene resin (I) used in the propylene resin composition (Z2) is specified in terms of the melting peak temperature, and can confer to the resulting multilayer sheet a heat resistance that prevents the innermost layers (3) from thermally fusing to one another at the time of heat treatment.
Therefore, the multilayer propylene resin sheet of the invention, and the heat-treatable packaging material obtained using such a multilayer sheet have an excellent transparency, flexibility, impact resistance and cleanliness, a reduced thickness fluctuation during lamination, suppress appearance defects such as interfacial roughness, and moreover mitigate the reduction in thickness during fabrication. This combination of properties make them highly suitable for use as retortable packaging materials and as IV bags.


DESCRIPTION OF EMBODIMENTS
The multilayer propylene resin sheet of the invention is composed of at least two layers: (1) an inner layer in which a (X) a propylene resin composition is used, and (2) an outer layer in which (Y) a propylene resin composition is used. The invention also provides a heat-treatable packaging material obtained using such a multilayer sheet. In a preferred embodiment, the multilayer sheet of the invention also has (3) an innermost layer, and thus is a multilayer sheet of at least three layers which is composed of, in order, (1) an outer layer, (2) an inner layer, and (3) an innermost layer.
The components making up each layer of the multilayer propylene resin sheet of the invention, the production of the components in each layer, and the heat-treatable packing material are described below in detail.
[I] Components Making Up Each Layer of Multilayer Propylene Resin Sheet
1. Inner Layer (1)
The inner layer (1) is formed of (X) a propylene resin composition containing the propylene resin composition (A) and the ethylene-α-olefin copolymer (B) described below. It is preferable for propylene resin composition (X) to additionally include (C) a propylene resin.
(1) Propylene Resin Composition (A)
(1-1) Properties of Propylene Resin Composition (A)
The propylene resin composition (A) (also referred to below as “component (A)”) which is used as a component of propylene resin composition (X) making up the inner layer (1) of the multilayer propylene resin sheet of the invention is required to have a high transparency, flexibility and impact resistance. To fulfill these requirements at a high level, component (A) must satisfy conditions (A-i) to (A-iii) below.
(A) Basic Conditions
Component (A) used in the invention is a propylene resin composition (A) which satisfies the following conditions (A-i) to (A-iii):
(A-i) includes from 30 to 70 wt % of (A1) a propylene-α-olefin random copolymer component having a melting peak temperature (Tm (A1)) of from 125 to 145° C., and from 70 to 30 wt % of (A2) a propylene-ethylene random copolymer component having an ethylene content (E [A2]) of from 7 to 17 wt % and obtained using a metallocene catalyst;
(A-ii) has a melt flow rate (MFR (A), at 230° C. and 2.16 kg) in a range of from 0.5 to 20 g/10 min; and
(A-iii) has, in a temperature-loss tangent (tan δ) curve obtained by dynamic mechanical analysis (DMA), a single peak at or below 0° C. on the tan δ curve representing the glass transition observed in a range of from −60 to 20° C.
The above conditions are described in detail in (i) to (v) below.
(i) Melting Peak Temperature (Tm (A1)) of Propylene-α-Olefin
Random Copolymer Component (A1)
Component (A1) is a component which determines the crystallinity in the propylene resin composition (component (A)). To increase the heat resistance of component (A), it is necessary for the melting peak temperature Tm (A1) (also referred to below as “Tm (A1)”) of component (A1) to be high. However, if Tm (A1) is too high, this interferes with the flexibility and transparency. On the other hand, if Tm (A1) is too low, the heat resistance worsens, as a result of which a reduction in the thickness of the sheet may proceed during heat sealing. Tm (A1) must be in a range of from 125 to 145° C., and is preferably from 125 to 138° C., and more preferably from 128 to 135° C. Component (A1) is preferably produced using a metallocene catalyst.
Here, the melting peak temperature Tm is a value determined with a differential scanning calorimeter (DSC, available from Seiko Instruments, Inc.). Specifically, it is the value determined as the melting peak temperature when a 5.0 mg sample that has been collected and held at 200° C. for 5 minutes is subsequently crystallized by lowering the temperature to 40° C. at a ramp-down rate of 10° C./min, then melted at a ramp-up rate of 10° C./min.
(ii) Ratio of Component (A1) in Component (A)
Although component (A1) confers heat resistance on component (A), if the ratio W(A1) of component (A1) in component (A) is too high, it will not be possible to exhibit a sufficient flexibility, impact resistance and transparency. Hence, it is essential for the ratio of component (A1) to be 70 wt % or less.
On the other hand, when the ratio of component (A1) is too low, even if Tm (A1) is sufficient, the heat resistance decreases, as a result of which deformation may occur in a sterilization step. Hence, the ratio of component (A1) must be at least 30 wt %. The preferred range in W(A1) is from 50 to 60 wt %.
(iii) Ethylene Content E[A2] in Propylene-Ethylene Random Copolymer Component (A2)
Component (A2) is a required component for increasing the flexibility, impact resistance and transparency of component (A), and is obtained using a metallocene catalyst. Generally, in propylene-ethylene random copolymers, when the ethylene content rises, the crystallinity decreases and the flexibility-increasing effect becomes larger. Hence, it is critical for the ethylene content E[A2] in component (A2) (sometimes referred to below as “E [A2]”) to be at least 7 wt %. When E[A2] is less than 7 wt %, a sufficient flexibility cannot be exhibited. E[A2] is preferably at least 8 wt %, and more preferably at least 10 wt %.
On the other hand, if E[A2] is increased excessively in order to lower the crystallinity of component (A2), the compatibility of component (A1) and component (A2) decreases and component (A2) forms domains rather than compatibilizing with component (A1). In such a phase-separated structure, if the matrix and the domains have differing refractive indices, the transparency abruptly decreases. Hence, the ratio E[A2] of component (A2) in component (A) used in this invention must be not more than 17 wt %, and is preferably not more than 14 wt %, and more preferably not more than 12 wt %.
(iv) Ratio of Component (A2) in Component (A)
If the ratio W(A2) of component (A2) in component (A) is too high, the heat resistance will decrease. Hence, it is critical for W(A2) to be held to not more than 70 wt %.
On the other hand, if W(A2) is too low, flexibility and impact resistance-improving effects cannot be obtained. Hence, it is critical for W(A2) to be at least 30 wt %. The preferred range for W(A2) is from 50 to 40 wt %.
Here, W(A1) and W(A2) are values determined by temperature rising elution fractionation (TREF), and the α-olefin content E[A1] and the ethylene content E[A2] are values obtained by nuclear magnetic resonance (NMR).
The following specific methods are used.
(a) Specifying W(A1) and W(A2) by Temperature Rising Elution Fractionation (TREF)
Techniques for evaluating the distribution in the crystallinity of, for example, propylene-ethylene random copolymers by the temperature rising elution fractionation (TREF) are familiar to those skilled in the art. For example, detailed measurement methods are described in the following literature.

    G. Glockner: J. Appl. Polym. Sci.: Appl. Polym, Symp., 45, 1-(1990)
    L. Wild: Adv. Polym, Sci., 98, 1-47 (1990)
    J. B. P. Soares, A. E. Hamielec: Polymer, 36, No. 8, 1639-1654 (1995)


In component (A) used in the invention, there is a large difference between the respective crystallinities of component (A1) and component (A2). Moreover, when both components are produced using a metallocene catalyst, the respective crystallinity distributions become narrow, so that intermediate components therebetween become very scarce, thus enabling both to be precisely fractionated using TREF.
In the invention, measurement is carried out specifically as follows.
A sample is dissolved in o-dichlorobenzene (containing 0.5 mg/mL of BHT) at 140° C. to form a solution. The solution is introduced into a 140° C. TREF column, following which it is cooled to 100° C. at a ramp-down rate of 8° C./min, then cooled to −15° C. at a ramp-down rate of 4° C./min, and held for 60 minutes. Next, −15° C. o-dichlorobenzene (containing 0.5 mg/mL of BHT) solvent is poured into the column at a rate of 1 mL/min, and the component dissolved in the −15° C. o-dichlorobenzene within the TREF column is eluted for 10 minutes, following which the temperature of the column is raised linearly to 140° C. at a ramp-up rate of 100° C./hour, thereby giving an elution curve.
In the resulting elution curve, component (A1) and component (A2), due to the difference in crystallinity therebetween, exhibit elution peaks at the respective temperatures T(A1) and T(A2). Because this difference is sufficiently large, substantial separation is possible at an intermediate temperature T(A3) (={T(A1)+T(A2)}/2).
Here, defining the cumulative amount of component eluted up to T(A3) as W(A2) wt % and the cumulative amount of component eluted at more than T(A3) as W(A1) wt %, W(A2) corresponds to the amount of component (A2) and the cumulative amount W(A1) of component eluted at more than T(A3) corresponds to the amount of component (A1) having a relatively high crystallinity.
The equipment and specifications used in measurement are shown below.
(Tref Apparatus)
TREF column: 4.3 mm diameter×150 mm stainless steel column
Column packing: 100 μm surface-deactivated glass beads
Heating method: aluminum heating block
Cooling method: Peltier element (water cooling was used to cool the Peltier element)
Temperature distribution: ±0.5° C.
Temperature regulator: KP 1000 (Chino Corporation) programmable digital temperature controller (valve open)
Heating system: air bath oven
Temperature at time of measurement: 140° C.
Temperature distribution: ±1° C.
Valves: 6-way valve, 4-way valve
(Sample Injection Apparatus)
Injection method: loop injection method
Injection amount: loop size, 0.1 mL
Injection port heating method: aluminum heating block
Temperature at time of measurement: 140° C.
(Detector)
Detector: MIRAN 1A (Foxboro) fixed wavelength type infrared detector
Detection wavelength: 3.42 μm
High-temperature flow cell: LC-IR microcell; optical path length, 1.5 mm; window shape, 2×4 mm oval; synthetic sapphire window
Temperature at time of measurement: 140° C.
(Pump)
Delivery pump: SSC-3461 pump (Senshu Kagaku)
(Measurement Conditions)
Solvent: o-dichlorobenzene (containing 0.5 mg/mL of BHT)
Sample concentration: 5 mg/mL
Sample injection amount: 0.1 mL
Solvent flow rate: 1 mL/min
(b) Specifying E[A1] and E[A2]
To determine the α-olefin (preferably ethylene) content E[A1] and ethylene content E[A2] of the respective components, the components are separated by temperature rising column fractionation using a preparative fractionation unit, and the ethylene (or α-olefin) contents of the respective components are determined by NMR.
Temperature rising column fractionation refers to a measurement method like that described in, for example, Macromolecules 21, 314-319 (1988). Specifically, the following method was used in this invention.
(c) Temperature Rising Column Fractionation
A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh), and is held at 140° C. Next, 200 mL of an o-dichlorobenzene solution (10 mg/mL) of the sample dissolved at 140° C. is introduced into the column. The column temperature is then cooled to 0° C. at a ramp-down rate of 10° C./hour. After being held at 0° C. for 1 hour, the column temperature is elevated at a ramp-up rate of 10° C./hour to T(A3) (obtained in TREF measurement) and held at that temperature for one hour. The column temperature control precision throughout the series of operations is set to ±1° C.
Next, with the column temperature held at T(A3), the component present within the column and soluble at T(A3) is eluted and recovered by passing through 800 mL of o-dichlorobenzene at T(A3) and a flow rate of 20 mL/min.
Next, the column temperature was raised to 140° C. at a ramp-up rate of 10° C./min and the column was left at rest for 1 hour at 140° C., following which the component insoluble at T(A3) was eluted and recovered by passing through 800 mL of the 140° C. solvent o-dichlorobenzene at a flow rate of 20 mL/min.
The polymer-containing solution obtained by fractionation was concentrated to 20 mL using an evaporator, then precipitated out in a five-fold amount of methanol. The precipitated polymer was recovered by filtration and dried overnight in a vacuum desiccator.
(d) Measurement of Ethylene Content by 13C-NMR
The ethylene contents E[A2] for each of the components (A2) obtained in the above fractionation were determined by analyzing the 13C-NMR spectrum measured under the following conditions by complete proton decoupling.
Apparatus: GSX-400 (JEOL Ltd.) or comparable unit (carbon nuclear resonance frequency of 100 MHz or more)
Solvents: o-dichlorobenzene/heavy benzene=4/1 (v/v)
Concentration: 100 mg/mL
Temperature: 130° C.
Pulse angle: 90°
Pulse interval: 15 seconds
Number of integrations: at least 5,000 times
Spectral assignments may be carried out by referring to, for example, Macromolecules 17, 1950 (1984). The spectral assignments measured according to the above conditions are shown in Table 1. Symbols such as Sαα in the table are in accordance with the method of notation by Carman et al. (Macromolecules 10, 636 (1977). In addition, “P” stands for a methyl carbon, “S” stands for a methylene carbon, and “T” stands for a methyne carbon.








TABLE 1





Chemical shift (ppm)
Assignment







45 to 48
Sαα


37.8 to 37.9
Sαγ


37.4 to 37.5
Sαδ


33.1
Tδδ


30.9
Tβδ


30.6
Sγγ


30.2
Sγδ


29.8
Sδδ


28.7
Tββ


27.4 to 27.6
Sβδ


24.4 to 24.7
Sββ


19.1 to 22.0
P









Below, letting “P” be a propylene unit in a copolymer chain and letting “E” be an ethylene unit, six types of triads (PPP, PPE, EPE, PEP, PEE and EEE) are capable of being present on the chain. As noted in Macromolecules 15, 1150 (1982), the concentrations of these triads and the spectral peak intensities can be connected by means of the following formulas (1) to (6).

[PPP]=k×I(Tββ)  (1)

[PPE]=k×I(Tβδ)  (2)

[EPE]=k×I(Tδδ)  (3)

[PEP]=k×I(Sββ)  (4)

[PEE]=k×I(Sβδ)  (5)

[EEE]=k×{I(Sδδ)/2+I(Sγδ)/4}  (6)

Here, [ ] represents the fraction of the triad. For example, [PPP] represents the fraction of the PPP triad among all the triads.
Therefore,

[PPP]+[PPE]+[EPE]+[PEP]+[PEE]+[EEE]=1  (7)

Also, k is a constant, and I indicates the spectral intensity. For example, I(Tββ) stands for the intensity of the peak at 28.7 ppm attributed to Tββ.

By using the above formulas (1) to (7), the fractions of each triad are determined, and the ethylene content is determined from the following formula

Ethylene content (mol %)=([PEP]+[PEE]+[EEE])×100.

The propylene-ethylene random copolymer of the invention includes a small amount of propylene heterobonds (2,1-bonds and/or 1,3-bonds), as a result of which the small peaks shown in Table 2 arise.








TABLE 2





Chemical shift (ppm)
Assignment







42.0
Sαα


38.2
Tαγ


37.1
Sαδ


34.1 to 35.6
Sαβ


33.7
Tγγ


33.3
Tγδ


30.8 to 31.2
Tβγ


30.5
Tβδ


30.3
Sαβ


27.3
Sβγ









In order to determine the correct ethylene content, there is a need to also take into account and include in the calculations the peaks attributable to such heterobonds, although the complete separation and identification of peaks attributable to heterobonds is difficult. Moreover, because the amount of heterobonds is small, the ethylene content in the invention shall be determined using formulas (1) to (7) in the same way as the analysis of copolymer produced with a Ziegler-Natta catalyst and containing substantially no heterobonds.
The conversion of ethylene content from mol % to wt % is carried out using the following formula.

Ethylene content (wt %)=(28×X/100)/{28×X/100+42×(1−X/100)}×100

(where X is the ethylene content expressed in mol %).

(v) Method of Preparing Component (A)

In a preferred method of preparing the component (A) used in the invention, successive polymerization is carried out using a metallocene catalyst. In a first step, from 30 to 70 wt %, and more preferably from 50 to 60 wt %, of the propylene-α-olefin random copolymer component (A1) having a melting peak temperature Tm(A1) in DSC measurement within a range of from 125 to 145° C., and more preferably from 125 to 138° C., is obtained. In a second step, from 70 to 30 wt %, and more preferably from 50 to 40 wt %, of the propylene-ethylene random copolymer component (A2) having an ethylene content E[A2] of from 7 to 17%, and more preferably from 8 to 14 wt %, is obtained. The specific method employed for the successive polymerization, using a metallocene catalyst, of component (A1) in a first step and component (A2) in a second step may be the method described in, for example, Japanese Patent Application Laid-open No. 2005-132979, the entire contents of which are incorporated herein by reference.
Alternatively, component (A) need not be a successive polymerization product, and may instead be a blend of a propylene-α-olefin copolymer (A1) which satisfies the above melting peak temperature Tm(A1) and a propylene-ethylene random copolymer (A2) which satisfies the ethylene content E[A2].
(A-ii) Melt Flow Rate of Component (A) (MFR (A))
The melt flow rate MFR (at 230° C. and 2.16 kg) of component (A) used in the invention (which melt flow rate is also referred to below as “MFR (A)”) must fall within a range of from 0.5 to 20 g/10 min.
MFR (A) may be determined by the ratio of the respective MFRs for component (A1) and component (A2) (also referred to below as “MFR (A1)” and “MFR (A2)”), although in this invention, so long as MFR (A) is in a range of from 0.5 to 20 g/10 min, MFR (A1) and MFR (A2) may be any values within ranges that do not compromise the objects of the invention. However, because there is a risk of appearance defects arising in cases where the MFR difference between the two is very large, it is desirable for both MFR (A1) and MFR (A2) to be within a range of from 4 to 10 g/10 min.
If MFR (A) is too low, resistance to turning of the extruder screw becomes large, which not only increases the motor load and the forward end pressure, but also roughens the sheet surface, worsening the appearance. As a result, MFR (A) is preferably at least 4 g/10 min, and more preferably at least 5 g/10 min.
On the other hand, if the MFR (A) is too high, sheet formation tends to become unstable, making a uniform sheet difficult to obtain. Therefore, the MFR is preferably not more than 10 g/10 min, and more preferably not more than 8 g/10 min.
Here, MFR is the value measured in general accordance with JIS K7210.
(A-iii) Temperature-Loss Tangent (tan δ) Curve Peak
It is critical that the propylene resin composition (component (A)) used in the invention have, in a temperature-loss tangent (tan δ) curve obtained by dynamic mechanical analysis (DMA), a single peak at or below 0° C. on the tan δ curve representing the glass transition observed in a range of from −60 to 20° C.
In cases where component (A) assumes a phase-separated structure, because the glass transition temperature of the non-crystalline portion included in component (A1) and the glass transition temperature of the non-crystalline portion included in component (A2) each differ, there are a plurality of peaks. In such a case, the transparency worsens markedly.
Generally, the glass transition temperature in a propylene-ethylene random copolymer is observed in a range of from −60 to 20°; in the tan δ curve obtained by dynamic mechanical analysis within this range, it can be determined whether component (A) has assumed a phase-separated structure. Avoidance of a phase-separated structure which affects the sheet transparency is brought about by having a single peak at or below 0° C.
Here, dynamic mechanical analysis (DMA) is carried out by imparting sinusoidal strain of a specific frequency to a strip-shaped test specimen, and detecting the stress that arises. A frequency of 1 Hz is used. The measurement temperature is raised in a stepwise fashion from −60° C., and the test is carried out until the sample melts and measurement becomes impossible. It is recommended that the size of the strain be from about 0.1 to about 0.5%. The storage modulus G′ and the loss modulus G′′ are determined by known methods from the resulting stress, and the loss tangent (=loss modulus/storage modulus) defined by this ratio is plotted versus temperature, yielding a sharp peak in the temperature region at or below 0° C. Generally, a peak in the tan δ curve at or below 0° C. is observed with the glass transition of amorphous regions. In the present invention, this peak temperature is defined as the glass transition temperature Tg (° C.).
(1-2) Proportion of Component (A) in Inner Layer (1)
It is critical that the proportion of the inner layer accounted for by the propylene resin composition (component (A)) be in a range of from 60 to 90 wt %, and preferably from 65 to 85 wt %, per 100 wt % of the combined weight of component (A) and component (B).
If the content of component (A) is too low, a good flexibility and transparency cannot be obtained. On the other hand, if the content of component (A) is too high, a marked reduction in thickness during fabrication such as heat sealing may arise.
(2) Ethylene-α-Olefin Copolymer (B)
(2-1) Properties of Component (B)
The ethylene-α-olefin copolymer (B) (also referred to below as “component (B)”) which is used as a component of the propylene resin composition (X) making up the inner layer (1) of the multilayer propylene resin sheet of the invention is a copolymer obtained by the copolymerization of ethylene with an α-olefin having preferably from 3 to 20 carbons. Preferred examples of the α-olefin include those having from 3 to 20 carbons, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-heptene. Component (B) is a component which acts to increase the transparency and flexibility of propylene resin composition (x), and must satisfy conditions (B-i) and (B-ii) below.
The multilayer propylene resin sheet of the invention is required to have flexibility and transparency. With regard to transparency, in cases where the refractive index of component (B) differs considerably from that of component (A), the transparency of the resulting sheet worsens. Hence, it is also important to have the refractive indices agree. Control of the refractive index by density is possible. In the invention, to obtain the required transparency, it is important for the density to be set within a specific range.
The addition of component (B) is also essential for further strengthening the low-temperature impact resistance of component (A).
(B-i) Density
Component (B) used in the invention must have a density in a range of from 0.860 to 0.910 g/cm3.
If the density is too low, the refractive index difference will become large, worsening the transparency. Hence, at a density below 0.860 g/cm3, the transparency required in this invention cannot be ensured.
On the other hand, if the density is too high, the crystallinity becomes high, resulting in an inadequate flexibility. Hence, the density must be no higher than 0.910 g/cm3, and is preferably not more than 0.905 g/cm3, and even more preferably not more than 0.900 g/cm3.
Here, the density is a value measured in general accordance with JIS K7112.
(B-ii) Melt Flow Rate of Component (B) (MFR (B))
It is critical for the inner layer (1) in the invention to have suitable flow properties in order to ensure good sheet formability.
Therefore, if the melt flow rate MFR of component (B) (at 190° C. and 2.16 kg) (also referred to below as “MFR (B)”) is too low, the flow properties will be inadequate, and problems such as poor dispersion will occur, giving rise to a decrease in transparency. Hence, it is critical for MFR (B) to be at least 0.5 g/10 min, preferably at least 1.5 g/10 min, and more preferably at least 2 g/10 min.
On the other hand, if MFR (B) is too high, sheet formation is unstable and film thickness variations arise. Hence, the MFR (B) is not more than 30 g/10 min, preferably not more than 10 g/10 min, and most preferably not more than 9 g/10 min.
The MFR is a value measured in general accordance with JIS K7210.
(2-2) Method of Producing Component (B)
Component (B) used in this invention must be set to a low density in order to make the refractive index difference with component (A) small. Moreover, to suppress tackiness and bleedout, it is desirable for the crystallinity and molecular weight distributions to be narrow. Hence, in the production of component (B), it is desirable to use a metallocene catalyst which is capable of providing narrow crystallinity and molecular weight distributions.
The catalyst and the polymerization process are described below.
(i) Metallocene Catalyst
Various types of known catalysts used to polymerize ethylene-α-olefin copolymers may be employed as the metallocene catalyst.
Illustrative examples include the metallocene catalysts mentioned in, e.g., Japanese Patent Application Laid-open Nos. S58-19309, S59-95292, S60-35006 and H3-163088.
(ii) Polymerization Process
Illustrative examples of polymerization processes include the following carried out in the presence of such catalysts: slurry processes, vapor phase fluidized bed processes, solution processes, and high-pressure bulk polymerization processes at a pressure of at least 200 kg/cm2 and a polymerization temperature of at least 100° C. An example of a preferred production method is high-pressure bulk polymerization.
The component (B) used may be suitably selected from among commercially available metallocene-based polyethylenes. Examples of commercial products include AFFINITY and ENGAGE (available under these trade names from DuPont-Dow), KERNEL (available under this trade name from Japan Polyethylene Corporation), and EXACT (available under this trade name from Exxon Mobil).
In using these, a grade which satisfies the density and MFR that are essential features of the invention should be suitably selected.
(2-3) Ratio of Component (B) in Inner Layer Composition
It is essential that the ratio of component (B) in the inner layer composition be in a range of from 10 to 40 wt % per 100 wt % of component (A) and component (B) combined.
If the content of component (B) is too low, the low-temperature impact resistance conferred will be inadequate. On the other hand, if the content of component (B) is too high, thickness irregularities will arise in the sheet, making it impossible to obtain a sheet having a good appearance.
Hence, it is critical for component (B) to account for a proportion of the inner layer composition in a range of from 10 to 40 wt %. At less than 10 wt %, the flexibility conferred is inadequate; at more than 40 wt %, the sheet formability is inadequate, making use impossible. The preferred content of component (B), per 100 wt % of component (A) and component (B) combined, is from 15 to 35 wt %.
(3) Propylene Resin (C)
(3-1) Properties of Component (C)
Propylene resin (C), which may be advantageously used as one component of propylene resin composition (X) in the inner layer of the invention, is employed as a component which confers formability and suppresses appearance defects and a reduction in thickness.
Component (A), which is used as the primary component of the propylene resin composition (X) of the inner layer, is very effective for imparting a high flexibility and transparency to a laminated sheet. However, because component (A1) is a relatively low-melting component, drawbacks include the presence of little high-crystallinity component and a reduction in thickness during heat sealing. This is especially pronounced because product obtained using a metallocene catalyst has a sharp crystallinity distribution.
When attempts are thus made to broaden the crystallinity distribution of component (A) and thereby achieve a relative increase in high-crystallinity components, the low-crystallinity components also inevitably increase. As a result, these low-crystallinity components bleed out to the surface of the laminated sheet, giving rising to stickiness and appearance defects, which makes the sheet unfit for applications requiring transparency.
By adding a specific amount of component (C) to component (A) having little high-crystallinity component, the high-crystallinity components and the high-molecular-weight components can be increased without increasing the low-crystallinity components and the low-molecular-weight components. It is possible in this way to suppress appearance defects such as thickness variations and interfacial roughness, and to suppress a reduction in thickness during heat sealing, without giving rise to appearance defects such as bleedout.
Component (C) is preferably a propylene resin which satisfies conditions (C-i) and (C-ii) below, and more preferably a propylene resin composition composed of propylene (co)polymer component (C1) and a propylene-ethylene random copolymer (C2).
(C-i) Melting Peak Temperature Tm (C)
Component (C) is preferably a propylene resin having a melting peak temperature (Tm (C)) which is at least 6° C. higher than the melting peak temperature (Tm (A1)) of propylene-α-olefin random copolymer component (A1). By having the melting peak temperature be at least 6° C. higher, the resulting multilayer sheet can be conferred with the ability to suppress a reduction in thickness during heat sealing without causing appearance defects such as bleedout. Tm (C) is more preferably at least 10° C. higher, and even more preferably at least 20° C. higher, than Tm (A1).
The melting peak temperature Tm (C) of component (C) is preferably in a range of from 150 to 170° C., and more preferably from 155 to 167° C. If Tm (C) is less than 150° C., the high crystallinity component is inadequate, as a result of which a sufficient decrease in flow and a reduction in thickness-suppressing effect may not be achievable. At Tm (C) in excess of 170° C., industrial production is difficult. Tm (C) is more preferably from 155 to 165° C.
(C-ii) Melt Flow Rate MFR(C)
Also, in order to ensure sheet formability, it is important for component (C) to have suitable flow properties. The melt flow rate MFR (at 230° C. and 2.16 kg loading) (also referred to below as “MFR(C)”), which is a measure of the flow properties, is preferably in a range of from 0.5 to 30 g/10 min, with the upper limit being more preferably 15 g/10 min, and even more preferably 12 g/10 min. It is especially preferable for the MFR range to be from 2.5 to 12 g/10 min.
When MFR(C) is less than 0.5 g/10 min, dispersion worsens, which tends to give rise to the appearance defects known as gels and fisheyes. On the other hand, at more than 30 g/10 min, the physical property-related drawback of a decrease in flexibility tends to arise.
Here, MFR is a value measured in general accordance with JIS K7210.
(3-2) Composition of Propylene (Co)polymer Component (C1) and Propylene-Ethylene Random Copolymer (C2)
Component (C) is more preferably a composition of a propylene (co)polymer component (C1) which satisfies condition (C1-i) below and a propylene-ethylene random copolymer (C2) which satisfies condition (C2-i) below, and is, moreover, preferably a propylene resin (C) which satisfies condition (C-iii) below.
Here, component (C1) is a polypropylene component, and is a high-crystallinity component. Because Component (C1) has a higher melting peak temperature than component (A), it is in a crystalline state (solid state) at the temperature at which component (A) melts and begins to undergo melt flow, and thus acts to suppress the melt flow of component (A), making it an effective component for suppressing a reduction in thickness during heat sealing. Hence, component (C1) must be a polypropylene or propylene-ethylene copolymer composed of a copolymer having a higher crystallinity than component (A). However, by adding component (C1), the crystallinity of the inner layer as a whole increases, as a result of which a loss of flexibility occurs. By adding component (C2), which is a propylene-ethylene random copolymer and a low-crystallinity component, flexibility is conferred, which is effective for flexibilizing the laminated sheet as a whole. That is, component (C2) is effective for suppressing increased stiffness due to the addition of the high-crystallinity component (C1).
(C1-i) Ratios of Components (C1) and (C2) in Component (C)
Component (C) may be a mixture of propylene (co)polymer component (C1) in a component ratio (also referred to below as “W(C1)”) of from 40 to 70 wt % and ethylene-propylene copolymer component (C2) in a component ratio (also referred to below as “W(C2)”) of from 30 to 60 wt %. From the standpoint of uniformly and finely dispersing component (C2), component (C) is preferably obtained by multistage polymerization.
Because component (C2) is a low-crystallinity component, when W(C2) is too high, a reduction in thickness-suppressing effect is difficult to obtain, and when W(C2) is too low, a loss of flexibility occurs. Here, W(C1) and W(C2) can be determined from the material balance.
(C2-i) Ethylene Content (E [C2])
Component (C2) is a flexibility-imparting component essential for minimizing the increase in stiffness due to the addition of the high-crystallinity component (C1). Hence, because component (C2) is controlled by the ethylene content (also referred to below as “E [C2]”), it is preferable to set the ethylene content E [C2] to from 15 to 40 wt %.
At an ethylene content E [C2] below 15 wt %, because this is a region of compatibility with propylene, a sufficient flexibility-imparting effect at a low amount of addition is difficult to obtain. On the other hand, at an ethylene content in excess of 40 wt %, the ethylene content E [C2] is too high, which tends to worsen the transparency of the inner layer (1) as a whole.
Here, E [C2] is a value determined by the above-described 13C-NMR spectroscopy.
(C-iii) Intrinsic Viscosity Ratio of Components (C1) and (C2) in Component (C)
Component (C2) in component (C) has an intrinsic viscosity [η]C2 (also referred to below as “[η]C2”), as measured in 135° C. tetralin, of preferably from 1.7 to 6.5 dL/g, and more preferably from 1.7 to 4.0 dL/g, and has an intrinsic viscosity ratio [η]C2/[η]C1 with the intrinsic viscosity [η]C1 (also referred to below as “[η]C1”) of component (C1) measured under the same conditions in a range of preferably from 0.6 to 1.2, and more preferably from 0.6 to 1.1.
[η]C1 influences in particular the processing properties such as, in particular, the sheet formability, and [η]C2/[η]C1 influences the dispersibility of component (C2) in component (C1). If [η]C1 is too large, the sheet formability tends to worsen, leading to production problems. If [η]C2 is too small, a sufficient flexibility is difficult to obtain, and if [η]C2 is too large, the transparency tends to worsen.
In cases where component (C) is obtained by consecutively producing components (C1) and (C2), because it is impossible to directly measure [η]C2 in component (C), this is determined as follows from the directly measurable [η]C1 and the intrinsic viscosity [η]C of component (C) (also referred to below as “[η]C”), and also from W(C2).

[η]C2={[η]C−(1−W(C2)/100)[η]C1}/(W(C2)/100)

Here, “consecutively producing” refers to producing component (C1) in the subsequently described first stage (first step), then successively producing component (C2) in a second stage (second step).
In the propylene resin (C) used in this invention, the product of the weight ratio (W(C2)/W(C1)) of W(C1) and W(C2) with the intrinsic viscosity ratio of the two components ([η]C2/[η]C1), which product is expressed as ([η]C2/[η]C2)×(W(C1)/W(C2)), is preferably in a range of from 0.2 to 4.5, and more preferably from 0.6 to 4.0.
The product of the weight ratio and the intrinsic viscosity ratio indicates the dispersion state of component (C2) dispersed in component (C1). Having the product fall within the above range is an essential condition for indicating a specific dispersed structure wherein domains of component (C2) are present in an elongated state as isolated domains in the machine direction during fabrication or are connected to other domains in at least one place. Having this value be in the above-mentioned range is desirable because the transparency and flexibility of the resulting sheet are good.
(3-3) Method of Producing Component (C)
The propylene resin (C) may be produced by any method, so long as the above properties are satisfied. In cases where a composition of (C1) a propylene (co)polymer component and (C2) a propylene-ethylene random copolymer is produced, the propylene resin (C) may be produced using an apparatus that mixes a propylene (co)polymer (C1) and a propylene-ethylene random copolymer (C2) which have been separately produced, or the propylene resin (C) may be consecutively produced by, in a first step, producing a propylene (co)polymer (C1) and subsequently, in a second step, producing a propylene-ethylene random copolymer (C2) in the presence of the propylene (co)polymer (C1).
Preferred examples of specific methods of production are described in Japanese Patent Application Laid-open Nos. 2006-35516 and 2001-172454, the entire contents of which are incorporated herein by reference.
It is also possible to suitably select and use component (C) from among commercially available products. Illustrative examples of commercially available products include NOVATEC PP (available under this trade name from Japan Polypropylene Corporation), NEWCON (available under this trade name from Japan Polypropylene Corporation), and ZELAS (available under this trade name from Mitsubishi Chemical Corporation). In using these, a grade which satisfies the melting peak temperature, MFR and intrinsic viscosity ratio that are conditions of the invention should be suitably selected.
(3-4) Proportion of Component (C) in Inner Layer Components
The proportion of component (C) in the inner layer (1) is preferably in a range of from 1 to 25 wt % per 100 wt % of above components (A), (B) and (C) combined. Because component (C1) in component (C) has a higher melting peak temperature than component (A), it retains a crystalline state even at the temperature at which component (A) melts, thus suppressing flow by component (A). Component (C2) in component (C) has a flexibility-imparting effect for minimizing the increase in stiffness due to the addition of component (C1), which is a high-crystallinity component.
When the amount of component (C) is too low, the high-crystallinity component will be inadequate and it will not be possible to obtain a sufficient reduction in thickness-suppressing effect. Hence, this amount is preferably at least 1 wt %, and more preferably at least 5 wt %. Conversely, when the amount of component (C) is too high, decreases in physical properties such as flexibility and transparency tend to become conspicuous, making it difficult to satisfy the quality required of the inventive resin composition. Hence, this amount is preferably not more than 25 wt %, and more preferably not more than 20 wt %.
(3-5) Proportions of Components (A) and (B) When Component (C) is Included in Inner Layer Components
The proportions of components (A) and (B) when component (C) is included in the inner layer components are as follows. The ratio of component (A) is preferably from 45 to 89 wt %, more preferably from 45 to 85 wt %, and most preferably from 50 to 80 wt %, per 100 wt % of component (A) to (C) combined. The ratio of component (B) is preferably from 15 to 25 wt % per 100 wt % of components (A) to (C) combined.
2. Outer Layer (2)
The outer layer (2) of the multilayer sheet of the invention is formed of a propylene resin composition (Y).
(1) Properties of Propylene Resin Composition (Y)
It is essential that the propylene resin composition (Y) (also referred to below as “component (Y)”) used as the outer layer (2) of the multilayer propylene resin sheet of the invention have an excellent transparency, flexibility, heat resistance and impact resistance. To obtain a transparency and flexibility as a multilayer sheet, not only the inner layer (1), but also the outer layer (2) must be made flexible and transparent. Moreover, the outer layer (2) must also have heat resistance, in addition to which it is necessary that it not deform even when subjected to heat treatment such as sterilization, and that it not stick to the heat sealing bar in heat-sealing during fabrication. Also, it is essential that the outer layer (2) has a good impact resistance as well so as to suppress notch (failure starting point) formation in bag drop tests following fabrication into heat-treatable packaging bags.
To satisfy these requirements at a high level, it is essential that component (Y) be a propylene resin (D) (also referred to below as “component (D)”) which satisfies condition (D-i) below.
It is preferable, moreover, for component Y to be a composition of a propylene (co)polymer component (D1) (also referred to below as “component (D1)”) which satisfies conditions (D-ii) and (D1-i) below, and a propylene-ethylene random copolymer (D2) (also referred to below as “component (D2)”) which satisfies conditions (D2-i) to (D2-iii) below.
Propylene resin (D) itself has a good impact resistance, although an ethylene-α-olefin copolymer (D3) (also referred to below as “component (D3)”) may also be added to provide impact resistance at low temperatures of 0 to 5° C.
(D-i) Melting Peak Temperature Tm (D)
Component (D) has a melting peak temperature Tm (D) in a range of from 135 to 170° C., preferably from 136 to 165° C., and more preferably from 136 to 163° C.
When Tm (D) is less than 135° C., the heat resistance is inadequate, as a result of which deformation may arise when heat treatment such as sterilization is carried out. At Tm
(D) above 170° C., industrial production is difficult.
(D-ii) Melt Flow Rate MFR (D)
Component (D) must have suitable flow properties in order to obtain a good formability that does not cause interface roughness and surface roughness during lamination and does not give rise to problems such as thickness variations. The melt flow rate MFR (at 230° C. and a load of 2.16 kg) (sometimes referred to below as “MFR (D)”) which is a measure of flowability is in a range of preferably from 4 to 15 g/10 min, and more preferably from 4.5 to 10 g/10 min.
At a MFR (D) of below 4 g/10 min, interfacial roughness and surface roughness tend to arise, as a result of which a sheet having a good appearance may not be obtained. On the other hand, at MFR (D) in excess of 15 g/10 min, thickness variations readily arise, and formability is often difficult.
Here, the MFR is a value measured in general accordance with JIS K7210.
(2) Composition of Propylene (Co)polymer Component (D1) and Propylene-Ethylene Random Copolymer (D2)
Component (D) is preferably a composition of a propylene (co)polymer component (D1) which satisfies condition (D1-i) below and a propylene-ethylene random copolymer (D2) which satisfies conditions (D2-i) to (D2-iii) below.
Here, component (D1) is a propylene component which is a high-crystallinity component. Component (D1) is a heat-resistant component having a higher melting peak temperature than component (D2). When component (D) is composed only of component (D1), it has a high stiffness, resulting in a loss in the flexibility of the multilayer sheet of the invention. Hence, imparting flexibility by adding component (D2), which is a propylene-ethylene random copolymer and a low-crystallinity component, is effective for making the outer layer (2) more flexible. In other words, component (D2) is an effective component for suppressing an increase in stiffness by component (D1), which is a high-crystallinity component.
(D1-i) Ratio of Component (D1) in Component (D)
Component (D) may be a mixture composed of a propylene (co)polymer component (D1) (also referred to below as “component (D1)”) in a component ratio (also referred to below as “W (D1)”) of from 40 to 70 wt % and a propylene-ethylene random copolymer component (D2) (also referred to below as “component (D2)”) in a component ratio (also referred to below as (W (D2)”) of from 30 to 60 wt %. However, from the standpoint of uniformly and finely dispersing component (D2), component (D) is preferably obtained by multistage polymerization.
Because component (D2) is a low-crystallinity component, when W(D2) is too high, heat resistance is difficult to obtain, and when W(D2) is too low, sufficient flexibility is not imparted.
Here, W(D1) and W(D2) can be determined from the material balance.
(D2-i) Ethylene Content (E [D2])
Component (D2) is a flexibility-imparting component essential for minimizing the increase in stiffness due to the addition of component (D1), which is a high-crystallinity component. Hence, because component (D2) is controlled by the ethylene content (also referred to below as “E [D2]”), it is preferable to set the ethylene content E [D2] to from 15 to 40 wt %.
At an ethylene content below 15 wt %, because this is a region of compatibility with propylene, a sufficient flexibility-imparting effect is difficult to obtain. On the other hand, at an ethylene content in excess of 40 wt %, the ethylene content E is too high, which tends to worsen the transparency of the inner layer (1) as a whole.
Here, E [D2] is a value determined by the above-described 13C-NMR spectroscopy.
(D2-ii) Intrinsic Viscosity
Component (D2) in component (D) has an intrinsic viscosity [η] D2 (also referred to below as “[η]D2”), as measured in 135° C. tetralin, of preferably from 1.7 to 6.5 dL/g, and more preferably from 1.7 to 4.0 dL/g, and has an intrinsic viscosity ratio [η]D2/[η]D1 with the intrinsic viscosity [η] D1 (also referred to below as “[η] D1”) of component (D1) measured under the same conditions in a range of preferably from 0.6 to 1.2, and more preferably from 0.6 to 1.1.
[η]D2 influences in particular the processing properties such as, in particular, the sheet formability, and [η]D2/[η]D1 influences the dispersibility of component (D2) in component (D1). If [η]D2 is too large, the sheet formability worsens, leading to production problems. If [η]D2 is too small, a sufficient flexibility cannot be obtained, and if [η]D2 is too large, the transparency worsens.
In cases where component (D) is obtained by consecutively producing components (D1) and (D, because it is impossible to directly measure [η]D2 in component (D), this is determined as follows from the directly measurable [η]D1 and the intrinsic viscosity [η]D of component (D) (also referred to below as “[η]D”), and also from W(D2).

