JPS62162541A - New laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides an adhesive layer comprising a base material and a terpolymer of ethylene, an unsaturated glycidyl group-containing monomer, and (meth)acrylic acid ester. The present invention relates to a novel laminate consisting of at least 2N.

[Prior art] Laminating agents have been developed in which different materials are laminated onto thermoplastic resin base materials such as polyolefins, polyamides, polyesters, saponified products of ethylene-vinyl acetate copolymers, etc., and the shortcomings of each base material are mutually compensated for. Various types are provided and put into practical use. For example, some food packaging devices are made by laminating polyolefin with polyamide, polyester, or the like. Polyolefins are widely used as food packaging materials because of their excellent transparency, flexibility, hygiene, heat sealability, and other aspects. However, polyolefins have drawbacks such as high permeability to gases such as oxygen and carbon dioxide, and the inability to preserve foods for long periods of time. On the other hand, polyamide has excellent heat resistance, oil resistance, etc., but has the disadvantage of poor moisture permeability and heat sealability. In addition, although polyester and saponified products of ethylene-vinyl acetate copolymers have low gas permeability and are excellent in heat resistance, they have drawbacks such as poor heat sealability, and it is difficult to laminate polyolefin and these base materials. This solves the above problem.

However, when these base materials are laminated, adhesiveness between each base material is poor, and delamination occurs extremely easily.

Conventionally, ethylene-vinyl acetate copolymers, ionomer resins, or resins obtained by modifying polyolefins with maleic anhydride have been used as adhesive resins to improve the interlayer peel strength (for example, JP-A-51-92880).
No. 1, JP-A-52-32080, JP-A-54-
No. 82, JP-A-54-87753, JP-A-Sho. 5
4-160481). However, these resins have good compatibility with polyolefins or polyamides and have a certain degree of delamination strength, but this is still not sufficient.

Furthermore, it does not have enough adhesive strength for practical use with polyester.

Furthermore, conventionally, ethylene-glycidyl methacrylate copolymer (hereinafter simply Et
-GMA) and ethylene-glycidyl methacrylate-vinyl acetate terpolymer (hereinafter simply Et-GMA-V).
(referred to as A) are well known (for example,
-27527@publication, JP-A-48-11388,
Japanese Patent Publication No. 52-28836, Japanese Patent Publication No. 48-8923
Publication No. 6, etc.).

However, the let-GMA binary copolymer has low adhesive strength to special thermoplastic resins such as saponified ethylene-vinyl acetate copolymer. Also Et-GMA-VA
Terpolymer copolymers have problems such as thermal decomposition during high-temperature molding, corroding extruders and molds, and emitting acetic acid odor, making them unsuitable for food packaging, etc. ing.

[Problems to be Solved by the Invention] In view of the problems of the prior art described above, the present invention further improves the delamination strength for resins such as polyolefin and polyamide, which have conventionally effective adhesive properties, and at the same time,
The object of the present invention is to provide a new laminate with excellent interlayer peel strength and which can significantly improve adhesion to saponified products of polyester and ethylene-vinyl acetate copolymers, which have hitherto had low adhesion.

[Means for Solving the Problems] The present invention provides a laminate consisting of at least two layers, a base material and an adhesive layer, the adhesive layer comprising ethylene, an unsaturated glycidyl group-containing monomer, and (meth)acrylic. Consisting of a terpolymer of acid esters, containing 1 to 10% by weight of an unsaturated glycidyl group-containing monomer, and (meta)
The ratio (weight ratio) to acrylic ester is 1 = 1 to 1:5
and an unsaturated glycidyl group-containing monomer and (meta)
This is a novel laminate characterized in that it contains a terpolymer in which the total amount of acrylic esters is 2 to 30% by weight.

The present invention will be explained in detail below.

Adhesive layer The adhesive layer used in the present invention is a terpolymer of ethylene, an unsaturated glycidyl group-containing monomer, and a (meth)acrylic acid ester, and is a terpolymer of ethylene, an unsaturated glycidyl group-containing monomer, and a (meth)acrylic acid ester.
Contains 10 m% of unsaturated glycidyl group-containing monomers and (
The ratio (weight ratio) to meth)acrylic acid ester is 1:1 ~
5, and an unsaturated glycidyl group-containing monomer (
The terpolymer in which the total amount of meth)acrylic acid ester is 2 to 30% by weight is an essential requirement.

