JPH10202799A - Laminate structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance an interlaminer adhesion strength between an ethylene vinyl acetate copolymer saponified polymer layer or the like and an olefin based polymer layer or the like by using a thermoplastic polyurethane and a polymer composition containing a specified block copolymer at a specified ratio. SOLUTION: An olefin based polymer layer or the like A and an ethylene.vinyl acetate copolymer saponified polymer layer or the like C are melted and bonded by a polymer layer B functioning as an adhesive. This polymer layer B is consisted of a polymer composition containing at least one of a thermoplastic polyurethane, a block copolymer formed of an aromatic compound based polymer block and a conjugated diene based polymer block, and a hydrogenated matter of this block copolymer at a weight ratio of [thermo plastic polyurethane]:[block copolymer and/or the hydrogenated matter thereof]=20-80:80-20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminated structure in which a plurality of organic polymer layers are laminated. More specifically, the present invention provides a polymer layer comprising an olefin polymer and / or a styrene polymer, a saponified ethylene-vinyl acetate copolymer, a vinylidene chloride polymer, a vinyl chloride polymer, and a polyamide. A laminate structure in which a polymer layer composed of at least one of polyester, polycarbonate, and an acrylic polymer is bonded by a polymer composition layer of a thermoplastic polyurethane and a specific block copolymer. And a method for producing the same, and a hot melt adhesive used for producing such a laminated structure. Since the laminated structure of the present invention has an extremely high adhesive strength between layers and no delamination between layers, it is extremely suitable for a wide range of applications including packaging films, depending on the characteristics of the organic polymer constituting the laminated structure. Can be used effectively.

[0002]

2. Description of the Related Art Saponified ethylene-vinyl acetate copolymer films, polyvinylidene chloride films, and polyamide films have excellent gas barrier properties, and take advantage of their high gas barrier properties to make use of polyethylene, polypropylene, polystyrene, and the like. Laminated with a plastic film with excellent heat sealing properties and other properties,
Widely used in packaging materials and other fields. In addition, polyvinyl chloride film has excellent transparency, chemical resistance, printability, mechanical properties, etc., and polyester film has excellent mechanical properties, chemical resistance, etc.
Taking advantage of those properties, alone or polyethylene,
Laminated with polystyrene and other plastic films, it is used for a wide range of applications. Furthermore, polycarbonate film is excellent in transparency, impact resistance, etc., and polymethyl methacrylate film is excellent in transparency, weather resistance, printability, etc., and by utilizing those characteristics, lamination with various plastic films is possible. Attempted.

In manufacturing a laminated film, bonding and lamination between plastic films are performed using a solvent-type adhesive such as a polyurethane solution, or lamination is performed using a hot-melt adhesive. And, when laminating a saponified ethylene-vinyl acetate copolymer film, a polyvinylidene chloride film, a polyvinyl chloride film, a polyester film, a polycarbonate film, and an acrylic polymer film with another polymer film, a solvent type has been conventionally used. Adhesives are widely used, but there are problems in terms of pollution of the natural environment, deterioration of the working environment, and safety due to the use of an organic solvent, and a lamination technique that does not use a solvent-type adhesive is required. In addition, among such films, polycarbonate film and acrylic polymer film are inferior in solvent resistance. Therefore, care must be taken in selecting a solvent. Furthermore, in the production of a laminated film using a solvent type adhesive, saponified ethylene-vinyl acetate copolymer film, polyvinylidene chloride film, polyvinyl chloride film, polyamide film, polyester film, polycarbonate film or acrylic polymer film. It is necessary to manufacture the film in advance and then laminate it with another polymer film that was also manufactured in advance using a solvent-type adhesive. After that, the number of steps such as a drying step for removing the solvent and a solvent recovery step becomes extremely large, and the work content becomes complicated, and the production cost becomes high, which causes various problems.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-strength adhesive layer between layers without using a solvent-type adhesive, which may cause environmental pollution and deterioration of the working environment. An object of the present invention is to provide a plastic laminated structure and a method of manufacturing the same. Particularly, the present invention relates to a saponified ethylene-vinyl acetate copolymer having excellent gas barrier properties, a layer made of a vinylidene chloride-based polymer or polyamide, a vinyl chloride having excellent transparency, chemical resistance, printability, mechanical properties, and the like. Polymer layer, polyester layer with excellent chemical resistance and mechanical properties, polycarbonate layer with excellent transparency and impact resistance, acrylic polymer layer with excellent transparency, weather resistance, printability, A laminate having a layer of an olefin-based polymer such as polyethylene or polypropylene and / or a layer of a styrene-based polymer having excellent heat sealing properties can be safely and favorably processed without using a solvent-type adhesive. It is intended to be provided at low cost with low workability.

[0005]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer, vinyl chloride-based polymer, At least one of polyamide, polyester, polycarbonate and acrylic polymer
When laminating a polymer layer containing a seed and a polymer layer containing at least one of an olefin polymer and a styrene polymer, together with a thermoplastic polyurethane, an aromatic vinyl compound polymer block and a conjugated diene When a polymer composition containing a block copolymer comprising a polymer block and / or at least one hydrogenated product of the block copolymer at a specific ratio as an adhesive is bonded and laminated under melting. A high-quality laminated structure with high interlayer adhesive strength and no delamination can be obtained safely and with good processability and workability without using harmful organic solvents and the like. It has been found that such a laminated structure can be obtained more smoothly by co-extrusion of the above-mentioned polymer, and the present invention has been completed based on those findings.

That is, the present invention provides (A) a polymer layer mainly composed of at least one of an olefin polymer and a styrene polymer; (B) a thermoplastic polyurethane, and an aromatic vinyl compound polymer block. And at least one hydrogenated product of a block copolymer comprising a conjugated diene-based polymer block and a hydrogenated product of the block copolymer: [thermoplastic polyurethane]: [block copolymer and / or hydrogenated product thereof] = 20 (C) a saponified ethylene-vinyl acetate copolymer, a vinylidene chloride-based polymer, a vinyl chloride-based polymer, a polyamide,
A polymer layer mainly composed of at least one of polyester, polycarbonate and acrylic polymer;
Is the polymer layer (A) / polymer layer (B) / polymer layer (C)
, At least in part.

The present invention relates to (a) a polymer mainly composed of at least one of an olefin polymer and a styrene polymer; (b) a thermoplastic polyurethane,
And at least one of a block copolymer consisting of an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block and a hydrogenated product of the block copolymer,
[Thermoplastic polyurethane]: [Block copolymer and / or hydrogenated product thereof] = Polymer composition containing at a weight ratio of 20 to 80:80 to 20; and (c) ethylene-vinyl acetate copolymer ken Compound, vinylidene chloride polymer, vinyl chloride polymer, polyamide, polyester,
A layer of the polymer composition (b) is provided between a layer of the polymer (a) and a layer of the polymer (c) by using at least a polymer mainly composed of at least one of polycarbonate and an acrylic polymer. A method for producing a laminated structure as described above, wherein co-extrusion molding is performed so as to interpose.