[η]D2={[η]D−(1−W(D2)/100) [η]D1}/(W(D2)/100)

Here, “consecutively producing” refers to producing component (D1) in the subsequently described first stage (first step), then successively producing component (D2) in a second stage (second step).
(D2-iii) Product of Weight Ratio and Intrinsic Viscosity Ratio of Components (D1) and (D2)
In the propylene resin composition (D) used in this invention, the product of the weight ratio (W(D2)/W(D1)) of W(D1) and W(D2) with the intrinsic viscosity ratio of the two components ([η]D2/[η]D1), which product is expressed as ([η]D2/[η]D2)×(W(D1)/W(D2)), is preferably in a range of from 0.2 to 4.5, and more preferably from 0.6 to 4.0.
The product of the weight ratio and the intrinsic viscosity ratio indicates the dispersion state of component (D2) dispersed in component (D1). Having the product fall within the above range is a condition for indicating a specific dispersed structure wherein domains of component (D2) are present in an elongated state as isolated domains in the machine direction during fabrication or are connected to other domains in at least one place. Having this value be in the above-mentioned range is desirable because the transparency and flexibility of the resulting sheet are good.
(3) Method of Producing Component (D)
The propylene resin (D) used in the invention may be produced by any method, so long as the above properties are satisfied. In cases where a composition of a propylene (co)polymer component (D1) and a propylene-ethylene random copolymer (D2) is produced as propylene resin (D), this may be done using an apparatus which mixes a propylene (co)polymer (D1) and a propylene-ethylene random copolymer (D2) which have been separately produced, or the propylene resin (D) may be consecutively produced by producing first a propylene (co)polymer (D1) and subsequently, producing a propylene-ethylene random copolymer (D2) in the presence of the propylene (co)polymer (D1). Preferred examples of specific methods of production are described in Japanese Patent Application Laid-open Nos. 2006-35516 and 2001-172454, the entire contents of which are incorporated herein by reference.
It is also possible to suitably select and use component (D) from among commercially available products. Illustrative examples of commercially available products include NOVATEC PP (available under this trade name from Japan Polypropylene Corporation), NEWCON (available under this trade name from Japan Polypropylene Corporation), and ZELAS (available under this trade name from Mitsubishi Chemical Corporation). In using these, a grade which satisfies the melting peak temperature, MFR and intrinsic viscosity ratio that are conditions of the invention should be suitably selected.
(4) Ethylene-α-Olefin Copolymer (D3)
The propylene resin (D) itself has a good impact resistance, although the ethylene-α-olefin copolymer (D3) described below may be added to impart further impact resistance at low temperature of 0 to 5° C.
The ethylene-α-olefin copolymer (D3) which may be used in the outer layer (2) of the multilayer polypropylene resin sheet of the invention is a copolymer obtained by the copolymerization of ethylene with an α-olefin having preferably from 3 to 20 carbons. Preferred examples of the α-olefin include those having from 3 to 20 carbons, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-heptene. Component (D3) is a component which acts to increase the low-temperature impact resistance of propylene resin composition (Y), and preferably satisfies condition (D3-i) below.
(D3-i) Density
Component (D3) which may be advantageously used in the invention has a density in a range of from 0.860 to 0.910 g/cm3. If the density is too low, the refractive index difference will become large, worsening the transparency. Hence, at a density below 0.860 g/cm3, the transparency required in this invention cannot be ensured.
On the other hand, if the density is too high, the crystallinity rises, as a result of which a low-temperature impact resistance is not adequately imparted. Moreover, as in cases where the density is too low, a density which is too high will result in a large refractive index difference, as a result of which the transparency will tend to worsen. The density is more preferably not higher than 0.905 g/cm3, and even more preferably not more than 0.900 g/cm3.
Here, the density is a value measured in general accordance with JIS K7112.
(5) Method of Producing Component (D3)
Component (D3) which may be advantageously used in this invention must be set to a low density in order to make the refractive index difference with component (D) small. Moreover, to suppress tackiness and bleedout, it is desirable for the crystallinity and molecular weight distributions to be narrow. Hence, in the production of component (D3), it is desirable to use a metallocene catalyst which is capable of providing narrow crystallinity and molecular weight distributions.
Various types of known catalysts used to polymerize ethylene-α-olefin copolymers may be employed as the metallocene catalyst. The same catalysts as those mentioned above in connection with ethylene-α-olefin copolymer (B) may be used. Illustrative examples of polymerization processes include the following carried out in the presence of such catalysts: slurry processes, vapor phase fluidized bed processes, solution processes, and high-pressure bulk polymerization processes at a pressure of at least 200 kg/cm2 and a polymerization temperature of at least 100° C. An example of a preferred production method is high-pressure bulk polymerization.
The component (D3) used may be suitably selected from among commercially available metallocene-based polyethylenes. Examples of commercial products include AFFINITY and ENGAGE (available under these trade names from DuPont-Dow), KERNEL (available under this trade name from Japan Polyethylene Corporation, and EXACT (available under this trade name from Exxon Mobil).
In using these, a grade which satisfies the density that is a condition of the invention should be suitably selected.
(6) Component Ratios within Component (Y) in Outer Layer (2) Composition
When component (D3) which may be advantageously used in the invention, is employed, it is preferable for the proportion of the outer layer (2) accounted for by component (D) to be in a range of from 80 to 99 wt %, and it is preferable for the proportion of the outer layer (2) accounted for by component (D3) to be in a range of from 1 to 20 wt %. The content of component (D) is more preferably from 85 to 95 wt %, and the content of component (D3) is more preferably from 5 to 15 wt %.
If the content of component (D) is less than 80 wt %, that is, if the content of component (D3) is 20 wt % or more, the heat resistance may be inadequate and deformation may arise in the heat treatment step. At a component (D) content of at 99 wt % or more, that is, at a component (D3) content of less than 1 wt %, the low temperature impact resistance-imparting effect is inadequate.
3. Innermost Layer (3)
In a preferred embodiment, the multilayer sheet of the invention also has an innermost layer (3). That is, the multilayer sheet is composed of at least three layers which include, in order, an outer layer (1), an inner layer (2) and an innermost layer (3). This innermost layer (3) is preferably formed of the propylene resin composition (Z) described below.
(1) Properties of Propylene Resin Composition (Z)
It is essential for the propylene resin composition (Z) (sometimes referred to below as “component (Z)”) which may be used as the innermost layer (3) of the multilayer sheet to have transparency, flexibility, and a heat resistance which prevents internal fusion. In addition, the innermost layer (3), because it comes into contact with the contents, must also have a cleanliness such as not to contaminate the contents, and must also have a low-temperature heat-sealability that facilitates bag-making.
To satisfy these requirements at a high level, component (Z) is preferably a propylene resin composition having a soluble content at or below 0° C. (S0) of 15 wt % or less, as measured by temperature rising elution fractionation (TREF).
Also, to obtain a high heat-sealing strength, it is preferable to use as the propylene resin composition (Z) either a propylene resin composition (Z1) (sometimes referred to below as “component (Z1)”) composed of (E) a propylene-ethylene random copolymer component and (F) an ethylene-α-olefin copolymer, or a propylene resin composition (Z2) (sometimes referred to below as “component (Z2)”) composed of (G) a propylene resin composition (sometimes referred to below as “component (G)”) to obtain greater flexibility, (H) an ethylene-α-olefin copolymer (sometimes referred to below as “component (H)”) and (I) a propylene resin (sometimes referred to below as “component (I)”).
Soluble Content of Component (Z) at or Below 0° C. (S0) in Temperature Rising Elution Fractionation (TREF)
The propylene resin composition (Z) (component (Z)) used in the innermost layer (3), because it comes into contact with the contents, must have a cleanliness that does not contaminate the contents. Component (Z) preferably has a soluble content (S0), as measured at or below 0° C. by temperature rising elution fractionation (TREF), of not more than 15 wt %.
The soluble content at or below 0° C. (S0) is preferably not more than 14 wt %, more preferably not more than 12 wt %, and most preferably not more than 12 wt %. At a soluble content at or below 0° C. (S0) of more than 15 wt %, the amount of low-crystallinity component is high, which may lead to contamination of the contents, making use of the multilayer sheet unsuitable in retort applications and IV bag applications, for which cleanliness is required.
The temperature rise elution fractionation (TREF) method is the same as described above, the ratio (wt %) components eluted at 0° C. or 40° C. with respect to the total weight being calculated from the resulting elution curve. The column, solvent, temperature and other conditions used are as follows.
Column size: 4.3 mm diameter×150 mm
Column packing: 100 μm surface-deactivated glass beads
Solvent: o-dichlorobenzene
Sample concentration: 5 mg/mL
Amount of sample injected: 0.1 mL
Solvent flow rate: 1 mL/min
Detector: MIRAN 1A (Foxboro) fixed wavelength type infrared detector
Measurement wavelength: 3.42 μm
Melt Flow Rate of Component (Z) (MFR (Z))
Also, to obtain an easy sheet formability in which interfacial roughness and surface roughness do not arise during lamination and problems such as thickness variations do not occur, it is necessary for component (Z) to have suitable flow properties. The melt flow rate MFR (at 230° C. and 2.16 kg loading) (also referred to below as “MFR (Z)”), which is a measure of the flow properties, is preferably in a range of from 2 to 15 g/10 min, and more preferably from 2.5 to 10 g/10 min.
When MFR (Z) is less than 2 g/10 min, interfacial roughness and surface roughness tend to arise, and a sheet having a good appearance may not be obtained. On the other hand, when MFR (Z) is more than 15 g/10 min, thickness variations tend to arise and difficulties with sheet formation occur.
Here, MFR is a value measured in general accordance with JIS K7210.
The above propylene resin composition (component (Z)) which may be used in the innermost layer (3) is preferably selected from among the propylene resin composition (Z1) and the propylene resin composition (Z2) described below.
(2) Propylene Resin Composition (Z1)
Component (Z1) is a composition made of a propylene-α-olefin copolymer component (E) (also referred to below as “component (E)”) which preferably satisfies condition (E-i) below, and an ethylene-α-olefin copolymer component (F) (also referred to below as “component (F)”) which preferably satisfies conditions (F-i) and (F-ii) below.
(2-1) Properties of Component (E)
The propylene-α-olefin copolymer component (E) which may be used in propylene resin composition (Z1) of the innermost layer (3) is a propylene-rich component which has a higher melting peak temperature than the ethylene-α-olefin copolymer component (F) and has heat resistance. When component (E) is used alone, the low-temperature impact resistance is poor.
Hence, imparting low-temperature impact resistance by adding component (F), which is an ethylene-α-olefin copolymer and is a low-crystallinity component, is effective for increasing the flexibility of the innermost layer (3). That is, component (F) is an effective component for imparting low-temperature impact resistance. The propylene-α-olefin copolymer (E) used in this invention has itself a good low-temperature heat-sealability. However, the productivity can be improved by further lowering the heat-sealing temperature within a range where internal fusion does not arise in heat treatment such as sterilization. The ethylene-α-olefin copolymer component (F) is added for this purpose.
Therefore, the propylene-α-olefin copolymer component (E) is preferably one which satisfies the following conditions.
(E-i) Melting Peak Temperature Tm (E)
It is desirable for component (E) to be a propylene resin composition having a melting peak temperature Tm (E) in a range of preferably from 130 to 145° C., and more preferably from 135 to 140° C.
When Tm (E) is less than 130° C., the heat resistance tends to be inadequate. For example, internal fusion may arise when heat treatment such as sterilization is carried out. When Tm (E) exceeds 145° C., the flexibility worsens due to the higher stiffness, and the higher heat sealing temperature tends to worsen the bag-making efficiency.
(E-ii) Ratio of Component (E) in Component (Z1)
Component (E) accounts for a proportion of the propylene resin composition (Z1) which is preferably from 80 to 99 wt %, and more preferably from 85 to 99 wt %. The content of component E is most preferably from 90 to 95 wt %.
When the content of component E is less than 80 wt %, the heat resistance tends to be inadequate and internal fusion may arise in the heat treatment step. At a component (E) content above 99 wt %, the low temperature heat-sealability-imparting effect tends to be inadequate.
(2-2) Method of Producing Component (E)
The propylene-ethylene random copolymer component (E) is preferably polymerized using a metallocene catalyst. The metallocene catalyst used may be any known catalyst which is composed of (i) a ligand-containing group 4 transition metal compound having a cyclopentadienyl skeleton (a so-called metallocene compound), (ii) a co-catalyst which reacts with the metallocene compound and can be activated to a stable ion stage and, optionally, (iii) an organoaluminum compound. The metallocene compound is preferably a bridged metallocene compound capable of the stereoregular polymerization of propylene, and most preferably a bridged metallocene compound capable of the isotactic polymerization of propylene. Each of the ingredients is described below.

    (i) Preferred examples of the metallocene compound include those mentioned in, for example, Japanese Patent Application Laid-open Nos. S60-35007, S61-130314, S63-295607, H1-275609, H2-41303, H2-131488, H2-76887, H3-163088, H4-300887, H4-211694, H5-43616, H5-209013, H6-239914, Japanese Translation of PCT Application No. H7-504934, and Japanese Patent Application Laid-open No. H8-85708, the entire contents of which are incorporated herein by reference.


Specific preferred examples include zirconium compounds such as methylenebis(2-methylindenyl)zirconium dichloride, ethylenebis(2-methylindenyl)zirconium dichloride, ethylene-1,2-(4-phenylindenyl)(2-methyl-4-phenyl-4H-azulenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropylidene(4-methylcyclopentadienyl)(3-t-butylindenyl)zirconium dichloride, dimethylsilylene(2-methyl-4-t-butyl-cyclopentadienyl) (3′-t-butyl-5′-methyl-cyclopentadienyl) zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, dimethylsilylenebis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-ethyl-4-phenylindenyl)]zirconium dichloride, dimethylsilylenebis[4-(1-phenyl-3-methylindenyl)]zirconium dichloride, dimethylsilylene(fluorenyl)-t-butylamidozirconium dichloride, methylphenylsilylenebis[1-(2-methyl-4-(1-naphthyl)-indenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-methyl-4-phenyl-4H-azulenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-ethyl-4-(4-chlorophenyl)-4H-azulenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-ethyl-4-naphthyl-4H-azulenyl)]zirconium dichloride, diphenylsilylenebis[1-(2-methyl-4-(4-chlorophenyl)-4H-azulenyl)]zirconium dichloride, dimethylsilylenebis[1-(2-ethyl-4-(3-fluorobiphenyryl)-4H-azurenyl)]zirconium dichloride, dimethylgermylenebis[1-(2-ethyl-4-(4-chlorophenyl)-4H-azulenyl)]zirconium dichloride and dimethylgermylenebis[1-(2-ethyl-4-phenylindenyl)]zirconium dichloride.
Advantageous use may likewise be made of those compounds in which zirconium has been substituted with titanium or hafnium in the above-mentioned compounds. The use of mixtures of zirconium compounds with hafnium compounds or the like is also possible. Also, chloride may be substituted with other halides, with hydrocarbon groups such as methyl, isobutyl or benzyl, with amide groups such as dimethylamide or diethylamide, with alkoxide groups such as methoxy or phenoxy, or with a hydride group.
Of these, metallocene compounds in which an indenyl group or azulenyl group is bridged with silyl or a germyl group are more preferred. Polymers obtained with a catalyst obtained by combining an azulenyl group-containing metallocene compound with a clay mineral are most preferred because they provide an excellent balance of film formability and low fisheyes.
The metallocene compound may be supported on an inorganic or organic compound carrier and used. A porous, inorganic or organic compound is preferred as the carrier. Illustrative examples include inorganic compounds such as ion-exchangeable layered silicates, zeolites, SiO2, Al2O3, silica alumina, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO and ThO2; organic compounds composed of porous polyolefin, styrene-divinyl benzene copolymers and olefin-acrylic acid copolymers, or mixtures thereof.

    (ii) Examples of co-catalysts which react with a metallocene compound and can be activated to a stable ion stage include organoaluminoxy compounds (e.g., aluminoxane compounds), ion-exchangeable layered silicates, Lewis acids, boron-containing compounds, ionic compounds and fluorine-containing organic compounds.
    (iii) Examples of organoaluminum compounds include trialkyaluminums such as triethylaluminum, triisopropylaluminum and triisobutylaluminum, dialkylaluminum halides, alkylaluminumsesquihalides, alkylaluminum dihalides, alkylaluminum hydrides and organoaluminum alkoxides.


Illustrative examples of the polymerization processes include the following carried out in the presence of such catalysts: slurry processes and solution processes which use an inert solvent, vapor phase processes which use substantially no solvent, and bulk polymerization processes in which the polymerization monomer serves as the solvent. As for the method of obtaining the propylene used in the invention, the desired polymer may be obtained by, for example, adjusting the polymerization temperature and amount of comonomer and suitably regulating the molecular weight and crystallinity distribution.
It is also possible to suitably select and use polypropylene from among products that are commercially available as metallocene-based polypropylene. Commercial products are exemplified by WINTEC (available under this trade name from Japan Polypropylene Corporation).
(2-3) Properties of Ethylene-α-Olefin Copolymer (F)
The ethylene-α-olefin copolymer (F) included in the propylene resin composition (Z1) used in the innermost layer (3) of the multilayer propylene resin sheet is a copolymer obtained by the copolymerization of ethylene with an α-olefin having preferably from 3 to 20 carbons. Preferred examples of the α-olefin include those having from 3 to 20 carbons, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-heptene. Component (F) is a component which acts to increase the low-temperature heat sealability of the propylene-α-olefin copolymer component (E), and preferably satisfies conditions (F-i) and (F-ii) below.
(F-i) Density
Component (F) used in the invention has a density in a range of preferably from 0.860 to 0.910 g/cm3.
If the density is too low, the refractive index difference will become large, worsening the transparency. Hence, at a density below 0.860 g/cm3, the transparency required in this invention cannot be ensured.
On the other hand, if the density is too high, the crystallinity becomes high, resulting in an inadequate low-temperature impact resistance-imparting effect. As when the density is too low, at too high a density, the refractive index difference becomes large, worsening the transparency. Hence, the density must be no higher than 0.910 g/cm3, and is preferably not more than 0.905 g/cm3, and even more preferably not more than 0.900 g/cm3.
Here, the density is a value measured in general accordance with JIS K7112.
(F-ii) Ratio of Component (F) in Component (Z1)
The ratio of component (F) in propylene resin composition (Z1) is in a range of preferably from 1 to 20 wt %, more preferably from 1 to 15 wt %, and even more preferably from 5 to 10 wt %.
At a component (F) content in excess of 20 wt %, the heat resistance is inadequate and internal fusion may arise in a heat treatment step. On the other hand, at a component F content of less than 1 wt %, the low temperature heat sealability-imparting effect is inadequate.
(2-4) Method of Producing Component (F)
The density of Component (F) used in this invention must be adjusted with that of component (E) in order to make the refractive index difference therewith small. Moreover, to suppress tackiness and bleedout, it is desirable for the crystallinity and molecular weight distributions to be narrow. Hence, in the production of component (F), it is desirable to use a metallocene catalyst which is capable of providing narrow crystallinity and molecular weight distributions.
Various types of known catalysts used to polymerize ethylene-α-olefin copolymers may be employed as the metallocene catalyst. Use may be made of metallocene catalysts similar to those mentioned above in connection with ethylene-α-olefin copolymer (B). Illustrative examples of polymerization processes include the following carried out in the presence of such catalysts: slurry processes, vapor phase fluidized bed processes, solution processes, and high-pressure bulk polymerization processes at a pressure of at least 200 kg/cm2 and a polymerization temperature of at least 100° C. An example of a preferred production method is high-pressure bulk polymerization.
The component (F) used may also be suitably selected from among commercially available metallocene-based polyethylenes. Examples of commercial products include AFFINITY and ENGAGE (available under these trade names from DuPont-Dow), KERNEL (available under this trade name from Japan Polyethylene Corporation), and EXACT (available under this trade name from Exxon Mobil).
In using these, a grade which satisfies the density that is an essential feature of the invention should be suitably selected.
(3) Propylene Resin Composition (Z2)
The other propylene resin composition (referred to below as “component (Z2)”) which may be preferably used as propylene resin composition (Z) in the innermost layer (3) is made of (G) a propylene resin composition and (H) an ethylene-α-olefin copolymer. Component (Z2) is suitable for obtaining a more flexible propylene resin multilayer sheet. It is preferable to also include in component (Z2) the subsequently described propylene resin (I).
(3-1) Properties of Propylene Resin Composition (G)
It is essential that the propylene resin composition (G) have a high transparency, flexibility and impact resistance. Also required are heat resistance so that internal fusion does not arise in the heating steps, and low temperature heat sealability to facilitate bag-making. To satisfy these requirements at a high level, it is preferable that component (G) satisfy condition (G-i) below.
(3-1) Basic Conditions of Component (G)
Component (G) used in the invention is a propylene resin composition (G) which satisfies the following condition (G-i):
(G-i) includes from 30 to 70 wt % of (G1) a propylene-α-olefin random copolymer component having a melting peak temperature (Tm (G1)) of from 125 to 145° C., and from 70 to 30 wt % of (G2) a propylene-ethylene random copolymer component having an ethylene content (E[G2]) of from 7 to 17 wt % and obtained using a metallocene catalyst;
The preferred conditions desired of component (G) are described in detail in (i) to (v) below.
(i) Melting Peak Temperature (Tm (G1)) of Component (G1)
Component (G1) is a component which determines the crystallinity in the propylene resin composition (component (G)). To increase the heat resistance of component (G), it is necessary for the melting peak temperature Tm (G1) (also referred to below as “Tm (G1)”) of component (G1) to be high. However, if Tm (G1) is too high, the heat sealing temperature becomes higher, making bags more difficult to fabricate. On the other hand, if Tm (G1) is too low, the heat resistance worsens, as a result of which internal fusion arises during heat treatment such as in a sterilization step. Tm (G1) must be in a range of from 125 to 145° C., and is preferably from 125 to 138° C., and more preferably from 128 to 135° C. Component (A1) is preferably produced using a metallocene catalyst.
Here, the method of measuring the melting peak temperature Tm is as described above in the description of propylene resin composition (A).
(ii) Ratio of Component (G1) in Component (G)
Although component (G1) confers heat resistance on component (G), if the ratio W(G1) of component (G1) in component (G) is too high, it will be difficult to exhibit a sufficient flexibility, impact resistance and transparency. Hence, the ratio of component (G1) is preferably not more than 70 wt %, and more preferably not more than 60 wt %.
On the other hand, when the ratio of component (G1) is too small, even if Tm (G1) is sufficient, the heat resistance decreases, as a result of which deformation may occur in a sterilization step. Hence, the ratio of component (G1) is preferably at least 30 wt %, and more preferably at least 50 wt %.
(iii) Ethylene Content (E) in Component (G2) (E[G2])
Component (G2) produced in the second step is a required component for increasing the flexibility, impact resistance and transparency of component (G1). Generally, in propylene-ethylene random copolymers, when the ethylene content rises, the crystallinity decreases and the flexibility-increasing effect becomes larger. Hence, the ethylene content E[G2] in component (G2) (sometimes referred to below as “E[G2]”) is preferably at least 7 wt %, and more preferably at least 8 wt %. When E[G2] is less than 7 wt %, a sufficient flexibility cannot be exhibited. E[G2] is preferably at least 10 wt %.
On the other hand, if E[G2] is increased excessively in order to lower the crystallinity of component (G2), the compatibility of component (G1) and component (G2) decreases and component (G2) forms domains rather than compatibilizing with component (G1). In such a phase-separated structure, if the matrix and the domains have differing refractive indices, the transparency abruptly decreases. Hence, the E[G2] of component (G2) in component (G) used in this invention is preferably not more than 17 wt %, more preferably not more than 14 wt %, and even more preferably not more than 12 wt %.
(iv) Ratio of Component (G2) in Component (G)
If the ratio W(G2) of component (G2) in component (G) is too high, the heat resistance will decrease. Hence, W(G2) is held to preferably not more than 70 wt %, and more preferably not more than 50 wt %.
On the other hand, if W(G2) is too low, flexibility and impact resistance-improving effects cannot be obtained. Hence, W(G2) is preferably at least 30 wt %, and more preferably at least 40 wt %.
Here, W(G1) and W(G2) are values determined by temperature rising elution fractionation (TREF). Also, as in the description provided for component (A) above, the ethylene content E[G2] is a value obtained by NMR.
(3-2) Temperature-Loss Tangent (tan δ) Curve Peak (G-ii)
It is preferable for component (G) used in the invention to have, in a temperature-loss tangent (tan δ) curve obtained by dynamic mechanical analysis (DMA), a single peak at or below 0° C. on the tan δ curve representing the glass transition observed in a range of from −60 to 20° C. The dynamic mechanical analysis method is defined in the same way as described above in connection with component (A).
In cases where component (G) assumes a phase-separated structure, because the glass transition temperature of the non-crystalline portion included in component (G1) and the glass transition temperature of the non-crystalline portion included in component (G2) each differ, there are a plurality of peaks. In such a case, the transparency worsens markedly.
Generally, the glass transition temperature in a propylene-ethylene random copolymer is observed in a range of from −60 to 20° C. and, in the tan δ curve obtained by dynamic mechanical analysis within this range, it can be determined whether component (G) has assumed a phase-separated structure. Avoidance of a phase-separated structure which affects the sheet transparency is brought about by having a single peak at or below 0° C.
(v) Method of Preparing Component (G)
The method of preparation described above for propylene resin composition (A) applies also to the method of preparing the component (G) used in the invention. Component (G) is obtained by using a metallocene catalyst to polymerize component (G1) in a first step and successively polymerize component (G2) in a second step. Production is preferably carried out by successively polymerizing from 50 to 60 wt % of the above-described propylene-α-olefin random copolymer component (C1) in the first step, and from 50 to 40 wt % of the above-described propylene-ethylene random copolymer component (G2) having an ethylene content E[G2] of from 8 to 14 wt % in the second step. The preferred method for producing component (G) is similar to the production method described in connection with propylene resin composition (A) above.
Alternatively, component (G) need not be a successive polymerization product, and may instead be produced by blending together component (G1) having the above properties with component (G2) having the above properties.
Ratio of Component (G) in Propylene Resin Composition (Z2)
Component (G) accounts for a proportion of component (Z2) which is preferably in a range of from 60 to 90 wt %, and more preferably from 65 to 85 wt %, per 100 wt % of components (G) and (H) combined.
If the content of component (G) is too low, a good flexibility and transparency may be difficult to achieve. On the other hand, if the content of component (G) is too high, it may be impossible to obtain a more preferable impact resistance and heat resistance.
(3-2) Ethylene-α-Olefin Copolymer (H)
(3-2-1) Properties of Component (H)
The ethylene-α-olefin copolymer (H) included in the propylene resin composition (Z2) is a copolymer obtained by the copolymerization of ethylene with an α-olefin having preferably from 3 to 20 carbons. Preferred examples of the α-olefin include those having from 3 to 20 carbons, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-heptene. Component (H) is a component which acts to increase the transparency and flexibility of the propylene resin composition, and preferably satisfies condition (H-i) below.
Propylene resin composition (Z) used in the invention is required to have flexibility and transparency. With regard to the transparency, in cases where the refractive index of component (H) differs considerably from that of component (G), the transparency of the resulting sheet will worsen. Hence, it is important for the refractive indices to agree. The refractive index can be controlled by density. To obtain the transparency required in the invention, it is important to set the density within a specific range.
The addition of component (H) is necessary to further strengthen the low-temperature impact resistance of component (G).
(H-i) Density
Component (H) used in the invention has a density in a range of preferably from 0.860 to 0.910 g/cm3.
If the density is too low, the refractive index difference will become large, worsening the transparency. Hence, at a density below 0.860 g/cm3, the transparency required in this invention cannot be ensured.
On the other hand, if the density is too high, the crystallinity becomes high, resulting in an insufficient flexibility. Hence, the density is preferably not higher than 0.910 g/cm3, more preferably not higher than 0.905 g/cm3, and even more preferably not higher than 0.900 g/cm3.
Here, the density is a value measured in general accordance with JIS K7112.
(3-2-2) Method of Producing Component (H)
To make the refractive index difference with component (G) small, component (H) used in this invention must be set to a low density. Moreover, to suppress tackiness and bleedout, it is desirable for the crystallinity and molecular weight distributions to be narrow. Hence, in the production of component (H), it is desirable to use a metallocene catalyst which is capable of providing narrow crystallinity and molecular weight distributions.
The metallocene catalyst and the polymerization process may be the same as those described above in connection with ethylene-α-olefin copolymer (F).
The component (H) used may be suitably selected from among commercially available metallocene-based polyethylenes. Examples of commercial products include AFFINITY and ENGAGE (available under these trade names from DuPont-Dow), KERNEL (available under this trade name from Japan Polyethylene Corporation), and EXACT (available under this trade name from Exxon Mobil).
In using these, a grade which satisfies the density that is an essential feature of the invention should be suitably selected.
(3-2-3) Ratio of Component (H) in Component (Z2)
Component (H) accounts for a proportion of component (Z2) which is in a range of preferably from 40 to 10 wt %, and more preferably from 35 to 15 wt %, per 100 wt % of components (G) and (H) combined.
If the content of component (H) is too low, the low-temperature impact resistance conferred is inadequate. On the other hand, if the content of component (H) is too high, thickness irregularities arise in the sheet, and obtaining a sheet having a good appearance is difficult.
Hence, the proportion of component (Z2) accounted for by component (H) is most preferably in a range of from 35 to 15 wt % per 100 wt % of components (G) and (H) combined. At less than 10 wt %, the flexibility imparted tends to be inadequate, whereas at more than 40 wt %, the sheet formability is inadequate, which is undesirable.
(3-3) Propylene Resin (I)
(3-3-1) Properties of Component (I)
The propylene resin (I) which is preferably included in the propylene resin composition (Z2) is used as component for suppressing the internal fusion which may arise in heating treatment steps such as a sterilization step.
In component (Z2), above-described component (G) which is used as the main component is very effective for imparting a high flexibility and transparency to a laminated sheet. However, because it is preferably produced with a metallocene catalyst and thus has a narrow crystallinity distribution, there remains some concern over the heat resistance owing to the low level of high-crystallinity components, and there is a high possibility that internal fusion will arise.
In light of this, when attempts are made to broaden the crystallinity distribution of component (G) and thereby achieve a relative increase in high-crystallinity components, the low-crystallinity components also inevitably increase. As a result, these low-crystallinity components bleed out to the surface of the laminated sheet, giving rising to stickiness and appearance defects, thus making the sheet unfit for applications requiring transparency.
By adding a specific amount of component (I) to component (G) having little high-crystallinity component, the high-crystallinity components and the high-molecular-weight components can be increased without increasing the low-crystallinity components and the low-molecular-weight components. As a result, appearance defects such as thickness variations and interfacial roughness can be suppressed without giving rise to appearance defects such as bleedout. Moreover, the addition of a specific amount of high crystallinity components, rather than broadening the crystallinity distribution, makes it easier to strike a good balance between a heat resistance which suppresses internal fusion and low-temperature heat sealability.
Therefore, component (I) is preferably a propylene resin which satisfies condition (I-i) below, and more preferably a propylene resin composed of the propylene (co)polymer component (I1) and propylene-ethylene random copolymer (I2) described below.
(I-i) Melting Peak Temperature Tm (I)
Component (I) preferably has a melting peak temperature (Tm (I)) which is at least 6° C. higher than the melting peak temperature (Tm (G1)) of the above-described propylene-α-olefin random copolymer component (G1). By having the melting peak temperature be at least 6° C. higher, the resulting multilayer sheet can be conferred with an ability to suppress appearance defects such as thickness variations and interfacial roughness, and also an ability to suppress a reduction in thickness during heat sealing, without giving rise to appearance defects such as bleedout. Tm (I) is more preferably at least 10° C. higher, and even more preferably at least 20° C. higher, than Tm (G1).
Component (I) is a propylene resin composition and has a melting peak temperature Tm (I) in a range of preferably from 150 to 170° C., and more preferably from 155 to 165° C.
If Tm (I) is less than 150° C., high-crystallinity components are inadequate, as a result of which a sufficient heat resistance may not be imparted. On the other hand, when Tm (I) is higher than 165° C., industrial production is difficult.
Propylene Resin Composed of Propylene (Co)polymer Component (I1) and Propylene-Ethylene Random Copolymer (I2)
Component (I) is preferably a propylene resin composed of (I1) a propylene (co)polymer component which satisfies component (I1-i) below and (I2) a propylene-ethylene random copolymer which satisfies condition (I2-i) below, and is, moreover, preferably a propylene resin (I) which satisfies condition (I-ii) below.
Here, component (I1) is a polypropylene component, and is a high-crystallinity component. Because component (I1) has a higher melting peak temperature than component (G), it is in a crystalline state (solid state) at the temperature at which component (G) melts and begins melt-flowing, and thus acts to suppress the melt flow of component (G), making it an effective component for suppressing internal fusion in a heating step such as sterilization treatment. Therefore, it is necessary for component (I1) to be a polypropylene or propylene-ethylene copolymer composed of a copolymer having a higher crystallinity than component (G). However, by adding component (I1), the crystallinity of the innermost layer (3) as a whole increases, as a result of which a loss of flexibility occurs. By adding component (I2), which is a propylene-ethylene random copolymer and a low-crystallinity component, flexibility is conferred, which is effective for flexibilizing the laminated sheet as a whole.
Component (H), too, is added to obtain similar effects, although too much component (H) worsens the sheet formability, making it difficult to obtain a sheet of uniform thickness. Hence, there is an upper limit to the amount added. In cases where the flexibility cannot be entirely provided by component (H) alone, adding component (I2) is effective. That is, component (I2) is effective for suppressing an increase in stiffness with the addition of the highly crystalline component (I1).
(I1-i) Ratios of Components (I1) and (I2) in Component (I)
Component (I) may be a mixture of a propylene (co)polymer component (I1) in a component ratio (also referred to below as “W(I1)”) of from 40 to 70 wt % and an ethylene-propylene copolymer component (I2) in a component ratio (also referred to below as “W(I2)”) of from 30 to 60 wt %. However, from the standpoint of uniformly and finely dispersing component (I2), component (I) is preferably obtained by multistage polymerization.
Because component (I2) is a low-crystallinity component, when W(I2) is too high, a heat resistance augmenting effect is difficult to obtain, and when W(I2) is too low, a flexibility augmenting effect is difficult to obtain. Here, W(I1) and W(I2) can be determined from the material balance.
(I2-i) Ethylene Content (E(I2))
Component (I2) is a flexibility-imparting component for minimizing the increase in stiffness due to the addition of component (I1), which is a high-crystallinity component. Hence, because component (I2) is controlled by the ethylene content (also referred to below as “E(I2)”), it is preferable to set the ethylene content to from 15 to 40 wt %.
At an ethylene content below 15 wt %, because this is a region of compatibility with propylene, a sufficient flexibility-imparting effect at a small amount of addition is difficult to obtain. On the other hand, at an ethylene content in excess of 40 wt %, the ethylene content is too high, which tends to worsen the transparency of the inner layer as a whole.
Here, E(I2) is a value determined by the above-described 13C-NMR spectroscopy.
(I-ii) Intrinsic Viscosity Ratio of Components (I1) and (I2) in Component (I)
Component (I2) in component (I) has an intrinsic viscosity [η]I2 (also referred to below as “[η]I2”), as measured in 135° C. tetralin, of preferably from 1.7 to 6.5 dL/g, and more preferably from 1.7 to 4.0 dL/g, and has an intrinsic viscosity ratio [η]I2/[η]I1 with the intrinsic viscosity [η]I1 (also referred to below as “[η]I1”) of component (I1) measured under the same conditions in a range of preferably from 0.6 to 1.2, and more preferably from 0.6 to 1.1.
[η]I1 influences the processing properties such as, in particular, the sheet formability, and [η]I2/[η]I1 influences the dispersibility of component (I2) in component (I1). If [η]I1 is too large, the sheet formability tends to worsen, leading to production problems. If [η]I2 is too small, a sufficient flexibility is difficult to obtain, and if [η]I2 is too large, the transparency tends to worsen.
In cases where component (I) is obtained by consecutively producing components (I1) and (I2), because it is impossible to directly measure [η]I2 in component (I), this is determined as follows from the directly measurable [η]I1 and the intrinsic viscosity [η]I of component (I) (also referred to below as “[η]I”), and also from W(I2).