When the content of the unsaturated glycidyl group-containing monomer in the terpolymer used in the present invention is less than 1% by weight, (meth)
Even if an acrylic ester is used in combination, only the adhesive strength equivalent to that of the ethylene-(meth)acrylic ester binary copolymer is obtained, and no improvement in adhesive strength is observed. On the other hand, if an amount exceeding 10% by weight is added, the adhesiveness will not be improved any further and the cost will increase.

Furthermore, when the ratio (weight ratio) of the (meth)acrylic acid ester to the unsaturated glycidyl group-containing monomer is less than 1, the adhesive strength is that of a binary copolymer of ethylene and the unsaturated glycidyl group-containing monomer. If the ratio exceeds 5, the copolymer becomes soft, the adhesive layer material breaks, and the adhesive strength decreases.

If the total amount of the comonomer Kurao, that is, the total amount of the unsaturated glycidyl group-containing monomer and (meth)acrylic acid ester, is less than 2% by weight, the adhesive strength will be low, and if it exceeds 30% by weight, the heat resistance will be poor. and material breakage due to a decrease in resin strength.

The feature of the present invention is that in addition to ethylene and an unsaturated glycidyl group-containing monomer, as a third component, (meth)acrylic acid ester is copolymerized with the unsaturated glycidyl group-containing semisolid at a specific ratio. The inventors have discovered an adhesive layer that has significantly improved adhesive strength (see Figure 1 below) and has significantly superior heat resistance.

Compared to the conventional ethylene-glycidyl methacrylate di-copolymer (Et-GMA copolymer), the terpolymer used in the present invention has the advantage that the third component (meth)acrylic ester component is copolymerized. This dramatically improves the adhesive strength. In particular, as is clear from the Examples described below, the adhesive strength is significantly improved regardless of the type of substrate.

Furthermore, the terpolymer used in the present invention is the well-known ethylene-glycidyl methacrylate-vinyl acetate (
Compared to the Et-GMA-VA) terpolymer, it does not undergo thermal decomposition during high-temperature molding, does not corrode the extruder or mold, and does not generate unpleasant odors such as acetic acid odor. Therefore, it is hygienic and can be sterilized at high temperatures, so it can be suitably used as packaging materials for food packaging, etc. (see Figure 2 below)
.

The melt index (hereinafter simply Ml) of the above terpolymer
) is 0.01 to 200 g/10 min, preferably 0.1 to 500 g/10 min, more preferably 0.5 to 2
A range of 0Q/10 minutes is desirable. Above M(
is less than 0.01 (1/10 minute or 200
If it exceeds g/10 minutes, there will be problems in processability.

Furthermore, among the above ternary copolymers, the melting point T (
°C) and the total comonomer content (wt%) (total of unsaturated glycidyl group-containing monomers and (meth)acrylic acid esters ff1) A is -0.8X A + 127
A terpolymer satisfying ≧T≧-0,8X A + 111 has a high melting point and is heat resistant, so it can be used for packaging materials that require boiling sterilization, such as food packaging materials and pharmaceutical packaging materials. It is preferably applied to.

If the above-mentioned melting point T ("C) exceeds -0, 8x A + 127, the resin becomes hard and the adhesive strength may decrease, and the melting point T ("C) exceeds -0, ax A + 1.
If it is less than 11, the heat resistance will be poor and it will be soft, causing problems in the strength of the adhesive layer.

Furthermore, in the present invention, the terpolymer may be blended with a thermoplastic resin and/or rubber, which will be described later, and used as an adhesive layer.

Examples of the unsaturated glycidyl group-containing mono-ω substance used in the present invention include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, tentricarboxylic acid triglycidyl ester, and α- chloroallyl, maleic acid, crotonic acid,
Examples include glycidyl esters such as fumaric acid, glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, etc. Particularly preferred examples include glycidyl methacrylate and acrylic glycidyl ether.

