A PROCESS FOR PRODUCING A LAMINATED MEMBER AND A LAMINATED MEMBER PRODUCED THEREBY

Abstract: A laminated member comprising a metal foil or sheet (1) and a thermoplastic resin film (4) bonded together with an adhesive selected from a carboxyl group-containing polyolefin and a polyolefin based resin prepared by heat-compounding a carboxyl group-containing polyolefin and a metal compound, is heated at a higher temperature than the melting temperature of the adhesive and pressed using a heated roll (3) and a nip roll (6). The laminated member is then cooled at the heat dis­ tortion of the adhesive or at a temperature somewhat higher than the heat distortion temperature while applying a pressure of at least 0.2 Kg/cm² with a cooling roll (10) and a nip roll (11).

Description: This invention relates to a process for production of a laminated member comprising a metal foil or sheet and a plastic film such as a polyolefin film. More particularly it relates to a process for producing a laminated member by using as an adhesive a carboxyl group-containing polyolefin or a polyolefin based resin prepared by heat-compounding a carboxyl group-containing polyolefin and a metal compound, in which laminated member there is no unevenness in adhesion strength and the occurrence of wrinkles is inhibited. Recently, as packaging materials for food, etc. or building materials, composite laminates having characteristics deriving from each component constituting the composite laminate have increasingly been used in place of single-layer members. In particular, a composite laminate comprising a polyolefin film or nylon film having hygienic properties and heat-seal-ability and an aluminum foil having excellent gas barrier properties has been used as one of the best food wrapping materials. In producing such composite laminates, a polyurethane based adhesive is generally used as an adhesive because of poor aadhesion between the polyolefin or nylon film and the metal (e.g., aluminium) foil. The polyurethane based adhesive, however, suffers disadvantages in that low molecular weight compounds contained in the polyurethane based adhesive may move into food, the foaming of the adhesive lowers the value of the composite laminate, and there is unevenness in adhesion strength. Under such circumstances, a method has been proposed in which a carboxyl group-containing polyolefin or a polyolefin based resin prepared by heat-compounding a carboxyl groupcontaining polyolefin and a metal compound is used in place of the polyurethane resin. In such a method, however, a sufficient adhesion strength cannot be obtained unless pressure is applied onto the laminate having the adhesive layer between the polyolefin ::ilm and the aluminium foil at a u-##rature higher thc > the melting temperature of the adhesive. The adhesives as used in such a method, therefore, are differen from conventional adhesives in that they need an additional heating and pressing step. Furthermore when the laminate is wound immediately after the application of heat and pressure, the layers of laminate stick together owing to the remaining heat. It is, therefore, necessary to wind the laminate after cooling it. Inventors' studies have revealed that the steps as described above produce partial unevenness in adhesion strength and often produce ##rinkles. As a result of extensive investigations to solve these problems, it has now been found that they can be removed by incorporating the pressure-application and cooling steps under specific conditions. This invention has been completed based upon the novel findings. On the other hand, for the purpose of preventing the formation of rust on a metal plate, improving its chemical resistance, and improving its decorative effect, or for the purpose of preventing contact between food or drink in a can and the metallic inner surface of the can, coating films are employed using a variety of coatings. In these days, however, the situation of supply of resources and energy has groin worse and the problem of consumption of a large quantity of energy required for baking coating has been highlighted not only in the coating of organic solvent-type coating material but also in the coating of aqueous solvent-type coating material. Another object of this invention, therefore, is to solve the problem of energy required for evaporation of a solvent contained in coating material and for baking, and to produce a laminated member which is excellent in its ce ents protection ability, hygienic properties, adhesion properties and post-moldability when used in a can, particularly a drink can or a food can, which is useful mainly as a material for forming a can, and which is free from unevenness in adhesion strength. As described in detail, the lamination of a metal plate and a plastic film using the adhesive needs a heat and pressure application step and furthermore produces unevenness in adhesion strength and wrinkles. This invention provides a process for producing a laminated member including a metal foil or sheet which may be