[η]I2={[η]I−(1−W(I2)/100)[η]I1}/(W(I2)/100)

Here, “consecutively producing” refers to producing component (I1) in the subsequently described first stage (first step), then successively producing component (I2) in a second stage (second step).
In the propylene resin (I) used in this invention, it is important that the product of the weight ratio (W(I2)/W(I1)) of W(I1) and W(I2) with the intrinsic viscosity ratio of the two components ([η]I2/[η]I1), which product is expressed as ([η]I2/[η]I1)×(W(I1)/W(I2)), be in a range of from 0.2 to 4.5, and preferably from 0.6 to 4.0.
The product of the weight ratio and the intrinsic viscosity ratio indicates the dispersion state of component (I2) dispersed in component (I1). Having the product fall within the above range is an essential condition for indicating a specific dispersed structure wherein domains of component (I2) are present in an elongated state as isolated domains in the machine direction during fabrication or are connected to other domains in at least one place. Having this value be in the above-mentioned range is desirable because the transparency and flexibility of the resulting sheet are good.
(3-3-3) Method of Producing Component (I)
The propylene resin (I) used in the invention may be produced by any method, so long as the above properties are satisfied. In cases where a composition of (I1) a propylene (co)polymer component and (I2) a propylene-ethylene random copolymer is produced, the propylene resin (I) may be produced using an apparatus that mixes a propylene (co)polymer (I1) and a propylene-ethylene random copolymer (I2) which have been separately produced, or the propylene resin (I) may be consecutively produced by, in a first step, producing a propylene (co)polymer (I1) and subsequently, in a second step, producing a propylene-ethylene random copolymer (I2) in the presence of the propylene (co)polymer (I1). Preferred examples of specific methods of production are described in Japanese Patent Application Laid-open Nos. 2006-35516 and 2001-172454, the entire contents of which are incorporated herein by reference.
It is also possible to suitably select and use component (I) from among commercially available products. Illustrative examples of commercially available products include NOVATEC PP (available under this trade name from Japan Polypropylene Corporation), NEWCON (available under this trade name from Japan Polypropylene Corporation), and ZELAS (available under this trade name from Mitsubishi Chemical Corporation). In using these, a grade which satisfies the melting peak temperature, MFR and intrinsic viscosity ratio that are conditions of the invention should be suitably selected.
(3-3-4) Proportion of Component (I) in Component (Z2)
Component (I) accounts for a proportion of component (Z2) which is preferably in a range of from 1 to 25 wt % per 100 wt % of components (G), (H) and (I) combined.
When component (I) is included in component (Z2), the ratio of component (G) is preferably from 45 to 89 wt %, more preferably from 45 to 85 wt %, and even more preferably from 50 to 80 wt %, per 100 wt % of components (G), (H) and (I) combined; and the ratio of component (H) is preferably from 15 to 25 wt %, per 100 wt % of components (G) to (I) combined.
Component (I1) in component (I), because it has a higher melting peak temperature than component (G), maintains a crystalline state even at the temperature at which component (G) melts, and thus has a heat resistance-imparting effect which suppresses the melting and flow of component (G). Component (I2) in component (I) has a flexibility-imparting effect for minimizing the increase in stiffness due to the addition of component (I1), which is a high crystallinity component.
If an amount of component (I) which is too low, the high crystallinity component will not suffice, making it impossible to obtain a sufficient heat resistance-imparting effect. Hence, the amount of (I) included is preferably at least 1 wt %, and more preferably at least 5 wt %, per 100 wt % of components (G), (H) and (I) combined. On the other hand, if the amount of component (I) is too high, pronounced decreases in physical properties such as flexibility and transparency occur, making it impossible to satisfy the quality required in the resin composition of the invention. Hence, the amount of (I) included is preferably not more than 25 wt %, and more preferably not more than 20 wt %.
4. Additional Ingredients (Additives)
To enable the multilayer propylene resin sheet of the invention to be suitably employed as a multilayer sheet, propylene resin compositions (X), (Y) and (Z) used in, respectively, the inner layer (1), outer layer (2) and innermost layer (3) of the inventive multilayer sheet may include optional additives within ranges that do not significantly diminish the advantageous effects of the invention with regard to bleedout and the like. Such optional ingredients are exemplified by antioxidants, crystal nucleating agents, clarifiers, lubricants, antiblocking agents, antistatic agents, haze inhibitors, neutralizing agents, metal inactivators, colorants, dispersants, peroxides, fillers and fluorescent whiteners used in ordinary polyolefin resin materials. Specific examples of the various additives are listed below. In addition, elastomers may be included as elasticity-imparting ingredients within a range which does not significantly diminish the advantageous effects of the invention.
(1) Antioxidants
Illustrative examples of antioxidants include phenolic antioxidants, such as tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythrityltetrakis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid.
Examples of phosphorus-based antioxidants include tris(mixed mono- and di-nonylphenylphosphite), tris(2,4-di-t-butylphenyl)phosphite, 4,4′-butylidenebis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite, 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, tetrakis(2,4,di-t-butylphenyl)-4,4′-biphenylene diphosphonite, tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4′-biphenylene diphosphonite and bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite.
Examples of sulfur-based antioxidants include distearyl thiodipropionate, dimyristyl thiodipropionate and pentaerythritol tetrakis(3-lauryl thiopropionate).
These antioxidants may be used singly or as combinations of two or more thereof, insofar as the advantageous effects of the invention are not compromised.
The amount of antioxidant included per 100 parts by weight of the respective resins is from 0.01 to 1.0 part by weight, preferably from 0.02 to 0.5 parts by weight, and more preferably from 0.05 to 0.1 parts by weight. If the amount included is below the above range, a thermal stability effect is not obtained and deterioration takes place when the resin is produced, causing scorching and fisheyes. On the other hand, at an amount in excess of the above range, the additive itself becomes a foreign substance, causing fisheyes, which is undesirable.
(2) Anti-Blocking Agents
The antiblocking agent has an average particle size of from 1 to 7 μm, preferably from 1 to 5 μm, and more preferably from 1 to 4 μm. At an average particle size below 1 μm, the slip characteristics and bag openability diminish, which is undesirable. On the other hand, at more than 7 μm, the transparency and tendency to scratch become markedly worse, which is undesirable. Here, the average particle size is a value measured by the coal tar counter method.
Examples of antiblocking agents that may be used include inorganic agents such as synthetic or natural silicas (silicon dioxide), magnesium silicate, aluminosilicates, talc, zeolites, aluminum borate, calcium carbonate, calcium sulfate, barium sulfate and calcium phosphate.
Examples of organic antiblocking agents include polymethyl methacrylate, polymethylsilsesquioxane (silicone), polyamides, polytetrafluoroethylene, epoxy resins, polyester resins, benzoguanamine formaldehyde (urea resin) and phenolic resins.
Synthetic silicas and polymethyl methacrylate are especially preferred from the standpoint of balance in dispersibility, transparency, antiblocking properties and scratch resistance.
The antiblocking agent may be one that has been surface-treated. Examples of surface treatment agents which may be used include surfactants, metal soaps, organic salts of acrylic acid, oxalic acid, citric acid and tartaric acid, higher alcohols, esters, silicones, fluoroplastics, silane coupling agents and condensed phosphates such as sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium trimetaphosphate. Organic acid treatment, particularly citric acid treatment, is especially preferred. The method of treatment is not subject to any particular limitation. Use may be made of a known method, such as surface spraying or dipping.
The particles of antiblocking agent may have any shape. For example, they may have a shape that is spheroidal, angular, columnar, needle-like, plate-like or amorphous.
These antiblocking agents may be used singly or as combinations of two or more thereof, insofar as the advantageous effects of the invention are not compromised.
The amount of antiblocking agent compounded per 100 parts by weight of resin is typically from 0.01 to 1.0 part by weight, preferably from 0.05 to 0.7 parts by weight, and more preferably from 0.1 to 0.5 parts by weight. When the amount included is less than the above range, the antiblocking properties, slip characteristics and bag openability tend to decrease. When the amount is greater than the above range, a loss tends to occur in the transparency of the sheet or the antiblocking agent itself becomes foreign matter and causes fisheyes, which is undesirable.
(3) Slip Agents
Exemplary slip agents include monoamides, substituted amides and bisamides. Any one or combinations of two or more may be used.
Examples of monoamides include saturated fatty acid monoamides, such as laurylamide, palmitamide, stearamide, behenamide and hydroxystearamide.
Examples of unsaturated fatty acid monoamides include oleamide, erucamide and ricinolamide.
Examples of substituted amides include N-stearyl stearamide, N-oleyl oleamide, N-stearyl oleamide, N-oleyl stearamide, N-stearyl erucamide and N-oleyl palmitamide.
Examples of bisamides include saturated fatty acid bisamides such as methylenebis(stearamide), ethylenebis(capramide), ethylenebis(lauramide), ethylenebis(stearamide), ethylenebis(isostearamide), ethylenebis(hydroxystearamide), ethylenebis(behenamide), hexamethylenebis(stearamide), hexamethylenebis(behenamide), hexamethylenebis(hydroxystearamide), N,N′-distearyladipamide and N,N′-distearylsebacinamide.
Examples of unsaturated fatty acid bisamides include ethylenebis(oleamide), hexamethylenebis(oleamide), N,N′-dioleyl adipamide, N,N′-dioleyl sebacamide.
Examples of aromatic bisamides include m-xylylenebis(stearamide) and N,N′-distearyl isophthalamide.
Of these, among the fatty acid amides, the use of oleamide, erucamide and behenamide is especially preferred.
The amount of slip agent compounded per 100 parts by weight of the resin is typically from 0.01 to 1.0 part by weight, preferably from 0.05 to 0.7 parts by weight, and more preferably from 0.1 to 0.4 parts by weight. Below the foregoing range, the bag openability and slip characteristics tend to be poor. Above the foregoing range, floating up of the strip agent becomes excessive, as a result of which the slip agent bleeds to the sheet surface, worsening the transparency.
(4) Nucleating Agent
Illustrative examples of nucleating agents include sodium 2,2-methylenebis(4,6-di-t-butylphenyl)phosphate, talc, sorbitol compounds such as 1,3,2,4-di(p-methylbenzylidene) sorbitol, hydroxy-di(t-butylbenzoic acid) aluminum, 2,2-methylenebis(4,6-di-t-butylphenyl)phosphoric acid, and lithium C8-20 aliphatic monocarboxylate mixtures (available from ADEKA under the trade name NA21).
The above nucleating agent is included in an amount per 100 parts by weight of the respective resins of typically from 0.0005 to 0.5 parts by weight, preferably from 0.001 to 0.1 parts by weight, and more preferably from 0.005 to 0.05 parts by weight. Below the foregoing range, effects as a nucleating agent are not obtained. Above the foregoing range, the nucleating agent itself becomes a foreign matter, causing fisheyes, which is undesirable.
Examples of nucleating agents other than the above include high-density polyethylene resins. The high-density polyethylene resin has a density of typically form 0.94 to 0.98 g/cm3, and preferably from 0.95 to 0.97 g/cm3. At densities outside this range, a transparency-improving effect cannot be obtained. The melt flow rate (MFR) of the high-density polyethylene resin at 190° C. is typically at least 5 g/10 min, preferably from 7 to 500 g/10 min, and more preferably from 10 to 100 g/10 min. At a MFR below 5 g/10 min, the dispersed diameter of high-density polyethylene resin does not become sufficiently small, as a result of which the high-density polyethylene resin itself becomes a foreign matter, causing fisheyes, which is undesirable. Also, in order for the high-density polyethylene resin to microdisperse, it is preferable that the high-density polyethylene resin have a higher MFR than the MFR of the propylene resin in the invention.
Production of the high-density polyethylene resin used as a nucleating agent is not subject to any particular limitation concerning the method of production and the catalyst, so long as a polymer having the desired physical properties can be obtained. Exemplary catalysts include Ziegler-Natta catalysts (i.e., catalysts based on a combination of a supported or unsupported halogen-containing titanium compound and an organoaluminum compound) and Kaminsky catalysts (catalysts based on a combination of a supported or unsupported metallocene compound and an organoaluminum compound, particularly an alumoxane). The shape of the high-density polyethylene resin is not subject to any particular limitation, and may be in the form of pellets or in powder form.
When used as a nucleating agent, the amount of high-density polyethylene compounded per 100 parts by weight of the resin is typically form 0.01 to 5 parts by weight, preferably from 0.05 to 3 parts by weight, and more preferably from 0.1 to 1 part by weight. Below the foregoing range, effects as a nucleating agent are not obtained. Above the foregoing range, the high-density polyethylene itself becomes a foreign matter, causing fisheyes, which is undesirable.
(5) Neutralizing Agent
Illustrative examples of neutralizing agents include calcium stearate, zinc stearate, hydrotalcite and Mizukalac (available from Mizusawa Industrial Chemicals, Ltd.).
When a neutralizing agent is included, the amount compounded per 100 parts by weight of the resin is typically from 0.01 to 1.0 part by weight, preferably form 0.02 to 0.5 parts by weight, and more preferably from 0.05 to 0.1 parts by weight. At an amount below the foregoing range, because effects as a neutralizing agent are not obtained, deteriorated resin at the interior of the extruder is scraped out, causing fisheyes. Above the foregoing range, the neutralizing agent itself becomes a foreign material, causing fisheyes, which is undesirable.
(6) Optical Stabilizers
Hindered amine stabilizers are suitably used as the optical stabilizer. Compounds known to the art which have a structure wherein all the hydrogens bonded to the carbons at the 2 and 6 positions of piperidine have been substituted with methyl groups may be used without particular limitation. Examples of compounds that may be used include those listed below.
Illustrative examples include polycondensates of dimethyl succinate with 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, the condensate of N,N-bis(3-aminopropyl)ethylenediamine with 2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{2,2,6,6-tetramethyl-4-piperidyl}imino] and poly[(6-morpholino-s-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}].
These hindered amine stabilizers may be used singly or as a combination of two or more thereof, insofar as the advantageous effects of the invention are not compromised.
In cases where a hindered amine stabilizer is included, it is desirable for the amount compounded per 100 parts by weight of the resin to be from 0.005 to 2 parts by weight, preferably from 0.01 to 1 part by weight, and more preferably from 0.05 to 0.5 parts by weight.
At a hindered amine stabilizer content below 0.005 parts by weight, there is no stability (e.g., heat resistance, antidegrading property) improving effect, whereas at above 2 parts by weight, the stabilizer itself becomes a foreign matter, causing fisheyes, which is undesirable.
(7) Antistatic Agent
Known additives that have hitherto been used as antistatic agents may be employed here as antistatic agents without any particular limitation. Exemplary antistatic agents include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.
Illustrative examples of anionic surfactants include carboxylates such as fatty acid or rosin acid soaps, N-acylcarboxylates, ether carboxylates and fatty acid amine salts; sulfonates such as sulfosuccinates, ester sulfonates and N-acylsulfonates; sulfates such as sulfonated oils, sulfuric acid esters, alkyl sulfates, alkylpolyoxyethylene salts of sulfuric acids, ether sulfates and amide sulfates; and phosphates such as alkyl phosphates, alkylpolyoxyethylene salts of phosphoric acid, ether phosphates and amide phosphates.
Illustrative examples of cationic surfactants include amine salts such as alkylamine salts, quaternary ammonium salts such as alkyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, alkyldihydroxyethylmethylammonium chloride, dialkyldimethylammonium chloride, tetraalkylammonium salts, N,N-di(polyoxyethylene)dialkylammonium salts and ammonium salts of N-alkylalkanamides; alkylimidazoline derivatives such as 1-hydroxyethyl-2-alkyl-2-imidazoline and 1-hydroxyethyl-1-alkyl-2-alkyl-2-imidazoline; and imidazolinium salts, pyridinium salts and isoquinolinium salts.
Illustrative examples of nonionic surfactants include those in the form of ethers, such as alkylpolyoxyethylene ether and p-alkylphenylpolyoxyethylene ether; those in the form of ether esters, such as fatty acid sorbitan polyoxyethylene ethers, fatty acid sorbitol polyoxyethylene ethers and fatty acid glycerol polyoxyethylene ethers; those in the form of esters, such as fatty acid polyoxyethylene esters, monoglycerides, diglycerides, sorbitan esters, sucrose esters, dihydric alcohol esters, and boric acid esters; and those in the form of nitrogen-containing compounds, such as dialcohol alkylamines, dialcohol alkylamine esters, fatty acid alkanolamides, N,N-di(polyoxyethylene)alkanamides, alkanolamine esters, N,N-di(polyoxyethylene)alkanamines, aminoxides and alkylpolyethyleneimines.
Illustrative examples of amphoteric surfactants include those in the form of amino acids, such as monoaminocarboxylic acids and polyaminocarboxylic acids; those in the form of N-alkyl-β-alanines, such as N-alkylaminopropionic acid salts and N,N-di(carboxymethyl)alkylamine salts; those in the form of betaines, such as N-alkylbetaines, N-alkylamide betaines, N-alkylsulfobetaines, N,N-di(polyoxyethylene)alkylbetaines and imidazolium betaine; and alkylimidazoline derivatives, such as 1-carboxymethyl-1-hydroxy-1-hydroxyethyl-2-alkyl-2-imidazoline and 1-sulfoethyl-2-alkyl-2-imidazoline.
Of these, nonionic surfactants and amphoteric surfactants are preferred. Nonionic surfactants, either in the form of esters, such as monoglycerides, diglycerides, boric acid esters, dialcohol alkylamines, dialcohol alkylamine esters and amides, or in the form of nitrogen-containing compounds, and amphoteric surfactants in the form of betaines are especially preferred.
Commercial products may be used as the antistatic agent. Illustrative examples include Electrostripper TS5 (glycerol monostearate, available under this trade name from Kao Corporation), Electrostripper TS6 (stearyl diethanolamine, available under this trade name from Kao Corporation), Electrostripper EA (lauryldiethanolamine, available under this trade name from Kao Corporation), Electrostripper EA-7 (polyoxyethylene laurylamine capryl ester, available under this trade name from Kao Corporation), Denon 331P (stearyl diethanolamine monostearate, available under this trade name from Marubishi Oil Chemical Co., Ltd.), Denon 310 (alkyl diethanolamine fatty acid monoester, available under this trade name from Marubishi Oil Chemical Co., Ltd.), Resistat PE-139 (stearic acid mono and diglyceride boric acid esters, available under this trade name from Dai-ichi Kogyo Seiyaku Co., Ltd.), Chemistat 4700 (alkyl dimethylbetaine, available under this trade name from Sanyo Chemical Industries, Ltd.) and Leostat S (alkyl diethanolamide, available under this trade name from Lion Corporation).
When an antistatic agent is included, the amount compounded per 100 parts by weight of resin is typically from 0.01 to 2 parts by weight, preferably from 0.05 to 1 part by weight, more preferably from 0.1 to 0.8 parts by weight, and even more preferably from 0.2 to 0.5 parts by weight. These antistatic agents may be used singly or as combinations of two or more thereof, insofar as the advantageous effects of the invention are not compromised. At an amount below 0.01 parts by weight, the antistatic agent is unable to reduce the surface resistivity and prevent damage due to static electricity. At more than 2 parts by weight, the surface of the sheet has a tendency to shed powder due to bleeding.
The elastomer in the invention is exemplified by styrene-based elastomers. Commercial products include Hybrar (available under this trade name from Kuraray Co., Ltd.) and Dynaron (available under this trade name from JSR Corporation).
[II] Production of Resin Compositions for Respective Layers of Multilayer Propylene Resin Sheet
The propylene resin composition (X) making up the inner layer (1) in the multilayer propylene resin sheet of the invention is obtained by a method which involves mixing the above-described propylene resin composition (A), ethylene-α-olefin copolymer (B), propylene resin (C) where desired, and other additives as needed in for example, a Henschel mixer, V blender, ribbon blender or tumbler blender, followed by kneading in a kneader such as a single-screw extruder, a multi-screw extruder, a kneader or a Banbury mixer.
The propylene resin composition (Y) making up the outer layer (2) in the multilayer propylene resin sheet of the invention is obtained by a method which involves mixing the above-described propylene resin (D) and other additives as needed in, for example, a Henschel mixer, V blender, ribbon blender or tumbler blender, followed by kneading in a kneader such as a single-screw extruder, a multi-screw extruder, a kneader or a Banbury mixer.
The propylene resin composition (Z) making up the innermost layer (3) in the multilayer propylene resin sheet of the invention is obtained by a method which involves mixing the above-described propylene resin composition (Z1) of propylene-α-olefin copolymer component (E) and ethylene-α-olefin copolymer (F), or the above-described propylene resin composition (Z2) of propylene resin composition (G), ethylene-α-olefin copolymer (H), propylene resin (I) where desired, and other additives as needed in, for example, a Henschel mixer, V blender, ribbon blender or tumbler blender, followed by kneading in a kneader such as a single-screw extruder, a multi-screw extruder, a kneader or a Banbury mixer.
The respective components may be mixed at the same time, or a portion may be prepared as a masterbatch, then mixed and kneaded.
[III] Multilayer Propylene Resin Sheet
The multilayer propylene resin sheet of the invention can be produced by a known method using the above-described propylene resin compositions. Production is carried out by a known technique, such as extrusion using a T-die or a circular die.
The multilayer propylene resin sheet of the invention has an excellent flexibility, transparency, impact resistance, heat resistance and cleanliness, and is able to suppress the loss of transparency due to appearance defects such as thickness irregularities and interfacial roughness. Moreover, the productivity is enhanced because reductions in thickness during fabrication operations such as heat sealing can be suppressed, enabling a good mechanical strength to be maintained and excellent heat sealability to be achieved. As a result, the sheet is ideally suited for use in heat-treatable packaging bags which must undergo a heat treatment operation such as sterilization, and particularly IV bags.
The multilayer propylene resin sheet of the invention is characterized by having an excellent flexibility even after heat treatment. It is desirable that the sheet have a tensile modulus, which is a measure of flexibility, of 330 Mpa or less. At a tensile modulus of 300 Mpa or less, and preferably 280 Mpa or less, because the sheet ceases to feel stiff, it has a good hand and is able to convey a sense of quality, which is a remarkable feature.
The multilayer propylene resin sheet of the invention, by having a haze (a measure of transparency) following heat treatment of 20% or less, preferably 18% or less, and more preferably 15% or less, allows the contents to be clearly seen, a quality which is highly desirable in that it enables one to check whether foreign matter is present in the bag contents.
The multilayer propylene resin sheet of the invention has an impact resistance, particularly at low temperatures of 0 to 5° C., which is excellent. In low-temperature bag drop tests, which are a measure of the low-temperature impact resistance, the sheet has an outstanding impact resistance, with bag failure not occurring even when dropped from a height of 100 cm. This is an excellent result in that it allows the sheet to be used as a product (bag) which will not fail even should it be dropped during, for example, transport or storage. The sheet preferably does not fail even when dropped from a height of 150 cm, and more preferably does not fail even when dropped from a height of 200 cm.
In addition, the multilayer propylene resin sheet of the invention has an excellent heat resistance. Namely, it exhibits an outstanding heat resistance without deformation or internal fusion even when heat treatment at about 121° C. is carried out. A deformed sheet has a bad appearance and a reduced product value. An internally fused sheet may interfere with discharge of the contents, making the sheet unfit for use as a product.
Furthermore, the multilayer propylene resin sheet of the invention has an excellent cleanliness. In the innermost layer (3) which comes into contact with the contents, it is desirable to employ a propylene resin composition which is obtained using a metallocene catalyst and has exceedingly low contents of low-molecular weight components and low-regularity components that may contaminate the contents.
Finally, the multilayer propylene resin sheet of the invention has an excellent low-temperature heat sealability, which is highly advantageous for enhancing productivity. The heat sealability of the sheet is such that, at a heat-sealing pressure of 3.4 kgf/cm2 and a heat-sealing time of 5 seconds, a heat-sealing strength of at least 3,000 gf/10 mm is obtained at a heat-sealing temperature of preferably 145° C. or less, and more preferably 140° C. or less.
EXAMPLES
To more concretely and clearly explain the invention, the invention is illustrated below by contrasting working examples of the invention with comparative examples, thereby demonstrating the rationality and significance of the constitution of the invention. However, the invention is not limited by these examples. The physical property measurement methods, characterization methods and resin materials used in the working examples and comparative examples are described below.
1. Resin Property Measurement Methods
(1) MFR
Propylene resin composition (A), propylene resin (C), propylene resin (D), propylene-ethylene random copolymer (E), propylene resin composition (G) and propylene resin (I) were measured in accordance with JIS K7210, Method A, Condition M; namely, at a test temperature of 230° C., a nominal load of 2.16 kg, and a die shape having a diameter of 2.095 mm and a length of 8.00 mm.
Ethylene-α-olefin copolymer (B), ethylene-α-olefin copolymer (D3), ethylene-α-olefin copolymer (F) and ethylene-α-olefin copolymer (H) were measured in accordance with JIS K7210, Method A, Condition D; namely, at a test temperature of 190° C., a nominal load of 2.16 kg, and a die shape having a diameter of 2.095 mm and a length of 8.00 mm.
(2) Density:
Using the extruded strand obtained at the time of MFR measurement, measurement was carried out by the density gradient tube method in general accordance with JIS K7112, Method D.
(3) Melting Peak Temperature:
A digital scanning calorimeter (DSC) manufactured by Seiko Instruments, Inc. was used. After placing a 5.0 mg sample in the calorimeter and holding it at 200° C. for 5 minutes, the sample was crystallized by lowering the temperature to 40° C. at a ramp-down rate of 10° C./min, then melted at a ramp-up rate of 10° C./min, at which time the melting peak temperature was measured.
(4) Dynamic Mechanical Analysis
The samples used were cut out in the form of strips (10 mm wide×18 mm long×2 mm thick) from a 2 mm thick sheet injection-molded under the conditions indicated below. The apparatus used was an ARES manufactured by Rheometric Scientific. The frequency was 1 Hz. The measurement temperature was ramped up in a stepwise manner from −60° C., and measurement was carried out until the sample melted and measurement became impossible. Measurement was carried out at a strain in a range of from 0.1 to 0.5%.
[Test Piece Fabrication]
Standard No.: JIS-7152 (ISO 294-1)
Molding machine: EC-20 injection molding machine (Toshiba Machine)
Molding machine temperature settings: from below hopper—−80, 80, 160, 200, 200, 200° C.
Mold temperature: 40° C.
Injection rate: 200 mm/s (rate in mold cavity)
Holding pressure: 20 MPa
Pressure-holding time: 40 seconds
Mold shape: flat plate (thickness, 2 mm; width, 40 mm; length, 80 mm)
(5) W(A1), W(A2), E[A1], E[A2], W(G1), W(G2), E(G1), E(G2)
Measured by the above-described methods.
(6) 0° C. Solubles (S0) of Component (E)
Measured by the temperature rising elution fractionation (TREF) method described below.
A sample is dissolved in o-dichlorobenzene at 140° C., forming a solution. The solution is introduced into a 140° C. TREF column, following which it is cooled to 100° C. at a ramp-down rate of 8° C./rain, then cooled to 40° C. at a ramp-down rate of 4° C./min, and held at that temperature for 10 minutes. Next, the o-dichlorobenzene serving as the solvent is passed through the column at a rate of 1 mL/min and the component dissolved in the 40° C. o-dichlorobenzene within the TREF column is eluted for 10 minutes, following which the temperature of the column is raised linearly to 140° C. at a ramp-up rate of 100° C./hour, thereby giving an elution curve.
The ratio (wt %) of the component eluted at 40° C. to the total weight is computed from the elution curve obtained according to the above conditions. Conditions such as the column used, the solvent and the temperature were as follows.
Column size: 4.3 mm diameter×150 mm
Column packing: 100 μm surface-deactivated glass beads
Solvent: o-dichlorobenzene
Sample concentration: 5 mg/mL
Sample insertion amount: 0.1 mL
Solvent flow rate: 1 mL/min
Detector: MIRAN 1A (Foxboro) fixed wavelength type infrared detector
Measurement wavelength: 3.42 μm
2. Method of Forming Multilayer Propylene Resin Sheet
Using a 3-kind, 3-layer water-cooled blown film forming machine (Placo Co., Ltd.; die diameter, 100 mm; die lip, 3 mm; die temperature, 200° C.), a tubular multilayer sheet was formed in which the outer layer (2) and innermost layer (3) each had thicknesses of 20 μm and the inner layer had a thickness of 160 μm, and which had a lay-flat width of 200 mm.
3. Evaluation Methods for Multilayer Propylene Resin Sheet
(1) Heat Resistance (Appearance)
The multilayer propylene resin sheet having a tubular shape was cut to a size of 210 mm in the machine direction, and the cut side was heat-sealed (heat-sealing conditions: pressure, 3.4 kgf/cm2; time, 5 seconds; temperature, 160° C.; using a heat sealer manufactured by Tester Sangyo Co., Ltd.) and formed into a bag shape. Next, the interior was filled with 500 mL of pure water, and the other end was sealed by heat-sealing with an impulse sealer. Sealing was carried out such that the distance between the two heat seals was 200 mm. The sample bag thus obtained was placed in a high-temperature and high-pressure cooking sterilization equipment (RCS-40 RTGN, manufactured by Hisaka Works, Ltd.), after which pressure was applied and the ambient temperature was raised to and held at 121° C. for 30 minutes. This was followed by cooling to about 40° C., whereupon the sample bag was removed from the equipment (the multilayer sheet (sample bag) which has been subjected to this sterilization treatment is sometimes referred to below as “the heat-treated multilayer sheet”).
The heat resistance of the heat-treated multilayer sheet was evaluated according to the following criteria.
Δ: Bag is not fit for use owing to deformation, wrinkling or internal fusion.
◯−: Some deformation, but of a degree that allows bag to be used.
◯: Condition of bag is good, with no deformation, wrinkling or internal fusion.
(2) Transparency (HAZE)
The transparency of the heat-treated multilayer sheet was measured with a hazemeter in general accordance with JIS K7136-2000. A smaller value signifies better transparency. A value of 20% or less is good because the contents are easy to check, giving a display effect. The value is preferably 18% or less, and more preferably 15% or less.
(3) Flexibility (Tensile Modulus)
The tensile modulus of the heat-treated multilayer sheet was measured under the following conditions in the machine direction (MD) in accordance with JIS K-7127-1989. A smaller value signifies better flexibility. A value of 330 MPa or less is desirable because the bag has a good hand, giving it a sense of quality. The value is preferably 300 MP or less, and more preferably 280 MPa or less.
Sample length: 150 mm
Sample width: 15 mm
Chuck interval: 100 mm
Crosshead speed: 1 mm/min
(4) Low-Temperature Impact Resistance (Cumulative Bag Drop Test)
Two water-filled heat-treated multilayer sheets were conditioned at 4° C. for 48 hours, following which they were dropped twice at that temperature onto an iron plate from a height of 50 cm. If the bags did not break, they were dropped twice from a height of 100 cm. If the bags still did not break, they were then dropped twice from a height of 150 cm. If the bags still remained unbroken, they were finally dropped twice from a height of 200 cm. It is desirable that failure not occur even when the bag is dropped from 100 cm, preferable that failure not occur even when the bag is dropped from 150 cm, and more preferable that failure not occur even when the bag is dropped from 200 cm. Sheets that did not fail were rated as “◯” for good. Sheets that failed were rated as “X”.
(5) Bag-Making Ease (Low-Temperature Heat Sealability: Heat-Sealing Strength)
A tubular multilayer propylene resin sheet was cut to a size of 100 mm in the machine direction and the cut side was heat-sealed to form a bag. The sheet was then conditioned for 24 hours in a 23° C., 50% RH atmosphere (heat-sealing conditions: pressure, 3.4 kgf/cm2; time, 5 seconds; temperature, from 125 to 160° C. in 5° C. intervals). Next, the interior was filled with 500 mL of pure water, and the other side was sealed by heat-sealing using an impulse sealer. The sample bag thus obtained was placed in a high-temperature and high-pressure cooking sterilization equipment (RCS-40 RTGN, manufactured by Hisaka Works, Ltd.), after which pressure was applied and the ambient temperature was raised to and held at 121° C. for 30 minutes. This was followed by cooling to about 40° C., whereupon the sample bag was removed from the equipment. Next, the water was drained, and the heat-sealed portion was cut into 10 mm wide strips. Using a universal testing machine (Tensilon universal testing machine, manufactured by Orientec Co., Ltd.), peel tests were carried out at a peel rate of 500 mm/min on these specimens, and the heat-sealing strength of the multilayer sheet was determined.
The higher the resulting numerical value, the stronger the heat seal between the laminated sheets. At a value of 3,000 gf/10 mm or more, the sheet is fully capable of being used in heat-treatable packaging bags.
Also, the lower the heat-sealing temperature at which a heat-sealing strength of 3,000 gf/10 mm or more can be achieved, the better the resulting productivity. That is, a lower heat-sealing temperature signifies a good bag-making ease. The heat-sealing temperature is preferably 145° C. or below, and more preferably 140° C.
4. Resins Used
(1) Propylene Resin Composition (A) for Inner Layer
(1-1) Resins PPCA-1) to PP(A-17) obtained by successive polymerization in Production Examples (A-1) to (A-17) below were used.
Production Example A-1
(i) Preparation of Prepolymerization Catalyst
(Chemical Treatment of Silicate)
A 10-liter glass separable flask equipped with a stirrer was charged with 3.75 liters of distilled water, followed by 2.5 kg of concentrated sulfuric acid (96%) slowly. In addition, 1 kg of montmorillonite (Benclay SL, available from Mizusawa Industrial Chemicals, Ltd.; average particle size, 25 μm; particle size distribution, 10 to 60 μm) was dispersed at 50° C., following which the temperature was raised to 90° C. and the flask was maintained at that temperature for 6.5 hours. After cooling to 50° C., the slurry was vacuum filtered and the cake was collected. Next, 7 liters of distilled water was added to the cake to as to reconstitute the slurry, which was then filtered. This washing operation was carried out until the pH of the wash fluid (filtrate) exceeded 3.5. The recovered cake was dried overnight in a nitrogen atmosphere at 110° C. The weight after drying was 707 g.
(Drying of Silicate)
The silicate which was chemically treated earlier was dried in a kiln dryer. The specifications and drying conditions were as follows.
Rotary cylinder: cylindrical shape, with inside diameter of 50 mm, heating zone of 550 mm (electric furnace), and with lifting flights
Rotating speed: 2 rpm
Inclination: 20/520
Silicate feed rate: 2.5 g/min
Gas flow rate: nitrogen, 96 L/hour
Countercurrent drying temperature: 200° C. (powder temperature)
(Preparation of Catalyst)
A 16-liter autoclave equipped with a stirrer and a temperature control device was thoroughly flushed with nitrogen. Dry silicate (200 g) was introduced, then 1,160 mL of mixed heptane was added, followed by 840 mL of a heptane solution of triethylaluminum (0.60 M), and the contents were stirred at room temperature. One hour later, washing with mixed heptane was carried out, thereby preparing 2,000 mL of a silicate slurry. Next, 9.6 mL of a heptane solution of triisobutylaluminum (0.71 M/L) was added to the prepared silicate slurry, and reacted at 25° C. for one hour. In a separate procedure, 33.1 mL of a heptane solution of triisobutylaluminum (0.71 M) was added to 2,180 mg (0.3 mM) of (r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azulenyl}]zirconium and 870 mL of mixed heptane, and reacted at room temperature for one hour. The mixture thus obtained was added to the silicate slurry and stirred for 1 hour, following which additional mixed heptane was added, bringing the volume up to 5,000 mL.
(Prepolymerization/Washing)
Next, the reactor temperature was raised to 40° C. Once the temperature had stabilized, propylene was fed in at a rate of 100 g/hour, and the temperature was maintained. The supply of propylene was stopped after 4 hours, and the temperature was maintained for another 2 hours.
After the completion of prepolymerization, the remaining monomer was purged, stirring was stopped, and the system was left at rest for about 10 minutes, following which 2,400 mL of supernatant was decanted. Next, 9.5 mL of a heptane solution of triisobutylaluminum (0.71 M/L) then 5,600 mL of mixed heptane were added, stirring was carried out at 40° C. for 30 minutes, and the system was left at rest for 10 minutes, after which 5,600 mL of supernatant was removed. This operation was repeated another three times. An ingredient analysis of the final supernatant was carried out, whereupon the concentration of the organoaluminum ingredient was 1.23 mM/L and the zirconium concentration was 8.6×10−6 g/L. Hence, the amount present in the supernatant relative to the amount charged was 0.016%. Next, 170 mL of a heptane solution of triisobutylaluinum (0.71 M/L) was added, following which vacuum drying was carried out at 45° C. This operation yielded a prepolymerization catalyst containing 2.0 g of polypropylene per gram of catalyst.
Using this prepolymerization catalyst, a propylene-ethylene block copolymer was produced according to the following procedure.
(ii) First Polymerization Step
A horizontal reactor (L/D=6; capacity, 100 liters) equipped with stirring blades was thoroughly dried, and the interior was thoroughly flushed with nitrogen gas. In the presence of a polypropylene powder bed and while stirring at a speed of 30 rpm, 0.568 g/hr of the prepolymerization catalyst prepared by the above-described method and 15.0 mmol/hr of triisobutylaluminum were continuously fed to the upstream portion of the reactor. Vapor phase polymerization was carried out by continuously passing a monomer mixed gas into the reactor in such a way as to give an ethylene-propylene molar ratio of 0.07 in the vapor phase portion within the reactor and to set the hydrogen concentration at 100 ppm, while holding the reactor temperature at 65° C. and the pressure at 2.1 MPaG. The polymer powder formed by the reaction was continuously removed from the downstream portion of the reactor in a manner such as to keep the size of the powder bed within the reactor constant. The polymer removal rate that reached a steady state at this time was 10.0 kg/hr.
Upon analysis, the propylene-ethylene random copolymer obtained in the first polymerization step was found to have a MFR of 6.0 g/10 min and an ethylene content of 2.2 wt %.
(iii) Second Polymerization Step
The propylene-ethylene copolymer removed from the first step was continuously fed to a horizontal reactor equipped with stirring blades (L/D=6; capacity, 100 liters). Vapor-phase polymerization was carried out by continuously passing a monomer mixed gas into the reactor in such a way as to give an ethylene-propylene molar ratio of 0.453 in the vapor phase portion within the reactor and to set the hydrogen concentration at 330 ppm, while stirring at a rate of 25 rpm and while holding the reactor temperature at 70° C. and the pressure at 2.0 MPaG. The polymer powder formed by the reaction was continuously removed from the downstream portion of the reactor in such a way as to keep the size of the powder bed within the reactor constant. Oxygen was supplied as an activity suppressor so as to set the polymer removal rate at this time to 17.9 kg/hr, thereby controlling the polymerization reaction rate in the second polymerization step. The activity was 31.429 kg/g of catalyst.
The various analytical results for the propylene resin composition PP(A-1) obtained in this way are shown in Table 3.
Production Examples A-2 to A-9
Aside from changing the polymerization conditions as shown in Table 3, catalyst preparation and polymerization were carried out by the same methods as in Production Example A-1.
Following reaction completion, various analyses of the resulting polymers were carried out. Table 3 shows the analytical results for the propylene resin compositions PP(A-2) to PP(A-9) thus obtained. These satisfy all the features of the invention for component (A).
Production Examples A-10 to A-17
Aside from changing the polymerization conditions as shown in Table 4, catalyst preparation and polymerization were carried out by the same methods as in Production Example A-1.
Following reaction completion, various analyses of the resulting polymers were carried out. Table 4 shows analytical results for the propylene resin compositions PPCA-10) to PP(A-17) thus obtained. These do not satisfy the features of the invention for component (A).