The (meth)acrylic acid ester used in the present invention is an alkyl such as methyl-, ethyl-, propyl-, butyl-, 2-ethylhexyl-, cyclohexyl-, dodecyl-, octadecyl-, etc. of acrylic acid or methacrylic acid. These include esters, hydroxyalkyl esters such as 2-hydroxyethyl methacrylate, aminoalkyl esters such as dimethylaminoethyl methacrylate, and the like.

Particularly preferred are alkyl esters of acrylic acid such as methyl, ethyl and propyl, among which ethyl acrylate is most preferred.

The terpolymer used in the present invention is produced by high-pressure radical polymerization. That is, based on the total weight ω of all monomers, o. Polymerization pressure 500-4000 k (1/Ci, preferably 100
0~3500kGl/cd1 reaction temperature 50~40
The monomers are brought into contact and polymerized simultaneously or in stages at 0°C, preferably from 100 to 350°C, in the presence of a chain transfer agent and, if necessary, an auxiliary agent, in a tank or tube reactor. can be obtained.

The free radical catalysts include customary initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, oxygen, and the like.

In addition, as a chain transfer agent, hydrogen, propylene, butene-
1, C1-CA. or higher saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons, such as methane, ethane, propane, butane, isobutane, n-hexadi, n
-Heptane, cycloparaffins, chloroform and carbon tetrachloride, 01-Cyu. or higher saturated aliphatic alcohols such as methanol, ethanol, propatool and isopropanol, 01 to Czo or higher saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone and aromatic compounds such as toluene, diethylbenzene and compounds such as xylene.

Substrate The substrate used in the present invention is not particularly limited and includes thermoplastic resins, metals, paper, fabrics, wood materials, glass, rubber, thermosetting resins, etc. In particular, food packaging materials Thermoplastic resins having remarkable effects such as the like are preferred.

The above thermoplastic resins include polyethylene, polypropylene, polybutene-1, poly4-methyl pentene-1
Homopolymers such as ethylene, propylene, butene-1,
Hexene-1,4-methyl pentene-1, octene-
Mutual copolymer of α-olefins, ethylene-
Vinyl acetate copolymer, ethylene-acrylic acid copolymer,
Ethylene-methacrylic acid copolymer, ethylene-(meth)
Polyolefin resins such as acrylic ester copolymers, saponified ethylene-vinyl acetate copolymers, nylon 6
, 66゜11.12 and other polyamide resins, polycarbonate resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyacrylonitrile resins, polystyrene resins, polyvinyl Alcohol resin, ABS resin, polymethyl methacrylate resin, fluorine resin, polyimide resin, polyamideimide resin, polyether/ether ketone resin, polyether sulfone resin, polysulfone resin, polyphenylene oxide resin, polyphenylene sulfide resin, polyacetal resin, or these One type or a mixture of two or more of these are used.

Among these thermoplastic resins, the adhesive layer used in the present invention is made of
In particular, it has a remarkable effect on adhesion to saponified ethylene-vinyl acetate copolymers and polyester resins. Moreover, these thermoplastic resins may be stretched.

Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, and alkyd resin.

Examples of the above rubbers include polybutadiene, polyisobutylene, neoprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, ethylene-butene-1 copolymer rubber, styrene-butadiene copolymer, Synthetic rubbers and natural rubbers such as styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, butyl rubber, polyurethane rubber, chlorosulfonated polyethylene, chlorinated boreethylene, fluororubber, thiocol, and the like can be mentioned.

Also included in the base material used in the present invention is a sheet made of the above-mentioned thermoplastic resin or rubber mixed with a filler.

The fillers include calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, antimony trioxide, graphite, silicon carbide, silicon nitride, Powder-like fillers such as silica, boron nitride, aluminum nitride, wood powder, carbon black, mica, glass plates,
Metal foils such as sericite, pyrophyllite, aluminum flakes, flat or scaly fillers such as graphite, hollow fillers such as shirasu balloons, metal balloons, glass balloons, pumice, glass fibers, carbon fibers, graphite mm ,
Whisker metal! Fibrous fillers such as mineral ta fibers such as l fibers, silicon carbide fibers, asbestos, and wollastonite, and organic fibers such as scose, polyamide, and vinylon; fiber woven fillers such as glass fiber mats and organic fiber mats, etc. Examples can be given.