backed with a heat-resistant resin layer, and a thermoplastic resin film. said process comprising the steps of heating the foil or sheet and the film with at least one adhesive disposed therebetween,said adhesive being selected from a carboxyl group-containing polyolefin and a polyolefin based resin prepared by heatcompounding a carboxyl group-containing polyolefin and a metal compound, at a temperature which is higher than the melting temperature of the adhesive and pressing to form a laminated member ; and cooling the laminated member when at the heat distortion temperature of the aadhesive or at a temperature higher than the heat distortion temperature while applying a pressure of at least 0.2 kg/cm2 using a cooling roll and a nip roll Figures 1 and 2 are schematic side views of apparatus used in processes for producing a laminated member according to this invention; The metal foil or sheet as used in this invention may be made of aluminium, tin plate, tin-free steel, jack plate, copper for example, and its thickness is usually about 5 to l,OOO#mand preferably about 10 to 300 although it varies depending upon the purpose. As necessary1 a sut le chemical treatment or plating treatment may be applied to the surface of the metal foil or sheet. Additionally, a metal foil or sheet which has already been subjected to treatment, e.g. printing or coating applied on the rear surface thereof can be used in this invention. In this invention, it is preferred to use a metal foil, e.g. an aluminium foil, which has previously been backed with a heat-resistant film, e.g. polyamide or polyester, since the metal foil is generally low in mechanical strength. Additionally, a suitable print layer may be formed between the heat-resistant resin layer and the aluminium foil. This provides a laminated member comprising polyester (or polyamide) layer/print layerjaluminlum foil/polyolefin-based adhesive layer/polyolefin film, and such a laminated member can be used as a soft packaging material with the polyester (or polyamide) layer as the outside layer and the polyolefin film as the inside layer. In producing a can or container using a laminated member including a metal plate, the laminated member is side-seamed with a thermoplastic resin film inside and the metal plate outside by use of a known technique, and top and bottom members stamped out from the laminated member are provided for the side-seamed laminated member. On the external surface of the metal plate can be laminated another resin film by use of the polyolefin resin as an adhesive in the same manner as in the internal surface thereby to provide a laminated member of five layer construction. Additionally, a suitable print layer, coating layer or film layer can be previously provided on a surface of the metal plate which is destined to become an external surface when molded to form a can or container. The thermoplastic resin film as used in this invention may be a single resin film produced from for example, pol-olefin, polyamide, polyester polyviln chlorine, polyvinarlidene chloride, polybutadi ene, polycarbonate, an ethylene-vinyl acetate copolymer or polyvinyl alcohol, or a composite film produced therefrom by coextrusion for example. If the thermoplastic resin film is to be used in a food or drink packaging material and is to be in contact with the food or drink, polyolefins (e.g. polyethylene, polypropylene, an ethylene-propylene copolymer or polybutene) or polyamides (e.g. 12-nylon or ll-nylon) are preferably used. The thickness of the thermoplastic resin film is usually about 10 to 1,000 P m and preferably about 30 to 100 8 m. The thermoplastic resin film may contain additives such as a filler or a coloring agent, as required. Furthermore, printing and/or painting may be applied to the thermoplastic resin film. In preparing a laminated member of this invention including two thermoplastic resin film layers as described above, the two layers may be produced from either the same resin or different resins. Furthermore, this invention includes an embodiment in which one of the two layers is paper. Hereinafter, the carboxyl group-containing polyolefin and the polyolefin-based resin prepared by heat-compounding the carboxyl group-containing polyolefin and the metal compound will be described. Carboxyl group-containing polyolefins are those prepared by copolymerizinÓ an olefinic monomer, e.g. etzylene, propylene or butene, with one or more #thrleneically unsaturated carboxylic acids (e.g. acrylic acid, methacrylic acid, itaconic acid, fumaric acid, eic acid or maleic anhydride) or by graft-polymerizing one or more ¯ R -ertylenically unsaturated carboxylic acids onto a polyolefin (e.g. polyethylene, polypropylenr an ethylene-propylene copolymer or polybutene). Other polymerizable monomers may be used as required. Alternatively, esters of & ss -ethylenrcally unsaturated carboxylic acids may be used and after copolymerization or graft-polymerization of the esters, the ester group is saponified to form a carboxyl group to provide the