TABLE 3







Production Examples
A-1
A-2
A-3
A-4
A-5





Propylene Resin Composition (A)
PP(A-1)
PP(A-2)
PP(A-3)
PP(A-4)
PP(A-5)















Production
Step 1
Catalyst amount
g/h
0.568
0.391
0.625
0.568
0.568


conditions

Temperature
° C.
65
65
65
65
65




Pressure
MPa
2.1
2.1
2.1
2.1
2.1




C2/C3 ratio
mol/mol
0.07
0.09
0.055
0.07
0.07




Hydrogen
ppm
100
150
90
100
100




concentration




Production amount
kg/h
10
10
10
10
10




(Polymerization
g/g-cat
17,600
25,600
16,000
17,600
17,600




activity)



Step 2
Temperature
° C.
70
70
70
70
70




Pressure
MPa
2.0
2.0
2.0
2.0
2.0




C2/C3 ratio
mol/mol
0.453
0.453
0.453
0.534
0.435




Hydrogen
ppm
330
330
330
350
320




concentration




Production amount
kg/h
17.9
17.9
17.9
19.2
16.7




(Polymerization
g/g-cat
31,429
45,714
28,571
33,846
29,333




activity)


Analytic
Tm(A1)
Melting peak
° C.
130
126
133
130
130


results

temperature



E(A1)
Ethylene content in
wt %
2.2
2.8
1.7
2.2
2.2




component (A1)



W(A1)
Ratio of
wt %
56
56
56
52
60




component (A1)



MFR(A1)
MFR of
g/10 min
6
6
6
6
6




component (A1)



E(A2)
Ethylene content in
wt %
11
11
11
12.8
10.6




component (A2)



W(A2)
Ratio of
wt %
44
44
44
48
40




component (A2)



MFR(A)
MFR of
g/10 min
6
6
6
6
6




component (A)



Tg
Glass transition
° C.
−14
−15
−13
−16
−13




point
















Production Examples
A-6
A-7
A-8
A-9







Propylene Resin Composition (A)
PP(A-6)
PP(A-7)
PP(A-8)
PP(A-9)
















Production
Step 1
Catalyst amount
g/h
0.568
0.568
0.649
0.535



conditions

Temperature
° C.
65
65
65
65





Pressure
MPa
2.1
2.1
2.1
2.1





C2/C3 ratio
mol/mol
0.07
0.07
0.07
0.07





Hydrogen
ppm
100
100
90
110





concentration





Production amount
kg/h
10
10
10
10





(Polymerization
g/g-cat
17,600
17,600
15,400
18,700





activity)




Step 2
Temperature
° C.
70
70
70
70





Pressure
MPa
2.0
2.0
2.0
2.0





C2/C3 ratio
mol/mol
0.435
0.534
0.453
0.453





Hydrogen
ppm
320
350
300
450





concentration





Production amount
kg/h
17.9
17.9
17.9
17.9





(Polymerization
g/g-cat
31,429
31,429
27,500
33,393





activity)



Analytic
Tm(A1)
Melting peak
° C.
130
130
130
130



results

temperature




E(A1)
Ethylene content in
wt %
2.2
2.2
2.2
2.2





component (A1)




W(A1)
Ratio of
wt %
56
56
56
56





component (A1)




MFR(A1)
MFR of
g/10 min
6
6
4.7
8





component (A1)




E(A2)
Ethylene content in
wt %
10.6
12.8
11
11





component (A2)




W(A2)
Ratio of
wt %
44
44
44
44





component (A2)




MFR(A)
MFR of
g/10 min
6
6
4.7
8





component (A)




Tg
Glass transition
° C.
−14
−15
−14
−14





point






















TABLE 4







Production Examples
A-10
A-11
A-12
A-13
A-14





Propylene Resin Composition (A)
PP(A-10)
PP(A-11)
PP(A-12)
PP(A-13)
PP(A-14)















Production
Step 1
Catalyst amount
g/h
0.284
1.250
0.568
0.568
0.568


conditions

Temperature
° C.
65
65
65
65
65




Pressure
MPa
2.1
2.1
2.1
2.1
2.1




C2/C3 ratio
mol/mol
0.12
0.02
0.07
0.07
0.07




Hydrogen
ppm
200
30
100
100
100




concentration




Production amount
kg/h
10
10
10
10
10




(Polymerization
g/g-cat
35,200
8,000
17,600
17,600
17,600




activity)



Step 2
Temperature
° C.
70
70
70
70
70




Pressure
MPa
2.0
2.0
2.0
2.0
2.0




C2/C3 ratio
mol/mol
0.453
0.453
0.453
0.453
0.228




Hydrogen
ppm
330
330
330
330
300




concentration




Production amount
kg/h
17.9
17.9
25.0
15.4
17.9




(Polymerization
g/g-cat
62,857
14,286
44,000
27,077
31,429




activity)


Analytic
Tm(A1)
Melting peak
° C.
120
140
130
130
130


results

temperature



E(A1)
Ethylene content in
wt %
3.8
0.5
2.2
2.2
2.2




component (A1)



W(A1)
Ratio of
wt %
56
56
40
65
56




component (A1)



MFR(A1)
MFR of
g/10 min
6
6
6
6
6




component (A1)



E(A2)
Ethylene content in
wt %
11
11
11
11
6




component (A2)



W(A2)
Ratio of
wt %
44
44
60
35
44




component (A2)



MFR(A)
MFR of
g/10 min
6
6
6
6
6




component (A)



Tg
Glass transition
° C.
−16
−12
−15
−11
−9




point















Production Examples
A-15
A-16
A-17







Propylene Resin Composition (A)
PP(A-15)
PP(A-16)
PP(A-17)















Production
Step 1
Catalyst amount
g/h
0.568
0.909
0.455



conditions

Temperature
° C.
65
65
65





Pressure
MPa
2.1
2.1
2.1





C2/C3 ratio
mol/mol
0.07
0.07
0.07





Hydrogen
ppm
100
20
200





concentration





Production amount
kg/h
10
10
10





(Polymerization
g/g-cat
17,600
11,000
22,000





activity)




Step 2
Temperature
° C.
70
70
70





Pressure
MPa
2.0
2.0
2.0





C2/C3 ratio
mol/mol
0.678
0.453
0.453





Hydrogen
ppm
380
330
330





concentration





Production amount
kg/h
17.9
17.9
17.9





(Polymerization
g/g-cat
31,429
19,643
39,286





activity)



Analytic
Tm(A1)
Melting peak
° C.
130
130
130



results

temperature




E(A1)
Ethylene content in
wt %
2.2
2.2
2.2





component (A1)




W(A1)
Ratio of
wt %
56
56
56





component (A1)




MFR(A1)
MFR of
g/10 min
6
2
15





component (A1)




E(A2)
Ethylene content in
wt %
16
11
11





component (A2)




W(A2)
Ratio of
wt %
44
44
44





component (A2)




MFR(A)
MFR of
g/10 min
6
2
15





component (A)




Tg
Glass transition
° C.
−12, −32
−14
−14





point










(1-2) Propylene Resin Composition (A) for Inner Layer, Obtained by Blending

The following <J1> propylene-α-olefin random copolymers ((J1-1) to (J1-7)) were used as component (A1), and the following <J2> propylene-ethylene random copolymers ((J2-1) to (J2-4)) were used as component (A2).
<J1>


    J1-1: The commercial product available from Japan Polypropylene


Corporation under the trade name WINTEC WFW4 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)

    J1-2: Produced in Production Example J1-2 below.
    J1-3: The commercial product available from Japan Polypropylene Corporation under the trade name NOVATEC PP FW4B (a propylene-α-olefin copolymer obtained with a Ziegler-Natta catalyst)
    J1-4: The commercial product available from Japan Polypropylene Corporation under the trade name NOVATEC PP EG7F (a propylene-ethylene random copolymer obtained with a Ziegler-Natta catalyst)
    J1-5: The commercial product available from Dow Chemical under the trade name VERSIFY 3000 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)
    J1-6: Produced in Production Example J1-6 below.
    J1-7: The commercial product available from Japan Polypropylene Corporation under the trade name NOVATEC PP SA06A (a propylene homopolymer obtained with a Ziegler-Natta catalyst)

<J2>

    J2-1: The commercial product available from Exxon-Mobil Chemical under the trade name VISTAMAXX 3000 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)
    J2-2: The commercial product available from Dow Chemical under the trade name VERSIFY 3000 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)
    J2-3: The commercial product available from LiondellBasell Industries under the trade name ADFLEX X100G (a propylene-ethylene random copolymer obtained with a Ziegler-Natta catalyst)
    J2-4: The commercial product available from Exxon-Mobil Chemical Under the trade name VISTAMAXX 2120 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)


Production Example J1-2
(i) Synthesis of Transition Metal Compound
The synthesis of [(r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azurenyl}]zirconium] was carried out in accordance with the working examples in Japanese Patent Application Laid-open No. H10-226712.
(ii) Chemical Treatment of Silicate
A 10-liter glass separable flask equipped with a stirrer was charged with 3.75 liters of distilled water, followed by 2.5 kg of concentrated sulfuric acid (96%) slowly. In addition, 1 kg of montmorillonite (Benclay SL, available from Mizusawa Industrial Chemicals, Ltd.; average particle size=25 μm; particle size distribution=10 μm to 60 μm) was dispersed at 50° C., following which the temperature was raised to 90° C. and the flask was maintained at that temperature for 6.5 hours. After cooling to 50° C., the slurry was vacuum filtered, and the cake was collected. Next, 7 liters of distilled water was added to the cake to as to reconstitute the slurry, which was then filtered. This washing operation was carried out until the pH of the wash fluid (filtrate) exceeded 3.5.
The recovered cake was dried overnight in a nitrogen atmosphere at 110° C. The weight after drying was 707 g.
(iii) Drying of Silicate
The silicate which was chemically treated earlier was dried in a kiln dryer. The specifications and drying conditions were as follows.
Rotary cylinder: cylindrical shape, with inside diameter of 50 mm, heating zone of 550 mm (electric furnace), and with lifting flights
Rotating speed: 2 rpm
Inclination: 20/520
Silicate feed rate: 2.5 g/min
Gas flow rate: nitrogen, 96 L/hour
Countercurrent drying temperature: 200° C. (powder temperature)
(iv) Preparation of Catalyst
The dry silicate (20 g) obtained as described above was placed in a 1 L glass reactor equipped with a stirrer, after which 116 mL of mixed heptane was added, followed by 84 mL of a heptane solution of triethylaluminum (0.60 M), and the contents were stirred at room temperature. One hour later, washing with mixed heptane was carried out, thereby preparing 200 mL of a silicate slurry.
Next, 0.96 mL of a heptane solution of triisobutylaluminum (0.71 M/L) was added to the silicate slurry prepared as described above, and reacted at 25° C. for one hour. In a separate procedure, 3.31 mL of a heptane solution of triisobutylaluminum (0.71 M) was added to 218 mg (0.3 mmol) of (r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azulenyl}]zirconium and 87 mL of mixed heptane, and reacted at room temperature for one hour. The mixture thus obtained was added to the silicate slurry and stirred for 1 hour, following which additional mixed heptane was added, bringing the volume up to 500 mL.
(v) Prepolymerization/Washing
Next, the silicate/metallocene complex slurry prepared above was placed in a 1.0 liter autoclave with stirrer which had been thoroughly flushed with nitrogen. Once the temperature had stabilized to 40° C., propylene was fed in at a rate of 10 g/hour, and the temperature was maintained. The supply of propylene was stopped after 4 hours, and the temperature was maintained for another 2 hours.
After the completion of prepolymerization, the remaining monomer was purged, stirring was stopped, and the system was left at rest for about 10 minutes, following which 240 mL of supernatant was decanted. Next, 0.95 mL of a heptane solution of triisobutylaluminum (0.71 M/L), then 560 mL of mixed heptane were added, stirring was carried out at 40° C. for 30 minutes, and the system was left at rest for 10 minutes, then 560 mL of supernatant was removed. This operation was repeated another three times. An ingredient analysis of the final supernatant was carried out, whereupon the concentration of the organoaluminum ingredient was 1.23 mM/L and the zirconium concentration was 8.6×10−6 g/L. Hence, the amount present in the supernatant relative to the amount charged was 0.016%.
Next, 17.0 mL of a heptane solution of triisobutylaluminum (0.71 M/L) was added, following which vacuum drying was carried out at 45° C. This operation yielded a prepolymerization catalyst containing 2.0 g of polypropylene per gram of solid catalyst component.
(vi) Polymerization
The interior of a 200 liter stirring-type autoclave was thoroughly flushed with propylene, following which 45 kg of thoroughly dehydrated, liquefied propylene was introduced. To this were added 500 mL (0.12 mol) of an n-heptane solution of triisobutylaluminum, 0.32 kg of ethylene and 2.5 liters (the volume under standard conditions) of hydrogen, and the internal temperature was maintained at 30° C. Next, 1.90 g (weight of solid catalyst component) of a metallocene type polymerization catalyst was injected with argon, thereby commencing polymerization. The temperature rose to 70° C. over a period of 40 minutes, and was held at that temperature for 60 minutes. At this point, 100 mL of ethanol was added, stopping the reaction. The remaining gas was purged, yielding 20.3 kg of polypropylene polymer. This operation was repeated five time, giving polypropylene-ethylene random copolymer PP(J1-2).
The MFR of this resin was 7 g/10 min, the ethylene content was 0.75 mol %, and the melting point was 142° C.
Production Example (J1-6)
(i) Production of Solid Component (A)
A 10 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and 2 L of purified n-heptane was introduced. In addition, 250 g of MgCl2 and 1.8 L of Ti(O-n-Bu)4 were added, and the reaction was carried out at 95° C. for 2 hours. The reaction product was cooled to 40° C., and 500 mL of methyl hydrogen polysiloxane (20 centistoke) was added. After the reaction was carried out at 40° C. for 5 hours, the precipitated solid product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced, and the concentration of the above solid product was adjusted to 200 g/L. At this point, 300 mL of SiCl4 was added, and the reaction was carried out at 90° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so as to set the concentration of the reaction product to 100 g/L. To this was added a mixture of 30 mL of phthaloyl dichloride with 270 mL of purified n-heptane, and the reaction was carried out at 90° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was added so as to bring the concentration of the reaction product to 200 g/L. Next, 1 L of TiCl4 was added, and the reaction was carried out at 95° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, giving a slurry of solid component (A). A portion of this slurry was sampled and dried. The analysis showed the titanium content of the solid component (A) to be 2.5 wt %.
(ii) Preparation of Solid Catalyst Component (B)
Next, a 20 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and the above slurry of solid component (A) was introduced in an amount corresponding to 100 g of solid component (A). Purified n-heptane was added so as to adjust the concentration of solid component (A) to 20 g/L. To this were added 25 mL of trimethylvinylsilane, 25 mL of (t-Bu)(Me)Si(OEt)2, and an amount of an n-heptane dilution of Et3Al corresponding to 50 g as Et3Al, and the reaction was carried out at 30° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane. A portion of the resulting slurry was sampled and dried. The analysis showed that the solid component contained 2.1 wt % of titanium and 6.1 wt % of (t-Bu) (Me)Si(OEt)2.
Using the solid component obtained above, preliminary polymerization was carried out according to the following procedure. Purified n-heptane was added to the above slurry, adjusting the concentration of the solid component to 10 g/L. The slurry was cooled to 10° C., following which an n-heptane dilution of Et3Al was added in an amount corresponding to 10 g of Et3Al, and 150 g of propylene was fed over a period of 2 hours. After the feeding of propylene was completed, the reaction was continued for another 30 minutes. Next, the vapor phase portion was thoroughly flushed with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The resulting slurry was removed from the autoclave and vacuum dried, giving solid catalyst component (B). This solid catalyst component (B) contained 1.2 g of polypropylene per gram of solid components. Upon analysis, the portion of this solid catalyst component (B) from which polypropylene had been removed contained 1.6 wt % of titanium and 5.5 wt % of (t-Bu)(Me)Si(OEt)2.
(iii) Polymerization
The interior of a 200 L stirring-type autoclave was thoroughly flushed with propylene, following which 80 L of purified n-heptane was introduced. The temperature was raised to 70° C., then an n-heptane dilution of Et3Al in an amount corresponding to 1.5 g of Et3Al, 5.0 NL of hydrogen, and 0.25 g of the above solid catalyst component (B) (but excluding the prepolymerization polymer) were added. The temperature was raised to 75° C., following which propylene was fed in to a pressure of 0.7 MPaG, and polymerization was begun. Propylene supply was continued so as to maintain the pressure during polymerization. Three hours later, polymerization was stopped by adding 1 L of butanol. The remaining propylene was purged, and thoroughly flushed with nitrogen. The slurry thus obtained was filtered with a centrifugal separator, then dried in a desiccator, thereby giving PP(J1-6).
Analytical results for above PP(J1-1) to PP(J1-7) and PP(J2-1) to PP(J2-4) are shown in Tables 5 and 6 below.














TABLE 5





Production Example
(J1-1)
J1-2
(J1-3)
(J1-4)
(J1-5)
J1-6
(J1-7)






















Propylene-α-olefin copolymer (J1)
PP
PP
PP
PP
PP
PP
PP



(J1-1)
(J1-2)
(J1-3)
(J1-4)
(J1-5)
(J1-6)
(J1-7)


Name of grade
WFW4

FW4B
EG7F
VERSIFY

SA06A







3000

















Analytic
Melt
Tm(J1)
° C.
135
142
139
142
108
161
161


Result
peak



temp.



Melt
MFR(J1)
g/10
 7
 7
 7
1.4
 8
 5
 60



flow

min



rate




















TABLE 6





Production Example
(J2-1)
(J2-2)
(J2-3)
(J2-4)



















Propylene-α-olefin copolymer
PP
PP
PP
PP


(J2)
(J2-1)
(J2-2)
(J2-3)
(J2-4)


Name of grade
VISTAMAXX
VERSIFY
ADFLEX
VISTAMAXX



3000
3000
X100G
2120














Analytic
Ethylene content
E(J2)
° C.
11
3
18
13


results



Melt
MFR(J2)
g/10
 8
8
 8
80



flow

min



rate



Catalyst
—
—
metallocene
metallocene
Ziegler-
metallocene








Natta









The above <J1> propylene-α-olefin random copolymers ((J1-1) to (J1-7)) as component (A1), and the above <J2> propylene-ethylene random copolymers ((J2-1) to (J2-4)) as component (A2) were weighed out in the compositional ratios shown below in Table 7 and mixed together by stirring in a Henschel mixer, thereby giving propylene resin compositions PP(A-18) to PPCA-33).
Analytical results for the above compositions are shown in Tables 7 and 8 below.















TABLE 7





Production Example
A-18
A-19
A-20
A-21
A-22
A-23
A-24
A-25























Propylene resin composition (A)
PP
PP
PP
PP
PP
PP
PP
PP



(A-18)
(A-19)
(A-20)
(A-21)
(A-22)
(A-23)
(A-24)
(A-25)


Propylene-α-olefin copolymer (J1)
PP
PP
PP
PP
PP
PP
PP
—



(J1-1)
(J1-1)
(J1-1)
(J1-2)
(J1-3)
(J1-4)
(J1-1)


Compounded amount (wt %)
50
40
60
50
50
50
100 
0


Propylene-ethylene copolymer (J2)
PP
PP
PP
PP
PP
PP
—
PP



(J2-1)
(J2-1)
(J2-1)
(J2-1)
(J2-1)
(J2-1)

(J2-1)


Compounded amount (wt %)
50
60
40
50
50
50
0
100


















Analytic
Melt flow
MFR
g/10
7.5
7.6
7.4
7.5
7.5
3.3
7
8


Results
rate
(A)
min



Glass
Tg
° C.
−15
−16
−14
−13
−13
−13
2
−23



transition



point
























TABLE 8





Production Example
A-26
A-27
A-28
A-29
A-30
A-31
A-32
A-33























Propylene resin composition (A)
PP
PP
PP
PP
PP
PP
PP
PP



(A-26)
(A-27)
(A-28)
(A-29)
(A-30)
(A-31)
(A-32)
(A-33)


Propylene-α-olefin copolymer (J1)
PP
PP
PP
PP
PP
PP
PP
PP



(J1-1)
(J1-1)
(J1-5)
(J1-6)
(J1-7)
(J1-1)
(J1-1)
(J1-1)


Compounded amount (wt %)
80
20
50
50
50
50
50
50


Propylene-ethylene copolymer (J2)
PP
PP
PP
PP
PP
PP
PP
PP



(J2-1)
(J2-1)
(J2-1)
(J2-1)
(J2-1)
(J2-2)
(J2-3)
(J2-4)


Compounded amount (wt %)
20
80
50
50
50
50
50
50


















Analytic
Melt flow
MFR
g/10
7.2
7.8
8
6.3
21.9
7.5
7.5
23.7


Results
rate
(A)
min



Glass
Tg
° C.
−8
−20
−20
−5
−5
−9
−20, −41
−16



transition



point









(2) Ethylene-α-Olefin Copolymer (B) in Inner Layer

The resins PE(B-1) to PE(B-6) obtained in Production Examples (B-1) to (B-6) below and the subsequently described commercial products PE(B-7) and PE(B-8) were used (Production Example B-1)
A copolymer of ethylene and 1-hexene was produced. Catalyst preparation was carried out by the method described in Japanese Translation of PCT Application No H7-508545 (preparation of catalyst system). That is, a catalyst solution was prepared by adding, to 2.0 mmol of the complex dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)hafnium dimethyl, an equimolar amount of tripentafluorophenylboron, then diluting to 10 liters with toluene.
A mixture of ethylene and 1-hexene was fed to a stirring autoclave-type continuous reactor having a capacity of 1.5 liters in a manner such as to set the 1-hexene content to 73 wt %, and the reaction was carried out at 127° C. while maintaining the pressure inside the reactor at 130 MPa. The amount of polymer produced per hour was about 2.5 kg.
Following reaction completion, various analyses were carried out on the polymer. Table 9 shows the analytical results obtained for the resulting ethylene-α-olefin copolymer PE(B-1).
Production Examples B-2 to B-6
Aside from varying the 1-hexene content at the time of polymerization and the polymerization temperature as shown in Table 9, catalyst preparation and polymerization were carried out by a method similar to that for Production Example (B-1).
Following reaction completion, various analyses were conducted on the resulting polymers.
The commercial products employed were as follows.

    B-7: The commercial product available from Japan Polyethylene Corporation under the trade name KERNEL KF283 (an ethylene-α-olefin copolymer obtained with a metallocene catalyst)
    B-8: The commercial product available from Japan Polyethylene Corporation under the trade name KERNEL KJ640T (an ethylene-α-olefin copolymer obtained with a metallocene catalyst)


Table 9 shows the analytical results obtained for PE(B-1) to PE(B-8). PE(B-1) to PE(B-6) satisfy all the conditions of the invention for component (B).
However, PE(B-7) and PE(B-8) do not satisfy the conditions of the invention for component B.















TABLE 9





Production Example
B-1
B-2
B-3
B-4
B-5
B-6
(B-7)
(B-8)























Ethylene-α-olefin copolymer (B)
PE
PE
PE
PE
PE
PE
PE
PE



(B-1)
(B-2)
(B-3)
(B-4)
(B-5)
(B-6)
(B-7)
(B-8)


Name of grade
—
—
—
—
—
—
KF283
KJ640T

















Production
1-Hexene
wt %
73
78
62
55
74
72
—
—


conditions
content



Pressure
MPa
130
130
130
130
130
130
—
—



Temperature
° C.
127
118
140
148
140
114
—
—


Analytic
Density
g/cc
0.880
0.865
0.898
0.905
0.880
0.880
0.921
0.880


results
MFR(B)
g/10
3.5
3.5
3.5
2.2
12
1
2.5
30




min









(3) Propylene Resin (C) for Inner Layer

Resins PP(C-1) to PP(C-5) obtained in Production Examples (C-1) to (C-5) below were used. PP(C-1) to PP(C-4) are homopolypropylenes obtained by single-stage polymerization, and PP(C-5) is a block copolymer polypropylene obtained by multistage polymerization.
The following commercial polypropylene resins were used.

    (C-6): The product available from Japan Polyethylene Corporation under the trade name WINTEC WFW4 (a random polypropylene obtained by single-stage polymerization)
    (C-7): The product available from Japan Polyethylene Corporation under the trade name WINTEC WFX4 (a random polypropylene obtained by single-stage polymerization)
    (C-8): The product available from Japan Polyethylene Corporation under the trade name NOVATEC PP SA06A (a homopolypropylene obtained by single-stage polymerization)


The MFR and Tm are shown in Table 10.
Production Example C-1
(i) Production of Solid Component (A)
A 10 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and 2 L of purified n-heptane was introduced. In addition, 250 g of MgCl2 and 1.8 L of Ti(O-n-Bu)4 were added, and the reaction was carried out at 95° C. for 2 hours. The reaction product was cooled to 40° C., and 500 mL of methyl hydrogen polysiloxane (20 centistoke) was added. After the reaction was carried out at 40° C. for 5 hours, the precipitated solid product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced, and the concentration of the above solid product was adjusted to 200 g/L. At this point, 300 mL of SiCl4 was added, and the reaction was carried out at 90° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced in a manner such as to set the concentration of the reaction product to 100 g/L. To this was added a mixture of 30 mL of phthaloyl dichloride with 270 mL of purified n-heptane, and the reaction was carried out at 90° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was added so as to bring the concentration of the reaction product to 200 g/L. Next, 1 L of TiCl4 was added, and the reaction was carried out at 95° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, giving a slurry of solid component (A). A portion of this slurry was sampled and dried. The analysis showed the titanium content of the solid component (A) to be 2.5 wt %.
(ii) Preparation of Solid Catalyst Component (B)
Next, a 20 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and the above slurry of solid component (A) was introduced in an amount corresponding to 100 g of solid component (A). Purified n-heptane was added so as to adjust the concentration of solid component (A) to 20 g/L. To this were added 25 mL of trimethylvinylsilane, 25 mL of (t-Bu)(Me)Si(OEt)2, and an amount of an n-heptane dilution of Et3Al corresponding to 50 g as Et3Al, and the reaction was carried out at 30° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane. A portion of the resulting slurry was sampled and dried. The analysis showed that the solid component contained 2.1 wt % of titanium and 6.1 wt % of (t-Bu)(Me)Si(OEt)2.
Using the solid component obtained above, preliminary polymerization was carried out according to the following procedure. Purified n-heptane was added to the above slurry, adjusting the concentration of the solid component to 10 g/L. The slurry was cooled to 10° C., following which an n-heptane dilution of Et3Al was added in an amount corresponding to 10 g of Et3Al, and 150 g of propylene was fed over a period of 2 hours. After the feeding of propylene was completed, the reaction was continued for another 30 minutes. Next, the vapor phase portion was thoroughly flushed with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The resulting slurry was removed from the autoclave and vacuum dried, giving solid catalyst component (B). This solid catalyst component (B) contained 1.2 g of polypropylene per gram of solid components. Upon analysis, the portion of this solid catalyst component (B) from which polypropylene had been removed contained 1.6 wt % of titanium and 5.5 wt % of (t-Bu)(Me)Si(OEt)2.
(iii) Polymerization
The interior of a 200 L stirring-type autoclave was thoroughly flushed with propylene, following which 80 L of purified n-heptane was introduced. The temperature was raised to 70° C., then an n-heptane dilution of Et3Al in an amount corresponding to 1.5 g of Et3Al, 5.0 NL of hydrogen, and 0.25 g of the above solid catalyst component (B) (but excluding the prepolymerization polymer) were added. The temperature was raised to 75° C., following which propylene was fed in to a pressure of 0.7 MPaG, and polymerization was begun. Propylene supply was continued so as to maintain the pressure during polymerization. Three hours later, polymerization was stopped by adding 1 L of butanol. The remaining propylene was purged, and thoroughly flushed with nitrogen. The slurry thus obtained was filtered with a centrifugal separator, then dried in a desiccator, thereby giving PP(C-1).
Production Examples C-2 to C-4
Aside from changing the amount of hydrogen used during polymerization, PP(C-2) to PP(C-4) were obtained in the same way as in Production Example C-1. The results are shown in Table 10.
Production Example C-5
(i) Production of Solid Component Catalyst
A nitrogen-flushed 50 L reactor equipped with a stirrer was charged with 20 liters of dehydrated and deoxygenated n-heptane, then 4 moles of magnesium chloride and 8 moles of tetrabutoxytitanium were added and the reactor contents were reacted at 95° C. for 2 hours. The temperature was subsequently lowered to 40° C., 480 mL of methyl hydrogen polysiloxane (20 centipoises) was added, and the contents were again reacted for 3 hours, following which the reaction mixture was removed and the solid component that had formed was washed with n-heptane.
Next, 15 liters of dehydrated and deoxygenated n-heptane was charged into the same type of reactor with stirrer as described above, following which the solid components were added in an amount equivalent to 3 moles of magnesium atoms. A mixture of 8 moles of silicon tetrachloride added to 25 mL of n-heptane was then introduced at 30° C. over a period of 30 minutes, the temperature was raised to 90° C., and the reactor contents were reacted for one hour, following which the reaction mixture was removed and the solid component that had formed was washed with n-heptane.
In addition, 5 liters of dehydrated and deoxygenated n-heptane was charged into the same type of reactor with stirrer as described above, following which 250 g of the silicon tetrachloride-treated titanium-containing solid component obtained above, 750 g of 1,5-hexadiene, 130 mL of t-butylmethyldimethoxysilane, 10 mL of divinyldimethylsilane and 225 g of triethylaluminum were each added, and reaction was effected at 30° C. for 2 hours. The reaction mixture was subsequently removed and washed with n-heptane, giving a solid component catalyst.
The amount of 1,5-hexadiene prepolymerization for the resulting solid component catalyst was 2.97 g per gram of the titanium-containing solid component.
(ii) Two-Stage Polymerization of Propylene/Propylene-Ethylene
Propylene, triethylaluminum, and an amount of the above solid component catalyst which sets the polymer-forming rate at 20 kg/hour were continuously fed into a first-stage reactor having a capacity of 550 liters at a temperature of 70° C. and under an applied pressure (about 3.2 MPa at 70° C.). In addition, hydrogen was continuously fed as a molecular weight adjusting agent, and first-stage polymerization was carried out in a liquid phase.
Next, the polymer that had formed was charged, through a propylene purging tank, into a second-stage reactor having a capacity of 1,900 liters, and propylene and ethylene in amounts corresponding to the compositional ratio of the target copolymer were continuously fed in at a temperature of 60° C. to a pressure of 3.0 MPa. In addition, hydrogen was continuously fed in as a molecular weight adjusting agent, and an active hydrogen compound (ethanol) was fed in an amount of 200 moles per mole of titanium atoms in the solid component catalyst supplied in the first stage and in an amount of 2.5 moles per mole of triethylaluminum, whereupon polymerization was carried out in a vapor phase. The polymer that formed was continuously transferred to a vessel, following which moisture-containing nitrogen gas was introduced, thereby stopping the reaction (second-stage polymerization).
The analytic results for the resulting PP(C-5) are shown in Table 10.
PP(C-1) to PP(C-5) satisfy all the preferred features for component (C) in the invention. However, PP(C-6) to PP(C-8) do not satisfy the preferred features for component (C) in the invention.















TABLE 10





Production Example
C-1
C-2
C-3
C-4
C-5
(C-6)
(C-7)
(C-8)























Propylene resin (C)
PP
PP
PP
PP
PP
PP
PP
PP



(C-1)
(C-2)
(C-3)
(C-4)
(C-5)
(C-6)
(C-7)
(C-8)


Name of grade
—
—
—
—
—
WFW4
WFX4
SA06A

















Analytic
Tm(C)
° C.
161
161
161
161
162 
135
125
161


results
MFR(C)
g/10
 5
 10
 1
 21
 7
 7
 7
 60




min



Elastomer
wt %
—
—
—
—
57
—
—
—



content



Ethylene
wt %
—
—
—
—
17
—
—
—



content



in elastomer









(4) Propylene Resin (D) for Outer Layer (2)

The commercial propylene-ethylene random copolymers shown below and the resins obtained in Production Examples (D-2) to (D-4) described below were used. The MFR and Tm are shown in Table 11.

    (D-1): The product available from Japan Polyethylene Corporation under the trade name WINTEC WFW4
    (D-5): The product available from Japan Polyethylene Corporation under the trade name WINTEC WFX4
    (D-2) and (D-3): Ziegler-Natta catalyst-based homopolypropylenes produced by the single-stage polymerization described below
    (D-4): Block copolymer polypropylene produced by the multistage polymerization described below


Production Example D-2
(i) Production of Solid Component (A)
A 10 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and 2 L of purified n-heptane was introduced. In addition, 250 g of MgCl2 and 1.8 L of Ti(O-n-Bu)4 were added, and the reaction was carried out at 95° C. for 2 hours. The reaction product was cooled to 40° C., and 500 mL of methyl hydrogen polysiloxane (20 centistoke) was added. The reaction was carried out at 40° C. for 5 hours, after which the precipitated solid product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced, and the concentration of the above solid product was adjusted to 200 g/L. At this point, 300 mL of SiCl4 was added, and the reaction was carried out at 90° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so as to set the concentration of the reaction product to 100 g/L. To this was added a mixture of 30 mL of phthaloyl dichloride with 270 mL of purified n-heptane, and the reaction was carried out at 90° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was added so as to bring the concentration of the reaction product to 200 g/L. Next, 1 L of TiCl4 was added, and the reaction was carried out at 95° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, giving a slurry of solid component (A). A portion of this slurry was sampled and dried. The analysis showed the titanium content of the solid component (A) to be 2.5 wt %.
(ii) Preparation of Solid Catalyst Component (B)
Next, a 20 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and the above slurry of solid component (A) was introduced in an amount corresponding to 100 g of solid component (A). Purified n-heptane was added so as to adjust the concentration of solid component (A) to 20 g/L. To this were added 25 mL of trimethylvinylsilane, 25 mL of (t-Bu)(Me)Si(OEt)2, and an amount of an n-heptane dilution of Et3Al corresponding to 50 g as Et3Al, and the reaction was carried out at 30° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane. A portion of the resulting slurry was sampled and dried. The analysis showed that the solid component contained 2.1 wt % of titanium and 6.1 wt % of (t-Bu) (Me)Si(OEt)2.
Using the solid component obtained above, preliminary polymerization was carried out according to the following procedure. Purified n-heptane was added to the above slurry, adjusting the concentration of the solid component to 10 g/L. The slurry was cooled to 10° C., following which an n-heptane dilution of Et3Al was added in an amount corresponding to 10 g of Et3Al, and 150 g of propylene was fed over a period of 2 hours. After the feeding of propylene was completed, the reaction was continued for another 30 minutes. Next, the vapor phase portion was thoroughly flushed with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The resulting slurry was removed from the autoclave and vacuum dried, giving solid catalyst component (B). This solid catalyst component (B) contained 1.2 g of polypropylene per gram of solid components. Upon analysis, the portion of this solid catalyst component (B) from which polypropylene had been removed contained 1.6 wt % of titanium and 5.5 wt % of (t-Bu)(Me)Si(OEt)2.
(iii) Polymerization
The interior of a 200 L stirring-type autoclave was thoroughly flushed with propylene, following which 80 L of purified n-heptane was introduced. The temperature was raised to 70° C., then an n-heptane dilution of Et3Al in an amount corresponding to 1.5 g of Et3Al, 5.0 NL of hydrogen, and 0.25 g of the above solid catalyst component (B) (but excluding the prepolymerization polymer) were added. The temperature was raised to 75° C., following which propylene was fed in to a pressure of 0.7 MPaG, and polymerization was begun. Propylene supply was continued so as to maintain the pressure during polymerization. Three hours later, polymerization was stopped by adding 1 L of butanol. The remaining propylene was purged, and thoroughly flushed with nitrogen. The slurry thus obtained was filtered with a centrifugal separator, then dried in a desiccator, thereby giving PP(D-2).
Production Example D-3
Aside from changing the amount of hydrogen used during polymerization, PP(D-3) was obtained in the same way as in Production Example D-2. The results are shown in Table 11.
Production Example D-4
(i) Production of Solid Component Catalyst
A nitrogen-flushed 50 L reactor equipped with a stirrer was charged with 20 liters of dehydrated and deoxygenated n-heptane, then 4 moles of magnesium chloride and 8 moles of tetrabutoxytitanium were added and the reactor contents were reacted at 95° C. for 2 hours. The temperature was subsequently lowered to 40° C., 480 mL of methyl hydrogen polysiloxane (20 centistoke) was added, and the contents were again reacted for 3 hours, following which the reaction mixture was removed and the solid component that had formed was washed with n-heptane.
Next, 15 liters of dehydrated and deoxygenated n-heptane was charged into the same type of reactor with stirrer as described above, following which the solid component was added in an amount equivalent to 3 moles of magnesium atoms. A mixture of 8 moles of silicon tetrachloride added to 25 mL of n-heptane was then introduced at 30° C. over a period of 30 minutes, the temperature was raised to 90° C., and the reactor contents were reacted for one hour, following which the reaction mixture was removed and the solid component that had formed was washed with n-heptane.
In addition, 5 liters of dehydrated and deoxygenated n-heptane was charged into the same type of reactor with stirrer as described above, following which 250 g of the silicon tetrachloride-treated titanium-containing solid component obtained above, 750 g of 1,5-hexadiene, 130 mL of t-butylmethyldimethoxysilane, 10 mL of divinyldimethylsilane and 225 g of triethylaluminum were each added, and the reaction was carried out at 30° C. for 2 hours. The reaction mixture was subsequently removed and washed with n-heptane, giving a solid component catalyst.
The amount of 1,5-hexadiene prepolymerization for the resulting solid component catalyst was 2.97 g per gram of the titanium-containing solid component.
(ii) Two-Stage Polymerization of Propylene/Propylene-Ethylene
Propylene, triethylaluminum, and an amount of the above solid component catalyst for setting the polymer-forming rate at 20 kg/hour were continuously fed into a first-stage reactor having a capacity of 550 liters at a temperature of 70° C. and under an applied pressure (about 3.2 MPa at 70° C.). In addition, hydrogen was continuously fed as a molecular weight adjusting agent, and first-stage polymerization was carried out in a liquid phase.
Next, the polymer that had formed was charged, through a propylene purging tank, into a second-stage reactor having a capacity of 1,900 liters, and propylene and ethylene in amounts corresponding to the compositional ratio of the target copolymer were continuously fed in at a temperature of 60° C. to a pressure of 3.0 MPa. In addition, hydrogen was continuously fed in as a molecular weight adjusting agent, and an active hydrogen compound (ethanol) was fed in an amount of 200 moles per mole of titanium atoms in the solid component catalyst supplied in the first stage and in an amount of 2.5 moles per mole of triethylaluminum, whereupon polymerization was carried out in a vapor phase. The polymer that formed was continuously transferred to a vessel, following which moisture-containing nitrogen gas was introduced, thereby stopping the reaction (second-stage polymerization).
The analytic results for the resulting PP(D-4) are shown in Table 11.
PP(D-1) to PP(D-5) satisfy all the preferred features for component (D) in the invention. However, PP(D-5) does not satisfy the preferred features for component (D) in the invention.