Examples of the base material include metal foils, metal plates, wire meshes, and panging plates made of metals such as chromium, iron, nickel, zinc, tin, aluminum, copper, brass, tinplate, and galvanized iron.

Examples of the above-mentioned fabrics include tapes made of the above-mentioned thermoplastic resin, woven fabrics and non-woven fabrics of fibers such as flat yarns and monofilaments, net-like bodies, split II fiber films obtained by cutting the above-mentioned resin films into thin pieces, vinylon, polyester, nylon, etc. Examples include synthetic fibers, woven fabrics of natural fibers such as cotton, silk, and linen, woven fabrics woven with inorganic fibers such as glass fibers, carbon fibers, and metals, mats, and felts.

The paper mentioned above is not particularly limited; for example, kraft paper,
Wrapping paper such as roll paper, thin paper such as glassine paper, paperboard and other Western papers, Japanese paper such as shoji paper, or synthetic paper such as polystyrene paper and vinylon paper are used.

In the present invention, at least two of the base material and the adhesive layer
Consisting of layers @! Although it is an i-layer structure, a multilayer structure of three or more layers using the above-mentioned different types of base materials is also included.

A specific example of a multilayer structure using the above-mentioned dissimilar base materials is polyester resin (hereinafter abbreviated as PE, T)/adhesive layer (hereinafter abbreviated as EGA)/high density polyethylene (hereinafter abbreviated as HDPE).
), PET/EGA/saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH), PET/EG
A/aluminum foil (hereinafter abbreviated as A1), ethylene-vinyl acetate copolymer (j), abbreviated as EVA and t> /EGA/
PET, EVA/EGA/EVOH/EGA/EVA1
PET/EGA,/EVOH/
Examples include (7) multilayer structures such as EGA/PET.

The method for producing the above-mentioned laminated structure includes an inflation method using a multilayer die, an extrusion method such as a T-die method, a blow molding method, an injection molding method, or a method of coating with a brush or the like.
Any method such as a fluidized dipping method, a powder injection method, an electrostatic coating method, a press method, etc. can be applied.

In the present invention, a method of melt bonding is preferably applicable, and a coextrusion molding method is particularly preferred because it significantly improves the adhesiveness of the adhesive layer used in the present invention.

Furthermore, in the present invention, antioxidants, ultraviolet absorbers, flame retardants, anti-corrosion agents, processability improvers, reinforcing agents, fillers, colorants, pigments, antistatic agents, etc. It may also contain additives such as anti-blocking agents, anti-blocking agents, and foaming agents.

EXAMPLES] The present invention will be described in more detail below based on Examples and Comparative Examples.

(Preparation of terpolymer for adhesive layer) Ethylene (filling ff 11.7 ka) and glycidyl methacrylate and ethyl acrylate as comonomers were mixed in a volume of 3.8. Ethylene-glycidylmethacrylate-
An ethyl acrylate copolymer (hereinafter referred to as Et-GMA-EA) was obtained. Other Et-GMA-EAA polymers were prepared in the same manner by changing the loading level of the comonomer.

Further, copolymerization was carried out in the same manner as above using vinyl acetate as a comonomer to prepare an ethylene-glycidyl methacrylate-vinyl acetate copolymer (hereinafter referred to as Et-GMA-VA).

(Base material) (a) Polyethylene terephthalate resin (PET
-RT 5330. (manufactured by Japan Unipet Four) (b) Polyethylene terephthalate resin (PET-G 67
63. (manufactured by Kodak Corporation) (hereinafter simply abbreviated as PET) (c) Saponified ethylene-vinyl acetate copolymer (EVAL E type, manufactured by Kuraray ■) (hereinafter simply abbreviated as EVOH) (d) Polypropylene resin (homotype) (Japanese) Stone Polypro J 130G, manufactured by Nippon Petrochemical Co., Ltd.) (hereinafter referred to as H-P
(abbreviated as P) (e) Polypropylene resin (block type) (Nisseki Polypro J 650G, Nippon Petrochemical Company 1) (hereinafter 8
-PP) (f) Aluminum (abbreviated as AJ) The copolymers and base materials used in each Example and Comparative Example are shown in Tables 1 and 2, respectively.