corresponding carboxyl group-containing polyolefin. there the laminated member obtained by the method of this invention is used for the production of a retort sterilization package or the like and is thus required to have heat resistance, it is preferred to amploy a highly crystalline polyolefin as the polyolefin, e.g. high density polyethylene or polypropylene. In connection with the amount of the ethylenically unsaturated carboxylic acid being used, it is preferred that 0.01 to 50 parts by weight of the carboxylic acid is reacted with 100 parts by weight of the olefin component. In smaller amounts than 0.01 part by weight, the adhesion capability of the adhesive obtained tends to be low. On the other hand, in greater amounts than 50 parts by weight, no increase in the adhesion capability can be observed. While the carboxyl group-containing polyolefin can satisfactorily be used in this invention, the following polyolefin based resin is preferably used in this invention because it is excellent in its adhesion capability after retort sterilization: The polyolefin based resin is prepared by compounding a metal compound with a carboxyl group-containing polyolefin. Metal compounds which can be used in preparing such polyolefin based resin include carbonates, sulfates, acetates, oxides, hydroxides and organic compounds of sodium, potassium, magnesium, zinc, aluminum copper and nickel. lMere the final laminated member is used in medicine, food and related applications, metal compounds of magnesium, calcium, zinc and aluminum are preferably used. In particular, an aluminum compound is preferred, with aluminum hydroxide being more preferred. The metal compound is preferably compounded in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the carboxyl group-containing polyolefin. Wilen the metal compound is used within the above range, high adhesion strength is obtained. When it is used in an amount of less than 0.05 part by weight, it can be difficult to obtain a high adhesion strength. On the other hand, the use of the metal compound in an amount of more than 10 parts by weight not only produces no increase in the adhesion strength, but also can cause foaming of the adhesive during heat-melting the polyolefin based resin composition, resulting in an uneven coating of the adhesive on the support. As an alternative to the metal compound being mixed with and dispersed in the carboxyl group-containing polyolefin, metal ions may be coordinated to form a salt or a cross-linkage of metal ions may be formed. A third component, e.g. polybutadiene, can be used together in synthesizing the polyolefin based resin composition. In this case, however, it is necessary to select a third component which exerts no adverse influences on the adhesive properties. Various methods can be employed to produce the polyolefin based resin. In one method the carboxyl groupcontaining polyolefin and the metal compound are mixed wh# t the same time heating. In so h a method the carboxyl group-containing polyolefin and the metal compomi: are heated at a temperature of about 100 to 220 0C and uniformly mixed for about 5 to 120 minutes. In another method, the polyolefin,1, -ethylenically unsaturated carboxylic acid and metal compound are heat-mixed at the same time to effect graft polymerization. In some cases, an unmodified polyolefin or a resin having excellent hygienic properties can be compounded with the polyolefin based resin. Far providing a layer of the thus obtained carboxyl group-containing polyolefin or polyolefin based resin, any suitable method may be employed for example, the polyolefin or resin may be dissolved or dispersed in an organic solvent, such as xylene or Solvesso (produced by Esso Company) and/or water and applied as a solution or a dispersion to one of the layers to be joined. The polyolefin or resin may be laminated on one of the layers to be joined or interposed between the layers to be joined by the use of an extruder. Alternatively, the polyolefin or resin may be ground into a powder and coated onto one of the layers to be joined. For the carboxyl group-containing polyolefin or polyolefin based resin, adhesive properties are, of course, required, and when it is used in a food packaging material for example, hygienic properties are strictly necessary. It is, therefore, preferred to wash the carboxyl-groupcontaining polyolefin or polyolefin based resin with for example, acetone, methyl ethyl ketone or ethyl acetate in the course of or after the synthesis thereof. The polyolefin or resin subjected to such a washing treatment exhibits markedly excellent adhesive properties. The completion of the washing can be confirmed by examining for the presence of low molecular weight compounds or homopolymers by liquid chromatography (GPC). The laminated member obtained by the method of this invention can advantageously be used as a wrapping material for food. :There it is used as a material for wrapping food to be sterilized in a retort, it is preferred to use high density polyethylene or polypropylene