TABLE 11





Production Example
(D-1)
D-2
D-3
D-4
(D-5)




















Propylene resin (D)
PP
PP
PP
PP
PP



(D-1)
(D-2)
(D-3)
(D-4)
(D-5)


Name of grade
WFW4
—
—
—
WFX4














Analytic
Tm(D)
° C.
135
161
161
162 
125


results
MFR(D)
g/10
 7
 5
 10
 7
 7




min



Elastomer
wt %
—
—
—
57
—



content



Ethylene
wt %
—


17



content in



elastomer









(5) Ethylene-α-Olefin Copolymer (D3) Compounded in Component D for Outer Layer (2)

The resin obtained in Production Example (D3-1) below was used. Also, the commercial product available from Japan Polypropylene Corporation under the trade name KERNEL KF283 was used as ethylene-α-olefin copolymer (D3-2). The analytical results are shown in Table 12.
Production Example D3-1
A copolymer of ethylene and 1-hexene was produced. Catalyst preparation was carried out by the method described in Japanese Translation of PCT Application No. H7-508545 (preparation of catalyst system). That is, a catalyst solution was prepared by adding, to 2.0 mmol of the complex dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)hafnium dimethyl, an equimolar amount of tripentafluorophenylboron, then diluting to 10 liters with toluene.
A mixture of ethylene and 1-hexene was fed to a stirring autoclave-type continuous reactor having a capacity of 1.5 liters in such a way as to set the 1-hexene content to 73 wt %, and the reaction was carried out at 127° C. while maintaining the pressure inside the reactor at 130 MPa. The amount of polymer produced per hour was about 2.5 kg.
Following reaction completion, various analyses were carried out on the polymer. Table 12 shows the analytical results obtained for the resulting ethylene-α-olefin copolymer PE(D3-1).









TABLE 12





Production Example
D3-1
(D3-2)

















Ethylene-α-olefin copolymer (D3)
PE(D3-1)
PE(D3-2)


Name of grade

KF283











Production
1-Hexene content
wt %
73
—


conditions
Pressure
MPa
130
—



Temperature
° C.
127
—


Analytic
Density
g/cc
0.880
0.921


results
MFR (D3)
g/10 min
3.5
2.2









(6) Propylene Resin Composition (Z1) for Innermost Layer (3)

(6-1) Propylene-Ethylene Random Copolymer (E)

The following propylene-ethylene random copolymer available from Japan Polypropylene Corporation under the trade names WINTEC, the following polypropylene available from Japan Polypropylene Corporation under the trade name NOVATEC PP, and the resins obtained in Production Examples (E-2) and (E-5) below were used. The MFR, Tm and soluble content at or below 0° C. (S0) are shown in Table 13.

    (E-1): A propylene-ethylene random copolymer obtained using a metallocene catalyst and available from Japan Polyethylene Corporation under the trade name WINTEC WFW4
    (E-2): The propylene-ethylene random copolymer produced in Production Example (E-2)
    (E-3): A propylene-α-olefin copolymer obtained using a Ziegler-Natta catalyst and available from Japan Polyethylene Corporation under the trade name NOVATEC PP FX3A
    (E-4): A propylene-ethylene random copolymer obtained using a metallocene catalyst and available from Dow Chemical under the trade name VERSIFY 3000
    (E-5): The propylene-ethylene random copolymer produced in Production Example (E-5)


Production Example (E-2)
(i) Synthesis of Transition Metal Compound
The synthesis of [(r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azurenyl}]zirconium] was carried out in accordance with the working examples in Japanese Patent Application Laid-open No. H10-226712.
(ii) Chemical Treatment of Silicate
A 10-liter glass separable flask equipped with a stirrer was charged with 3.75 liters of distilled water, followed by 2.5 kg of concentrated sulfuric acid (96%) slowly. In addition, 1 kg of montmorillonite (Benclay SL, available from Mizusawa Industrial Chemicals, Ltd.; average particle size, 25 μm; particle size distribution, 10 μm to 60 μm) was dispersed at 50° C., following which the temperature was raised to 90° C. and the flask was maintained at that temperature for 6.5 hours. After cooling to 50° C., the slurry was vacuum filtered, and the cake was collected. Next, 7 liters of distilled water was added to the cake to as to reconstitute the slurry, which was then filtered. This washing operation was carried out until the pH of the wash fluid (filtrate) exceeded 3.5.
The recovered cake was dried overnight in a nitrogen atmosphere at 110° C. The weight after drying was 707 g.
(iii) Drying of Silicate
The silicate which was chemically treated earlier was dried in a kiln dryer. The specifications and drying conditions were as follows.
Rotary cylinder: cylindrical shape, with inside diameter of 50 mm, heating zone of 550 mm (electric furnace), and with lifting flights
Rotating speed: 2 rpm
Inclination: 20/520
Silicate feed rate: 2.5 g/min
Gas flow rate: nitrogen, 96 L/hour
Countercurrent drying temperature: 200° C. (powder temperature)
(iv) Preparation of Catalyst
The dry silicate (20 g) obtained as described above was placed in a 1 L glass reactor equipped with a stirrer, after which 116 mL of mixed heptane was added, followed by 84 mL of a heptane solution of triethylaluminum (0.60 M), and the contents were stirred at room temperature. One hour later, washing with mixed heptane was carried out, thereby preparing 200 mL of a silicate slurry.
Next, 0.96 mL of a heptane solution of triisobutylaluminum (0.71 M/L) was added to the silicate slurry prepared as described above, and reacted at 25° C. for one hour. In a separate procedure, 3.31 mL of a heptane solution of triisobutylaluminum (0.71 M) was added to 218 mg (0.3 mmol) of (r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azulenyl}]zirconium and 87 mL of mixed heptane, and reacted at room temperature for one hour. The mixture thus obtained was added to the silicate slurry and stirred for 1 hour, following which additional mixed heptane was added, bringing the volume up to 500 mL.
(v) Prepolymerization/Washing
Next, the silicate/metallocene complex slurry prepared above was placed in a 1.0 liter autoclave with stirrer which had been thoroughly flushed with nitrogen. Once the temperature had stabilized to 40° C., propylene was fed in at a rate of 10 g/hour, and the temperature was maintained. The supply of propylene was stopped after 4 hours, and the temperature was maintained for another 2 hours.
After the completion of prepolymerization, the remaining monomer was purged, stirring was stopped, and the system was left at rest for about 10 minutes, following which 240 mL of supernatant was decanted. Next, 0.95 mL of a heptane solution of triisobutylaluminum (0.71 M/L), then 560 mL of mixed heptane were added, stirring was carried out at 40° C. for 30 minutes, and the system was left at rest for 10 minutes, following which 560 mL of supernatant was removed. This operation was repeated another three times. An ingredient analysis of the final supernatant was carried out, whereupon the concentration of the organoaluminum ingredient was 1.23 mM/L and the zirconium concentration was 8.6×10−6 g/L. Hence, the amount present in the supernatant relative to the amount charged was 0.016%.
Next, 17.0 mL of a heptane solution of triisobutylaluminum (0.71 M/L) was added, following which vacuum drying was carried out at 45° C. This operation yielded a prepolymerization catalyst containing 2.0 g of polypropylene per gram of solid catalyst component.
(vi) Polymerization
The interior of a 200 liter stirring-type autoclave was thoroughly flushed with propylene, following which 45 kg of thoroughly dehydrated, liquefied propylene was introduced. To this were added 500 mL (0.12 mol) of an n-heptane solution of triisobutylaluminum, 0.32 kg of ethylene and 2.5 liters (the volume under standard conditions) of hydrogen, and the internal temperature was maintained at 30° C. Next, 1.90 g (weight of solid catalyst component) of a metallocene-type polymerization catalyst was injected with argon, thereby commencing polymerization; the temperature rose to 70° C. over a period of 40 minutes, and was held at that temperature for 60 minutes. At this point, 100 mL of ethanol was added, stopping the reaction. The remaining gas was purged, yielding 20.3 kg of polypropylene polymer. This operation was repeated five time, giving polypropylene-ethylene random copolymer PP(E-2).
The MFR of this resin was 7 g/10 min, the ethylene content was 0.75 mol %, and the melting point was 142° C.
Production Example (E-5)
(i) Production of Solid Component (A)
A 10 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and 2 L of purified n-heptane was introduced. In addition, 250 g of MgCl2 and 1.8 L of Ti(O-n-Bu)4 were added, and the reaction was carried out at 95° C. for 2 hours. The reaction product was cooled to 40° C., and 500 mL of methyl hydrogen polysiloxane (20 centistoke) was added. After the reaction was carried out at 40° C. for 5 hours, the precipitated solid product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced, and the concentration of the above solid product was adjusted to 200 g/L. At this point, 300 mL of SiCl4 was added, and the reaction was carried out at 90° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so as to set the concentration of the reaction product to 100 g/L. To this was added a mixture of 30 mL of phthaloyl dichloride with 270 mL of purified n-heptane, and the reaction was carried out at 90° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was added so as to bring the concentration of the reaction product to 200 g/L. Next, 1 L of TiCl4 was added, and the reaction was carried out at 95° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, giving a slurry of solid component (A). A portion of this slurry was sampled and dried. The analysis showed the titanium content of the solid component (A) to be 2.5 wt %.
(ii) Preparation of Solid Catalyst Component (B)
Next, a 20 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and the above slurry of solid component (A) was introduced in an amount corresponding to 100 g of solid component (A). Purified n-heptane was added so as to adjust the concentration of solid component (A) to 20 g/L. To this were added 25 mL of trimethylvinylsilane, 25 mL of (t-Bu)(Me)Si(OEt)2, and an amount of an n-heptane dilution of Et3Al corresponding to 50 g as Et3Al, and the reaction was carried out at 30° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane. A portion of the resulting slurry was sampled and dried. The analysis showed that the solid component contained 2.1 wt % of titanium and 6.1 wt % of (t-Bu) (Me)Si(OEt)2.
Using the solid component obtained above, preliminary polymerization was carried out according to the following procedure. Purified n-heptane was added to the above slurry, adjusting the concentration of the solid component to 10 g/L. The slurry was cooled to 10° C., following which an n-heptane dilution of Et3Al was added in an amount corresponding to 10 g of Et3Al, and 150 g of propylene was fed over a period of 2 hours. After propylene feeding was completed, the reaction was continued for another 30 minutes. Next, the vapor phase portion was thoroughly flushed with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The resulting slurry was removed from the autoclave and vacuum dried, giving solid catalyst component (B). This solid catalyst component (B) contained 1.2 g of polypropylene per gram of solid components. Upon analysis, the portion of this solid catalyst component (B) from which polypropylene had been removed contained 1.6 wt % of titanium and 5.5 wt % of (t-Bu) (Me)Si(OEt)2.
(iii) Polymerization
The interior of a 200 L stirring-type autoclave was thoroughly flushed with propylene, following which 80 L of purified n-heptane was introduced. The temperature was raised to 70° C., then an n-heptane dilution of Et3Al in an amount corresponding to 1.5 g of Et3Al, 5.0 NL of hydrogen, and 0.25 g of the above solid catalyst component (B) (but excluding the prepolymerization polymer) were added. The temperature was raised to 75° C., following which propylene was fed in to a pressure of 0.7 MPaG, and polymerization was begun. Propylene feeding was continued so as to maintain the pressure during polymerization. Three hours later, polymerization was stopped by adding 1 L of butanol. The remaining propylene was purged, and thoroughly flushed with nitrogen. The slurry thus obtained was filtered with a centrifugal separator, then dried in a desiccator, thereby giving PP(E-5).
Analytical results for above PP(E-1) to PP(E-5) are shown in Table 13.
PP(E-1) to PP(E-3) satisfy all the preferred features of the invention for component (E). However, PP(E-4) and PP(E-5) do not satisfy the features of the invention for component (E).












TABLE 13





Production Example
(E-1)
E-2
(E-3)
(E-4)
E-5




















Propylene-α-olefin copolymer (E1)
PP
PP
PP
PP
PP



(E-1)
(E-2)
(E-3)
(E-4)
(E-5)


Name of grade
WFW4

FW4B
VERSIFY






3000















Analytic
Melt peak
Tm
° C.
135
142
139
108
161


results
temp.
(E)



Melt flow
MFR
g/10
7
7
7
8
5



rate
(E)
min









(6-2) Ethylene-α-Olefin Copolymer (F) Included in Propylene Resin Composition (Z1) for Innermost Layer (3)

The resins obtained in Production Examples (F-1) to (F-4) below, and the commercial ethylene-α-olefin copolymer (F-5) shown below were used.

    (F-5): An ethylene-α-olefin copolymer obtained with a metallocene catalyst, available from Japan Polyethylene Corporation under the trade name KERNEL KF283


Production Example (F-1)
A copolymer of ethylene and 1-hexene was produced. Catalyst preparation was carried out by the method described in Japanese Translation of PCT Application No. H7-508545 (preparation of catalyst system). That is, a catalyst solution was prepared by adding, to 2.0 mmol of the complex dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)hafnium dimethyl, an equimolar amount of tripentafluorophenylboron, then diluting to 10 liters with toluene.
A mixture of ethylene and 1-hexene was fed to a stirring autoclave-type continuous reactor having a capacity of 1.5 liters in such a way as to set the 1-hexene content to 73 wt %, and the reaction was carried out at 127° C. while maintaining the pressure inside the reactor at 130 MPa. The amount of polymer produced per hour was about 2.5 kg.
Following reaction completion, various analyses were carried out on the resulting polymer. Table 14 shows the analytical results obtained for the resulting ethylene-α-olefin copolymer PE(F-1).
Production Examples F-2 to F-4
Aside from varying the 1-hexene content at the time of polymerization and the polymerization temperature as shown in Table 14, catalyst preparation and polymerization were carried out by a method similar to that for Production Example (F-1).
Following reaction completion, various analyses were conducted on the resulting polymers. Analytical results for the resulting ethylene-α-olefin copolymers PE(F-2) to PE(F-5) are shown in Table 14. PE(F-1) to PE(F-4) satisfy all the preferred features of the invention for component (F). However, PE(F-5) does not satisfy the preferred features of the invention for component (F).












TABLE 14





Production Example
F-1
F-2
F-3
F-4
(F-5)




















Ethylene-α-olefin copolymer (F)
PE
PE
PE
PE
PE



(F-1)
(F-2)
(F-3)
(F-4)
(F-5)


Name of grade
—
—
—
—
KF283














Production
1-Hexene
wt %
73
78
62
55
—


conditions
content



Pressure
MPa
130
130
130
130
—



Temperature
° C.
127
118
140
148
—


Analytic
Density
g/cc
0.880
0.865
0.898
0.905
0.921


results
MFR (F)
g/10
3.5
3.5
3.5
2.2
2.5




min









(7) Propylene Resin Composition (Z2) for Innermost Layer (3)

(7-1) Propylene Resin Composition (G)

(7-1-1)

The resins (PP(K-1) to PP(K-15)) obtained by successive polymerization in Production Examples (K-1) to (K-15) below were used.
(Production Example K-1
(i) Preparation of Prepolymerization Catalyst
Chemical Treatment of Silicate
A 10-liter glass separable flask equipped with a stirrer was charged with 3.75 liters of distilled water, followed by 2.5 kg of concentrated sulfuric acid (96%) slowly. In addition, 1 kg of montmorillonite (Benclay SL, available from Mizusawa Industrial Chemicals, Ltd.; average particle size, 25 μm; particle size distribution, 10 to 60 μm) was dispersed at 50° C., following which the temperature was raised to 90° C. and the flask was maintained at that temperature for 6.5 hours. After cooling to 50° C., the slurry was vacuum filtered, and the cake was collected. Next, 7 liters of distilled water was added to the cake to as to reconstitute the slurry, which was then filtered. This washing operation was carried out until the pH of the wash fluid (filtrate) exceeded 3.5. The recovered cake was dried overnight in a nitrogen atmosphere at 110° C. The weight after drying was 707 g.
(Drying of Silicate)
The silicate that had been chemically treated earlier was dried in a kiln dryer. The specifications and drying conditions were as follows.
Rotary cylinder: cylindrical shape, with inside diameter of 50 mm, heating zone of 550 mm (electric furnace), and with lifting flights
Rotating speed: 2 rpm
Inclination: 20/520
Silicate feed rate: 2.5 g/min
Gas flow rate: nitrogen, 96 L/hour
Countercurrent drying temperature: 200° C. (powder temperature)
(Preparation of Catalyst)
A 16-liter autoclave equipped with a stirrer and a temperature control device was thoroughly flushed with nitrogen. Dry silicate (200 g) was introduced, then 1,160 mL of mixed heptane was added, followed by 840 mL of a heptane solution of triethylaluminum (0.60 M), and the contents were stirred at room temperature. One hour later, washing with mixed heptane was carried out, thereby preparing 2,000 mL of a silicate slurry. Next, 9.6 mL of a heptane solution of triisobutylaluminum (0.71 M/L) was added to the prepared silicate slurry, and 1 hour of reaction was effected at 25° C. In a separate procedure, 33.1 mL of a heptane solution of triisobutylaluminum (0.71 M) was added to 2,180 mg (0.3 mM) of (r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azulenyl}]zirconium and 870 mL of mixed heptane, and 1 hour of reaction was effected at room temperature. The mixture thus obtained was added to the silicate slurry and stirred for 1 hour, following which additional mixed heptane was added, bringing the volume up to 5,000 mL.
(Prepolymerization/Washing)
Next, the reactor temperature was raised to 40° C. Once the temperature had stabilized, propylene was fed in at a rate of 100 g/hour, and the temperature was maintained. The supply of propylene was stopped after 4 hours, and the temperature was maintained for another 2 hours.
After the completion of prepolymerization, the remaining monomer was purged, stirring was stopped, and the system was left at rest for about 10 minutes, following which 2,400 mL of supernatant was decanted. Next, 9.5 mL of a heptane solution of triisobutylaluminum (0.71 M/L), then 5,600 mL of mixed heptane were added, and stirring was carried out at 40° C. for 30 minutes. The system was then left at rest for 10 minutes, following which 5,600 mL of supernatant was removed. This operation was repeated another three times. An ingredient analysis of the final supernatant was carried out, whereupon the concentration of the organoaluminum ingredient was 1.23 mM/L and the zirconium concentration was 8.6×10−6 g/L. Hence, the amount present in the supernatant relative to the amount charged was 0.016%. Next, 170 mL of a heptane solution of triisobutylaluinum (0.71 M/L) was added, following which vacuum drying was carried out at 45° C. A prepolymerization catalyst containing 2.0 g of polypropylene per gram of catalyst was obtained.
Using this prepolymerization catalyst, the production of a propylene-ethylene block copolymer was carried out according to the procedure described below.
(ii) First Polymerization Step
A horizontal reactor (L/D=6; capacity, 100 liters) equipped with stirring blades was thoroughly dried, and the interior was thoroughly flushed with nitrogen gas. In the presence of a polypropylene powder bed and while stirring at a speed of 30 rpm, 0.568 g/hr of the prepolymerization catalyst prepared by the above-described method and 15.0 mmol/hr of triisobutylaluminum were continuously fed to the upstream portion of the reactor. Vapor phase polymerization was carried out by continuously passing a monomer mixed gas into the reactor in such a way as to give an ethylene-propylene molar ratio of 0.07 in the vapor phase portion within the reactor and to set the hydrogen concentration at 100 ppm, while holding the reactor temperature at 65° C. and the pressure at 2.1 MPaG. The polymer powder formed by the reaction was continuously removed from the downstream portion of the reactor in such manner as to keep the size of the powder bed within the reactor constant. The polymer removal rate that reached a steady state at this time was 10.0 kg/hr.
Upon analysis, the propylene-ethylene random copolymer obtained in the first polymerization step was found to have a MFR of 6.0 g/10 min and an ethylene content of 2.2 wt %.
(iii) Second Polymerization Step
The propylene-ethylene copolymer removed from the first step was continuously fed to a horizontal reactor equipped with stirring blades (L/D=6; capacity, 100 liters). Vapor-phase polymerization was carried out by continuously passing a monomer mixed gas into the reactor in such a way as to give an ethylene-propylene molar ratio of 0.453 in the vapor phase portion within the reactor and to set the hydrogen concentration at 330 ppm, while stirring at a rate of 25 rpm and while holding the reactor temperature at 70° C. and the pressure at 2.0 MPaG. The polymer powder formed by the reaction was continuously removed from the downstream portion of the reactor in such manner as to keep the size of the powder bed within the reactor constant. Oxygen was supplied as an activity suppressor so as to set the polymer removal rate at this time to 17.9 kg/hr, thereby controlling the polymerization reaction rate in the second polymerization step. The activity was 31.429 kg/g of catalyst.
The analytical results for the resulting propylene resin composition PP(K-1) are shown in Table 15.
Production Examples K-2 to K-9
Aside from changing the polymerization conditions as shown in Table 15, catalyst preparation and polymerization were carried out by the same methods as in Production Example K-1.
Following reaction completion, various analyses of the resulting polymers were carried out. Table 15 shows the analytical results for propylene resin compositions PP(K-2) to PP(K-9) thus obtained. These satisfy all the preferred features of the invention for component (G).












TABLE 15







Production Examples
K-1
K-2
K-3
K-4
K-5





Propylene Resin Composition (K)
PP
PP
PP
PP
PP



(K-1)
(K-2)
(K-3)
(K-4)
(K-5)















Production
Step 1
Catalyst
g/h
0.568
0.391
0.625
0.568
0.568


conditions

amount




Temperature
° C.
65
65
65
65
65




Pressure
MPa
2.1
2.1
2.1
2.1
2.1




C2/C3 ratio
mol/mol
0.07
0.09
0.055
0.07
0.07




Hydrogen
ppm
100
150
90
100
100




concentration




Production
kg/h
10
10
10
10
10




amount




(Polymerization
g/g-cat
17,600
25,600
16,000
17,600
17,600




activity)



Step 2
Temperature
° C.
70
70
70
70
70




Pressure
MPa
2.0
2.0
2.0
2.0
2.0




C2/C3 ratio
mol/mol
0.453
0.453
0.453
0.534
0.435




Hydrogen
ppm
330
330
330
350
320




concentration




Production
kg/h
17.9
17.9
17.9
19.2
16.7




amount




(Polymerization
g/g-cat
31,429
45,714
28,571
33,846
29,333




activity)


Analytic
Tm(K1)
Melting peak
° C.
130
126
133
130
130


results

temperature



E(K1)
Ethylene
wt %
2.2
2.8
1.7
2.2
2.2




content in




component (K1)



W(K1)
Ratio of
wt %
56
56
56
52
60




component (K1)



MFR(K1)
MFR of
g/10 min
6
6
6
6
6




component (K1)



E(K2)
Ethylene
wt %
11
11
11
12.8
10.6




content in




component (K2)



W(K2)
Ratio of
wt %
44
44
44
48
40




component (K2)



MFR(K)
MFR of
g/10 min
6
6
6
6
6




component K



Tg
Glass
° C.
−14
−15
−13
−16
−13




transition




point
















Production Examples
K-6
K-7
K-8
K-9







Propylene Resin Composition (K)
PP
PP
PP
PP




(K-6)
(K-7)
(K-8)
(K-9)
















Production
Step 1
Catalyst
g/h
0.568
0.568
0.649
0.535



conditions

amount





Temperature
° C.
65
65
65
65





Pressure
MPa
2.1
2.1
2.1
2.1





C2/C3 ratio
mol/mol
0.07
0.07
0.07
0.07





Hydrogen
ppm
100
100
90
110





concentration





Production
kg/h
10
10
10
10





amount





(Polymerization
g/g-cat
17,600
17,600
15,400
18,700





activity)




Step 2
Temperature
° C.
70
70
70
70





Pressure
MPa
2.0
2.0
2.0
2.0





C2/C3 ratio
mol/mol
0.435
0.534
0.453
0.453





Hydrogen
ppm
320
350
300
450





concentration





Production
kg/h
17.9
17.9
17.9
17.9





amount





(Polymerization
g/g-cat
31,429
31,429
27,500
33,393





activity)



Analytic
Tm(K1)
Melting peak
° C.
130
130
130
130



results

temperature




E(K1)
Ethylene
wt %
2.2
2.2
2.2
2.2





content in





component (K1)




W(K1)
Ratio of
wt %
56
56
56
56





component (K1)




MFR(K1)
MFR of
g/10 min
6
6
4.7
8





component (K1)




E(K2)
Ethylene
wt %
10.6
12.8
11
11





content in





component (K2)




W(K2)
Ratio of
wt %
44
44
44
44





component (K2)




MFR(K)
MFR of
g/10 min
6
6
4.7
8





component K




Tg
Glass
° C.
−14
−15
−14
−14





transition





point










Production Examples K-10 to K-15
Aside from changing the polymerization conditions as shown in Table 16, catalyst preparation and polymerization were carried out by the same methods as in Production Example K-1.
Following reaction completion, various analyses of the resulting polymers were carried out. Table 16 shows the analytical results for propylene resin compositions PP(K-10) to PP(K-15) thus obtained. These satisfy all the preferred features of the invention for component (G).













TABLE 16





Production Examples
K-10
K-11
K-12
K-13
K-14
K-15





















Propylene Resin Composition (K)
PP
PP
PP
PP
PP
PP



(K-10)
(K-11)
(K-12)
(K-13)
(K-14)
(K-15)
















Production
Step 1
Catalyst
g/h
0.284
1.250
0.568
0.568
0.568
0.568


conditions

amount




Temperature
° C.
65
65
65
65
65
65




Pressure
MPa
2.1
2.1
2.1
2.1
2.1
2.1




C2/C3 ratio
mol/mol
0.12
0.02
0.07
0.07
0.07
0.07




Hydrogen
ppm
200
30
100
100
100
100




concentration




Production
kg/h
10
10
10
10
10
10




amount




(Polymerization
g/g-cat
35,200
8,000
17,600
17,600
17,600
17,600




activity)



Step 2
Temperature
° C.
70
70
70
70
70
70




Pressure
MPa
2.0
2.0
2.0
2.0
2.0
2.0




C2/C3 ratio
mol/mol
0.453
0.453
0.453
0.453
0.228
0.678




Hydrogen
ppm
330
330
330
330
300
380




concentration




Production
kg/h
17.9
17.9
25.0
15.4
17.9
17.9




amount




(Polymerization
g/g-cat
62,857
14,286
44,000
27,077
31,429
31,429




activity)


Analytic
Tm(K1)
Melting peak
° C.
120
140
130
130
130
130


results

temperature



E(K1)
Ethylene
wt %
3.8
0.5
2.2
2.2
2.2
2.2




content in




component (K1)



W(K1)
Ratio of
wt %
56
56
40
65
56
56




component (K1)



MFR(K1)
MFR of
g/10 min
6
6
6
6
6
6




component (K1)



E(K2)
Ethylene
wt %
11
11
11
11
6
16




content in




component (K2)



W(K2)
Ratio of
wt %
44
44
60
35
44
44




component (K2)



MFR(K)
MFR of
g/10 min
6
6
6
6
6
6




component K



Tg
Glass
° C.
−16
−12
−15
−11
−9
−12, −32




transition




point









(7-1-2) Propylene Resin Composition (G) for Inner Layer, Obtained by Blending

The following <K1> propylene-α-olefin random copolymers ((K1-1) to (K1-5)) were used as component (G1), and the following <K2> propylene-ethylene random copolymers ((K2-1) to (K2-3)) were used as component (G2).
<K1>


    K1-1: The commercial product available from Japan Polypropylene Corporation under the trade name WINTEC WFW4 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)
    K1-2: Produced in Production Example K1-2 below.
    K1-3: The commercial product available from Japan Polypropylene Corporation under the trade name NOVATEC PP FW4B (a propylene-α-olefin copolymer obtained with a Ziegler-Natta catalyst)
    K1-4: The commercial product available from Dow Chemical under the trade name VERSIFY 3000 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)
    K1-5: Produced in Production Example K1-5 below.

<K2>

    K2-1: The commercial product available from Exxon-Mobil Chemical under the trade name VISTAMAXX 3000 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)
    K2-2: The commercial product available from Dow Chemical under the trade name VERSIFY 3000 (a propylene-ethylene random copolymer obtained with a metallocene catalyst)
    K2-3: The commercial product available from LiondellBasell Industries under the trade name ADFLEX X100G (a propylene-ethylene random copolymer obtained with a Ziegler-Natta catalyst)


Production Example (K1-2)
(i) Synthesis of Transition Metal Compound
The synthesis of [(r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azurenyl}]zirconium] was carried out in accordance with the working examples in JP-A-H10-226712.
(ii) Chemical Treatment of Silicate
A 10-liter glass separable flask equipped with a stirrer was charged with 3.75 liters of distilled water, followed by 2.5 kg of concentrated sulfuric acid (96%) slowly. In addition, 1 kg of montmorillonite (Benclay SL, available from Mizusawa Industrial Chemicals, Ltd.; average particle size, 25 μm; particle size distribution, 10 μm to 60 μm) was dispersed at 50° C., following which the temperature was raised to 90° C. and the flask was maintained at that temperature for 6.5 hours. After cooling to 50° C., the slurry was vacuum filtered, and the cake was collected. Next, 7 liters of distilled water was added to the cake to as to reconstitute the slurry, which was then filtered. This washing operation was carried out until the pH of the wash fluid (filtrate) exceeded 3.5.
The recovered cake was dried overnight in a nitrogen atmosphere at 110° C. The weight after drying was 707 g.
(iii) Drying of Silicate
The silicate that had been chemically treated earlier was dried in a kiln dryer. The specifications and drying conditions were as follows.
Rotary cylinder: cylindrical shape, with inside diameter of 50 mm, heating zone of 550 mm (electric furnace), and with lifting flights
Rotating speed: 2 rpm
Inclination: 20/520
Silicate feed rate: 2.5 g/min
Gas flow rate: nitrogen, 96 L/hour
Countercurrent drying temperature: 200° C. (powder temperature)
(iv) Preparation of Catalyst
The dry silicate (20 g) obtained as described above was placed in a 1 L glass reactor equipped with a stirrer, after which 116 mL of mixed heptane was added, followed by 84 mL of a heptane solution of triethylaluminum (0.60 M), and the contents were stirred at room temperature. One hour later, washing with mixed heptane was carried out, thereby preparing 200 mL of a silicate slurry.
Next, 0.96 mL of a heptane solution of triisobutylaluminum (0.71 M/L) was added to the silicate slurry prepared as described above, and reaction carried out at 25° C. for one hour. In a separate procedure, 3.31 mL of a heptane solution of triisobutylaluminum (0.71 M) was added to 218 mg (0.3 mmol) of (r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azulenyl}]zirconium and 87 mL of mixed heptane, and reaction carried out at room temperature for one hour. The mixture thus obtained was added to the silicate slurry and stirred for 1 hour, following which additional mixed heptane was added, bringing the volume up to 500 mL.
(v) Prepolymerization/Washing
Next, the silicate/metallocene complex slurry prepared above was placed in a 1.0 liter autoclave with stirrer which had been thoroughly flushed with nitrogen. Once the temperature had stabilized to 40° C., propylene was fed in at a rate of 10 g/hour, and the temperature was maintained. The supply of propylene was stopped after 4 hours, and the temperature was maintained for another 2 hours.
After the completion of prepolymerization, the remaining monomer was purged, stirring was stopped, and the system was left at rest for about 10 minutes, following which 240 mL of supernatant was decanted. Next, 0.95 mL of a heptane solution of triisobutylaluminum (0.71 M/L), then 560 mL of mixed heptane were added, and stirring was carried out at 40° C. for 30 minutes. The system was then left at rest for 10 minutes, following which 560 mL of supernatant was removed. This operation was repeated another three times. An ingredient analysis of the final supernatant was carried out, whereupon the concentration of the organoaluminum ingredient was 1.23 mM/L and the zirconium concentration was 8.6×10−6 g/L. Hence, the amount present in the supernatant relative to the amount charged was 0.016%.
Next, 17.0 mL of a heptane solution of triisobutylaluminum (0.71 M/L) was added, following which vacuum drying was carried out at 45° C. This operation yielded a prepolymerization catalyst containing 2.0 g of polypropylene per gram of solid catalyst component.
(vi) Polymerization
The interior of a 200 liter stirring-type autoclave was thoroughly flushed with propylene, following which 45 kg of thoroughly dehydrated, liquefied propylene was introduced. To this were added 500 mL (0.12 mol) of an n-heptane solution of triisobutylaluminum, 0.32 kg of ethylene and 2.5 liters (the volume under standard conditions) of hydrogen, and the internal temperature was maintained at 30° C. Next, 1.90 g (weight of solid catalyst component) of a metallocene type polymerization catalyst was injected with argon, thereby commencing polymerization, the temperature rose to 70° C. over a period of 40 minutes, and was held at that temperature for 60 minutes. At this point, 100 mL of ethanol was added, stopping the reaction. The remaining gas was purged, yielding 20.3 kg of polypropylene polymer. This operation was repeated five time, giving polypropylene-ethylene random copolymer PP(E-2).
The MFR of this resin was 7 g/10 min, the ethylene content was 0.75 mol %, and the melting point was 142° C.
Production Example (K1-5)
(i) Production of Solid Component (A)
A 10 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and 2 L of purified n-heptane was introduced. In addition, 250 g of MgCl2 and 1.8 L of Ti(O-n-Bu)4 were added, and the reaction was carried out at 95° C. for 2 hours. The reaction product was cooled to 40° C., and 500 mL of methyl hydrogen polysiloxane (20 centistoke) was added. The reaction was carried out at 40° C. for 5 hours, following which the precipitated solid product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced, and the concentration of the above solid product was adjusted to 200 g/L. At this point, 300 mL of SiCl4 was added, and the reaction was carried out at 90° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so as to set the concentration of the reaction product to 100 g/L. To this was added a mixture of 30 mL of phthaloyl dichloride with 270 mL of purified n-heptane, and the reaction was carried out at 90° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was added so as to bring the concentration of the reaction product to 200 g/L. Next, 1 L of TiCl4 was added, and the reaction was carried out at 95° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, giving a slurry of solid component (A). A portion of this slurry was sampled and dried. The analysis showed the titanium content of the solid component (A) to be 2.5 wt %.
(ii) Preparation of Solid Catalyst Component (B)
Next, a 20 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and the above slurry of solid component (A) was introduced in an amount corresponding to 100 g of solid component (A). Purified n-heptane was added so as to adjust the concentration of solid component (A) to 20 g/L. To this were added 25 mL of trimethylvinylsilane, 25 mL of (t-Bu)(Me)Si(OEt)2 and an amount of an n-heptane dilution of Et3Al corresponding to 50 g as Et3Al, following which the reaction was carried out at 30° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane. A portion of the resulting slurry was sampled and dried. The analysis showed that the solid component contained 2.1 wt % of titanium and 6.1 wt % of (t-Bu) (Me)Si(OEt)2.
Using the solid component obtained above, preliminary polymerization was carried out according to the following procedure. Purified n-heptane was added to the above slurry, adjusting the concentration of the solid component to 10 g/L. The slurry was cooled to 10° C., following which an n-heptane dilution of Et3Al was added in an amount corresponding to 10 g of Et3Al, and 150 g of propylene was fed over a period of 2 hours. After the feeding of propylene was completed, the reaction was continued for another 30 minutes. Next, the vapor phase portion was thoroughly flushed with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The resulting slurry was removed from the autoclave and vacuum dried, giving solid catalyst component (B). This solid catalyst component (B) contained 1.2 g of polypropylene per gram of solid components. Upon analysis, the portion of this solid catalyst component (B) from which polypropylene had been removed contained 1.6 wt % of titanium and 5.5 wt % of (t-Bu) (Me)Si(OEt)2.
(iii) Polymerization
The interior of a 200 L stirring-type autoclave was thoroughly flushed with propylene, following which 80 L of purified n-heptane was introduced. The temperature was raised to 70° C., then an n-heptane dilution of Et3Al in an amount corresponding to 1.5 g of Et3Al, 5.0 NL of hydrogen, and 0.25 g of the above solid catalyst component (B) (but excluding the prepolymerization polymer) were added. The temperature was raised to 75° C., following which propylene was fed in to a pressure of 0.7 MPaG, and polymerization was begun. Propylene supply was continued so as to maintain the pressure during polymerization. Three hours later, polymerization was stopped by adding 1 L of butanol. The remaining propylene was purged, and thoroughly flushed with nitrogen. The slurry thus obtained was filtered with a centrifugal separator, then dried in a desiccator, thereby giving PP(K1-5).
Various analytical results for above PP(K1-1) to PP(K1-5) and PP(K2-1) to PP(K2-3) are shown in Tables 17 and 18 below. PP(K1-4), PP(K1-5), PP(K2-2) and PP(K2-3) satisfy the preferred features for component (G) in the invention.












TABLE 17





Production Example
(K1-1)
K1-2
(K1-3)
(K1-4)
K1-5




















Propylene-α-olefin copolymer (K1)
PP
PP
PP
PP
PP



(K1-1)
(K1-2)
(K1-3)
(K1-4)
(K1-5)


Name of grade
WFW4

FW4B
VERSIFY






3000















Analytic
Melt
Tm(K1)
° C.
135
142
139
108
161


results
peak



temp.



Melt
MFR(K1)
g/10
7
7
7
8
5



flow

min



rate



















TABLE 18





Production Example
(K2-1)
(K2-2)
(K2-3)


















Propylene-α-olefin copolymer (K2)
PP
PP
PP



(K2-1)
(K2-2)
(K2-3)


Name of grade
VISTAMAXX
VERSIFY
ADFLEX



3000
3000
X100G













Analytic
Ethylene
E(K2)
° C.
11
3
18


results
content



Melt flow
MFR(K2)
g/10
 8
8
 8



rate

min



Catalyst
—
—
metallocene
metallocene
Ziegler-








Natta









(7-2) Production of Component (G) by Blending

The above <K1> propylene-α-olefin random copolymers ((K1-1) to (K1-5)) as component (G1), and the above <K2> propylene-ethylene random copolymers ((K2-1) to (K2-3)) as component (G2) were weighed out in the compositional ratios shown below in Tables 19 and 20 and mixed together by stirring in a Henschel mixer, thereby giving PP(K-16) to PP(K-28) as propylene resin composition (G).
Various analytical results for the above composition (G) are shown in Table 19 and 20 below.
Of PP(K-16) to PP(K-28), PP(K-16) to PP(K-21) satisfy all the preferred features in the invention. However, PP(K-22) to PP(K-28) do not satisfy all the preferred features in the invention.