Examples 1 to 3 and Comparative Examples 1 to 3 Et prepared as described above using a three-layer die for three types.
-GMA-EAA original copolymer as a swallowing layer at 180℃
EVOH was supplied to the die at 220°C as the innermost layer, and PET (b) was supplied as the outermost layer at 25°C.
The three layers were fed into a die at 0° C. and adhered in the die set at 260° C. to obtain a blown tubular multilayer film.

The average thickness of the film was 75μ, and the thicknesses of the innermost layer/adhesive layer/outermost layer were 35μ/20μ/20μ.

The film was made into a test piece having a width of 25 m, and a 180° peel test was conducted at a tensile rate of 50 InIR/min.

In this test, the strength when peeled is shown in Table 1 as the interlayer peel strength.

Example 4 Et-GMA-EA tertiary copolymer used in Example 2. Polymer containing edyl acrylate 8.7% polymer. MI5,
Example 1 Using a composition blended with 100 parts by weight of 8 (1/10 minutes) (hereinafter abbreviated as EEA) as the adhesive layer.
A multilayer film was obtained in the same manner as above. Table 1 shows the results of evaluation in the same manner as in Example 1.

Comparative Examples 4 to 5 Only ethyl acrylate or glycidyl methacrylate was used as a comonomer, and ethylene-ethyl acrylate binary copolymer (EEA: Comparative Example 4) or ethylene-ethyl acrylate was used as a comonomer.
Binary copolymer of glycidyl methacrylate (Et-G
MA: A multilayer film was obtained in the same manner as in Example 1, except that Comparative Example 5) was used as the adhesive layer. Table 1 shows the results of evaluation in the same manner as in Example 1.

Comparative Example 6 A multilayer film was obtained in the same manner as in Example 1, except that the EC-GMA-VA#ffi combination was used instead of the Et-GMA-EA copolymer used in the present invention.

Table 1 shows the results of evaluation in the same manner as in Example 1.

On the left side 5 to 8 and Comparative Examples 7 to 12 The adherend sheet of the base material (a), (c), (d) or ku) (the thickness of each base material is 2III111 thickness) and Example 1
- 4 and Comparative Examples 1 to 6, the sheets of the copolymers or their compositions (thickness: 11rIIR) were laminated, and further A-foil was added to reinforce the sheets of the copolymers or their compositions. (thickness: 50 μm), preheated, and after 5 minutes, PET (A) at 290℃, PP (D) and (E) at 230℃, and other base materials at 180℃ at 50kQ/c.
After being pressed under pressure for 5 minutes, the sample was cooled and cut into a width of 25M to obtain a test piece.

Using this test piece, the tensile speed was 50 m/m in the same manner as in Example 1.
A 180° peel test was conducted for 10 minutes, and the strength at that time was defined as the adhesive strength. The results are shown in Table 2.

In Table 2, "Material breakage pa" indicates that the material has broken, and the value in parentheses indicates the strength at the time of breakage.

In addition, Examples 1 to 3 and 5 to 7 and Comparative Example 2゜5.8
Based on the results of No. 1 and No. 11, changes in adhesive strength depending on the EA/GMA ratio are shown in FIG.

Test Example In order to compare the heat resistance, Et-G used in Example 1 was used.
MA-EA terpolymer and Et used in Comparative Example 6
A weight change curve was determined using a thermobalance using the -GMA-VA terpolymer. The results are shown in FIG.

<Measurement method> The above weight change curve was calculated by accurately weighing a sample of approximately 10#Iy, setting it on a thermobalance, and measuring the temperature from room temperature to 450°C at a rate of 10°C/min in a nitrogen atmosphere using α-alumina as a standard substance. It was determined from the weight change during the temperature increase up to ℃.

(Evaluation) As is clear from the results of Examples 1 to 4 in which coextrusion molding was applied and Examples 5 to 8 in which press molding was applied, the terpolymer used in the present invention has a Adhesive strength is significantly improved.