Further, the present invention relates to a thermoplastic polyurethane, a block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, and a hydrogenated product of the block copolymer. , [Thermoplastic polyurethane]: [Block copolymer and / or hydrogenated product thereof] = 20-80: 80-2
It is a hot-melt adhesive comprising a polymer composition contained at a weight ratio of 0.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the polymer layer (B) that functions as an adhesive layer for bonding the polymer layer (A) and the polymer layer (C) in the laminated structure of the present invention will be described. As described above, the polymer layer (B) is made of a thermoplastic polyurethane, a block copolymer composed of an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, and a hydrogenated product of the block copolymer. It is composed of a polymer composition containing at least one kind in a weight ratio of [thermoplastic polyurethane]: [block copolymer and / or hydrogenated product thereof] = 20 to 80:80 to 20.

In the present invention, any of the thermoplastic polyurethanes can be used as the thermoplastic polyurethane in the polymer layer (B), and the type and production method of the thermoplastic polyurethane are not particularly limited. The thermoplastic polyurethane used in B) can generally be produced using a polymer diol, an organic diisocyanate and a chain extender.

Examples of the polymer diol which can be used for forming the thermoplastic polyurethane include polyester diol, polycarbonate diol, polyester polycarbonate diol, polyether diol, and the like. It can be formed using two or more kinds.

The polyester diol used for forming the thermoplastic polyurethane is, for example, glutaric acid, succinic acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-
Aliphatic dicarboxylic acids such as methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecandioic acid, and 3,7-dimethyldecandioic acid; terephthalic acid A dicarboxylic acid component comprising one or more of an aromatic dicarboxylic acid such as isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid; a dicarboxylic acid such as an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; or an ester-forming derivative thereof. For example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-pentanediol,
1,4-butanediol, neopentyl glycol,
1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, Aliphatic diols such as 1,9-nonanediol, 1,10-decanediol;
It can be produced by performing an esterification reaction or a transesterification reaction by a conventional method using one or more diol components of alicyclic diols such as cyclohexanedimethanol and cyclohexanediol.

The polyester polycarbonate diol which can be used for forming a thermoplastic polyurethane includes:
A product obtained by simultaneously reacting a diol, a dicarboxylic acid and a carbonate compound, a product obtained by reacting a previously prepared polyester diol and a polycarbonate diol with a carbonate compound, a product obtained by reacting a diol with a dicarboxylic acid And the like. Further, conventionally known polycarbonate diols can be used.

The polyether diol used for forming the thermoplastic polyurethane includes, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
Species or two or more species can be used, and among them, polytetramethylene glycol is preferably used.

The high molecular weight diol used for forming the thermoplastic polyurethane has a number average molecular weight of 700 to 800.
When it is 0, more preferably 800 to 5000, the coextrusion moldability of the polymer composition constituting the polymer layer (B) is improved, and the cold resistance and heat resistance of the polymer layer (B) are improved. It is preferable from the viewpoint that it becomes good.

The type of the organic diisocyanate used for forming the thermoplastic polyurethane in the polymer layer (B) is not particularly limited, and any of the organic diisocyanates used for producing the thermoplastic polyurethane can be used. Among them, one or more of aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate having a molecular weight of 500 or less are preferably used. Examples of such organic diisocyanates include:
4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, and the like. One or more of these organic diisocyanates can be used.

As the chain extender used to form the thermoplastic polyurethane in the polymer layer (B), any of the chain extenders conventionally used in the production of thermoplastic polyurethanes can be used. Molecular weight 3 having at least two active hydrogen atoms capable of reacting in the molecule
A low molecular weight compound having a molecular weight of 00 or less is preferably used. Such chain extenders include, for example, ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis- (β-hydroxyethyl) terephthalate,
Diols such as xylylene glycol; hydrazine,
Diamines such as ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, adipic dihydrazide and isophthalic dihydrazide; amino alcohols such as aminoethyl alcohol and aminopropyl alcohol And the like, and one or more of these can be used.

In the present invention, as the thermoplastic polyurethane in the polymer layer (B), a polymer diol obtained by reacting an aliphatic dicarboxylic acid component with an aliphatic diol is selected from 4,4′-diphenylmethane diisocyanate and Aliphatic diols having 2 to 10 carbon atoms, especially 1,
Using a thermoplastic polyurethane obtained by reacting with a chain extender consisting of 4-butanediol has mechanical properties,
Saponified ethylene-vinyl acetate copolymer constituting the polymer layer (C), vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide, polyester, polycarbonate,
It is preferable because it has excellent adhesiveness with an acrylic polymer.

Further, it is preferable to use a thermoplastic polyurethane having an intrinsic viscosity of 0.3 or more from the viewpoint of mechanical properties, adhesiveness, moldability, etc., and it is more preferable to use a thermoplastic polyurethane having a viscosity of 0.8 or more. .

The method for producing the thermoplastic polyurethane used for the polymer layer (B) is not particularly limited as described above. It may be produced by any of the prepolymer method and the one-shot method utilizing the technology. Among them, it is preferable to carry out melt polymerization substantially in the absence of a solvent, and particularly preferable to carry out continuous melt polymerization using a multi-screw extruder.

A block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, which is the other polymer component constituting the polymer layer (B) (hereinafter referred to as "aromatic vinyl compound / conjugated A block copolymer having at least one aromatic vinyl compound-based polymer block and at least one conjugated diene-based polymer block is used as the “diene block copolymer”. In the block copolymer used for the polymer layer (B), the unsaturated bond in the conjugated diene-based polymer block may be hydrogenated, and the hydrogenation ratio in that case is 0 to 100 mol%. Can be appropriately selected from the range. In particular, in the present invention, it is preferable to use an aromatic vinyl compound / conjugated diene block copolymer in which 50 mol% or more of the unsaturated bonds of the conjugated diene-based polymer block is hydrogenated. It is preferable from the viewpoint of improving the properties and the like, and it is more preferable to use a block copolymer in which 80 mol% or more is hydrogenated.