having a relatively high heat resistance as the polyolefin. This invention vill be described in greater detail with reference to Figures 1 and 2 of the accompanying drawings . Referring to Figure 1, a metal foil or sheet 1, which may be backed with a heat-resistant resin, travels from a feed roll (not shown) through a guide roll 2 to a heated roll 3, and a thermoplastic resin film 4 travels from a feed roll (not shown) through a guide roll 5 to a nip roll 6. A carboxyl group-containing polyolefin or polyolefin based resin used as an adhesive is melted in an extruder (not sho#rn) , extruded through a T-die 7 in the form of z film, and pressed between the heated roll 3 and nip 2 roll 6 at about 0.2 to 20 kg/cm2 whereby the adhesive bonds the metal foil or sheet 1 and the thermoplastic resin film i# together to provide a laminated member S. In this embodiment, an elastomeric rubber material is used in the surface of the nip roll 6 and becomes heated and sticky. The surface of the nip roll 5 is therefore preferably cooled by bringing it in contact rih a cooling ba.ck-up roll 9. The cooling back-up roll 9 is itself cooled by passing a cooling medium, e.g. sates, through the interior thereof. The laminated member Maybe cooled by a suitable cooling means, if desired, for example, by alloying it to cool, by forced air cooling bar bringing into contact ith a preliminary cooling roll (not sho:n), the merfter 3 is then passed between a cooling roll 10 and a nip roll 11 at r.3 heat distortion temperature of the adhesive or at a temperature higher than the heat distortion ter: :t#e#ure, usually between the heat distortion temperature and the melting point, preferably at or above the softening point, where it is pressed at a pressure of 0.2 kg/cm2 or more and at the same time, cooled. Thereafter, the laminated member 3 is wound onto 2 roll 12 or transferred to a subsequent cutting step (not shown). The cooling roll 10 is cooled b7 a 'inolm technique, for example, by passing a cooling medium, e.g. water, through the interior thereof. The temperature of the cooling roll 10 is usually about 50 to 50 C. A cooling means can be employed which is so designed that the temperature of the laminated member S just after passing through the second step is usually about 600C or less and preferably about 40 C or less. when a polyethylene-based adhesive is used, it is preferred that the laminated member 3 enters the second step where pressure and cooling arc applied, at a temperature of about 90 to 160 c. then a polypropylene based adhesive ls used, it is preferred for the laminated member 8 to enter the second step at a temperature of about 1100 to 180 c. If the temperature is too low, the objects of this invention will not be attained, whereas if the temperature is extremely high, the thermoplastic resin film will be deteriorated, with the result that the turns of the laminated member S on the roll 12 will tend to stick together to form a block on the roll 12 which makes the operation difficult. The pressure applied at the second step is about 0.2 kg/cm2 or more and preferably about 1 sg/cm2 or more. Lower pressures cannot inhibit the occurrence of wrini#es and remove the unevenness in adhesion strength. Commcially the pressure is preferably about 1 to 20 kg/cm2. 1:hile he reason why the un@@@@@ess in adhesive Srer#1##d the formation of lvriS;l¯- are soled by the second step, i.e. pressure application and cooling step of this inventions is not yet fully understood it is believed that the adhesive, just after being heated to above its melting point, has no definite direction of orientation, but the direction of orientation becomes defines at the subsequent pressure application and cooling step whereby stabilized adhesion strength is attained. To ensure the most effective removal of #:rini#es, it is preferred for the laminated member S to come into contact first vith the nip roll ll and then with the cooling roll 10. Figure 2 shows another embodiment of this invention in which an adhesive is passed between 2 cooling roll 13 and a nip roll 14 where it is previously cooled and a preliminarily bonded member 16 is formed, and the preli.m- inarily bonded member 16 is passed to a heating and pressure application step as described with reference to Figure 1 where laminated member S is obtained. Thereafter, the laminated member S is passed to the same pressure application and cooling step as in Figure 1 (not shown). In Figure 2 the reference numerals 15 and 17 indicate a cooling back-up roll and a guide roll, respectively. The first step and the second step of this invention are not necessarily connected continuously, and in some cases, they may be completely separated. An additional step prior to the first step or an additional step after the second step can be employed as necessary. The nip roll 11 applies uniform pressure on the whole surface of the laminated member S travelling thereon, and it preferably has an elastic material at at least the surface thereof. A typical Example of such elastic material is silicone rubber. This application. of pres5u. pet to remove the unevenness in adhesion strength which occurs at the centre and ends of the roll when the tension is applied by application of pressure, and furthermore to inhibit the formation of wrinkles. The following examples are given to illustrate this invention in greater detail. All parts are by weight. EXAMPLE 1 100 parts of a carboxyl group-containing polyolefin which had been prepared by graft polymerizing maleic anhydride onto polypropylene in a proportion of about O.2% by weight and fully washed, and 1.0 part of aluminum hydro=- ide were compounded, fully mixed in a Henschel mi.