TABLE 19





Production Example
K-16
K-17
K-18
K-19
K-20
K-21





















Propylene resin composition
PP
PP
PP
PP
PP
PP


(K)
(K-16)
(K-17)
(K-18)
(K-19)
(K-20)
(K-21)


Propylene-α-olefin copolymer
PP
PP
PP
PP
PP
PP


(K1)
(K1-1)
(K1-1)
(K1-1)
(K1-2)
(K1-3)
(K1-1)


Compounded amount (wt %)
50
40
60
50
50
100 


Propylene-ethylene copolymer
PP
PP
PP
PP
PP
—


(K2)
(K2-1)
(K2-1)
(K2-1)
(K2-1)
(K2-1)


Compounded amount (wt %)
50
60
40
50
50
0
















Analytic
Glass
Tg
° C.
−15  
−16  
−14  
−13  
−13  
2


results
transition



point























TABLE 20





Production Example
K-22
K-23
K-24
K-25
K-26
K-27
K-28






















Propylene resin composition
PP
PP
PP
PP
PP
PP
PP


(K)
(K-22)
(K-23)
(K-24)
(K-25)
(K-26)
(K-27)
(K-28)


Propylene-α-olefin copolymer
—
PP
PP
PP
PP
PP
PP


(K1)

(K1-1)
(K1-1)
(K1-4)
(K1-5)
(K1-1)
(K1-1)


Compounded amount (wt %)
 0
80
20
50
50
50
50


Propylene-ethylene copolymer
PP
PP
PP
PP
PP
PP
PP


(K2)
(K2-1)
(K2-1)
(K2-1)
(K2-1)
(K2-1)
(K2-2)
(K2-3)


Compounded amount (wt %)
100
20
80
50
50
50
50

















Analytic
Glass
Tg
° C.
−23
−8
−20  
−20  
−5
−9
−20, −41


results
transition



point









(7-2) Ethylene-α-Olefin Copolymer (H) Included in Propylene Resin Composition (Z2) for Innermost Layer (3)

Ethylene-α-olefin copolymer PE(H-1) to PE(H-4) obtained in Production Examples (H-1) to (H-4) below and the following commercial ethylene-α-olefin copolymer PE(H-5) were used. PE(H-5): The commercial product available from Japan Polyethylene Corporation under the trade name KERNEL KF283 (an ethylene-α-olefin copolymer obtained with a metallocene catalyst)
Production Example H-1
A copolymer of ethylene and 1-hexene was produced. Catalyst preparation was carried out by the method described in Japanese Translation of PCT Application No. H7-508545 (preparation of catalyst system). That is, a catalyst solution was prepared by adding, to 2.0 mmol of the complex dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)hafnium dimethyl, an equimolar amount of tripentafluorophenylboron, then diluting to 10 liters with toluene.
A mixture of ethylene and 1-hexene was fed to a stirring autoclave-type continuous reactor having a capacity of 1.5 liters in such a way as to set the 1-hexene content to 73 wt %, and the reaction was carried out at 127° C. while maintaining the pressure inside the reactor at 130 MPa. The amount of polymer produced per hour was about 2.5 kg.
Following reaction completion, various analyses were carried out on the resulting polymer. Table 21 shows the analytical results obtained for the resulting ethylene-α-olefin copolymer PE(H-1).
Production Examples H-2 to H-4
Aside from varying the 1-hexene content at the time of polymerization and the polymerization temperature as shown in Table 21, catalyst preparation and polymerization were carried out by the same methods as in Production Example (H-1).
Following reaction completion, various analyses were conducted on the resulting polymers. Various analytical results for the resulting ethylene-α-olefin copolymers PE(H-2) to PE(H-4) and PE(H-5) are shown in Table 21.
PE(H-1) to PE(H-4) satisfy all the features in the invention regarded as desirable for component (H). However, PE(H-5) does not satisfy the features in the invention regarded as desirable for component (H).












TABLE 21





Production Example
H-1
H-2
H-3
H-4
(H-5)




















Ethylene-α-olefin copolymer (H)
PE
PE
PE
PE
PE



(H-1)
(H-2)
(H-3)
(H-4)
(H-5)


Name of grade
—
—
—
—
KF283














Production
1-Hexene
wt %
73
78
62
55
—


conditions
content



Pressure
MPa
130
130
130
130
—



Temperature
° C.
127
118
140
148
—


Analytic
Density
g/cc
0.880
0.865
0.898
0.905
0.921


results
MFR(H)
g/10
3.5
3.5
3.5
2.2
2.5




min









(7-3) Propylene Resin (I) Included in Propylene Resin Composition (Z2) for Innermost Layer (3)

Resins PP(I-1) to PP(I-3) obtained in Production Examples (I-1) to (I-3) below and the commercial products shown below were used. PP(I-1) and PP(I-2) are homopolypropylenes obtained by single-stage polymerization, and PP(I-3) is a block copolymer polypropylene obtained by multistage polymerization.

    PP(I-4): The product available from Japan Polyethylene Corporation under the trade name WINTEC WFW4 (a propylene-ethylene random copolymer obtained by single-stage polymerization)
    PP(I-5): The product available from Japan Polyethylene Corporation under the trade name WINTEC WFX4 (a propylene-ethylene random copolymer obtained by single-stage polymerization)


The MFR and Tm of the above resins are shown in Table 22.
Production Example I-1
(i) Production of Solid Component (A)
A 10 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and 2 L of purified n-heptane was introduced. In addition, 250 g of MgCl2 and 1.8 L of Ti(O-n-Bu)4 were added, and the reaction was carried out at 95° C. for 2 hours. The reaction product was cooled to 40° C., and 500 mL of methyl hydrogen polysiloxane (20 centistoke) was added. After the reaction was carried out at 40° C. for 5 hours, the precipitated solid product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced, and the concentration of the above solid product was adjusted to 200 g/L. At this point, 300 mL of SiCl4 was added, and the reaction was carried out at 90° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so as to set the concentration of the reaction product to 100 g/L. To this was added a mixture of 30 mL of phthaloyl dichloride with 270 mL of purified n-heptane, and the reaction was carried out at 90° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was added so as to bring the concentration of the reaction product to 200 g/L. Next, 1 L of TiCl4 was added, and the reaction was carried out at 95° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, giving a slurry of solid component (A). A portion of this slurry was sampled and dried. The analysis showed the titanium content of the solid component (A) to be 2.5 wt %.
(ii) Preparation of Solid Catalyst Component (B)
Next, a 20 L autoclave equipped with a stirrer was thoroughly flushed with nitrogen, and the above slurry of solid component (A) was introduced in an amount corresponding to 100 g of solid component (A). Purified n-heptane was added so as to adjust the concentration of solid component (A) to 20 g/L. To this were added 25 mL of trimethylvinylsilane, 25 mL of (t-Bu) (Me)Si(OEt)2, and an amount of an n-heptane dilution of Et3Al corresponding to 50 g as Et3Al, and the reaction was carried out at 30° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane. A portion of the resulting slurry was sampled and dried. The analysis showed that the solid component contained 2.1 wt % of titanium and 6.1 wt % of (t-Bu)(Me)Si(OEt)2.
Using the solid component obtained above, preliminary polymerization was carried out according to the following procedure. Purified n-heptane was added to the above slurry, adjusting the concentration of the solid component to 10 g/L. The slurry was cooled to 10° C., following which an n-heptane dilution of Et3Al was added in an amount corresponding to 10 g of Et3Al, and 150 g of propylene was fed over a period of 2 hours. After the supply of propylene was completed, the reaction was continued for another 30 minutes. Next, the vapor phase portion was thoroughly flushed with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The resulting slurry was removed from the autoclave and vacuum dried, giving solid catalyst component (B). This solid catalyst component (B) contained 1.2 g of polypropylene per gram of solid components. Upon analysis, the portion of this solid catalyst component (B) from which polypropylene had been removed contained 1.6 wt % of titanium and 5.5 wt % of (t-Bu)(Me)Si(OEt)2.
(iii) Polymerization
The interior of a 200 L stirring-type autoclave was thoroughly flushed with propylene, following which 80 L of purified n-heptane was introduced. The temperature was raised to 70° C., then an n-heptane dilution of EtAl in an amount corresponding to 1.5 g of Et3Al, 5.0 NL of hydrogen and 0.25 g of the above solid catalyst component (B) (but excluding the prepolymerization polymer) were added. The temperature was raised to 75° C., following which propylene was fed in to a pressure of 0.7 MPaG, and polymerization was begun. Propylene supply was continued so as to maintain the pressure during polymerization. Three hours later, polymerization was stopped by adding 1 L of butanol. The remaining propylene was purged, and thoroughly flushed with nitrogen. The slurry thus obtained was filtered with a centrifugal separator, then dried in a desiccator, thereby giving PP(I-1).
Production Example I-2
Aside from changing the amount of hydrogen used during polymerization, PP(I-2) was obtained in the same way as in Production Example I-1. The results are shown in Table 22.
Production Example I-3
(i) Production of Solid Component Catalyst
A nitrogen-flushed 50 L reactor equipped with a stirrer was charged with 20 liters of dehydrated and deoxygenated n-heptane, then 4 moles of magnesium chloride and 8 moles of tetrabutoxytitanium were added and the reactor contents were reacted at 95° C. for 2 hours. The temperature was subsequently lowered to 40° C., 480 mL of methyl hydrogen polysiloxane (20 centistoke) was added, and the contents were again reacted for 3 hours, following which the reaction mixture was removed and the solid component that had formed was washed with n-heptane.
Next, 15 liters of dehydrated and deoxygenated n-heptane was charged into the same type of reactor with stirrer as described above, following which the solid component was added in an amount equivalent to 3 moles of magnesium atoms. A mixture of 8 moles of silicon tetrachloride added to 25 mL of n-heptane was then introduced at 30° C. over a period of 30 minutes, the temperature was raised to 90° C., and the reactor contents were reacted for one hour, following which the reaction mixture was removed and the solid component that had formed was washed with n-heptane.
In addition, 5 liters of dehydrated and deoxygenated n-heptane was charged into the same type of reactor with stirrer as described above, following which 250 g of the silicon tetrachloride-treated titanium-containing solid component obtained above, 750 g of 1,5-hexadiene, 130 mL of t-butylmethyldimethoxysilane, 10 mL of divinyldimethylsilane and 225 g of triethylaluminum were each added, and the reaction was carried out at 30° C. for 2 hours. The reaction mixture was subsequently removed and washed with n-heptane, giving a solid component catalyst.
The amount of 1,5-hexadiene prepolymerization for the resulting solid component catalyst was 2.97 g per gram of the titanium-containing solid component.
(ii) Two-Stage Polymerization of Propylene/Propylene-Ethylene
Propylene, triethylaluminum, and an amount of the above solid component catalyst for setting the polymer-forming rate at 20 kg/hour were continuously fed into a first-stage reactor having a capacity of 550 liters at a temperature of 70° C. and under an applied pressure (about 3.2 MPa at 70° C.). In addition, hydrogen was continuously fed as a molecular weight adjusting agent, and first-stage polymerization was carried out in a liquid phase.
Next, the polymer that had formed was charged, through a propylene purging tank, into a second-stage reactor having a capacity of 1,900 liters, and propylene and ethylene in amounts corresponding to the compositional ratio of the target copolymer were continuously fed in at a temperature of 60° C. to a pressure of 3.0 MPa. In addition, hydrogen was continuously fed in as a molecular weight adjusting agent, and an active hydrogen compound (ethanol) was fed in an amount of 200 moles per mole of titanium atoms in the solid component catalyst supplied in the first stage and in an amount of 2.5 moles per mole of triethylaluminum, whereupon polymerization was carried out in a vapor phase. The polymer that formed was continuously transferred to a vessel, following which moisture-containing nitrogen gas was introduced, thereby stopping the reaction (second-stage polymerization).
The analytic results for the resulting PP(I-3) are shown in Table 22.
PP(I-1) to PP(I-3) satisfy all the preferred features for component (I) in the invention. However, PP(I-4) and PP(I-5) do not satisfy the preferred features for component (I) in the invention.












TABLE 22





Production Example
I-1
I-2
I-3
(I-4)
(I-5)




















Propylene resin (I)
PP
PP
PP
PP
PP



(I-1)
(I-2)
(I-3)
(I-4)
(I-5)


Name of grade
—
—
—
WFW4
WFX4














Analytic
Tm(I)
° C.
161
161
162 
135
125


results
MFR(I)
g/10
 5
 10
 7
 7
 7




min



Elastomer
wt %
—
—
57
—
—



content



Ethylene
wt %
—
—
17
—
—



content in



elastomer









Working Examples, Comparative Examples and Reference Examples
(1-i) Inner Layer Formulation
The propylene resin composition (X) for forming the inner layer was obtained by weighing out the propylene resin composition (component (A)), ethylene-α-olefin copolymer (component (B)) and propylene resin PP (as component (C)) shown in the respective tables below in the proportions indicated in the tables. In each example, the composition (X) was charged into a Henschel mixer, following which 0.07 parts by weight of antioxidant 1 below, 0.07 parts by weight of antioxidant 2 below, and 0.01 parts by weight of the neutralizing agent shown below were added per 100 parts by weight of the propylene resin composition (X), and the ingredients were thoroughly mixed to give a compound.
Antioxidant 1: Tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane (available from Ciba Specialty Chemicals under the trade name Irganox 1010)
Antioxidant 2: Tris(2,4-di-t-butylphenyl)phosphate (available from Ciba Specialty Chemicals under the trade name Irganox 168)
Neutralizing agent: Calcium stearate (available from Nitto Kasei Kogyo KK under the trade name Ca-St)
(1-ii) Outer Layer (2)
The propylene resin composition (Y) for forming the outer layer was obtained either by using the propylene resin (component (D)) shown in the respective tables below alone, or dry blending component (D) with an ethylene-α-olefin copolymer (component (D3)) and other ingredients in the proportions shown in each table to form a compound.
(1-iii) Innermost Layer (3)
The propylene-α-olefin copolymer (component (E)) and the ethylene-α-olefin copolymer (component (F)) shown in the respective tables below which make up propylene resin composition (Z1) for forming the innermost layer, or the propylene resin composition (G) and the ethylene-α-olefin copolymer (component (H)) shown in the respective tables below which make up propylene resin composition (Z2) for forming the innermost layer, were dry blended together with component (H), (I) and other components shown in the respective tables below in the proportions shown in each table to form a compound.
(2) Granulation
Each of the resulting compounds was melt-blended in a PCM twin-screw extruder (screw bore, 30 mm; Ikegai Seisakusho) at a screw speed of 200 rpm, a discharge rate of 10 kg/hr and an extruder temperature of 190° C. The molten resin extruded from the strand die was taken up while being cooled and solidified in a cooling water tank. Using a strand cutter, the strand was cut to a diameter of about 2 mm and a length of about 3 mm, giving pellets for use as the feedstock.
(3) Evaluating the Physical Properties of the Multilayer Sheet
Using a single-screw extruder having a 50 mm bore as the inner layer extruder and using a single-screw extruder having a 40 mm bore as the surface layer extruder, the feedstock pellets obtained above were extruded at a temperature setting of 200° C. from a circular die having a mandrel diameter of 100 mm and a lip width of 3.0 mm, water-cooled, and shaped at a speed of 10 m/min, thereby giving a 200 μm thick tubular shaped body having a layer ratio of 1/8/1. Next, the tubular shaped body was cut along one side with a cutter to form a laminated sheet, after which the laminated sheet was conditioned for at least 24 hours in a 23° C., 50% RH atmosphere.
The physical properties of the laminated sheet were evaluated. The results of the evaluations are shown in the Tables below.
Laminated sheets which satisfied the constitution of the invention had an excellent transparency, flexibility, heat resistance, impact resistance, heat-sealability, cleanliness and suitability for fabrication.















TABLE 23







EX 1
EX 2
EX 3
EX 4
EX 5
EX 6
EX 7


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-2)
PP(A-3)
PP(A-4)
PP(A-5)



layer
amount
wt %
80
70
70
70
70
70
70




Component (B)
—
PE(H-3)
PE(B-3)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
—
PP(C-2)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
31
31
35
28
31
31



Innermost
Component (K)
—
—
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
—
—
70
70
70
70
70




Component H
—
—
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
—
—
20
20
20
20
20




Component I
—
—
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
—
—
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
31
31
31
31
31
31




S(0)
wt %
1.6
2.2
2.2
2.2
2.2
2.2
2.2
















Film
Appearance
—
◯—
◯
◯
◯
◯
◯
◯


properties
Total haze
%
19
14
13
13
13
13
13

















after 30
Tensile
MD
MPa
195
251
240
236
244
242
244


minutes
modulus


of heat
Heat-
125° C.
gf/10
1350
1756
1800
1846
1817
1879
1797


treatment at
sealing
130° C.
mm
2546
2756
2856
2546
2849
2864
2879


121° C.
strength
135° C.

3041
3102
3135
3187
3144
3179
3179




140° C.

3154
3325
3326
3465
3467
3468
3471




145° C.

3477
3711
3562
3654
3554
3567
3598




150° C.

3844
4798
4598
4687
4567
4577
4512




155° C.

3910
5102
5165
5026
5100
5167
5147




160° C.

4098
5201
5249
5163
5164
5203
5207



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

X/X
◯X/◯X
◯◯/X  
 X/◯X
◯◯/X  
 X/◯X
 X/◯X




200 cm

—/—
—/—
 X/—
—/—
 X/—
—/—
—/—
























TABLE 24







EX 8
EX 9
EX 10
EX 11
EX 12
EX 13
EX 14


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-6)
PP(A-7)
PP(A-8)
PP(A-9)
PP(A-11)
PP(A-12)
PP(A-13)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
21
31
31



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.2
2.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
13
13
13
13
14
13
14

















after 30
Tensile
MD
MPa
242
236
240
240
289
233
301


minutes
modulus


of heat
Heat-
125° C.
gf/10
1813
1846
1899
1784
1857
1890
1877


treatment at
sealing
130° C.
mm
2846
2846
2811
2877
2557
2587
2579


121° C.
strength
135° C.

3177
3111
3146
3176
3226
3220
3236




140° C.

3412
3416
3498
3478
3499
3514
3516




145° C.

3577
3519
3579
3564
3699
3671
3705




150° C.

4517
4587
4569
4578
4730
4732
4692




155° C.

5189
5198
5177
5144
5064
5038
5067




160° C.

5211
5279
5317
5243
5185
5209
5182



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯◯/X  
◯◯/X  
◯X/X 
◯X/◯X
X/X
X/X
X/X




200 cm

 X/—
 X/—
 X/—
—/—
—/—
—/—
—/—
























TABLE 25







EX 15
EX 16
EX 17
EX 18
EX 19
EX 20
EX 21


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-15)
PP(A-16)
PP(A-17)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-2)
PE(B-3)
PE(B-4)
PE(B-5)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.2
2.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
20
19
19
15
13
15
13

















after 30
Tensile
MD
MPa
242
244
310
235
244
247
241


minutes
modulus


of heat
Heat-
125° C.
gf/10
1856
1872
1895
1812
1854
1817
1810


treatment at
sealing
130° C.
mm
2582
2596
2587
2872
2889
2821
2828


121° C.
strength
135° C.

3223
3211
3213
3142
3180
3114
3133




140° C.

3498
3518
3503
3340
3339
3315
3312




145° C.

3694
3678
3676
3508
3561
3553
3543




150° C.

4702
4725
4712
4591
4595
4610
4525




155° C.

5056
5033
5046
5137
5110
5115
5116




160° C.

5177
5193
5173
5256
5234
5310
5235



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/◯X
X/X
X/X
 X/◯X
 X/◯X
 X/◯X
◯X/X 




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 26







EX 22
EX 23
EX 24
EX 25
EX 26
EX 27
EX 28


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-3)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component A
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
65
70
70




Component (B)
—
PE(B-6)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-2)
PP(C-3)
PP(C-4)
PP(C-5)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
15
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
32
31
31



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.2
2.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
13
13
13
13
12
13
14

















after 30
Tensile
MD
MPa
242
242
239
245
232
262
270


minutes
modulus


of heat
Heat-
125° C.
gf/10
1886
1839
1900
1818
1867
1770
1733


treatment at
sealing
130° C.
mm
2901
2882
2839
2847
2891
2851
2854


121° C.
strength
135° C.

3158
3125
3144
3183
3174
3137
3130




140° C.

3366
3310
3315
3389
3356
3400
3326




145° C.

3504
3581
3581
3530
3582
3506
3567




150° C.

4520
4521
4523
4511
4510
4578
4573




155° C.

5174
5186
5153
5199
5190
5127
5129




160° C.

5275
5270
5254
5257
5206
5227
5255



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

 X/◯X
◯X/X 
 X/◯X
◯X/X 
  X/◯◯
◯◯/◯◯
◯◯/◯◯




200 cm

—/—
—/—
—/—
—/—
—/X 
◯◯/◯◯
◯◯/◯◯
























TABLE 27







EX 29
EX 30
EX 31
EX 32
EX 33
EX 34
EX 35


























Layer
Outer
Component (D)
—
PP(D-4)
PP(D-4)
PP(D-4)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
90
100
100
100
100
100


and resin

Component (D3)
—
—
PE(D3-1)
—
—
—
—
—


formulations

amount
wt %
—
10
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
65
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-5)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
15
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
32
31
31
31
31



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-2)
PP(K-3)
PP(K-4)



layer
amount
wt %
70
70
70
80
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-3)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
—
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
—
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
—
35
28
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.2
2.2
















Film
Appearance
—
◯
◯
◯
◯—
◯
◯
◯


properties
Total haze
%
16
12
15
15
13
13
14

















after 30
Tensile
MD
MPa
221
215
209
230
238
241
239


minutes
modulus


of heat
Heat-
125° C.
gf/10
1512
1399
1707
2043
1883
1823
1890


treatment at
sealing
130° C.
mm
2638
2520
2881
2982
2869
2835
2894


121° C.
strength
135° C.

3022
3199
3152
3072
3162
3191
3123




140° C.

3111
3213
3404
3365
3342
3313
3332




145° C.

3349
3237
3567
3431
3548
3555
3556




150° C.

4353
4236
4513
4635
4548
4531
4520




155° C.

4913
4798
5162
5045
5149
5154
5170




160° C.

5028
4922
5306
5205
5280
5303
5213



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
X/X
X/X
 X/◯X
 X/◯X




200 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
—/—
—/—
—/—
—/—
























TABLE 28







EX 36
EX 37
EX 38
EX 39
EX 40
EX 41
EX 42


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31



Innermost
Component (K)
—
PP(K-5)
PP(K-6)
PP(K-7)
PP(K-8)
PP(K-9)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-2)
PE(H-3)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.3
2.1
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
12
12
14
13
13
15
12

















after 30
Tensile
MD
MPa
240
242
235
240
240
233
243


minutes
modulus


of heat
Heat-
125° C.
gf/10
1883
1806
1866
1845
1865
1841
1903


treatment at
sealing
130° C.
mm
2863
2834
2884
2878
2810
2892
2864


121° C.
strength
135° C.

3176
3169
3171
3161
3107
3186
3183




140° C.

3313
3351
3341
3360
3405
3339
3364




145° C.

3533
3519
3587
3577
3558
3521
3596




150° C.

4529
4556
4546
4578
4548
4541
4514




155° C.

5199
5138
5123
5134
5170
5142
5141




160° C.

5281
5291
5212
5307
5255
5267
5250



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X 
 X/◯X
◯X/X 
◯X/X 
X/X
 X/◯X
 X/◯X




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 29







EX 43
EX 44
EX 45
EX 46
EX 47
EX 48
EX 49


























Layer
Outer
Component D
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
80
100
100
100


and resin

Component D3
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
7125
—
—
—




amount
wt %
—
—
—
20
—
—
—



Inner
Component A
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
60
50
70




Component B
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component C
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
7125
7125
—




amount
wt %
—
—
—
—
10
20
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31



Innermost
Component K
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
65
70
70
70
60




Component H
—
PE(H-4)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component I
—
PP(I-1)
PP(I-2)
PP(I-3)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
15
10
10
10
10




Other components
—
—
—
—
—
—
—
7125




amount
wt %
—
—
—
—
—
—
10




Tm(C) - Tm(Al)
° C.
31
31
32
26
26
26
26




S(0)
wt %
2.1
2.2
7
2.2
2.2
2.2
11
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
15
13
12
12
12
11
12

















after 30
Tensile
MD
MPa
248
244
231
254
231
196
228


minutes
modulus


of heat
Heat-
125° C.
gf/10
1822
1883
1841
1848
1593
1403
1912


treatment at
sealing
130° C.
mm
2822
2827
2887
2811
2578
2499
2992


121° C.
strength
135° C.

3183
3112
3201
3169
3307
3113
3194




140° C.

3321
3366
3369
3380
3346
3383
3328




145° C.

3565
3575
3596
3586
3608
3601
3534




150° C.

4598
4589
4569
4547
4567
4577
4577




155° C.

5185
5150
5141
5153
5168
5207
5168




160° C.

5257
5228
5248
5282
5254
5216
5251



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X  
 X/◯X
◯X/X 
◯◯/◯◯
 ◯X/◯◯
◯◯/◯◯
 ◯X/◯◯




200 cm

—/—
—/—
—/—
◯◯/◯◯
—/X 
◯X/◯X
—/X 

























TABLE 30







EX 50
EX 51
EX 52
EX 53
EX 54
EX 55
EX 56
EX 57



























Layer
Outer
Component (D)
—
PP(D-3)
PP(D-3)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
40
100
100
100
100
100
100
100


and resin

Component (D3)
—
PP(D3-1)
—
—
—
—
—
—
—


formulations

amount
wt %
20
—
—
—
—
—
—
—




Other components
—
PP(A-1)
—
—
—
—
—
—
—




amount
wt %
40
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
75
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-3)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-2)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
5
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31
31



Innermost
Component (K)
—
PP(K-1)
—
PP(K-10)
PP(K-11)
PP(K-12)
PP(K-13)
PP(K-14)
PP(K-15)



layer
amount
wt %
70
—
70
70
70
70
70
70




Component (H)
—
PE(H-1)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
—
20
20
20
20
20
20




Component (I)
—
PP(I-1)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
—
10
10
10
10
10
10




Other components
—
—




amount
wt %
—




Tm(C) - Tm(Al)
° C.
31
31
41
21
31
31
31
31




S(0)
wt %
2.2
2.2
2.4
2.1
2.2
2.2
2.2
2.3

















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
12
13
13
14
13
13
12
19


















after 30
Tensile
MD
MPa
221
268
237
241
234
248
244
230


minutes
modulus


of heat
Heat-
125° C.
gf/10
1356
1754
2028
1686
1873
1843
1867
1875


treatment at
sealing
130° C.
mm
2546
2846
2988
2566
2817
2822
2840
2844


121° C.
strength
135° C.

3182
3166
3185
3114
3142
3125
3137
3122




140° C.

3216
3347
3501
3462
3393
3345
3339
3362




145° C.

3278
3567
3682
3633
3511
3539
3515
3565




150° C.

4289
4599
4436
4366
4560
4587
4554
4533




155° C.

4756
5201
4834
4722
5108
5199
5128
5138




160° C.

4980
5209
5020
4917
5266
5300
5215
5256



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯◯/◯◯
◯◯/◯◯
X/X
X/X
X/X
X/X
X/X
X/X




200 cm

◯◯/◯◯
◯◯/◯◯
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 31











Comp.
Comp.
Comp.
Comp.
Comp.






Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5





Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100


and resin

Component (D3)
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—




Other components
—
—
—
—
—
—




amount
wt %
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-10)



layer
amount
wt %
100
50
70
50
70




Component (B)
—
—
PE(B-1)
—
PE(B-1)
PE(B-1)




amount
wt %
—
50
—
40
20




Component (C)
—
—
—
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
—
30
10
10




Other components
—
—
—
—
—
—




amount
wt %
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
—
31
31
41



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10




Other components
—
—
—
—
—
—




amount
wt %
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31




S(0)
wt %
2.2
  2.2
2.2
2.2
2.2














Film
Appearance
—
◯
Pockmarked
◯
Δ
◯


properties
Total haze
%
10
pattern
28
27
15















after 30
Tensile
MD
MPa
235
arose due
332
219
240


minutes
modulus



to


of heat
Heat-
125° C.
gf/10
1586
inadequate
1979
1258
1903


treatment at
sealing
130° C.
mm
2195
heat
2413
2009
2557


121° C.
strength
135° C.

2849
resistance;
2797
2619
3214




140° C.

3288
good
3231
3294
3523




145° C.

3490
samples
3391
4071
3680




150° C.

4500
could not
3893
4269
4706




155° C.

4489
be
4479
4435
5068




160° C.

4695
obtained
4627
4630
5188



Cumulative
 50 cm
—
X/X

X/X
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

—/—

—/—
 ◯X/◯◯
◯◯/◯X 



test
150 cm

—/—

—/—
 —/◯X
◯X/— 




200 cm

—/—

—/—
—/—
—/—























Comp.
Comp.
Comp.
Comp.







Ex. 6
Ex. 7
Ex. 8
Ex. 9







Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-5)



compositions
layer
amount
wt %
100
100
100
100 



and resin

Component (D3)
—
—
—
—
—



formulations

amount
wt %
—
—
—
—





Other components
—
—
—
—
—





amount
wt %
—
—
—
—




Inner
Component (A)
—
PP(A-14)
PP(A-1)
PP(A-1)
PP(A-1)




layer
amount
wt %
70
70
70
70





Component (B)
—
PE(B-1)
PE(B-7)
PE(B-8)
PE(B-1)





amount
wt %
20
20
20
20





Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)





amount
wt %
10
10
10
10





Other components
—
—
—
—
—





amount
wt %
—
—
—
—





Tm(C) - Tm(Al)
° C.
31
31
31
31




Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)




layer
amount
wt %
70
70
70
70





Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)





amount
wt %
20
20
20
20





Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)





amount
wt %
10
10
10
10





Other components
—
—
—
—
—





amount
wt %
—
—
—
—





Tm(C) - Tm(Al)
° C.
31
31
31
31





S(0)
wt %
2.2
2.2
2.2
  2.2















Film
Appearance
—
◯
◯
◯
Pockmarked



properties
Total haze
%
13
35
26
pattern
















after 30
Tensile
MD
MPa
293
262
287
arose due



minutes
modulus





to



of heat
Heat-
125° C.
gf/10
1867
1822
1570
inadequate



treatment at
sealing
130° C.
mm
2593
2811
2097
heat



121° C.
strength
135° C.

3231
3149
2870
resistance;





140° C.

3517
3347
3361
good





145° C.

3677
3527
3512
samples





150° C.

4737
4511
4578
could not





155° C.

5056
5187
5167
be





160° C.

5197
5265
5230
obtained




Cumulative
 50 cm
—
◯◯/◯◯
 X/◯X
◯◯/◯◯




bag drop
100 cm

◯X/◯X
—/—
◯◯/◯◯




test
150 cm

◯X/— 
—/—
◯X/X 





200 cm

—/—
—/—
—/—

























TABLE 32







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5
Ex. 6
Ex. 7


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-4)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
90
100
100 


and resin

Component (D3)
—
—
—
—
—
PE(D3-2)
—
—


formulations

amount
wt %
—
—
—
—
10
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
60
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
10
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-6)
PP(C-7)
PP(C-8)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
30
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
5
−5
31
31
31
31



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
100
50




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
—
PE(H-1)




amount
wt %
20
20
20
20
20
—
50




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
—
—




amount
wt %
10
10
10
10
10
—
—




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
—
—




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.6
  2.4
















Film
Appearance
—
◯
◯
◯
◯
◯
Δ
Internal


properties
Total haze
%
28
14
14
21
28
29
fusion due

















after 30
Tensile
MD
MPa
326
225
220
306
234
230
to


minutes
modulus








inadequate


of heat
Heat-
125° C.
gf/10
1259
1683
1664
1346
1594
2001
heat


treatment at
sealing
130° C.
mm
1991
2625
2643
1877
2727
3072
resistance


121° C.
strength
135° C.

2594
2923
2978
2592
3397
3375
occurred




140° C.

3301
3140
3139
3501
3416
3337
during




145° C.

4031
3363
3330
3572
3434
3563
steriliza-




150° C.

4283
4323
4313
4084
4438
4508
tion;




155° C.

4412
4956
4983
4688
4999
5009
could




160° C.

4627
5100
5105
4993
5113
5287
not be



Cumulative
 50 cm
—
X/X
◯◯/X  
◯X/◯X
◯◯/◯◯
◯◯/◯◯
X/X
evaluated



bag drop
100 cm

—/—
◯X/— 
—/—
 ◯X/◯◯
◯◯/◯◯
—/—



test
150 cm

—/—
—/—
—/—
—/X 
◯◯/◯◯
—/—




200 cm

—/—
—/—
—/—
—/—
◯◯/◯◯
—/—























TABLE 33







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 8
Ex. 9
Ex. 10
Ex. 11
Ex. 12
Ex. 13

























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100 
100 


and resin

Component (D3)
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
40
60
70
70
70




Component (H)
—
—
PE(H-1)
PE(H-1)
PE(H-5)
PE(H-1)
PE(H-1)




amount
wt %
—
50
10
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-4)
PP(I-5)




amount
wt %
30
10
30
10
10
10




Other components
—




amount
wt %




Tm(C) - Tm(Al)
° C.
31
31
31
31
 5
−5




S(0)
wt %
1.9
  2.1
1.8
2.1
  2.2
  2.2















Film
Appearance
—
◯
Internal
◯
◯
Internal
Internal


properties
Total haze
%
22
fusion due
21
28
fusion due
fusion due
















after 30
Tensile
MD
MPa
318
to
312
251
to
to


minutes
modulus



inadequate


inadequate
inadequate


of heat
Heat-
125° C.
gf/10
197
heat
388
1588
heat
heat


treatment at
sealing
130° C.
mm
592
resistance
734
2749
resistance
resistance


121° C.
strength
135° C.

1046
occurred
1303
3026
occurred
occurred




140° C.

1677
during
1763
3282
during
during




145° C.

1759
steriliza-
1842
3435
steriliza-
steriliza-




150° C.

2021
tion;
1940
4476
tion;
tion;




155° C.

2111
could
2020
4922
could
could




160° C.

2548
not be
2569
4827
not be
not be



Cumulative
 50 cm
—
X/X
evaluated
X/X
◯◯/X  
evaluated
evaluated



bag drop
100 cm

—/—

—/—
◯X/— 



test
150 cm

—/—

—/—
—/—




200 cm

—/—

—/—
—/—
























TABLE 34







EX 58
EX 59
EX 60
EX 61
EX 62
EX 63
EX 64


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-2)
PP(A-3)
PP(A-4)
PP(A-5)
PP(A-6)



layer
amount
wt %
80
70
70
70
70
70
70




Component (B)
—
PE(B-3)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
31
35
28
31
31
31



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0.2
0.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
18
12
12
13
12
12
13

















after 30
Tensile
MD
MPa
251
280
277
286
275
284
291


minutes
modulus


of heat
Heat-
125° C.
gf/10
765
1569
1549
1544
1578
1536
1547


treatment at
sealing
130° C.
mm
2219
2672
2594
2548
2489
2612
2487


121° C.
strength
135° C.

3101
3753
3687
3644
3612
3679
3674




140° C.

3390
3637
3555
3647
3574
3677
3680




145° C.

4121
4122
4236
4342
4287
4247
4105




150° C.

4587
4656
4657
4689
4713
4699
4671




155° C.

5290
5274
5347
5247
5246
5298
5278




160° C.

5311
5320
5359
5347
5346
5311
5329



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

XX/XX
◯X/◯X
◯X/X 
X/X
 X/◯X
X/X
X/X




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 35







EX 65
EX 66
EX 67
EX 68
EX 69
EX 70
EX 71


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-7)
PP(A-8)
PP(A-9)
PP(A-11)
PP(A-12)
PP(A-13)
PP(A-15)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
21
31
31
31



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0.2
0.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
12
12
12
14
13
14
19

















after 30
Tensile
MD
MPa
273
280
280
321
273
325
282


minutes
modulus


of heat
Heat-
125° C.
gf/10
1579
1574
1577
1552
1554
1581
1552


treatment at
sealing
130° C.
mm
2546
2469
2555
2595
2551
2499
2496


121° C.
strength
135° C.

3643
3641
3655
3695
3651
3621
3683




140° C.

3678
3679
3667
3557
3649
3580
3689




145° C.

4279
4394
4317
4238
4349
4294
4115




150° C.

4703
4781
4689
4662
4691
4714
4681




155° C.

5200
5234
5349
5357
5257
5249
5283




160° C.

5341
5304
5397
5362
5357
5353
5338



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/◯X
◯X/X 
◯X/X 
X/X
X/X
X/X
X/X




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 36







EX 72
EX 73
EX 74
EX 75
EX 76
EX 77
EX 78


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-16)
PP(A-17)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-2)
PE(B-3)
PE(B-4)
PE(B-5)
PE(B-6)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—




amount
wt %




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0.2
0.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
19
20
15
12
15
12
12

















after 30
Tensile
MD
MPa
284
306
276
285
286
280
281


minutes
modulus


of heat
Heat-
125° C.
gf/10
1585
1576
1541
1567
1543
1556
1536


treatment at
sealing
130° C.
mm
2554
2471
2585
2613
2583
2604
2573


121° C.
strength
135° C.

3647
3646
3567
3603
3573
3602
3583




140° C.

3679
3683
3478
3505
3469
3492
3466




145° C.

4285
4397
4173
4195
4158
4186
4154




150° C.

4704
4789
4526
4544
4526
4544
4505




155° C.

5203
5237
5128
5163
5121
5144
5103




160° C.

5345
5313
5252
5244
5247
5254
5247



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

X/X
X/X
 X/◯X
 X/◯X
 X/◯X
◯X/X 
 X/◯X




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 37







EX 79
EX 80
EX 81
EX 82
EX 83
EX 84
EX 85


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-3)
PP(D-4)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
65
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-2)
PP(C-3)
PP(C-4)
PP(C-5)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
32
31
31
31



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—




amount
wt %




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0.2
0.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
12
12
12
11
13
14
16

















after 30
Tensile
MD
MPa
281
278
284
271
298
298
251


minutes
modulus


of heat
Heat-
125° C.
gf/10
1573
1556
1573
1553
1786
1763
1562


treatment at
sealing
130° C.
mm
2614
2585
2614
2585
2861
2884
2672


121° C.
strength
135° C.

3595
3562
3605
3575
3182
3168
3069




140° C.

3498
3491
3514
3478
3443
3339
3147




145° C.

4187
4183
4187
4156
3520
3592
3369




150° C.

4532
4526
4553
4533
4594
4622
4394




155° C.

5124
5136
5168
5139
5179
5164
4923




160° C.

5242
5253
5250
5250
5241
5269
5075



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X 
 X/◯X
◯X/X 
  X/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯




200 cm

—/—
—/—
—/—
—/X 
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
























TABLE 38







EX 86
EX 87
EX 88
EX 89
EX 90
EX 91
EX 92


























Layer
Outer
Component (D)
—
PP(D-4)
PP(D-4)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
90
100
100
100
100
100
100


and resin

Component (D3)
—
PE(D3-1)
—
—
—
—
—
—


formulations

amount
wt %
10
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
65
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-5)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
15
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
32
31
31
31
31
31



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-2)
PP(E-3)
PP(E-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
90
90
90
90
90
85
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-2)
PE(F-3)
PE(F-4)




amount
wt %
10
10
10
10
10
15
10




Component (I)
—


—
—
—
—
—




amount
wt %


—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.6
0.2
0.2
0.1
















Film
Appearance
—
◯
◯
◯
◯—
◯
◯
◯


properties
Total haze
%
12
14
13
17
15
13
15

















after 30
Tensile
MD
MPa
243
235
281
285
281
282
280


minutes
modulus


of heat
Heat-
125° C.
gf/10
1436
1764
1367
1214
1755
1561
1579


treatment at
sealing
130° C.
mm
2579
2902
2472
2551
2582
2647
2587


121° C.
strength
135° C.

3248
3208
3322
3253
3425
3621
3488




140° C.

3228
3433
3488
3422
3571
3616
3511




145° C.

3285
3593
4183
4103
4017
4073
4315




150° C.

4290
4564
4472
4464
4459
4463
4141




155° C.

4833
5206
5081
5020
5023
5020
5133




160° C.