The aromatic vinyl compound-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product used in the polymer layer (B) is mainly composed of structural units derived from the aromatic vinyl compound. It is a polymer block. As the aromatic vinyl compound in that case, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
1,3-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene,
-(Phenylbutyl) styrene and the like. The aromatic vinyl compound-based polymer block may have a structural unit composed of one or more of the above-mentioned monomers. Among them, the aromatic vinyl compound-based polymer block is preferably mainly composed of structural units composed of styrene and / or α-methylstyrene. Further, the aromatic vinyl compound-based polymer block may have a structural unit composed of a small amount of another unsaturated monomer in some cases.

The conjugated diene-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer used in the polymer layer (B) is 1,3-butadiene, isoprene, 2,3-dimethyl-1,3. -Butadiene, 1,3
-A polymer block formed from one or more conjugated diene compounds such as pentadiene and 1,6-hexadiene, and a hydrogenated aromatic vinyl compound / conjugated diene block copolymer in a hydrogenated aromatic vinyl compound / conjugated diene block copolymer. Some or all of the unsaturated bond portions in the polymer block have become saturated bonds by hydrogenation. Among them, in the present invention, the conjugated diene-based polymer block is a polymer block composed of 1,3-butadiene, isoprene or a mixture thereof, and is hydrogenated.
It is preferable from the viewpoint of excellent adhesiveness with the olefin polymer constituting the polymer layer (A). When the conjugated diene-based polymer block is an isoprene / butadiene copolymer block or a hydrogenated polymer block, the arrangement of the structural units derived from butadiene and the structural units derived from isoprene is random. , Block shape,
Any form of a tapered shape or a mixture of two or more of them may be used.

The molecular structure of the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product has a linear,
It may be branched, radial, or any combination thereof. Among them, in the present invention, one aromatic vinyl compound polymer block and one conjugated diene polymer block are linearly formed as an aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof. A diblock copolymer, an aromatic vinyl compound polymer block, a conjugated diene polymer block, and a triblock copolymer in which three polymer blocks are linearly bonded in this order. And one or more of these hydrogenated products are preferably used from the viewpoint of easy production, easy availability, compatibility with thermoplastic polyurethane, mechanical properties, and the like.

In the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product, the content of the structural unit derived from the aromatic vinyl compound is 5 to 90% by weight based on the total weight of the block copolymer. Is preferred from the viewpoint of increasing the adhesive force between the polymer layer (A) and the polymer layer (C), the mechanical characteristics, and the like, and more preferably from 10 to 90% by weight. In particular, when the polymer layer (A) is formed from an olefin polymer, the content of the structural unit derived from the aromatic vinyl compound in the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product is low. The content of 5 to 60% by weight is preferable from the viewpoint of increasing the adhesive strength between the polymer layer (A) and the polymer layer (B). When the polymer layer (A) is formed from a styrene-based polymer, the content of the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product derived from the aromatic vinyl compound in the structural unit is reduced. 50
It is preferable that the content be from 90 to 90% by weight from the viewpoint of increasing the adhesive strength between the layers.

When the polymer layer (A) is formed of polypropylene, the conjugated diene-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer has 3,4-bonds of 30 mol% or more. That the polymer layer (A) and the polymer layer (B) are composed of isoprene polymer blocks and / or hydrogenated products thereof.
It is preferable because the adhesive strength with the adhesive increases.

Further, the aromatic vinyl compound / conjugated diene block copolymer and the hydrogenated product thereof preferably have a hydroxyl group at the molecular terminal. In this case, the aromatic vinyl compound / conjugated diene block copolymer and the hydrogenated product thereof may have a hydroxyl group at one end of the molecule or at both ends, particularly at one end. Is preferred. Aromatic vinyl compound /
A polymer comprising a thermoplastic polyurethane and an aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof because the conjugated diene block copolymer and a hydrogenated product thereof have a hydroxyl group at a molecular terminal. The film formation stability during melt extrusion of the composition is remarkably improved, so that the film can be stably formed and laminated even when the film thickness is reduced. In the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product, the number average molecular weight of the aromatic vinyl compound-based polymer block is 2500 to 5000.
0, the number average molecular weight of the conjugated diene-based polymer block before hydrogenation is 10,000 to 100,000, and the number average molecular weight of the entire aromatic vinyl compound / conjugated diene block copolymer is 15,000 to 150,000. Are preferred from the viewpoint of mechanical properties, moldability and adhesiveness.

The method for producing and obtaining the aromatic vinyl compound / conjugated diene block copolymer and the hydrogenated product thereof are not particularly limited, and the aromatic vinyl compound-based polymer block and the conjugated diene-based polymer block are not particularly limited. Any copolymer can be used as long as it has an aromatic vinyl compound / conjugated diene block copolymer or a hydrogenated product thereof for the laminated structure of the present invention. Or may be obtained in other ways. Although not limited, the aromatic vinyl compound / conjugated diene block copolymer and the hydrogenated product thereof used in the present invention can be prepared by, for example, using an aromatic vinyl compound and a conjugated diene by an anionic polymerization method and a cationic polymerization method. It can be obtained by preparing a block copolymer by a synthetic method, a Ziegler polymerization method, a single-site polymerization method, a radical polymerization method, or the like, and hydrogenating it if necessary.

In the present invention, the polymer layer (B) comprises:
The above-mentioned thermoplastic polyurethane and at least one of an aromatic vinyl compound / conjugated diene block copolymer and a hydrogenated product of the block copolymer are treated with [thermoplastic polyurethane] (when a plurality of thermoplastic polyurethanes are used, ): [Aromatic vinyl compound / conjugated diene block copolymer and / or hydrogenated product thereof] (when using a plurality of aromatic vinyl compound / conjugated diene block copolymers and / or hydrogenated product thereof, ) = 20-80: It is necessary to be formed from a polymer composition containing at a weight ratio of 80-20.
It is preferably formed from a polymer composition containing 70:70 to 30 by weight, and 35:65 to 65: 3.
More preferably, it is formed from a polymer composition containing at a weight ratio of 5. In the polymer composition constituting the polymer layer (B), the content of the thermoplastic polyurethane is less than 20% by weight based on the total weight of the thermoplastic polyurethane and the block copolymer and / or a hydrogenated product thereof. When the content of the block copolymer and / or its hydrogenated product exceeds 80% by weight, the polymer layer (B)
And the adhesiveness of the polymer layer (C) decreases. On the other hand, the content of the thermoplastic polyurethane exceeds 80% by weight (the content of the block copolymer and / or its hydrogenated product is 20%).
% By weight), the adhesiveness between the polymer layer (B) and the polymer layer (A) decreases, and in any case, the polymer layer (B) and the polymer layer (A) overlap with each other. The united layer (C) is not well bonded, and a laminated structure having excellent bonding strength cannot be obtained.