#er, melted in an extruder heated up to 180 C, and extruded in the form of pellets. The polyolefin composition thus obtained had a heat distortion temperature of 120 C, a Vicatsoftening temperature of 14500 and a melting point of 16500. These pellets were melted at about 18000 and extruded through a T-die 7 in the apparatus as described with reference to Figure 2 between a 9)um aluminum foil backed with a polyester film and a 70 1 polypropylene film. The peripheral speed of the cooling roll 13 was about 70 m/min, which was the same as that of each film. The surface temperature of the cooling roll 13 was maintained at about 300C by passing water through the interior of the cooling roll 13. The polyolefin composition so extruded as uniformly sandviched. Troubles such as protrusion of adhesive and breScage of the adhesive layer did not occur and the operation proceeded smoothly. The#fter, the three layer member as obtained above as brought in contact with the heat roll 3 having a surface temperature Of 200 C for 0.5 second, pressed @@ about 2 kg/cm2 and then alloyed to cool. The member :as then trans- ferred to the pressure application and cooling step as shorn in Figure 1. First, the dependency of adhesion strength on the temperature of the polyolefin composition was examined by varying the temperature of the polyolefin composition just before entering the second step at an interval of 100C within a temperature range of from 60 C to 160 C while 2 maintaining the applied pressure at 3 /cm2, . The laminates obtained did not suffer formation of wrinkles but exhibited excellent adhesion strength without any unevenness therein when the temperature of the polyolefin composition was above 120 c. On the other hand, ten the temperatuie as bern; 110 C formation of wrinkles occurred and remarkable wrinkle formation was observed at a temperature of below 100 c. Upon formation of bags from the laminates produced using various temperatures of the polyolefin composition not all bags that were made from laminates having wrinkles at their sealing portion could provide perfect sealability or air-tightness. Secondly, the dependency of the adhesion strength on the pressure applied on the member was e#amined by varying the pressure, i.e. using a pressure of 0.2, 1, 3 or 10 kg/cm2 while maintaining the temperature of the polyolefin composition just before entering the second step at 145 c. The laminates thus obtained did not form wrinkles regardless of the pressure employed. her, , bags produced from the laminates obtained according to the process of this invention were free from the defects ;hìch the laminated packaging materials produced according to the conventional process suffer. Comparative Example 1 The procedure of Example 1 was repeated wherein the nip roll 11 was removed the temperature of the polyolefin composition just before entering the second step was maintained at 140 C, and-an average 2 tension value 2.0 Eg/cm2 was used. The central area of the laminated member so obtained showed an adhesion strength of about 1,050 r g/15 mm, whereas side areas, an adhesion strength of only about 580 g/15 mm. It can thus be seen that the unevenness in adhesion strength is great, and furthermore the formation of wrinkles was observed. This is considered due to the fact that çen tension is applied onto the laminated member 8, the force is concentrated only at the central area. Example 2 The procedure of Example 1 was repeated wherein a composition prepared by mixing a carboxyl group-containing polyolefin and an unmodified polypropylene in a weight ratio of 1: 1, said carboy7 group-containing polyolefin being obtained by graft-polymerizing maleic anhydride onto polypropylene in a proportion of 0. 