In comparison, Comparative Examples 1 to 3 and 7 outside the scope of the present invention
-9, the effect of improving adhesive strength is low.

In Comparative Examples 5 and 11, the adhesive strength to metals was high, but the adhesive strength to thermoplastic resins was low.

In Comparative Examples 6 and 12, although the effect of improving adhesive strength was high to some extent, they had problems such as poor heat resistance.

[Operations and Effects of the Invention] As described above, the Et-GMA-E terpolymer used in the present invention can be used regardless of the type of substrate by setting the EA/GMA ratio of the comonomers within a specific range. , the adhesive strength is dramatically improved, and the improvement effect is particularly remarkable on thermoplastic resins. Therefore, according to the present invention, a new laminate with excellent delamination strength can be obtained.

The terpolymer used in the present invention has a remarkable improvement effect particularly on EVO) I resin and PET resin, for which good adhesives have not been found in the past, and has a remarkable improvement effect on EVOH/EGA/PET resin,
PET/EGA/EVOH/EGA/PET, HDPE
/EGA/EVOH/EGA/HDPE, a laminate with good gas permeability, oil resistance, heat resistance, heat sealability, etc. can be obtained.

Since such laminates can be heat sterilized, they can be used as food packaging films, sheets, food bottles for mayonnaise, soy sauce, beer, carbonated drinks, oil, etc., pharmaceutical packaging films, sheets, bottles, gasoline tanks, etc. It can be used particularly suitably.

[Brief explanation of drawings]

Figure 1 is a diagram showing the relationship between EA/GMA ratio and adhesive strength;
FIG. 2 is a diagram showing a double base change curve based on a thermobalance.

Claims (1)

[Scope of Claims] 1. A laminate consisting of at least two layers, a base material and an adhesive layer, wherein the adhesive layer is a ternary combination of ethylene, an unsaturated glycidyl group-containing monomer, and a (meth)acrylic acid ester. It consists of a polymer, contains 1 to 10% by weight of an unsaturated glycidyl group-containing monomer, and has a ratio (weight ratio) of the unsaturated glycidyl group-containing monomer to (meth)acrylic acid ester of 1:1 to 1: 5, and the total amount of the unsaturated glycidyl group-containing monomer and (meth)acrylic acid ester is 2 to 30% by weight. 2. The novel laminate according to claim 1, wherein the unsaturated glycidyl group-containing monomer is glycidyl (meth)acrylate. 3. The novel laminate according to claim 1 or 2, wherein the (meth)acrylic acid ester is an alkyl (meth)acrylic ester. 4. The novel laminate according to claim 3, wherein the (meth)acrylic acid alkyl ester is ethyl acrylate. 5. The relationship between the melting point T (°C) of the terpolymer and the total content A (% by weight) of the unsaturated glycidyl group-containing monomer and (meth)acrylic acid ester is expressed by the following formula -0.8× A+127
The novel laminate according to any one of claims 1 to 4, which satisfies ≧T≧−0.8×A+111. 6. The novel laminate according to claims 1 to 5, wherein the terpolymer is obtained by a high-pressure radical polymerization method. 7. The novel laminate according to any one of claims 1 to 6, wherein the adhesive layer is a composition in which the terpolymer is blended with a thermoplastic resin and/or rubber. 8. The novel laminate according to any one of claims 1 to 7, wherein the laminate is formed by melt-bonding. 9. The novel laminate according to claim 8, wherein the laminate is obtained by coextrusion. 10. The novel laminate according to any one of claims 1 to 9, wherein the base material is a thermoplastic resin. 11. The thermoplastic resin may be an olefin resin, a saponified product of ethylene-vinyl acetate copolymer, a polyamide resin, a polycarbonate resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polyester resin, or a polyacrylonitrile resin. 11. The novel laminate according to claim 10, which is made of a polystyrene resin, a polyvinyl alcohol resin, an ABS resin, or a mixture of one or more of these resins. 12. Claim 1, wherein the laminate has at least a three-layer structure in which a polyester resin layer, an adhesive layer, and a saponified ethylene-vinyl acetate copolymer layer are laminated in this order.
The new laminate described in item 1.