Further, the polymer composition containing the thermoplastic polyurethane forming the polymer layer (B) and the aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof is used as the polymer layer (B). ), Heat stabilizer, light stabilizer, antioxidant, dye / pigment, antistatic agent, filler, colorant, flame retardant, ultraviolet absorber, plasticizer, water 1 of additives such as decomposition inhibitors
Species or two or more species may be contained.

The polymer layer (A) in the laminated structure of the present invention mainly comprises at least one of an olefin polymer and a styrene polymer.
Examples of the olefin polymer in this case include homopolymers of olefins such as ethylene, propylene and butylene, olefin copolymers composed of two or more of the above-mentioned olefins, and one or more of the above-mentioned olefins and other And a copolymer with one or more vinyl monomers. Specific examples of the olefin polymer include low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, polybutylene, ethylene-vinyl acetate copolymer (preferably having a vinyl acetate content of 5 to 30% by weight), ethylene- Acrylic acid copolymer (preferably having an acrylic acid content of 5 to 30% by weight),
Examples thereof include an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, and an ethylene-butylene copolymer. The polymer layer (A) can be formed from one or more of the above-mentioned olefin homopolymer and olefin copolymer.

As the styrene-based polymer constituting the polymer layer (A), a polymer containing a structural unit derived from a styrene-based monomer in an amount of 10% by weight or more is preferably used. Is more preferably used. In this case, the styrene monomer includes styrene, α-methylstyrene, p-methylstyrene, pt
-Butylstyrene, 3,4-dimethylstyrene and the like. The styrene-based polymer has a structural unit derived from one or more of the above-mentioned styrene-based monomers.

The styrenic polymer constituting the polymer layer (A) may be, together with the structural unit derived from the above-mentioned styrenic monomer, 90% by weight or less, preferably 50% by weight or less, if it is other vinyl type. It may have a structural unit derived from a monomer. In this case, other vinyl monomers include, for example, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; and methyl, ethyl, propyl, n-butyl and i-butyl of acrylic acid or methacrylic acid.
C1-C18 alkyl esters such as hexyl, 2-ethylhexyl, dodecyl and octadecyl; diol esters of acrylic acid or methacrylic acid such as ethylene glycol, propylene glycol and butanediol; C1-C6 such as acetic acid and propionic acid Vinyl esters of carboxylic acids; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid; anhydrides of unsaturated dicarboxylic acids such as maleic anhydride; (meth) such as acrylamide, methacrylamide, and N, N-dimethylacrylamide. A) acrylamides; N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; and conjugated dienes such as butadiene and isoprene. Styrene polymer can have a structural unit derived from one or more of these vinyl monomers. Among them, when the styrene-based polymer is a copolymer of a styrene-based monomer and another vinyl-based monomer, the styrene-based monomer, acrylonitrile, methyl methacrylate, butyl acrylate, N-
A copolymer with one or more of phenylmaleimide, maleic anhydride and butadiene is preferred from the viewpoint of mechanical properties and the like.

The styrenic polymer constituting the polymer layer (A) may be a styrenic polymer containing a rubbery polymer. In that case, the rubbery polymer preferably has a glass transition temperature of 0 ° C or lower, more preferably -20 ° C or lower. As such a rubbery polymer,
Examples thereof include polybutadiene, styrene-butadiene copolymer, styrene-butadiene copolymer containing lower alkyl (meth) acrylate in an amount of 30% by weight or less, polyisoprene, and polychloroprene.

Another rubbery polymer that may be contained in the styrenic polymer constituting the polymer layer (A) is an acrylic rubber. In this case, the acrylic rubber has a carbon number of acrylic acid. Preference is given to alkyl acrylate rubbers based on 1 to 8 alkyl esters, in particular ethyl acrylate, butyl acrylate and / or ethylhexyl acrylate. The alkyl acrylate rubber may have structural units derived from other monomers such as vinyl acetate, methyl methacrylate, styrene, acrylonitrile, and vinyl ether in an amount of 30% by weight or less in some cases. Further, in some cases, it may have a structural unit derived from a crosslinkable unsaturated monomer such as alkylene diol (meth) acrylate, divinylbenzene, triallyl cyanurate at a ratio of 5% by weight or less. The alkyl acrylate rubber has a core of a crosslinked diene rubber obtained by cross-linking polybutadiene, butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, etc., and the alkyl acrylate rubber is present in a sheath shape around the core. Core-sheath type rubber.

The rubbery polymer which may be contained in the styrenic polymer constituting the polymer layer (A) is, in addition to the above,
For example, ethylene-propylene-non-conjugated diene copolymer rubber such as ethylene-propylene-ethylidene norbornene copolymer and the like, hydrogenated block copolymer composed of styrene-based polymer block-butadiene-based polymer block, styrene Examples include a hydrogenated product of a block copolymer composed of a system-based polymer block and an isoprene-based polymer block.

The rubbery polymer which may be contained in the styrene-based polymer constituting the polymer layer (A) includes the above-mentioned rubbery polymers and styrene-based monomers and other various types. Examples include a graft copolymer obtained by graft-polymerizing an unsaturated monomer.

When the styrenic polymer constituting the polymer layer (A) contains a rubbery polymer, among the various rubbery polymers described above, polybutadiene and styrene-butadiene copolymer And a styrene-based polymer containing one or more of polybutyl acrylate-based rubber and ethylene-propylene-non-conjugated diene copolymer.

In some cases, the polymer layer (A)
May be composed of a polymer composition containing one or more of the above-mentioned olefin-based polymers and one or more of the above-mentioned styrene-based polymers.

The polymer layer (A) may contain, if necessary, a heat stabilizer, a light stabilizer, an antioxidant, a dye, a pigment, a lubricant, an antistatic agent, as long as it does not hinder its original properties. One or more additives such as a release agent, a filler, a colorant, a flame retardant, and an ultraviolet absorber may be contained.

The polymer layer (C) in the laminated structure of the present invention comprises a saponified ethylene-vinyl acetate copolymer, a vinylidene chloride polymer, a vinyl chloride polymer, a polyamide, a polyester, a polycarbonate and an acrylic resin. It is mainly composed of at least one of the polymers. As the saponified ethylene-vinyl acetate copolymer in this case, those having 20 to 60 mol%, preferably 25 to 60 mol% of ethylene and a saponification degree of 95% or more are preferably used. The saponified ethylene-vinyl acetate copolymer has a melt index of 0.1 to 25 g / measured in accordance with ASTM D-1238-65T.
It is preferably 10 minutes (measured at 190 ° C. under a load of 2160 g) from the viewpoint of moldability, and 0.3 to 20 g / 10
More preferably, it is minutes.