40/o by weight, was used as an adhesive. This adhesive has substantially the same heat distortion temperature, softening point and melting point as those of the adhesive used in Example 1. The results obtained are nearly the same as those obtained in Example 1. The laminated members obtained in Examples 1 and 2 were formed into a bag. These bags were charged with chinese mixed flavoring and sealed. They were subjected to retort sterilization at 1200C for 30 minutes, and then the adhesion strength between the aluminum foil and the polypropylene film was measured in each bag. The adhesion strength of each of the bags was within the range that can pratically be used. However, the adhesion strength of the laminated member of Example 1 was 1,050 g/15 mm, whereas that of the laminated member of Example 2 was lower by about 20% Example 3 In this example, a carboxyl group-containing polypropylene prepared by graft-polymerizing maleic anhydride onto polypropylene in a proportion of about o. 3% by wight was used as an adhesive. This adhesive had substantially the same heat distortion temperature softening point and melting point as those of the adhesive used in Example 1 it was melted at about 200 c and and extruded through a T-die in an apparatus, between a tin plate and a 70 u polypropylene film. The member so obtained was brought in contact with the heat roll 3 having a surface temperature of 220 C for 0.4 second, pressed 2 at about 0.7 Kg/cm and then allowed to cool. The member was then transferred to the pressure application and cooling step as shown in Fig. 1. In order to examine the dependency of the adhesion strength on the temperature, the procedure of Example 1 was repeated wherein the pressure applied was maintained 2 at 2.5 Kgism2. The results obtained are nearly the same as those obtained in Example 1. Moreover, in order to examine the dependency of the adhesion strength on the pressure, the procedure of ,Example 1 was repeated wherein the temperature of the adhesive just before entering the second step was maintained at 140 C. The results obtained are nearly the same as those obtained in Example 1. Example 4 In this example, an aqueous dispersion of an ethylene-acrylic acid copolymer (acrylic acid content 5% by weight) was used as an adhesive. The dispersion 0 had a Vicat-softening temperature of 105 C. This adhesive was coated in a thickness of about 10 pm on a 9m aluminum foil backed with a nylon film and dried at 1400C. The aluminum foil was superposed on a 70 fm polyethylene film. The member so obtained was brought in contact with a heat roll having a surface temperature of 160 C for 1.5 seconds 2 and pressed at a pressure of about 2.5 Kg/cm . Thereafter, the member was cooled to a tempratum of 1100C at 2 a pressure of 4 kg/cm by use of a cooling roll of a tempera ture of 250C and an elastic nip roll. In thelaminated member so obtained, no wrinkles and stripes were observed. The adhesion strength between the polyethylene film and the aluminum foil was 850 Kg/15 mm.

Claims: Claims 1. A process for producing a laminated member including a metal foil or sheet (1) and a thermoplastic resin film (4), said process comprising the steps of heating the foil or sheet (1) and the film (4) with at least one adhesivedisposed therebetween,said adhesive being selected from a carboxyl group-containing polyolefin and a polyolefin based resin prepared by heat-compounding a carboxyl group-containing polyolefin and a metal compound, at a temperature which is higher than the melting temperature of the adhesive and pressing to form a laminated member (8); and cooling the laminated member (8) when at the heat distortion temperature of the adhesive or at a temperature higher than the heat distortion temperature 2 while applying a pressure at least 0.2 Kg/cm using a cooling roll (10) a# a nip roll (11). 2. The process as claimed in Claim 1, wherein the adhesive is a graft polymer of polyolefin and a:# # - ethylenically unsaturated carboxylic acid. 3. The process as claimed in Claim 1 wherein the adhesive is a polyolefin based resin prepared by heat -compounding a graft polymer of polyolefin and an 4,# ethylenically unsaturated carboxylic acid, and a metal compound. 4. The process as claimed in Claim 3,wherein the polyolefin based resin is prepared from 100 part weight of the carboxyl group-containing polyolefin and 0.05 to 10 parts by weight of the metal compound. 5. The process as claimed in Claim 4, wherein the polyolefin based resin is prepared from a graft polymer of polypropylene and maleic acid, and aluminum hydroxide. 6. The process as claimed in Claim 1, 2, 3, 4 or wherein the heating and pressing step is carried out by bringing the metal foil or sheet (1) of the laminated member in contact with a heated roll (3). 7. The process as claimed in Claim 1, 2, 3, 4, 5 or 6, wherein the adhesive is extruded as a molten film and sandwiched between the metal foil or sheet (1) and the thermoplastic resin film (4). 8. The process as claimed in Claim 1, 2, 3, 4, 5, 6 or 7,wherein the thermoplastic resin film (4) is a polyolefin film or a nylon film. 9. The process as claimed in Claim 1, 2, 3, 4, 5, 6, 7 or 8,wherein the metal foil (1) is backed with a heat resistant resin. 10. The process as claimed in any preceding claim, wherein the second step is effected at or above the softening point of the adhesive. 11. A laminated member when produced by the process as claimed in any preceding claim.

Inventors: ISHINO, HIROKICHI, OHTSUKI, AKIRA, SAKAI, HIROMU, TAWARA, KAZUO, TSUCHIKO, SUSUMU, YAMASOBA, TAKAHIKO
Applicants: TOYO INK MANUFACTURING CO., LTD.
Application year: 1980
Main classification: C08J5
IPC codes: B29C55, B32B15, C09J151, B29C65, C08J5, B29C63, B32B37, C09J5