4949
5356
5129
5164
5195
5121
5219



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯◯/◯◯
◯◯/◯◯
 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 




200 cm

◯◯/◯◯
◯◯/◯◯
—/—
—/—
—/—
—/—
—/—





















TABLE 39







EX 93
EX 94
EX 95
EX 96























Layer
Outer
Component (D)
—
PP(D-2)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
80
100
100
100


and resin

Component (D3)
—
—
—
—
—


formulations

amount
wt %
—
—
—
—




Other components
—
7125
—
—
—




amount
wt %
20
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
60
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10




Other components
—
—
7125
7125
—




amount
wt %
—
10
20
—




Tm(C) - Tm(Al)
° C.
26
26
26
26



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
85




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
5




Component (I)
—




amount
wt %




Other components
—
—
—
—
7125




amount
wt %
—
—
—
10




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
8.9













Film
Appearance
—
◯
◯
◯
◯


properties
Total haze
%
11
11
10
11














after 30
Tensile
MD
MPa
284
271
234
268


minutes
modulus


of heat
Heat-
125° C.
gf/10
2052
1819
1569
2177


treatment at
sealing
130° C.
mm
3169
2874
2826
3367


121° C.
strength
135° C.

3490
3673
3493
3542




140° C.

3805
3724
3756
3681




145° C.

3989
3980
4037
3939




150° C.

5084
5065
5122
5038




155° C.

5723
5745
5785
5745




160° C.

5826
5795
5769
5793



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯◯/◯◯
 ◯X/◯◯
◯◯/◯◯
 ◯X/◯◯




200 cm

◯◯/◯◯
—/X 
◯X/◯X
—/X 
























TABLE 40







Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Ex. 10
Ex. 11
Ex. 12
Ex. 13
Ex. 14
Ex. 15
Ex. 16


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-10)
PP(A-14)
PP(A-1)



layer
amount
wt %
100
50
70
40
70
70
70




Component (B)
—
—
PE(B-1)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-7)




amount
wt %
—
50
—
50
20
20
20




Component (C)
—
—
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
—
30
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
—
31
31
41
31
31



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—




amount
wt %




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
  0.2
0.2
0.2
0.2
0.2
0.2
















Film
Appearance
—
◯
Pockmarked
◯
Δ
◯
◯
◯


properties
Total haze
%
9.5
pattern
27
22
15
13
34

















after 30
Tensile
MD
MPa
260
arose due
376
263
280
293
297


minutes
modulus



to


of heat
Heat-
125° C.
gf/10
1522
inadequate
1532
1389
1559
1539
1566


treatment at
sealing
130° C.
mm
2611
heat
2584
1984
2604
2621
2617


121° C.
strength
135° C.

3374
resistance;
3574
2984
3690
3683
3612




140° C.

3544
good
3678
3290
3557
3687
3498




145° C.

4267
samples
4287
4019
4244
4254
4197




150° C.

4623
could not
4586
4239
4666
4704
4548




155° C.

4769
be
5188
4728
5352
5302
5147




160° C.

4772
obtained
5208
5297
5367
5318
5245



Cumulative
 50 cm
—
X/X

◯X/◯X
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
 X/◯X



bag drop
100 cm

—/—

—/—
◯◯/◯X 
◯◯/◯X 
◯X/◯X
—/—



test
150 cm

—/—

—/—
◯X/— 
◯X/— 
◯X/— 
—/—




200 cm

—/—

—/—
—/—
—/—
—/—
—/—



















TABLE 41







Comp.
Comp.



Ex. 17
Ex. 18





















Layer
Outer
Component (D)
—
PP(D-1)
PP(D-5)


compositions
layer
amount
wt %
100
100 


and resin

Component (D3)
—
—
—


formulations

amount
wt %
—
—




Other components
—
—
—




amount
wt %
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70




Component (B)
—
PE(B-8)
PE(B-1)




amount
wt %
20
20




Component (C)
—
PP(C-1)
PP(C-1)




amount
wt %
10
10




Other components
—
—
—




amount
wt %
—
—




Tm(C) - Tm(Al)
° C.
31
31



Innermost
Component (E)
—
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90




Component (F)
—
PE(F-1)
PE(F-1)




amount
wt %
10
10




Component (I)
—




amount
wt %




Other components
—
—
—




amount
wt %
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
  0.2











Film
Appearance
—
◯
Pockmarked


properties
Total haze
%
35
pattern












after 30
Tensile
MD
MPa
329
arose due


minutes
modulus



to


of heat
Heat-
125° C.
gf/10
1549
inadequate


treatment at
sealing
130° C.
mm
2594
heat


121° C.
strength
135° C.

3577
resistance;




140° C.

3482
good




145° C.

4165
samples




150° C.

4518
could not




155° C.

5116
be




160° C.

5253
obtained



Cumulative
 50 cm
—
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯



test
150 cm

◯X/X 




200 cm

—/—
























TABLE 42







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 14
Ex. 15
Ex. 16
Ex. 17
Ex. 18
Ex. 19
Ex. 20


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-4)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
90
100
100 


and resin

Component (D3)
—
—
—
—
—
PE(D3-2)
—
—


formulations

amount
wt %
—
—
—
—
10
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
60
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
10
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-6)
PP(C-7)
PP(C-8)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
30
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
5
−5
31
31
31
31



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
100
70




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
—
PE(F-1)




amount
wt %
10
10
10
10
10
—
30




Component (I)
—




amount
wt %




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0
  0.6
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
Internal


properties
Total haze
%
31
13
13
21
28
9
fusion due

















after 30
Tensile
MD
MPa
368
265
359
348
248
284
to


minutes
modulus








inadequate


of heat
Heat-
125° C.
gf/10
1564
1571
1552
1571
1603
85
heat


treatment at
sealing
130° C.
mm
2566
2608
2592
2626
2728
459
resistance


121° C.
strength
135° C.

3599
3609
3585
3606
3407
3194
occurred




140° C.

3621
3516
3490
3507
3418
3260
during




145° C.

4357
4201
4182
4193
3437
3647
steriliza-




150° C.

4597
4547
4532
4551
4441
4317
tion;




155° C.

5288
5134
5144
5178
5003
4825
could




160° C.

5361
5249
5264
5258
5122
4422
not be



Cumulative
 50 cm
—
 X/◯X
◯◯/X  
◯X/◯X
◯◯/◯◯
◯◯/◯◯
X/X
evaluated



bag drop
100 cm

—/—
◯X/— 
—/—
 ◯X/◯◯
◯◯/◯◯
—/—



test
150 cm

—/—
—/—
—/—
—/X 
◯◯/◯◯
—/—




200 cm

—/—
—/—
—/—
—/—
◯◯/◯◯
—/—




















TABLE 43







Ref.
Ref.
Ref.



Ex. 21
Ex. 22
Ex. 23






















Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100 
100
100


and resin

Component (D3)
—
—
—
—


formulations

amount
wt %
—
—
—




Other components
—
—
—
—




amount
wt %
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31



Innermost
Component (E)
—
PP(E-4)
PP(E-5)
PP(E-1)



layer
amount
wt %
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-5)




amount
wt %
10
10
10




Component (I)
—
—
—
—




amount
wt %
—
—
—




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
  0.3
0.4
0.1












Film
Appearance
—
Internal
◯
◯


properties
Total haze
%
fusion due
19
27













after 30
Tensile
MD
MPa
to
501
285


minutes
modulus


inadequate


of heat
Heat-
125° C.
gf/10
heat
22
1162


treatment at
sealing
130° C.
mm
resistance
261
1365


121° C.
strength
135° C.

occurred
448
3131




140° C.

during
785
3249




145° C.

steriliza-
1359
3558




150° C.

tion;
1577
4322




155° C.

could
2156
4992




160° C.

not be
3001
5104



Cumulative
 50 cm
—
evaluated
X/X
◯◯/◯◯



bag drop
100 cm


—/—
X/X



test
150 cm


—/—
—/—




200 cm


—/—
—/—
























TABLE 44







EX 97
EX 98
EX 99
EX 100
EX 101
EX 102
EX 103


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-2)
PP(A-3)
PP(A-4)
PP(A-5)
PP(A-6)
PP(A-7)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
35
28
31
31
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
1.3
1.3
1.3
1.3
1.3
1.3
1.3
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
13
13
13
13
13
13
13

















after 30
Tensile
MD
MPa
240
236
244
242
244
242
236


minutes
modulus


of heat
Heat-
125° C.
gf/10
1807
1852
1822
1887
1803
1816
1850


treatment at
sealing
130° C.
mm
2865
2548
2853
2870
2881
2850
2853


121° C.
strength
135° C.

3141
3197
3147
3181
3185
3182
3120




140° C.

3331
3468
3472
3470
3477
3419
3421




145° C.

3567
3664
3563
3569
3599
3580
3525




150° C.

4606
4695
4576
4585
4513
4518
4595




155° C.

5170
5032
5105
5177
5156
5193
5201




160° C.

5251
5167
5171
5204
5211
5213
5283



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯◯/X  
 X/◯X
◯◯/X  
 X/◯X
 X/◯X
◯◯/X  
◯◯/X  




200 cm

 X/—
—/—
 X/—
—/—
—/—
 X/—
 X/—
























TABLE 45







EX 104
EX 105
EX 106
EX 107
EX 108
EX 109
EX 110


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-8)
PP(A-9)
PP(A-11)
PP(A-12)
PP(A-13)
PP(A-15)
PP(A-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
21
31
31
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
1.3
1.3
1.3
1.3
1.3
1.3
1.3
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
13
13
14
13
14
20
19

















after 30
Tensile
MD
MPa
240
240
289
233
301
242
244


minutes
modulus


of heat
Heat-
125° C.
gf/10
1901
1789
1855
1885
1868
1850
1863


treatment at
sealing
130° C.
mm
2817
2885
2548
2578
2574
2580
2591


121° C.
strength
135° C.

3153
3185
3222
3216
3232
3215
3201




140° C.

3499
3486
3490
3509
3515
3491
3508




145° C.

3581
3573
3691
3661
3704
3693
3670




150° C.

4578
4586
4726
4731
4690
4695
4722




155° C.

5187
5145
5063
5033
5058
5052
5030




160° C.

5324
5253
5179
5203
5178
5172
5185



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X 
◯X/◯X
X/X
X/X
X/X
X/X
X/X




200 cm

 X/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 46







EX 111
EX 112
EX 113
EX 114
EX 115
EX 116
EX 117


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-17)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-2)
PE(B-3)
PE(B-4)
PE(B-5)
PE(B-6)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-2)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
1.3
1.3
1.3
1.3
1.3
1.3
1.3
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
20
15
13
15
13
13
13

















after 30
Tensile
MD
MPa
310
235
244
247
241
242
242


minutes
modulus


of heat
Heat-
125° C.
gf/10
1893
1832
1881
1871
1832
1922
1850


treatment at
sealing
130° C.
mm
2585
2923
2912
2844
2863
2917
2904


121° C.
strength
135° C.

3211
3178
3232
3128
3138
3211
3170




140° C.

3496
3350
3374
3343
3344
3418
3339




145° C.

3673
3543
3598
3575
3601
3518
3616




150° C.

4704
4644
4641
4616
4528
4532
4553




155° C.

5037
5177
5171
5144
5145
5207
5191




160° C.

5171
5305
5239
5317
5251
5283
5311



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯X/◯X
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

—/—
 X/◯X
 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 47







EX 118
EX 119
EX 120
EX 121
EX 122
EX 123
EX 124


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-3)
PP(D-4)
PP(D-4)


compositions
layer
amount
wt %
100
100
100
100
100
100
90


and resin

Component (D3)
—
—
—
—
—
—
—
PE(D3-1)


formulations

amount
wt %
—
—
—
—
—
—
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
65
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-3)
PP(C-4)
PP(C-5)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
15
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
32
31
31
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
1.3
1.3
1.3
1.3
1.3
1.3
1.3
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
13
13
12
13
15
16
12

















after 30
Tensile
MD
MPa
239
245
232
262
270
221
215


minutes
modulus


of heat
Heat-
125° C.
gf/10
1943
1878
1915
1786
1763
1562
1436


treatment at
sealing
130° C.
mm
2846
2857
2935
2861
2884
2672
2579


121° C.
strength
135° C.

3186
3194
3189
3182
3168
3069
3248




140° C.

3346
3426
3376
3443
3339
3147
3228




145° C.

3633
3579
3606
3520
3592
3369
3285




150° C.

4535
4528
4540
4594
4622
4394
4290




155° C.

5166
5230
5225
5179
5164
4923
4833




160° C.

5281
5302
5244
5241
5269
5075
4949



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

 X/◯X
◯X/X 
  X/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯




200 cm

—/—
—/—
—/X 
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
























TABLE 48







EX 125
EX 126
EX 127
EX 128
EX 129
EX 130
EX 131


























Layer
Outer
Component (D)
—
PP(D-4)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
65
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-5)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
15
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
32
31
31
31
31
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-17)
PP(K-18)
PP(K-19)
PP(K-20)
PP(K-16)



layer
amount
wt %
70
80
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-3)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-2)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
—
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
—
19
22
53
0
26




S(0)
wt %
1.3
1.1
1.5
1.1
1.3
1.5
1.4
















Film
Appearance
—
◯
◯—
◯
◯
◯
◯—
◯


properties
Total haze
%
15
15
13
13
16
17
15

















after 30
Tensile
MD
MPa
209
235
238
241
241
240
235


minutes
modulus


of heat
Heat-
125° C.
gf/10
1764
2101
1860
1930
1908
1936
1870


treatment at
sealing
130° C.
mm
2902
3018
2949
2879
2889
2850
2912


121° C.
strength
135° C.

3208
3124
3238
3194
3221
3181
3195




140° C.

3433
3451
3332
3415
3357
3415
3388




145° C.

3593
3512
3576
3554
3569
3610
3540




150° C.

4564
4681
4617
4607
4529
4596
4632




155° C.

5206
5123
5205
5184
5249
5166
5193




160° C.

5356
5234
5261
5262
5310
5284
5309



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯◯/◯◯
X/X
 X/◯X
◯X/X 
 X/◯X
◯X/X 
 X/◯X




200 cm

◯◯/◯◯
—/—
—/—
—/—
—/—
—/—
—/—





















TABLE 49







EX 132
EX 133
EX 134
EX 135























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100


and resin

Component (D3)
—
—
—
—
—


formulations

amount
wt %
—
—
—
—




Other components
—
—
—
—
—




amount
wt %
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
60
50
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10




Other components
—
7125
7125
—
—




amount
wt %
10
20
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
60
60




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
10




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
30




Other components
—
—
—
7125
—




amount
wt %
—
—
10
—




Tm(C) - Tm(Al)
° C.
26
26
26
26




S(0)
wt %
1.3
1.3
10
1.1













Film
Appearance
—
◯
◯
◯
◯


properties
Total haze
%
12
11
12
21














after 30
Tensile
MD
MPa
231
196
228
312


minutes
modulus


of heat
Heat-
125° C.
gf/10
1771
1533
2095
416


treatment at
sealing
130° C.
mm
2859
2764
3309
769


121° C.
strength
135° C.

3661
3425
3518
1301




140° C.

3698
3734
3653
1786




145° C.

3966
3981
3884
1854




150° C.

5047
5058
5043
1941




155° C.

5683
5759
5689
2070




160° C.

5794
5736
5785
2620



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

 ◯X/◯◯
◯◯/◯◯
 ◯X/◯◯
X/X




200 cm

—/X 
◯X/◯X
—/X 
—/—
























TABLE 50







Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Ex. 19
Ex. 20
Ex. 21
Ex. 22
Ex. 23
Ex. 24
Ex. 25


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-10)
PP(A-14)
PP(A-1)



layer
amount
wt %
100
50
70
50
70
70
70




Component (B)
—
—
PE(B-1)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-7)




amount
wt %
—
50
—
40
20
20
20




Component (C)
—
—
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
—
30
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
—
31
31
41
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
1.3
  1.3
1.3
1.3
1.3
1.3
1.3
















Film
Appearance
—
◯
Pockmarked
◯
Δ
◯
◯
◯


properties
Total haze
%
10
pattern
28
27
15
13
35

















after 30
Tensile
MD
MPa
235
arose due
332
219
240
293
262


minutes
modulus



to


of heat
Heat-
125° C.
gf/10
1578
inadequate
1977
1249
1896
1862
1869


treatment at
sealing
130° C.
mm
2192
heat
2406
2002
2553
2588
2820


121° C.
strength
135° C.

2844
resistance;
2787
2609
3213
3226
3196




140° C.

3281
good
3224
3291
3514
3507
3377




145° C.

3481
samples
3383
4063
3670
3667
3572




150° C.

4491
could not
3884
4265
4701
4727
4534




155° C.

4482
be
4473
4434
5065
5053
5217




160° C.

4689
obtained
4622
4627
5182
5187
5321



Cumulative
 50 cm
—
X/X

X/X
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
 X/◯X



bag drop
100 cm

—/—

—/—
 ◯X/◯◯
◯◯/◯X 
◯X/◯X
—/—



test
150 cm

—/—

—/—
 —/◯X
◯X/— 
◯X/— 
—/—




200 cm

—/—

—/—
—/—
—/—
—/—
—/—



















TABLE 51







Comp. Ex. 26
Comp. Ex. 27





















Layer compositions
Outer layer
Component (D)
—
PP(D-1)
PP(D-5)


and resin

amount
wt %
 100
100 


formulations

Component (D3)
—
—
—




amount
wt %
—
—




Other components
—
—
—




amount
wt %
—
—



Inner layer
Component (A)
—
PP(A-1)
PP(A-1)




amount
wt %
 70
70




Component (B)
—
PE(B-8)
PE(B-1)




amount
wt %
 20
20




Component (C)
—
PP(C-1)
PP(C-1)




amount
wt %
 10
10




Other components
—
—
—




amount
wt %
—
—




Tm(C)-Tm(Al)
° C.
 31
31



Innermost layer
Component (K)
—
PP(K-16)
PP(K-16)




amount
wt %
 70
70




Component (H)
—
PE(H-1)
PE(H-1)




amount
wt %
 20
20




Component (I)
—
PP(I-1)
PP(I-1)




amount
wt %
 10
10




Other components
—
—
—




amount
wt %
—
—




Tm(C)-Tm(Al)
° C.
 26
26




S(0)
wt %
   1.3
  1.3


Film properties
Appearance

—
◯
Pockmarked


after 30 minutes
Total haze

%
 26
pattern arose due


of heat treatment
Tensile modulus
MD
MPa
 287
to inadequate


at 121° C.
Heat-sealing
125° C.
gf/10 mm
1600
heat resistance;



strength
130° C.

2123
good samples were




135° C.

2877
not obtained




140° C.

3386




145° C.

3570




150° C.

4633




155° C.

5200




160° C.

5259



Cumulative
 50 cm
—
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯



test
150 cm

◯X/X 




200 cm

—/—
























TABLE 52







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 24
Ex. 25
Ex. 26
Ex. 27
Ex. 28
Ex. 29
Ex. 30


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-4)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
90
100
100 


and resin

Component (D3)
—
—
—
—
—
PE(D3-2)
—
—


formulations

amount
wt %
—
—
—
—
10
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
60
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
10
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-6)
PP(C-7)
PP(C-8)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
30
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
5
−5
31
31
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
100
50




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
—
PE(H-1)




amount
wt %
20
20
20
20
20
—
50




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
—
—




amount
wt %
10
10
10
10
10
—
—




Other components
—
—
—
—

—
—
—




amount
wt %
—
—
—

—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
—
—




S(0)
wt %
1.3
1.3
1.3
1.3
1.3
1.3
  1.5
















Film
Appearance
—
◯
◯
◯
◯
◯
Δ
Internal


properties
Total haze
%
28
14
14
21
28
29
fusion due

















after 30
Tensile
MD
MPa
326
225
220
306
234
230
to


minutes
modulus








inadequate


of heat
Heat-
125° C.
gf/10
1256
1729
1678
1374
1603
2019
heat


treatment at
sealing
130° C.
mm
1985
2670
2698
1893
2728
3041
resistance


121° C.
strength
135° C.

2593
2971
3032
2610
3407
3391
occurred




140° C.

3291
3177
3159
3549
3418
3321
during




145° C.

4022
3377
3363
3631
3437
3594
steriliza-




150° C.

4278
4357
4358
4099
4441
4538
tion;




155° C.

4405
5015
5005
4719
5003
5023
could




160° C.

4625
5150
5122
5045
5122
5285
not be



Cumulative
 50 cm
—
X/X
◯◯/X  
◯X/◯X
◯◯/◯◯
◯◯/◯◯
XX
evaluated



bag drop
100 cm

—/—
◯X/— 
—/—
 ◯X/◯◯
◯◯/◯◯
—/—



test
150 cm

—/—
—/—
—/—
—/X 
◯◯/◯◯
—/—




200 cm

—/—
—/—
—/—
—/—
◯◯/◯◯
—/—
























TABLE 53







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 31
Ex. 32
Ex. 33
Ex. 34
Ex. 35
Ex. 36
Ex. 37


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100 
100
100 
100 


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-21)
PP(K-22)
PP(K-23)
PP(K-24)
PP(K-25)



layer
amount
wt %
70
40
70
70
70
70
70




Component (H)
—
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
—
50
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
30
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
—
26
26
53




S(0)
wt %
1
  1.3
0.4
  2.2
0.8
  1.9
  1.3
















Film
Appearance
—
◯
Internal
◯
Internal
◯
Internal
Internal


properties
Total haze
%
22
fusion due
22
fusion due
21
fusion due
fusion due

















after 30
Tensile
MD
MPa
318
to
329
to
319
to
to


minutes
modulus



inadequate

inadequate

inadequate
inadequate


of heat
Heat-
125° C.
gf/10
233
heat
2065
heat
1905
heat
heat


treatment at
sealing
130° C.
mm
633
resistance
3008
resistance
2854
resistance
resistance


121° C.
strength
135° C.

1069
occurred
3226
occurred
3153
occurred
occurred




140° C.

1724
during
3507
during
3439
during
during




145° C.

1805
steriliza-
3689
steriliza-
3535
steriliza-
steriliza-




150° C.

2055
tion;
4475
tion;
4611
tion;
tion;




155° C.

2162
could
4874
could
5143
could
could




160° C.

2548
not be
5032
not be
5306
not be
not be



Cumulative
 50 cm
—
X/X
evaluated
◯◯/◯◯
evaluated
◯◯/◯◯
evaluated
evaluated



bag drop
100 cm

—/—

◯◯/◯X 

 ◯X/◯◯



test
150 cm

—/—

 X/—

 —/◯X




200 cm

—/—

—/—

—/—























TABLE 54







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 38
Ex. 39
Ex. 40
Ex. 41
Ex. 42
Ex. 43

























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100 
100 


and resin

Component (D3)
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)
PP(A-1)



layer
amount
wt %
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31



Innermost
Component (K)
—
PP(K-26)
PP(K-27)
PP(K-28)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-5)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-4)
PP(I-5)




amount
wt %
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
0
26
26
26
 0
−10  




S(0)
wt %
1.4
0.4
13.4
1.2
  1.3
  1.3















Film
Appearance
—
◯
◯
Δ
◯
Internal
Internal


properties
Total haze
%
31
28
29
28
fusion due
fusion due
















after 30
Tensile
MD
MPa
478
251
230
251
to
to


minutes
modulus






inadequate
inadequate


of heat
Heat-
125° C.
gf/10
65
1597
1875
1629
heat
heat


treatment at
sealing
130° C.
mm
251
2791
2867
2778
resistance
resistance


121° C.
strength
135° C.

516
3058
3306
3039
occurred
occurred




140° C.

771
3313
3303
3249
during
during




145° C.

1353
3461
3554
3465
steriliza-
steriliza-




150° C.

1636
4497
4569
4342
tion;
tion;




155° C.

2129
4964
5021
4911
could
could




160° C.

2846
4840
5252
4868
not be
not be



Cumulative
 50 cm
—
X/X
◯◯/X  
◯◯/◯◯
◯◯/X  
evaluated
evaluated



bag drop
100 cm

—/—
◯X/— 
◯◯/◯◯
◯X/— 



test
150 cm

—/—
—/—
◯X/X 
—/—




200 cm

—/—
—/—
—/—
—/—
























TABLE 55







EX 136
EX 137
EX 138
EX 139
EX 140
EX 141
EX 142


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-19)
PP(A-20)
PP(A-21)
PP(A-22)
PP(A-23)



layer
amount
wt %
80
70
70
70
70
70
70




Component (B)
—
PE(B-3)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
26
26
26
19
22
19



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.2
2.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
19
13
13
13
16
17
17

















after 30
Tensile
MD
MPa
200
240
238
241
260
251
255


minutes
modulus


of heat
Heat-
125° C.
gf/10
1024
1837
1896
1852
1839
1838
1863


treatment at
sealing
130° C.
mm
2456
2845
2895
2836
2872
2840
2891


121° C.
strength
135° C.

3009
3190
3181
3175
3110
3189
3153




140° C.

3254
3354
3312
3357
3379
3383
3400




145° C.

3345
3520
3507
3533
3536
3531
3572




150° C.

4157
4563
4577
4543
4503
4577
4578




155° C.

4412
5165
5142
5133
5112
5172
5170




160° C.

4351
5259
5211
5247
5240
5286
5271



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

X/X
 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 
◯X/X 




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 56







EX 143
EX 144
EX 145
EX 146
EX 147
EX 148
EX 149


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-2)
PE(B-3)
PE(B-4)
PE(B-5)
PE(B-6)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-2)
PP(C-3)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.2
2.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
15
13
15
13
13
13
13

















after 30
Tensile
MD
MPa
235
244
247
241
242
242
239


minutes
modulus


of heat
Heat-
125° C.
gf/10
1802
1851
1816
1807
1881
1835
1895


treatment at
sealing
130° C.
mm
2871
2881
2814
2822
2899
2874
2830


121° C.
strength
135° C.

3133
3173
3106
3123
3151
3118
3134




140° C.

3336
3337
3312
3310
3358
3303
3306




145° C.

3501
3553
3544
3539
3503
3575
3579




150° C.

4586
4585
4600
4515
4511
4518
4517




155° C.

5130
5109
5110
5110
5166
5177
5143




160° C.

5249
5226
5300
5227
5267
5265
5246



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

 X/◯X
 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 
 X/◯X




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 57







EX 150
EX 151
EX 152
EX 153
EX 154
EX 155
EX 156


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-3)
PP(D-4)
PP(D-4)
PP(D-4)


compositions
layer
amount
wt %
100
100
100
100
100
90
100


and resin

Component (D3)
—
—
—
—
—
—
PE(D3-1)
—


formulations

amount
wt %
—
—
—
—
—
10
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
65
70
70
70
70
65




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-4)
PP(C-5)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-5)




amount
wt %
10
15
10
10
10
10
15




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
27
26
26
26
26
27



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.2
2.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
13
12
13
15
16
12
15

















after 30
Tensile
MD
MPa
245
232
262
270
221
215
209


minutes
modulus


of heat
Heat-
125° C.
gf/10
1817
1866
1760
1726
1507
1394
1706


treatment at
sealing
130° C.
mm
2844
2889
2845
2851
2632
2519
2871


121° C.
strength
135° C.

3177
3171
3131
3128
3012
3198
3148




140° C.

3388
3354
3398
3322
3103
3209
3399




145° C.

3526
3572
3501
3560
3341
3228
3559




150° C.

4510
4505
4575
4564
4345
4232
4503




155° C.

5190
5186
5119
5126
4907
4794
5160




160° C.

5255
5201
5220
5245
5026
4913
5298



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X 
  X/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯




200 cm

—/—
—/X 
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
























TABLE 58







EX 157
EX 158
EX 159
EX 160
EX 161
EX 162
EX 163


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26



Innermost
Component (K)
—
PP(K-6)
PP(K-7)
PP(K-8)
PP(K-9)
PP(K-10)
PP(K-11)
PP(K-12)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—




amount
wt %
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
41
21
31




S(0)
wt %
2.2
2.2
2.2
2.2
2.4
2.1
2.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯

















properties
Total haze
%
%
12
14
13
13
13
14
13


after 30
Tensile
MD
MPa
242
235
240
240
237
241
234


minutes
modulus


of heat
Heat-
125° C.
gf/10
1802
1858
1835
1858
2019
1684
1868


treatment at
sealing
130° C.
mm
2831
2878
2874
2807
2983
2563
2811


121° C.
strength
135° C.

3164
3163
3152
3103
3183
3109
3134




140° C.

3350
3338
3350
3399
3492
3461
3391




145° C.

3511
3584
3576
3549
3673
3627
3503




150° C.

4551
4539
4568
4541
4428
4361
4557




155° C.

5137
5117
5132
5162
4829
4718
5102




160° C.

5283
5208
5299
5252
5019
4911
5257



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

 X/◯X
◯X/X 
◯X/X 
X/X
X/X
X/X
X/X




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 59







EX 164
EX 165
EX 166
EX 167
EX 168
EX 169
EX 170


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
80
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
7125
—
—
—




amount
wt %
—
—
—
20
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
60
50
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
7125
7125
—




amount
wt %
—
—
—
—
10
20
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
65
70
70
70
60




Component (H)
—
PE(H-4)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-2)
PP(I-3)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
15
10
10
10
10




Other components
—
—
—
—
—
—
—
7125




amount
wt %
—
—
—
—
—
—
10




Tm(C) - Tm(Al)
° C.
31
31
32
31
31
31
31




S(0)
wt %
2.1
2.2
7
2.2
2.2
2.2
11
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
15
13
12
12
12
11
12

















after 30
Tensile
MD
MPa
248
244
231
254
231
196
228


minutes
modulus


of heat
Heat-
125° C.
gf/10
1817
1881
1838
1841
1583
1394
1904


treatment at
sealing
130° C.
mm
2820
2821
2881
2805
2576
2494
2988


121° C.
strength
135° C.

3175
3106
3199
3166
3298
3103
3189




140° C.

3313
3358
3362
3371
3337
3380
3325




145° C.

3555
3572
3592
3576
3598
3591
3531




150° C.

4591
4586
4567
4544
4565
4571
4572




155° C.

5183
5145
5131
5148
5166
5200
5160




160° C.

5251
5219
5239
5274
5251
5215
5246



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X 
 X/◯X
◯X/X 
◯◯/◯◯
 ◯X/◯◯
◯◯/◯◯
 ◯X/◯◯




200 cm

—/—
—/—
—/—
◯◯/◯◯
—/X 
◯X/◯X
—/X 
























TABLE 60







Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Ex. 28
Ex. 29
Ex. 30
Ex. 31
Ex. 32
Ex. 33
Ex. 34


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100
100 
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-24)
PP(A-25)
PP(A-26)



layer
amount
wt %
100
50
70
50
70
70
70




Component (B)
—
—
PE(B-1)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
—
50
—
40
20
20
20




Component (C)
—
—
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
—
30
10
10
10
10




Other components
—
—

—
—
—
—
—




amount
wt %
—

—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
—
26
26
26
—
26



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
2.2
  2.2
2.2
2.2
2.2
  2.2
2.2
















Film
Appearance
—
◯
Pockmarked
◯
Δ
◯
Pockmarked
◯


properties
Total haze
%
10
pattern
28
27
19
pattern
17

















after 30
Tensile
MD
MPa
235
arose due
332
219
348
arose due
329


minutes
modulus



to



to


of heat
Heat-
125° C.
gf/10
1578
inadequate
1948
1232
1923
inadequate
1766


treatment at
sealing
130° C.
mm
2193
heat
2383
1984
2302
heat
2145


121° C.
strength
135° C.

2984
resistance;
2784
2589
2941
resistance;
2784




140° C.

3378
good
3193
3290
3674
good
3517




145° C.

3543
samples
3348
4019
4239
samples
4082




150° C.

4382
could not
3847
4239
4402
could not
4245




155° C.

4763
be
4431
4402
4629
be
4472




160° C.

4689
obtained
4589
4593
4897
obtained
4740



Cumulative
 50 cm
—
X/X

X/X
◯◯/◯◯
◯◯/◯◯

◯◯/◯◯



bag drop
100 cm

—/—

—/—
◯◯/◯X 
X/X

X/X



test
150 cm

—/—

—/—
◯X/— 
—/—

—/—




200 cm

—/—

—/—
—/—
—/—

—/—
























TABLE 61







Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Ex. 35
Ex. 36
Ex. 37
Ex. 38
Ex. 39
Ex. 40
Ex. 41


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100 
100 
100
100 
100
100
100 


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-27)
PP(A-28)
PP(A-29)
PP(A-30)
PP(A-31)
PP(A-32)
PP(A-33)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
53
0
0
26
26
26



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
31
31




S(0)
wt %
  2.2
  2.2
2.2
  2.2
2.2
2.2
  2.2
















Film
Appearance
—
Pockmarked
Pockmarked
◯
Due to
◯
◯
Due to


properties
Total haze
%
pattern
pattern
34
unstable
18
36
unstable

















after 30
Tensile
MD
MPa
arose due
arose due
546
film
476
262
film


minutes
modulus


to
to

thickness,


thickness,


of heat
Heat-
125° C.
gf/10
inadequate
inadequate
1942
good
1841
1830
good


treatment at
sealing
130° C.
mm
heat
heat
2321
samples
2906
2895
samples


121° C.
strength
135° C.

resistance;
resistance;
2960
could
3161
3150
could




140° C.

good
good
3693
not be
3362
3351
not be




145° C.

samples
samples
4258
obtained
3542
3531
obtained




150° C.

could not
could not
4421

4564
4553




155° C.

be
be
4648

5207
5196




160° C.

obtained
obtained
4916

5302
5291



Cumulative
 50 cm
—


 X/◯X

◯◯/◯◯
◯◯/◯◯



bag drop
100 cm



—/—

◯X/X 
◯◯/◯◯



test
150 cm



—/—

—/—
◯X/X 




200 cm



—/—

—/—
—/—




















TABLE 62







Comp.
Comp.
Comp.



Ex. 42
Ex. 43
Ex. 44






















Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-5)


compositions
layer
amount
wt %
100
100
100 


and resin

Component (D3)
—
—
—
—


formulations

amount
wt %
—
—
—




Other components
—
—
—
—




amount
wt %
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70




Component (B)
—
PE(B-7)
PE(B-8)
PE(B-1)




amount
wt %
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31




S(0)
wt %
2.2
2.2
  2.2












Film
Appearance
—
◯
◯
Pockmarked


properties
Total haze
%
35
26
pattern













after 30
Tensile
MD
MPa
262
287
arose due


minutes
modulus




to


of heat
Heat-
125° C.
gf/10
1815
1569
inadequate


treatment at
sealing
130° C.
mm
2805
2094
heat


121° C.
strength
135° C.

3146
2864
resistance;




140° C.

3345
3353
good




145° C.

3520
3508
samples




150° C.

4503
4571
could not




155° C.

5177
5163
be




160° C.

5263
5221
obtained



Cumulative
 50 cm
—
 X/◯X
◯◯/◯◯



bag drop
100 cm

—/—
◯◯/◯◯



test
150 cm

—/—
◯X/X 




200 cm

—/—
—/—
























TABLE 63







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 44
Ex. 45
Ex. 46
Ex. 47
Ex. 48
Ex. 49
Ex. 50


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-4)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
90
100
100 


and resin

Component (D3)
—
—
—
—
—
PE(D3-2)
—
—


formulations

amount
wt %
—
—
—
—
10
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
60
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
10
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-6)
PP(C-7)
PP(C-8)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
30
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
0
−10
26
26
26
26



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
70
70
70
70
100
50




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
—
PE(H-1)




amount
wt %
20
20
20
20
20
—
50




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
—
—




amount
wt %
10
10
10
10
10
—
—




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
31
31
31
31
31
—
—




S(0)
wt %
2.2
2.2
2.2
2.2
2.2
2.6
  2.4
















Film
Appearance
—
◯
◯
◯
◯
◯
Δ
Internal


properties
Total haze
%
28
14
14
21
28
29
fusion due

















after 30
Tensile
MD
MPa
326
225
220
306
234
230
to


minutes
modulus








inadequate


of heat
Heat-
125° C.
gf/10
1854
1675
1655
1345
1592
2005
heat


treatment at
sealing
130° C.
mm
2593
2618
2638
1875
2717
3066
resistance


121° C.
strength
135° C.

3584
2915
2977
2589
3396
3372
occurred




140° C.

3573
3131
3129
3499
3407
3336
during




145° C.

4292
3356
3321
3569
3426
3562
steriliza-




150° C.

4593
4314
4303
4082
4430
4515
tion;




155° C.

4738
4955
4976
4684
4992
5013
could




160° C.

4983
5093
5095
4987
5111
5289
not be



Cumulative
 50 cm
—
X/X
◯◯/X  
◯X/◯X
◯◯/◯◯
◯◯/◯◯
X/X
evaluated



bag drop
100 cm

—/—
◯X/— 
—/—
◯X/◯◯
◯◯/◯◯
—/—



test
150 cm

—/—
—/—
—/—
—/X 
◯◯/◯◯
—/—




200 cm

—/—
—/—
—/—
—/—
◯◯/◯◯
—/—























TABLE 64







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 51
Ex. 52
Ex. 53
Ex. 54
Ex. 55
Ex. 56

























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100 
100 


and resin

Component (D3)
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26



Innermost
Component (K)
—
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)
PP(K-1)



layer
amount
wt %
70
40
60
70
70
70




Component (H)
—
—
PE(H-1)
PE(H-1)
PE(H-5)
PE(H-1)
PE(H-1)




amount
wt %
—
50
10
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-4)
PP(I-5)




amount
wt %
30
10
30
10
10
10




Other components
—




amount
wt %




Tm(C) - Tm(Al)
° C.
31
31
31
31
 5
−5




S(0)
wt %
1.9
  2.1
1.8
2.1
  2.2
  2.2















Film
Appearance
—
◯
Internal
◯
◯
Internal
Internal


properties
Total haze
%
22
fusion due
21
28
fusion due
fusion due
















after 30
Tensile
MD
MPa
318
to
312
251
to
to


minutes
modulus



inadequate


inadequate
inadequate


of heat
Heat-
125° C.
gf/10
194
heat
382
1582
heat
heat


treatment at
sealing
130° C.
mm
583
resistance
732
2748
resistance
resistance


121° C.
strength
135° C.

1038
occurred
1294
3019
occurred
occurred




140° C.

1674
during
1753
3281
during
during




145° C.

1758
steriliza-
1832
3428
steriliza-
steriliza-




150° C.

2019
tion;
1932
4471
tion;
tion;




155° C.

2109
could
2019
4918
could
could




160° C.

2538
not be
2567
4819
not be
not be



Cumulative
 50 cm
—
X/X
evaluated
X/X
◯◯/X  
evaluated
evaluated



bag drop
100 cm

—/—

—/—
◯X/— 



test
150 cm

—/—

—/—
—/—




200 cm

—/—

—/—
—/—
























TABLE 65







EX 171
EX 172
EX 173
EX 174
EX 175
EX 176
EX 177


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-19)
PP(A-20)
PP(A-21)
PP(A-22)
PP(A-23)



layer
amount
wt %
80
70
70
70
70
70
70




Component (B)
—
PE(B-3)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
26
26
26
19
22
19



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0.2
0.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
18
12
12
12
16
17
17

















after 30
Tensile
MD
MPa
240
280
278
281
310
305
308


minutes
modulus


of heat
Heat-
125° C.
gf/10
784
1547
1578
1557
1568
1553
1582


treatment at
sealing
130° C.
mm
2240
2588
2622
2588
2616
2587
2618


121° C.
strength
135° C.

3190
3578
3612
3580
3616
3588
3614




140° C.

3400
3492
3518
3478
3501
3476
3516




145° C.

3694
4183
4198
4164
4196
4163
4201




150° C.

3981
4533
4555
4539
4554
4525
4547




155° C.

4129
5138
5172
5138
5155
5121
5138




160° C.