As the vinylidene chloride polymer used in the polymer layer (C), a thermoplastic polymer having a structural unit derived from vinylidene chloride in a proportion of 50% by weight or more is preferably used. A thermoplastic polymer having a ratio of 70 to 98% by weight is more preferably used. When the vinylidene chloride-based polymer is a copolymer of vinylidene chloride and other monomers, vinylidene chloride and other unsaturated monomers such as vinyl chloride, acrylonitrile, acrylates and acrylic acid are used. A copolymer with one or more kinds is preferably used. The degree of polymerization of the vinylidene chloride-based polymer is not particularly limited, but generally those having a degree of polymerization of 100 to 10,000 are preferably used, and those having a degree of polymerization of 400 to 5,000 are more preferably used.

The vinyl chloride polymer used in the polymer layer (C) includes a vinyl chloride homopolymer,
One or two or more copolymers of vinyl chloride having a structural unit derived from vinyl chloride in an amount of 70% by weight or more and other copolymerizable monomers and chlorinated products thereof are preferably used. When the vinyl chloride polymer is a vinyl chloride copolymer, one or two of vinyl chloride and a copolymerizable monomer such as ethylene, propylene, vinyl acetate, vinyl bromide, vinylidene chloride, acrylonitrile, and maleimide are used. More than one type of copolymer is preferably used. The degree of polymerization of the vinyl chloride polymer is not particularly limited, but generally,
Those having a polymerization degree of 100 to 10,000 are preferably used, and those having a polymerization degree of 400 to 5,000 are more preferably used.

As the polyamide used in the polymer layer (C), an amide bond (—CO—N
H-) is not particularly limited as long as it can be heated and melted. Examples of the polyamide that can be used in the present invention include a polyamide (polylactam) obtained by ring-opening polymerization of a lactam having three or more members, a polyamide obtained by polycondensation of an ω-amino acid, and a polycondensation of a dibasic acid and a diamine. And one or more of these polyamides can be used.

In this case, specific examples of the above-mentioned lactam which is a raw material of polyamide include ε-caprolactam,
Enatlactam, caprylactam, lauryllactam, α-pyrrolidone and the like can be mentioned. Also,
Specific examples of the above-mentioned ω-amino acid which is a raw material of polyamide include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and the like.

Specific examples of the above-mentioned dibasic acids which are raw materials for polyamide include malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, Aliphatic dicarboxylic acids such as adipic acid, sebacic acid and suberic acid; 1,3-
Alicyclic dicarboxylic acids such as cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid;
2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid,
1,3-phenylenedioxydiacetic acid, diphenic acid, 4,
4'-oxydibenzoic acid, diphenylmethane-4,4 '
-Dicarboxylic acid, aromatic dicarboxylic acids such as diphenylsulfone-4,4'-dicarboxylic acid and 4,4'-diphenyldicarboxylic acid.

Specific examples of the above-mentioned diamines which are raw materials for polyamide include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, and 1,9-nonanediamine. 1,1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,2
4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-
Aliphatic diamines such as nonanediamine; cycloaliphatic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine; p-phenylenediamine, m-phenylenediamine, xylylenediamine, xylenediamine, 4,4′-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfone, 4,4 '
And aromatic diamines such as diaminodiphenyl ether.

The polyester used in the polymer layer (C) has an ester bond in the polymer main chain,
There is no particular limitation as long as it can be heated and melted. Examples of the polyester that can be used in the present invention include a polyester obtained by reacting a dicarboxylic acid component and a diol component, a polyester (polylactone) obtained by ring-opening polymerization of a lactone, a polycondensation of a hydroxycarboxylic acid or an ester-forming derivative thereof. And the like. One or more of these polyesters can be used. Among them, in the present invention, a polyester substantially formed from a dicarboxylic acid component and a diol component is preferably used.

In this case, specific examples of the above-mentioned dicarboxylic acid component which is a raw material of polyester include terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid and sodium 5-sulfoisophthalate; aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, dodecanedioic acid; cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acids; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid;
Halogen-containing dicarboxylic acids such as tetrabromophthalic acid; and ester-forming derivatives thereof.

Specific examples of the above-mentioned diol component which is a raw material of polyester include ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
5-pentanediol, neopentyl glycol, 1,
6-hexanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonnadiol,
Aliphatic diols such as 1,10-decanediol, 3-methyl-1,5-pentanediol and 2-methyl-1,8-octanediol; cyclohexanedimethanol;
Alicyclic diols such as cyclohexanediol; diethylene glycol, polyethylene glycol, poly-1,
Examples thereof include diols derived from polyalkylene glycols having a molecular weight of 6000 or less, such as 3-propylene glycol and polytetramethylene glycol.

The polyester may be, if necessary, one or two structural units derived from trifunctional or higher functional compounds such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid and pyromellitic acid. Any of the above may be provided as long as the amount is small.

Examples of the polycarbonate used in the polymer layer (C) include a polycarbonate obtained by reacting a substantial dihydroxy compound with phosgene, carbonic acid diester or halogen formate. In this case, as the dihydroxy compound as a raw material, for example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as “bisphenol A”), tetramethylbisphenol A, tetrabromobisphenol A, bis ( 4-hydroxyphenyl)-
Examples thereof include aromatic dihydroxy compounds such as p-diisopropylbenzene, hydroquinone, resorcinol, and 4,4′-dihydroxyphenyl. Among these, bisphenol A is preferable. In addition, polycarbonate is optionally used as 4,6-dimethyl-2,4,4.
6-tri (4-hydroxyphenyl) heptene-2,
4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ) One or more structural units derived from a tri- or higher-functional polyhydroxy compound such as ethane may be present in a small amount.

The acrylic polymer used in the polymer layer (C) may be an acrylic polymer mainly composed of structural units derived from a (meth) acrylate. In that case, the proportion of the structural unit derived from the (meth) acrylate in the acrylic polymer is preferably 50% by weight or more, more preferably 80% by weight or more. Examples of the (meth) acrylate constituting the acrylic polymer include, for example, methyl (meth) acrylate and (meth) acrylate.
Alkyl esters of (meth) acrylic acid such as ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like, It may have a structural unit derived from one or more of (meth) acrylic esters. In addition, the acrylic polymer may include one or more structural units derived from an unsaturated monomer other than the (meth) acrylic acid ester, if necessary.
It may have one or more species. For example, the methacrylic resin may have a structural unit derived from a vinyl cyanide monomer such as (meth) acrylonitrile in a proportion of preferably 50% by weight or less, and styrene, o-methylstyrene. Having a structural unit derived from an aromatic vinyl compound such as m-methylstyrene, p-methylstyrene, o-chlorostyrene, m-chlorostyrene and p-chlorostyrene, preferably in a proportion of 10% by weight or less. May be.

The polymer layer (C) is composed of the above-mentioned saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer,
It may consist of only one kind of vinyl chloride polymer, polyamide, polyester, polycarbonate and acrylic polymer, or may consist of a mixture of two or more kinds, and consist of a mixture of two or more kinds. In this case, the mixing ratio of each polymer is not particularly limited.

Further, the polymer layer (C) is composed of the polymer layer (C)
If necessary, a heat stabilizer (for example, metal soap, phosphorus compound, sulfur compound, phenolic compound, L-ascorbic acid, epoxy compound, etc.), a plasticizer (for example, aliphatic dibasic acid) Ester, hydroxy polycarboxylic acid ester, fatty acid ester, polyester compound, phosphate ester, etc.), impact modifier (for example, MBS resin, ABS resin, ethylene-vinyl acetate copolymer, etc.), inorganic fine powder, organic One or more of lubricants, dispersants, dyes and pigments, antistatic agents, antioxidants and the like may be contained.

In the laminated structure of the present invention, the thickness of each layer is not particularly limited, and may be adjusted according to the type of polymer constituting each layer, the total number of layers in the laminated structure, the use of the laminated structure, and the like. In general, the thickness of the polymer layer (A) is 10
μm to 5 mm, thickness of the polymer layer (B) is 1 μm to 1 m
m, the thickness of the polymer layer (C) is preferably set to 10 μm to 5 mm in view of easiness of production of the laminated structure, interlayer adhesive strength, and the like.

Further, the total number of layers in the laminated structure of the present invention is not particularly limited, and a structure in which polymer layers (A) / polymer layers (B) / polymer layers (C) are laminated in this order. Any structure may be used as long as the structure has at least a part thereof. Further, the laminated structure of the present invention comprises a polymer layer (A),
Even if it is formed only of the three layers of the polymer layer (B) and the polymer layer (C), or a layer made of another material together with the three layers (for example, other polymers, paper, fabric, metal,
(A layer made of ceramic, wood, or the like).

Although there is no particular limitation, examples of the laminated structure of the present invention include a three-layer structure comprising a polymer layer (A) / polymer layer (B) / polymer layer (C); (Four-layer structure consisting of (paper, cloth or metal) / polymer layer (A) / polymer layer (B) / polymer layer (C); polymer layer (A) / polymer layer (B) / weight Five-layer structure consisting of a coalescence layer (C) / polymer layer (B) / polymer layer (A); polymer layer (C) / polymer layer (B) / polymer layer (A) / polymer layer (B) / 5-layer structure composed of polymer layer (C); (paper, cloth or metal)
/ Polymer layer (A) / polymer layer (B) / polymer layer (C) /
Seven-layer structure composed of polymer layer (B) / polymer layer (A) / (paper, fabric or metal); (paper, fabric or metal) / polymer layer (C) / polymer layer (B) / Polymer layer (A) / polymer layer (B) / polymer layer (C) / (paper, cloth or metal)
And the like. And, in one laminated structure, two or more polymer layers (A)
Is present, the two or more polymer layers (A)
As long as the polymer specified in the present invention is used, the polymer may be composed of the same polymer or different polymers, which means that the laminated structure has two or more polymer layers. The same applies to the case having (B) and / or two or more polymer layers (C).

The method for producing the laminated structure of the present invention includes: (i) a polymer for the polymer layer (A), a polymer for the polymer layer (B), and a polymer for the polymer layer (C). A method of producing a laminated structure by melt-coextrusion molding them and laminating them at the same time as extrusion molding of the respective layers; (ii) a film, a sheet constituting the polymer layer (A),
A plate or the like is manufactured in advance, and / or a molded product such as a film, a sheet, and a plate constituting the polymer layer (C) is manufactured in advance, and the polymer layer (B) is melt-extruded. If one of the polymer layer (A) and the polymer layer (C) is not preformed, the molded product for the polymer layer (A) that has been manufactured in advance is also melt extruded. And / or a method of producing a laminated structure by laminating and integrating with a molded article for the polymer layer (C); (iii) a molded article such as a film, a sheet, and a plate constituting the polymer layer (A). And a molded product such as a film, a sheet, and a plate constituting the polymer layer (C) is manufactured in advance, and the polymer for the polymer layer (B) is also preliminarily formed into a film or a sheet. The film or sheet for the polymer layer (B) is combined with the molded article for the polymer layer (A). The film or sheet for the polymer layer (B) is melted under heating while being sandwiched between the molded product for the united layer (C) and the polymer layer (A) and the polymer layer (C) are melted. A method of producing a laminated structure by bonding and integrating through (B); and the like.

In any of the above-mentioned methods (i) to (iii), the polymer layer (A) and the polymer layer (C) are bonded via the molten polymer layer (B). Since the adhesive layer does not contain an organic solvent, the intended laminated structure can be obtained without causing problems or trouble such as destruction of the natural environment by the organic solvent, deterioration of the working environment, and recovery of the solvent. . Among them, the method of co-extrusion molding of the above (i) requires only a small number of steps and has high productivity, and furthermore, the method among the polymer layers (A), (B) and (C) This is most preferable because a laminated structure having high adhesive strength and no delamination can be obtained.

When the laminated structure of the present invention is manufactured by a co-extrusion molding method, for example, three or more extruders are connected to one die in accordance with the number of layers of the laminated structure, and a plurality of extruders are formed. The union can be manufactured by laminating and integrating inside or outside the die. As the die in that case, a T die, an annular die, or the like can be used, and the shape and structure of the extruder and the die are not particularly limited.

In the present invention, instead of producing a laminated structure, the above-mentioned polymer composition for the polymer layer (B) used for producing the laminated structure, that is, a thermoplastic polyurethane, and an aromatic vinyl compound Copolymer containing at least one of a block copolymer composed of a base polymer block and a conjugated diene polymer block and a hydrogenated product of the block copolymer in a weight ratio of 20 to 80:80 to 20 Is stored as it is as a hot-melt adhesive, distributed, sold, and when necessary, using the hot-melt adhesive to manufacture the laminated structure of the present invention, and in some cases other laminated structures. Therefore, the present invention includes the hot melt adhesive in the scope of the present invention.

The laminated structure of the present invention can be used for various purposes depending on the properties of the polymer layer (A), the polymer layer (B) and the polymer layer (C) constituting the laminated structure. For example, packaging materials for foods and medical agents that dislike oxygen; packaging materials for clothing; packaging materials for other products; building materials such as wallpaper and decorative boards; Substrates for use; marking films; agricultural films; miscellaneous goods such as tablecloths, raincoats, umbrellas, curtains, covers, etc .;

[0064]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples. In the following Examples and Comparative Examples,
The evaluation of the film forming property and the measurement of the adhesive strength of the obtained laminated structure were performed as follows.