4351
5259
5259
5259
5259
5259
5259



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

X/X
 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 
◯X/X 




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 66







EX 178
EX 179
EX 180
EX 181
EX 182
EX 183
EX 184


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-2)
PE(B-3)
PE(B-4)
PE(B-5)
PE(B-6)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-2)
PP(C-3)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—




amount
wt %




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0.2
0.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
15
12
15
12
12
12
12

















after 30
Tensile
MD
MPa
275
284
287
281
282
282
279


minutes
modulus


of heat
Heat-
125° C.
gf/10
1543
1570
1547
1559
1546
1577
1559


treatment at
sealing
130° C.
mm
2586
2614
2584
2606
2579
2616
2592


121° C.
strength
135° C.

3572
3606
3575
3608
3584
3604
3571




140° C.

3484
3515
3475
3500
3470
3508
3493




145° C.

4177
4197
4163
4189
4161
4193
4186




150° C.

4529
4548
4530
4552
4515
4539
4529




155° C.

5129
5170
5130
5149
5113
5129
5144




160° C.

5257
5253
5257
5257
5253
5251
5263



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

 X/◯X
 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 
 X/◯X




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 67







EX 185
EX 186
EX 187
EX 188
EX 189
EX 190
EX 191


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-3)
PP(D-4)
PP(D-4)
PP(D-4)


compositions
layer
amount
wt %
100
100
100
100
100
90
100


and resin

Component (D3)
—
—
—
—
—
—
PE(D3-1)
—


formulations

amount
wt %
—
—
—
—
—
10
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
65
70
70
70
70
65




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-4)
PP(C-5)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-5)




amount
wt %
10
15
10
10
10
10
15




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
27
26
26
26
26
27



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—




amount
wt %




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0.2
0.2
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
12
11
12
14
15
11
14

















after 30
Tensile
MD
MPa
285
272
290
297
241
251
249


minutes
modulus


of heat
Heat-
125° C.
gf/10
1576
1555
1771
1737
1354
1245
1354


treatment at
sealing
130° C.
mm
2624
2586
2856
2862
2345
2215
2354


121° C.
strength
135° C.

3613
3582
3415
3139
3154
3057
3057




140° C.

3516
3482
3409
3333
3245
3220
3410




145° C.

4191
4160
4015
4152
4123
4135
4187




150° C.

4556
4539
4478
4575
4623
4587
4514




155° C.

5172
5141
5130
5137
5014
5045
5171




160° C.

5259
5253
5231
5256
5037
4924
5309



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X 
  X/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯




200 cm

—/—
—/X 
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
























TABLE 68







EX 192
EX 193
EX 194
EX 195
EX 196
EX 197
EX 198


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
80
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
7125
—




amount
wt %
—
—
—
—
—
20
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70
60




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
7125




amount
wt %
—
—
—
—
—
—
10




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26



Innermost
Component (E)
—
PP(E-2)
PP(E-3)
PP(E-1)
PP(K-1)
PP(K-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
85
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-2)
PE(F-3)
PE(F-4)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
15
10
10
10




Component (I)
—
—
—
—
—
—




amount
wt %
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.6
0.2
0.2
0.1
0.2
0.2
















Film
Appearance
—
◯
◯—
◯
◯
◯
◯
◯


properties
Total haze
%
13
17
15
13
15
11
11

















after 30
Tensile
MD
MPa
281
285
281
282
280
284
271


minutes
modulus


of heat
Heat-
125° C.
gf/10
1357
1204
1751
1557
1574
2043
1812


treatment at
sealing
130° C.
mm
2467
2541
2578
2645
2579
3162
2866


121° C.
strength
135° C.

3321
3245
3415
3616
3487
3487
3669




140° C.

3481
3415
3561
3610
3510
3803
3714




145° C.

4177
4098
4015
4065
4305
3981
3972




150° C.

4468
4457
4456
4457
4135
5082
5059




155° C.

5079
5018
5018
5015
5124
5718
5737




160° C.

5124
5157
5187
5112
5210
5816
5794



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 
◯◯/◯◯
 ◯X/◯◯




200 cm

—/—
—/—
—/—
—/—
—/—
◯◯/◯◯
—/X 



















TABLE 69







EX 199
EX 200





















Layer compositions
Outer layer
Component (D)
—
PP(D-1)
PP(D-1)


and resin

amount
wt %
 100
 100


formulations

Component (D3)
—
—
—




amount
wt %
—
—




Other components
—
—
—




amount
wt %
—
—



Inner layer
Component (A)
—
PP(A-18)
PP(A-18)




amount
wt %
 70
 70




Component (B)
—
PE(B-1)
PE(B-1)




amount
wt %
 20
 20




Component (C)
—
PP(C-1)
PP(C-1)




amount
wt %
 10
 10




Other components
—
7125
—




amount
wt %
 20
—




Tm(C)-Tm(Al)
° C.
 26
 26



Innermost layer
Component (E)
—
PP(E-1)
PP(E-1)




amount
wt %
 90
 85




Component (F)
—
PE(F-1)
PE(F-1)




amount
wt %
 10
  5




Component (I)
—




amount
wt %




Other components
—
—
7125




amount
wt %
—
 10




Tm(C)-Tm(Al)
° C.




S(0)
wt %
   0.2
   8.9











Film properties
Appearance
—
◯
◯


after 30 minutes
Total haze
%
 10
 11












of heat treatment
Tensile modulus
MD
MPa
 234
 268


at 121° C.
Heat-sealing
125° C.
gf/10 mm
1565
2170



strength
130° C.

2824
3362




135° C.

3483
3541




140° C.

3754
3679




145° C.

4032
3934




150° C.

5112
5032




155° C.

5779
5740




160° C.

5763
5790



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯



test
150 cm

◯◯/◯◯
 ◯X/◯◯




200 cm

◯X/◯X
—/X 
























TABLE 70







Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Ex. 45
Ex. 46
Ex. 47
Ex. 48
Ex. 49
Ex. 40
Ex. 51


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100
100 
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-24)
PP(A-25)
PP(A-26)



layer
amount
wt %
100
50
70
40
70
70
70




Component (B)
—
—
PE(B-1)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
—
50
—
50
20
20
20




Component (C)
—
—
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
—
30
10
10
10
10




Other components
—
—

—
—
—
—
—




amount
wt %
—

—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
—
26
26
26
—
26



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component F
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—




amount
wt %




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
  0.2
0.2
0.2
0.2
  0.2
0.2
















Film
Appearance
—
◯
Pockmarked
◯
Δ
◯
Pockmarked
◯


properties
Total haze
%
9
pattern
27
22
19
pattern
17

















after 30
Tensile
MD
MPa
276
arose due
345
263
388
arose due
269


minutes
modulus



to



to


of heat
Heat-
125° C.
gf/10
1290
inadequate
1784
1391
1938
inadequate
1673


treatment at
sealing
130° C.
mm
2193
heat
2681
1985
2302
heat
2511


121° C.
strength
135° C.

3342
resistance;
3492
2976
2941
resistance;
2789




140° C.

3378
good
3193
3269
3674
good
3517




145° C.

3543
samples
3348
4002
4239
samples
4082




150° C.

4382
could not
4594
4239
4402
could not
4329




155° C.

4763
be
4841
4722
4781
be
4472




160° C.

4689
obtained
5297
5201
5297
obtained
4740



Cumulative
 50 cm
—
X/X

X/X
◯◯/◯◯
◯◯/◯◯

◯◯/◯◯



bag drop
100 cm

—/—

—/—
◯◯/◯X 
X/X

X/X



test
150 cm

—/—

—/—
◯X/— 
—/—

—/—




200 cm

—/—

—/—
—/—
—/—

—/—
























TABLE 71







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 52
Ex. 53
Ex. 54
Ex. 55
Ex. 56
Ex. 57
Ex. 58


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100 
100 
100
100 
100
100
100 


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-27)
PP(A-28)
PP(A-29)
PP(A-30)
PP(A-31)
PP(A-32)
PP(A-33)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
53
0
0
26
26
26



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10
10
10
10
10




Component (I)
—




amount
wt %




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
  0.2
  0.2
0.2
  0.2
0.2
0.2
  0.2
















Film
Appearance
—
Pockmarked
Pockmarked
◯
Due to
◯
◯
Due to


properties
Total haze
%
pattern
pattern
34
unstable
18
36
unstable

















after 30
Tensile
MD
MPa
arose due
arose due
612
film
512
297
film


minutes
modulus


to
to

thickness,


thickness,


of heat
Heat-
125° C.
gf/10
inadequate
inadequate
1971
good
1571
1548
good


treatment at
sealing
130° C.
mm
heat
heat
2513
samples
2499
2532
samples


121° C.
strength
135° C.

resistance;
resistance;
3453
could
3456
3421
could




140° C.

good
good
3693
not be
3362
3351
not be




145° C.

samples
samples
4258
obtained
3542
3531
obtained




150° C.

could not
could not
4421

4564
4553




155° C.

be
be
4648

5207
5196




160° C.

obtained
obtained
4916

5302
5291



Cumulative
 50 cm
—


 X/◯X

◯◯/◯◯
◯◯/◯◯



bag drop
100 cm



—/—

◯X/X 
◯◯/◯◯



test
150 cm



—/—

—/—
◯X/X 




200 cm



—/—

—/—
—/—




















TABLE 72







Comp.
Comp.
Comp.



Ex. 59
Ex. 60
Ex. 61






















Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-5)


compositions
layer
amount
wt %
100
100
100 


and resin

Component (D3)
—
—
—
—


formulations

amount
wt %
—
—
—




Other components
—
—
—
—




amount
wt %
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70




Component (B)
—
PE(B-7)
PE(B-8)
PE(B-1)




amount
wt %
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)




amount
wt %
10
10
10




Component (I)
—




amount
wt %




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
  0.2












Film
Appearance
—
0
0
Pockmarked


properties
Total haze
%
34
35
pattern













after 30
Tensile
MD
MPa
297
329
arose due


minutes
modulus




to


of heat
Heat-
125° C.
gf/10
1567
1558
inadequate


treatment at
sealing
130° C.
mm
2621
2595
heat


121° C.
strength
135° C.

3622
3585
resistance;




140° C.

3501
3485
good




145° C.

4198
4166
samples




150° C.

4554
4519
could not




155° C.

5155
5123
be




160° C.

5254
5262
obtained



Cumulative
 50 cm
—
 X/◯X
◯◯/◯◯



bag drop
100 cm

—/—
◯◯/◯◯



test
150 cm

—/—
◯X/X 




200 cm

—/—
—/—
























TABLE 73







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 57
Ex. 58
Ex. 59
Ex. 60
Ex. 61
Ex. 62
Ex. 63


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-4)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
90
100
100 


and resin

Component (D3)
—
—
—
—
—
PE(D3-2)
—
—


formulations

amount
wt %
—
—
—
—
10
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
60
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
10
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-6)
PP(C-7)
PP(C-8)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
30
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
0
−10
26
26
26
26



Innermost
Component (E)
—
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)
PP(E-1)



layer
amount
wt %
90
90
90
90
90
100
70




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
PE(F-1)
—
PE(F-1)




amount
wt %
10
10
10
10
10
—
30




Component (I)
—





—
—




amount
wt %





—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
0.2
0.2
0.2
0.2
0.2
0
  0.6
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
Internal


properties
Total haze
%
27
13
13
21
28
9
fusion due

















after 30
Tensile
MD
MPa
361
265
359
348
274
284
to


minutes
modulus








inadequate


of heat
Heat-
125° C.
gf/10
1812
1574
1560
1578
1457
75
heat


treatment at
sealing
130° C.
mm
2593
2611
2602
2632
2485
456
resistance


121° C.
strength
135° C.

3584
3610
3588
3614
3153
3184
occurred




140° C.

3573
3518
3497
3516
3418
3256
during




145° C.

4292
4208
4192
4196
4087
3645
steriliza-




150° C.

4593
4548
4541
4560
4441
4312
tion;




155° C.

4981
5135
5147
5180
5003
4821
could




160° C.

5297
5257
5268
5266
5122
4415
not be



Cumulative
 50 cm
—
X/X
◯◯/X  
◯X/◯X
◯◯/◯◯
◯◯/◯◯
X/X
evaluated



bag drop
100 cm

—/—
◯X/— 
—/—
 ◯X/◯◯
◯◯/◯◯
—/—



test
150 cm

—/—
—/—
—/—
—/X 
◯◯/◯◯
—/—




200 cm

—/—
—/—
—/—
—/—
◯◯/◯◯
—/—




















TABLE 74







Ref.
Ref.
Ref.



Ex. 64
Ex. 65
Ex. 66






















Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100 
100
100


and resin

Component (D3)
—
—
—
—


formulations

amount
wt %
—
—
—




Other components
—
—
—
—




amount
wt %
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26



Innermost
Component (E)
—
PP(E-4)
PP(E-5)
PP(E-1)



layer
amount
wt %
90
90
90




Component (F)
—
PE(F-1)
PE(F-1)
PE(F-5)




amount
wt %
10
10
10




Component (I)
—
—
—
—




amount
wt %
—
—
—




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.




S(0)
wt %
  0.3
0.4
0.1












Film
Appearance
—
Internal
◯
◯


properties
Total haze
%
fusion due
19
27













after 30
Tensile
MD
MPa
to
501
285


minutes
modulus


inadequate


of heat
Heat-
125° C.
gf/10
heat
19
1154


treatment at
sealing
130° C.
mm
resistance
251
1357


121° C.
strength
135° C.

occurred
445
3125




140° C.

during
784
3245




145° C.

steriliza-
1354
3548




150° C.

tion;
1568
4315




155° C.

could
2150
4987




160° C.

not be
2991
5102



Cumulative
 50 cm
—
evaluated
X/X
◯◯/◯◯



bag drop
100 cm


—/—
X/X



test
150 cm


—/—
—/—




200 cm


—/—
—/—
























TABLE 75







EX 201
EX 202
EX 203
EX 204
EX 205
EX 206
EX 207


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-19)
PP(A-20)
PP(A-21)
PP(A-22)



layer
amount
wt %
80
70
70
70
70
70
70




Component (B)
—
PE(B-3)
PE(B-3)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
—
PP(C-2)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
31
26
26
26
19
22



Innermost
Component (K)
—
—
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
—
—
70
70
70
70
70




Component (H)
—
—
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
—
—
20
20
20
20
20




Component (I)
—
—
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
—
—
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
31
26
26
26
26
26




S(0)
wt %
1.6
2.2
1.3
1.3
1.3
1.3
1.3
















Film
Appearance
—
◯—
◯
◯
◯
◯
◯
◯


properties
Total haze
%
19
14
13
13
13
16
17

















after 30
Tensile
MD
MPa
195
255
240
238
241
261
250


minutes
modulus


of heat
Heat-
125° C.
gf/10
1350
1732
1878
1816
1874
1881
1875


treatment at
sealing
130° C.
mm
2546
2792
2840
2897
2843
2867
2808


121° C.
strength
135° C.

3041
3102
3131
3184
3181
3185
3162




140° C.

3154
3320
3315
3320
3382
3327
3376




145° C.

3477
3700
3572
3550
3534
3524
3563




150° C.

3844
4751
4599
4594
4567
4501
4573




155° C.

3910
5104
5196
5167
5128
5196
5124




160° C.

4098
5211
5275
5207
5227
5286
5262



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

X/X
◯X/◯X
 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 76







EX 208
EX 209
EX 210
EX 211
EX 212
EX 213
EX 214


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
100
100
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-23)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-2)
PE(B-3)
PE(B-4)
PE(B-5)
PE(B-6)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-2)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
19
26
26
26
26
26
26



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
1.3
1.3
1.3
1.3
1.3
1.3
1.3
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
17
15
13
15
13
13
13

















after 30
Tensile
MD
MPa
255
235
244
247
241
242
242


minutes
modulus


of heat
Heat-
125° C.
gf/10
1844
1814
1863
1828
1819
1893
1847


treatment at
sealing
130° C.
mm
2891
2883
2893
2826
2834
2911
2886


121° C.
strength
135° C.

3149
3145
3185
3118
3135
3163
3130




140° C.

3395
3348
3349
3324
3322
3370
3315




145° C.

3566
3513
3565
3556
3551
3515
3587




150° C.

4562
4598
4597
4612
4527
4523
4530




155° C.

5181
5142
5121
5122
5122
5178
5189




160° C.

5268
5261
5238
5312
5239
5279
5277



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X 
 X/◯X
 X/◯X
 X/◯X
◯X/X 
 X/◯X
◯X/X 




200 cm

—/—
—/—
—/—
—/—
—/—
—/—
—/—
























TABLE 77







EX 215
EX 216
EX 217
EX 218
EX 219
EX 220
EX 221


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-2)
PP(D-3)
PP(D-4)
PP(D-4)


compositions
layer
amount
wt %
100
100
100
100
100
100
90


and resin

Component (D3)
—
—
—
—
—
—
—
PE(D3-2)


formulations

amount
wt %
—
—
—
—
—
—
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
65
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-3)
PP(C-4)
PP(C-5)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
15
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
27
26
26
26
26



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
1.3
1.3
1.3
1.3
1.3
1.3
1.3
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
13
13
12
13
15
16
12

















after 30
Tensile
MD
MPa
239
245
232
262
270
221
215


minutes
modulus


of heat
Heat-
125° C.
gf/10
1907
1829
1878
1771
1737
1518
1405


treatment at
sealing
130° C.
mm
2842
2856
2901
2856
2862
2643
2530


121° C.
strength
135° C.

3146
3189
3183
3142
3139
3023
3209




140° C.

3318
3400
3366
3409
3333
3114
3220




145° C.

3591
3538
3584
3512
3571
3352
3239




150° C.

4529
4522
4517
4586
4575
4356
4243




155° C.

5155
5202
5198
5130
5137
4918
4805




160° C.

5258
5267
5213
5231
5256
5037
4924



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

 X/◯X
◯X/X 
  X/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯




200 cm

—/—
—/—
—/X 
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
























TABLE 78







EX 222
EX 223
EX 224
EX 225
EX 226
EX 227
EX 228


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-2)


compositions
layer
amount
wt %
100
100
100
100
100
100
80


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
7125




amount
wt %
—
—
—
—
—
—
20



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-2)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26



Innermost
Component (K)
—
PP(K-20)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
65
70




Component (H)
—
PE(H-1)
PE(H-2)
PE(H-3)
PE(H-4)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-2)
PP(I-3)
PP(I-1)




amount
wt %
10
10
10
10
10
15
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
0
26
26
26
26
27
26




S(0)
wt %
1.5
1.4
1.3
1.2
1.3
6.5
1.3
















Film
Appearance
—
◯
◯
◯
◯
◯
◯
◯


properties
Total haze
%
17
15
13
15
13
12
12

















after 30
Tensile
MD
MPa
240
235
244
247
242
232
254


minutes
modulus


of heat
Heat-
125° C.
gf/10
1886
1821
1870
1835
1854
1885
2023


treatment at
sealing
130° C.
mm
2819
2890
2900
2833
2893
2908
3077


121° C.
strength
135° C.

3173
3152
3192
3125
3137
3190
3476




140° C.

3387
3355
3356
3331
3322
3373
3706




145° C.

3574
3520
3572
3563
3594
3591
3928




150° C.

4584
4605
4604
4619
4537
4524
4995




155° C.

5135
5149
5128
5129
5196
5205
5655




160° C.

5273
5268
5245
5319
5284
5220
5798



Cumulative
 50 cm
—
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



bag drop
100 cm

◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯
◯◯/◯◯



test
150 cm

◯X/X 
 X/◯X
 X/◯X
 X/◯X
◯X/X 
 X/◯◯
◯◯/◯◯




200 cm

—/—
—/—
—/—
—/—
—/—
—/X 
◯◯/◯◯
























TABLE 79







Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Ex. 62
Ex. 63
Ex. 64
Ex. 65
Ex. 66
Ex. 67
Ex. 68


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100
100 
100


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-24)
PP(A-25)
PP(A-26)



layer
amount
wt %
100
50
70
50
70
70
70




Component (B)
—
—
PE(B-1)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
—
50
—
40
20
20
20




Component (C)
—
—
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
—
—
30
10
10
10
10




Other components
—
—

—
—
—
—
—




amount
wt %
—

—
—
—
—
—




Tm(C) - Tm(Al)
° C.
—
—
26
26
26
—
26



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
1.3
  1.3
1.3
1.3
1.3
  1.3
1.3
















Film
Appearance
—
◯
Pockmarked
◯
Δ
◯
Pockmarked
◯


properties
Total haze
%
10
pattern
28
27
19
pattern
17

















after 30
Tensile
MD
MPa
235
arose due
332
219
348
arose due
329


minutes
modulus



to



to


of heat
Heat-
125° C.
gf/10
1562
inadequate
1932
1216
1907
inadequate
1750


treatment at
sealing
130° C.
mm
2177
heat
2367
1968
2286
heat
2129


121° C.
strength
135° C.

2968
resistance;
2768
2573
2925
resistance;
2768




140° C.

3362
good
3177
3274
3658
good
3501




145° C.

3527
samples
3332
4003
4223
samples
4066




150° C.

4366
could not
3831
4223
4386
could not
4229




155° C.

4747
be
4415
4386
4613
be
4456




160° C.

4673
obtained
4573
4577
4881
obtained
4724



Cumulative
 50 cm
—
X/X

X/X
◯◯/◯◯
◯◯/◯◯

◯◯/◯◯



bag drop
100 cm

—/—

—/—
◯◯/◯◯
X/X

X/X



test
150 cm

—/—

—/—
◯X/— 
—/—

—/—




200 cm

—/—

—/—
—/—
—/—

—/—
























TABLE 80







Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Ex. 69
Ex. 70
Ex. 71
Ex. 72
Ex. 73
Ex. 74
Ex. 75


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100 
100 
100
100 
100
100
100 


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-27)
PP(A-28)
PP(A-29)
PP(A-30)
PP(A-31)
PP(A-32)
PP(A-33)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
53
0
0
26
26
26



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26




S(0)
wt %
  1.3
  1.3
1.3
  1.3
1.3
1.3
  1.3
















Film
Appearance
—
Pockmarked
Pockmarked
◯
Due to
◯
◯
Due to


properties
Total haze
%
pattern
pattern
34
unstable
18
36
unstable

















after 30
Tensile
MD
MPa
arose due
arose due
546
film
476
262
film


minutes
modulus


to
to

thickness,


thickness,


of heat
Heat-
125° C.
gf/10
inadequate
inadequate
1926
good
1825
1814
good


treatment at
sealing
130° C.
mm
heat
heat
2305
samples
2890
2879
samples


121° C.
strength
135° C.

resistance;
resistance;
2944
could
3145
3134
could




140° C.

good
good
3677
not be
3346
3335
not be




145° C.

samples
samples
4242
obtained
3526
3515
obtained




150° C.

could not
could not
4405

4548
4537




155° C.

be
be
4632

5191
5180




160° C.

obtained
obtained
4900

5286
5275



Cumulative
 50 cm
—


 X/◯X

◯◯/◯◯
◯◯/◯◯



bag drop
100 cm



—/—

◯X/X 
◯◯/◯◯



test
150 cm



—/—

—/—
◯X/X 




200 cm



—/—

—/—
—/—




















TABLE 81







Comp.
Comp.
Comp.



Ex. 76
Ex. 77
Ex. 78






















Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-5)


compositions
layer
amount
wt %
100
100
100 


and resin

Component (D3)
—
—
—
—


formulations

amount
wt %
—
—
—




Other components
—
—
—
—




amount
wt %
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70




Component (B)
—
PE(B-7)
PE(B-8)
PE(B-1)




amount
wt %
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
10
10
10




Other components
—
—
—
—




amount
wt %
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26




S(0)
wt %
1.3
1.3
  1.3












Film
Appearance
—
◯
◯
Pockmarked


properties
Total haze
%
35
26
pattern













after 30
Tensile
MD
MPa
262
287
arose due


minutes
modulus




to


of heat
Heat-
125° C.
gf/10
1827
1581
inadequate


treatment at
sealing
130° C.
mm
2817
2106
heat


121° C.
strength
135° C.

3158
2876
resistance;




140° C.

3357
3365
good




145° C.

3532
3520
samples




150° C.

4515
4583
could not




155° C.

5189
5175
be




160° C.

5275
5233
obtained



Cumulative
 50 cm
—
 X/◯X
◯◯/◯◯



bag drop
100 cm

—/—
◯◯/◯◯



test
150 cm

—/—
◯X/X 




200 cm

—/—
—/—
























TABLE 82







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 67
Ex. 68
Ex. 69
Ex. 70
Ex. 71
Ex. 72
Ex. 73


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-4)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100
100
100
90
100
100 


and resin

Component (D3)
—
—
—
—
—
PE(D3-2)
—
—


formulations

amount
wt %
—
—
—
—
10
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
60
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
10
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-6)
PP(C-7)
PP(C-8)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
30
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
0
−10
26
26
26
26



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
100
50




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
—
PE(H-1)




amount
wt %
20
20
20
20
20
—
50




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
—
—




amount
wt %
10
10
10
10
10
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
—
—




S(0)
wt %
1.3
1.3
1.3
1.3
1.3
1.3
  1.5
















Film
Appearance
—
◯
◯
◯
◯
◯
Δ
Internal


properties
Total haze
%
28
14
14
21
28
29
fusion due

















after 30
Tensile
MD
MPa
326
225
220
306
234
229
to


minutes
modulus








inadequate


of heat
Heat-
125° C.
gf/10
1838
1687
1667
1357
1603
2011
heat


treatment at
sealing
130° C.
mm
2577
2630
2650
1887
2728
3076
resistance


121° C.
strength
135° C.

3568
2927
2989
2601
3407
3382
occurred




140° C.

3557
3143
3141
3511
3418
3345
during




145° C.

4276
3368
3333
3581
3437
3572
steriliza-




150° C.

4577
4326
4315
4094
4441
4518
tion;




155° C.

4722
4967
4988
4696
5003
5019
could




160° C.

4967
5105
5107
4999
5122
5291
not be



Cumulative
 50 cm
—
X/X
◯◯/X  
◯X/◯X
◯◯/◯◯
◯◯/◯◯
X/X
evaluated



bag drop
100 cm

—/—
◯X/— 
—/—
◯X/◯◯
◯◯/◯◯
—/—



test
150 cm

—/—
—/—
—/—
—/X 
◯◯/◯◯
—/—




200 cm

—/—
—/—
—/—
—/—
◯◯/◯◯
—/—
























TABLE 83







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 74
Ex. 75
Ex. 76
Ex. 77
Ex. 78
Ex. 79
Ex. 80


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100
100 
100
100
100 
100
100 


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26



Innermost
Component (K)
—
PP(K-16)
PP(K-16)
PP(K-16)
PP(K-21)
PP(K-22)
PP(K-23)
PP(K-24)



layer
amount
wt %
70
40
60
70
70
70
70




Component (H)
—
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)




amount
wt %
—
50
10
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)




amount
wt %
30
10
30
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
—
26
26




S(0)
wt %
1
  1.3
1.1
0.4
  2.2
0.8
  1.9
















Film
Appearance
—
◯
Internal
◯
◯
Internal
◯
Internal


properties
Total haze
%
22
fusion due
21
22
fusion due
21
fusion due

















after 30
Tensile
MD
MPa
318
to
312
329
to
319
to


minutes
modulus



inadequate


inadequate

inadequate


of heat
Heat-
125° C.
gf/10
198
heat
386
2023
heat
1872
heat


treatment at
sealing
130° C.
mm
587
resistance
736
2987
resistance
2815
resistance


121° C.
strength
135° C.

1042
occurred
1298
3187
occurred
3138
occurred




140° C.

1678
during
1757
3496
during
3395
during




145° C.

1762
steriliza-
1836
3677
steriliza-
3507
steriliza-




150° C.

2023
tion;
1936
4432
tion;
4561
tion;




155° C.

2113
could
2023
4833
could
5106
could




160° C.

2542
not be
2571
5023
not be
5261
not be



Cumulative
 50 cm
—
X/X
evaluated
X/X
◯◯/◯◯
evaluated
◯◯/◯◯
evaluated



bag drop
100 cm

—/—

—/—
◯◯/◯X 

 ◯X/◯◯



test
150 cm

—/—

—/—
 X/—

 —/◯X




200 cm

—/—

—/—
—/—

—/—
























TABLE 84







Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.



Ex. 81
Ex. 82
Ex. 83
Ex. 84
Ex. 85
Ex. 86
Ex. 87


























Layer
Outer
Component (D)
—
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)
PP(D-1)


compositions
layer
amount
wt %
100 
100
100
100
100
100 
100 


and resin

Component (D3)
—
—
—
—
—
—
—
—


formulations

amount
wt %
—
—
—
—
—
—
—




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—



Inner
Component (A)
—
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)
PP(A-18)



layer
amount
wt %
70
70
70
70
70
70
70




Component (B)
—
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)
PE(B-1)




amount
wt %
20
20
20
20
20
20
20




Component (C)
—
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)
PP(C-1)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
26
26
26
26
26
26
26



Innermost
Component (K)
—
PP(K-25)
PP(K-26)
PP(K-27)
PP(K-28)
PP(K-16)
PP(K-16)
PP(K-16)



layer
amount
wt %
70
70
70
70
70
70
70




Component (H)
—
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-1)
PE(H-5)
PE(H-1)
PE(H-1)




amount
wt %
20
20
20
20
20
20
20




Component (I)
—
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-1)
PP(I-4)
PP(I-5)




amount
wt %
10
10
10
10
10
10
10




Other components
—
—
—
—
—
—
—
—




amount
wt %
—
—
—
—
—
—
—




Tm(C) - Tm(Al)
° C.
53
0
26
26
26
0
−10  




S(0)
wt %
  1.3
1.4
0.4
13.4
1.2
  1.3
  1.3
















Film
Appearance
—
Internal
◯
◯
Δ
◯
Internal
Internal


properties
Total haze
%
fusion due
31
28
29
28
fusion due
fusion due

















after 30
Tensile
MD
MPa
to
478
251
230
251
to
to


minutes
modulus


inadequate




inadequate
inadequate


of heat
Heat-
125° C.
gf/10
heat
18
1586
1874
1582
heat
heat


treatment at
sealing
130° C.
mm
resistance
248
2752
2855
2748
resistance
resistance


121° C.
strength
135° C.

occurred
489
3023
3290
3011
occurred
occurred




140° C.

during
742
3285
3302
3201
during
during




145° C.

steriliza-
1349
3432
3548
3428
steriliza-
steriliza-




150° C.

tion;
1592
4475
4529
4339
tion;
tion;




155° C.

could
2091
4922
5011
4872
could
could




160° C.

not be
2819
4823
5251
4819
not be
not be



Cumulative
 50 cm
—
evaluated
X/X
◯◯/X  
◯◯/◯◯
◯◯/X  
evaluated
evaluated



bag drop
100 cm


—/—
◯X/— 
◯◯/◯◯
◯X/— 



test
150 cm


—/—
—/—
◯X/X 
—/—




200 cm


—/—
—/—
—/—
—/—









Regarding Working Examples 1 to 228
The multilayer propylene sheets obtained within the scope of this application had excellent flexibility, transparency, heat resistance, low-temperature impact resistance, low-temperature heat sealability and cleanliness.
Regarding Comparative Examples 1 to 78
Because the propylene multilayer sheets obtained outside the scope of this application had a poor flexibility, discharging of the contents was difficult without forming air vents, in addition to which the sheets had a poor hand. Also, the transparency was poor, making it difficult to check the contents. Because a sufficient heat resistance could not be retained, internal fusion occurred in the sterilization step and a pockmarked pattern (spotted pattern) and wrinkles arose, worsening the appearance. A satisfactory low-temperature impact resistance was not obtained, as a result of which breakage tended to occur when, for example, bags made from the sheets were dropped during low-temperature transport or storage. Other problems were the inability to obtain a sufficient low-temperature heat sealability, which worsened productivity, and the need for high-temperature heat-sealing treatment, which worsened the energy efficiency.
Regarding Reference Examples 1 to 66
In cases where use was made of additional, desirable ingredients which may also be included in this application, it is apparent that differences in performance arose as a result of the additional ingredients used.
Upon considering and contrasting the above working examples of the invention with the comparative examples and, if necessary, the reference examples, it is apparent that multilayer propylene resin sheets which are obtained from the novel combinations of propylene resin composition according to the invention and which satisfy the various provisions of the invention have excellent flexibility, transparency, heat resistance, low-temperature impact resistance, low-temperature heat sealability and cleanliness, have a good sheet formability that discourages appearance defects such as interface roughness and thickness fluctuations from arising during multilayer sheet formation, and do not readily give rise to problems such as molten resin flow and a reduction in thickness even under harsh heat-sealing conditions. Hence, multilayer propylene resin sheets of excellent strength and appearance can be obtained.
Industrial Applicability
The multilayer propylene resin sheets of the invention have an excellent flexibility, transparency, heat resistance, low-temperature impact resistance, low-temperature heat sealability and cleanliness, possess a fabricability that minimizes the occurrence of appearance defects such as interfacial roughness and thickness fluctuations during multilayer formation and, because they do not readily give rise to molten resin flow and a reduction in thickness even under harsh heat sealing conditions, exhibit an excellent bag breaking strength. Heat-treatable packaging material obtained using such a sheet will be highly useful in IV bag and retort packaging bag applications.

## Claims

1. A multilayer propylene resin sheet of at least three layers comprising an inner layer, an outer layer and an innermost layer in order of the outer layer, the inner layer, and the innermost layer, wherein:
(1) the inner layer is made of a propylene resin composition (X) which comprises:
(A) from 45 to 89 wt % of the propylene resin composition (A),
a) the propylene resin composition (A) comprising:
(i) from 30 to 70 wt % of a propylene-α-olefin random copolymer component (A1) with a melting peak temperature (Tm (A1)) of from 125 to 145° C., and
(ii) from 30 to 70 wt % of a propylene-ethylene random copolymer component (A2) with an ethylene content (E [A2]) of from 7 to 17 wt % and obtained with a metallocene catalyst,

b) has a melt flow rate (MFR (A), at 230° C. and 2.16 kg) in a range of from 0.5 to 20 g/10 min, and
c) has a single peak at or below 0° C. on a temperature — loss tangent (tan δ) curve obtained by dynamic mechanical analysis (DMA), and representing a glass transition observed in a range of from −60 to 20° C.,

(B) from 10 to 30 wt % of the ethylene-α-olefin copolymer (B); wherein the ethylene-α-olefin copolymer (B):
a) has a density in a range of from 0.860 to 0.910 g/cm3, and
b) has a melt flow rate (MFR (B), at 190° C. and 2.16 kg) in a range of from 0.1 to 20 g/10 min, and
(C) from 1 to 25 wt % of a propylene resin (C), and the propylene resin (C):
a) has a melting peak temperature (Tm (C)) which is at least 6° C. higher than the melting peak temperature (Tm (A1)) of the propylene-α-olefin random copolymer component (A1), and
b) has a melt flow rate (MFR (C), at 230° C. and 2.16 kg) in a range of from 0.5 to 30 g/10 min; and

(2) the outer layer is made of a propylene resin composition (Y) comprising
(D) a propylene resin having a melting peak temperature (Tm (D)) in a range of from 135 to 170° C.; and

(3) the innermost layer is made of propylene resin composition (Z) having a soluble content of 15 wt % or less, at or below 0° C. (S0), as measured in o-dichlorobenzene by temperature rising elution fractionation (TREF); and the propylene resin composition (Z) comprises:
a) a propylene resin composition (Z1) comprising from 80 to 99 wt % of a propylene-α-olefin copolymer (E) having a melting peak temperature (Tm (E)) of from 130 to 145° C., and from 1 to 20 wt % of an ethylene-α-olefin copolymer (F) which has an ethylene component as the major component and having a density of from 0.860to 0.910 g/cm3; or
b) a propylene resin composition (Z2) comprising:
(i) from 60 to 90 wt % of a propylene resin composition (G) which comprises from 30 to 70 wt % of a propylene-α-olefin random copolymer component (G1) having a melting peak temperature (Tm (G1)) in a range of from 125 to 145° C., and from 70to 30 wt % of a propylene-ethylene random copolymer component (G2) having an ethylene content (E(G2)) of from 7 to 17wt % and obtained with a metallocene catalyst; and
(ii) from 40 to 10 wt % of an ethylene-α-olefin copolymer (H) having a density in a range of from 0.860 to 0.910 g/cm3, and

(4) the multilayer propylene resin sheet has a heat-sealing temperature of 145° C. or below and a heat-sealing strength of 3,000 gf/10mm or more.

2. The multilayer propylene resin sheet of claim 1, wherein the propylene-α-olefin random copolymer component (A1) is obtained with a metallocene catalyst.

3. The multilayer propylene resin sheet of claim 1, wherein the propylene-α-olefin random copolymer component (A1) and the propylene-ethylene random copolymer component (A2) are obtained by successive polymerization with a metallocene catalyst, the successive polymerization comprising:
(1) polymerizing from 50 to 60 wt % of the propylene-α-olefin random copolymer component (A1), and then
(2) polymerizing from 40 to 50 wt % of the propylene-ethylene random copolymer component (A2),
wherein the propylene-ethylene random copolymer component (A2) has an ethylene content (E [A2]) of from 8 to 14 wt %.

4. The multiplayer propylene resin sheet of claim 1, wherein:
a) the propylene resin composition (Z) comprises a propylene resin composition (Z2) comprising:
(1) from 45 to 89 wt % of a propylene resin composition (G)
(2) from 10 to 30 wt % of an ethylene-α-olefin copolymer (H), and
(3) from 1 to 25 wt % of a propylene resin (I)

b) the propylene resin composition (G) comprises:
(1) from 30 to 70 wt % of a propylene-α-olefin random copolymer component (G1) with a melting peak temperature (Tm (G1)) in a range of from 125 to 145° C., and
(2) from 70 to 30 wt % of a propylene-ethylene random copolymer component (G2) with an ethylene content (E[G2]) from 7 to 17 wt % and obtained with a metallocene catalyst,

c) the ethylene-α-olefin copolymer (H) has a density in a range of from 0.860 to 0.910 g/cm3, and
d) the propylene resin (I) has a melting peak temperature (Tm(I)) which is at least 6° C. higher than the melting peak temperature (Tm(G1)) of the propylene-α-olefin random copolymer component (G1).

5. The multilayer propylene resin sheet of claim 1, wherein the propylene resin composition (G) has a single peak at or below 0° C. on a temperature-loss tangent (tan δ) curve obtained by dynamic mechanical analysis (DMA), and representing a glass transition observed in a range of from −60 to 20° C.

6. The multilayer propylene resin sheet of claim 1, wherein the propylene-α-olefin random copolymer component (G1) is obtained with a metallocene catalyst.

7. The multilayer propylene resin sheet claim 1, wherein the propylene-α-olefin random copolymer component (G1) and the propylene-ethylene random copolymer component (G2) are obtained by successive polymerization with a metallocene catalyst, the successive polymerization comprising:
(1) polymerizing from 50 to 60 wt % of the propylene-a-olefin random copolymer component (G1), and then
(2) polymerizing from 40 to 50 wt % of the propylene-ethylene random copolymer component (G2) with an ethylene content (E[G2]) from 8 to 14 wt %.

8. A heat-treatable packaging material, comprising the multilayer propylene resin sheet of claim 1.

9. The heat-treatable packaging material of claim 8, which is an IV bag.