[Film Formability] (1) In the following examples, the outermost layer (50 μm) / adhesive layer (10 μm) / intermediate layer (50 μm) / adhesive layer (10 μm)
m) / outermost layer (50 μm) to form a five-layer laminated structure, and the surface smoothness was visually observed. In addition, the thickness of the laminated structure was measured at 10 locations along a length direction thereof at an interval of 2 m using calipers, and the difference between the maximum thickness and the minimum thickness at that time was determined. (2) Outer layer (50 μm) / adhesive layer (2-3 μm) in the same manner except that the thickness of the two adhesive layers was changed to 2-3 μm.
m) / intermediate layer (50 μm) / adhesive layer (2-3 μm) / outermost layer (50 μm) to form a five-layer laminated structure,
The surface smoothness was observed with the naked eye, and the thickness of the laminated structure was measured at 10 locations along the length direction at intervals of 2 m, and the difference between the maximum thickness and the minimum thickness at that time was determined. (3) Based on the results obtained in the above (1) and (2), the film forming properties were evaluated according to the evaluation criteria shown in Table 1 below.

[0066]

[Table 1] [Evaluation criteria for film-forming properties] ：: In both cases (1) and (2), the surface of the laminated structure was smooth, no irregularities or curvatures occurred, and the maximum thickness and the minimum thickness of the laminated structure of (1) above. The difference in thickness is less than 5 μm and the difference between the maximum thickness and the minimum thickness in the laminated structure of (2) is less than 5 μm, and the film-forming properties are extremely good. ：: In each of the above cases (1) and (2), the surface of the laminated structure was almost smooth, there was no unevenness or curvature, and the maximum thickness and the minimum thickness of the laminated structure of the above (1) were small. Is 5 μm or more and less than 10 μm, and the difference between the maximum thickness and the minimum thickness in the laminated structure of (2) is 5 μm or more and less than 12 μm, and the film forming property is almost good. ×: In any of the above cases (1) and (2), whether the surface of the laminated structure is not smooth and has irregularities or curves, or the maximum thickness and the minimum thickness of the laminated structure of the above (1) The difference is 10 μm or more, and / or the difference between the maximum thickness and the minimum thickness of the laminated structure of (2) is 12 μm or more, resulting in poor film-forming properties.

[Adhesive Strength] The outermost layer (50 μm) / adhesive layer (10 μm) / intermediate layer (50 μm) manufactured in the following example
m) / adhesive layer (10 μm) / outermost layer (50 μm) of a five-layer laminated structure of 1 cm (in the width direction of the laminated structure)
Cut out to 10 cm (length direction of the laminated structure), cut out from the outermost layer with a cutter knife, and peel off the interface between the outermost layer and the adhesive layer, and the interface between the adhesive layer and the intermediate layer, manufactured by Shimadzu Corporation JIS K
A 180 degree peel test was performed according to 6854. However,
In the case where the adhesive strength at the interface is very high and it is difficult to peel out by human power, a 180 ° peel test could not be performed.

The thermoplastic polyurethane, polyethylene, polypropylene, and the like used in the following Examples and / or Comparative Examples
Contents of polystyrene, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, vinylidene chloride-based polymer, nylon 6, polymethyl methacrylate, polyethylene terephthalate, polycarbonate, hydrogenated aromatic vinyl compound / conjugated diene block copolymer , And abbreviations are shown below.

○ Thermoplastic polyurethane-1 (PU) :
Polyester polyol having a hydroxyl group at both terminals (number average molecular weight: 3500), 4,4′-diphenylmethane diisocyanate and 1,4-butanediol produced by reacting 3-methyl-1,5-pentanediol with adipic acid Thermoplastic polyurethane obtained by reacting at a molar ratio of 1: 7: 6 (logarithmic viscosity: 1.22).

○ Thermoplastic polyurethane-2 (PU) :
A polyester polyol having a hydroxyl group at both terminals (number average molecular weight of 2,000), 4,4′-diphenylmethane diisocyanate and 1,4-butanediol prepared by reacting 1,4-butanediol and adipic acid in a ratio of 1: 6: Thermoplastic polyurethane obtained by reacting at a molar ratio of 5 (logarithmic viscosity 1.15).

○ Thermoplastic polyurethane-3 (PU) :
A polyester polyol having a hydroxyl group at both terminals (number average molecular weight of 2,000) produced by reacting 1,4-butanediol with adipic acid, 4,4′-diphenylmethane diisocyanate and 1,4-butanediol in a ratio of 1: 8: A thermoplastic polyurethane obtained by reacting at a molar ratio of 7 (logarithmic viscosity 1.21).

PE : Polyethylene ("Mirason NEO23H" manufactured by Mitsui Petrochemical Industries, Ltd.) PP : Polypropylene ("Mitsubishi Polypro EX6" manufactured by Mitsubishi Chemical Corporation) PS : Polystyrene (Sumiprite M192 manufactured by Sumitomo Chemical Co., Ltd.) )

EVEV : Ethylene-vinyl acetate copolymer [“EVAL ES-F101” manufactured by Kuraray Co., Ltd.] PVC : polyvinyl chloride (“Shin-Etsu PVCCK-500” manufactured by Shin-Etsu Chemical Co., Ltd.) ○ PVDC : chloride Vinylidene-based polymer (in a copolymer of 82% by weight of vinylidene chloride and 18% by weight of vinyl chloride,
1.7 parts by weight of dibutyl sebacate as a plasticizer and 1.0 part by weight of epoxidized soybean oil are contained per 100 parts by weight of the copolymer.

○ NY-6 : Nylon 6 (“UBE Nylon 1013B” manufactured by Ube Industries, Ltd.) ○ PMMA : Polymethyl methacrylate (“Parapet EB” manufactured by Kuraray Co., Ltd.) ○ PET : Polyethylene terephthalate (Kuraray “Kurapet Co., Ltd.”) KS760K ”) PC : Polycarbonate (“ Panlite L-1225 ”manufactured by Teijin Chemicals Limited)

Hydrogenated SBIS-OH (1) : a hydrogenated polystyrene block having a hydroxyl group at a terminal / 1/3
-Triblock copolymer consisting of butadiene and isoprene copolymer block / polystyrene block: [Content: number average molecular weight of two polystyrene blocks =
6000, number average molecular weight of 1,3-block and isoprene copolymer block = 28,000, number average molecular weight of triblock copolymer = 40000; hydroxyl group bonded to terminal of one polystyrene block; average in triblock copolymer Hydroxyl content = 0.7 / molecule; 1,3 in 1,3-butadiene and isoprene copolymer block
-Molar ratio of butadiene units to isoprene units = 1/1;
Unsaturation in 1,3-butadiene / isoprene copolymer block = 5% (95% hydrogenation); Styrene unit content in triblock copolymer before hydrogenation = 30
%, 1,4-butadiene units in the 1,3-butadiene-isoprene copolymer block before hydrogenation = 95%, 1,2-bond amounts = 5%, 1,2-butadiene units = 5%, in isoprene units 1,4-bond amount = 95%, 3,4-
Binding amount = 5%]

Hydrogenated SBIS-OH (2) : a hydrogenated polystyrene block having a hydroxyl group at a terminal / 1/3
-Triblock copolymer consisting of butadiene and isoprene copolymer block / polystyrene block: [Content: number average molecular weight of two polystyrene blocks =
137000, number average molecular weight of 1,3-block and isoprene copolymer block = 146000, number average molecular weight of triblock copolymer = 42000; hydroxyl group bonded to terminal of one polystyrene block; average in triblock copolymer Hydroxyl group content = 0.7 / molecule; 1,
The molar ratio of 1,3-butadiene units to isoprene units in the 3-butadiene / isoprene copolymer block = 1
/ 1; degree of unsaturation in 1,3-butadiene / isoprene copolymer block = 5% (hydrogenation rate: 95%); styrene unit content in triblock copolymer before hydrogenation = 65% by weight, hydrogenation 1,4-bond amount = 95%, 1,2-bond amount = 5 in 1,3-butadiene unit in the previous 1,3-butadiene / isoprene copolymer block
%, 1,4-bond amount in isoprene unit = 95%,
3,4-bond amount = 5%]

Hydrogenated SIS-OH (1) : a triblock copolymer comprising a hydrogenated polystyrene block / polyisoprene block / polystyrene block having a hydroxyl group at a terminal; (contents: number average molecular weight of two polystyrene blocks) =
6000, number average molecular weight of polyisoprene block = 2
8000, number average molecular weight of triblock copolymer = 40
000; hydroxyl group bonded to one end of polystyrene block; average hydroxyl group content in triblock copolymer = 0.7 / molecule; unsaturation degree in polyisoprene block = 15%; triblock copolymer before hydrogenation Styrene unit content in the coalescence = 30% by weight, 1,4-bond content in the polyisoprene block before hydrogenation = 45
%, 3,4-bond amount = 55%)

Hydrogenated SIS-OH (2) : triblock copolymer consisting of hydrogenated polystyrene block / polyisoprene block / polystyrene block having a hydroxyl group at the terminal; (contents: number average molecular weight of two polystyrene blocks) =
9000, number average molecular weight of polyisoprene block = 4
2000, number average molecular weight of triblock copolymer = 60
000; hydroxyl group bonded to the end of one polystyrene block; average hydroxyl group content in triblock copolymer = 0.72 / molecule; degree of unsaturation in polyisoprene block = 15%; triblock copolymer before hydrogenation Styrene unit content in the coalesced = 30% by weight, 1,4-bond content in the polyisoprene block before hydrogenation = 4
(5%, 3,4-bond amount = 55%)

Example 1 [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b1) / PVDC / Polymer Composition (b1) / PP] (1) Preliminarily dried 100 parts by weight of PU and 100 parts by weight of hydrogenated SBIS-OH (1) were preliminarily mixed, melt-kneaded at a temperature of 220 ° C. using a twin-screw extruder, and then extruded in a strand form and cut to produce pellets. The pellets were heated and aged in a vacuum dryer at 80 ° C. for 6 hours,
A polymer composition of PU and hydrogenated SBIS-OH (1) was obtained [referred to as "polymer composition (b1)"]. (2) PP is applied to each extruder by using an extruder in which three extruders are connected to one die.
Supplying the polymer composition (b1) and PVDC obtained in
The maximum temperature at the time of extrusion was set such that PP was 240 ° C., polymer composition (b1) was 220 ° C., and PDVC was 200 ° C., and PP (50 μm) was passed through a die of an extrusion molding apparatus.
/ Polymer composition (b1) (10 μm) / PVDC (50
μm) / polymer composition (b1) (10 μm) / PP (5
0 μm), and co-extrusion was performed so as to form a five-layer structure, a PP layer on both surfaces and a PVDC layer in the middle, and a polymer composition (b1) between the PP layer and the intermediate layer A laminated structure consisting of five layers with each layer interposed was produced. (3) A laminated structure consisting of five layers was prepared in the same manner as in (2) except that the thickness of the two polymer composition (b1) layers interposed between the PP layer and the PVDC layer was 2 μm. Manufactured. (4) When the film-forming properties of the multilayer structure obtained in (2) and the multilayer structure obtained in (3) were evaluated by the above-described method, it was very good (（). . When the adhesive strength between the layers of the laminated structure obtained in the above (2) was measured by the above method, the adhesion between the PP layer on both surfaces and the polymer composition (b1) layer inside the PP layer was extremely high. The adhesive was so strong that it could not be peeled off, so that the adhesive strength was not measured. The adhesive strength between the polymer composition (b1) and the intermediate PVDC layer in the laminated structure obtained in the above (2) was 830 g / cm, which was a high value.

Example 2 [Production of Laminated Structure Consisting of Five Layers of PE / Polymer Composition (b2) / PVDC / Polymer Composition (b2) / PE] (1) Preliminarily dried 100 parts by weight of PU and 100 parts by weight of hydrogenated SIS-OH (1) were premixed, melt-kneaded at a temperature of 220 ° C. using a twin-screw extruder, and then extruded in a strand form and cut to produce pellets. The pellets were heated and aged for 6 hours in a vacuum dryer at 80 ° C.
A polymer composition of U and hydrogenated SIS-OH (1) was obtained [referred to as "polymer composition (b2)"]. (2) Using the same extruder as used in Example 1, PE, the polymer composition (b2) obtained in (1) above, and PVDC were supplied to each extruder and extruded. The highest temperature was set such that PE was 235 ° C, polymer composition (b2) was 220 ° C, and PDVC was 200 ° C.
A five-layer structure in which PE (50 μm) / polymer composition (b2) (10 μm) / PVDC (50 μm) / polymer composition (b2) (10 μm) / PE (50 μm) are laminated in this order from the die of the extrusion molding apparatus. Coextrusion molding is performed so that both surfaces are a PE layer and an intermediate layer is a PVDC layer.
A laminated structure composed of five layers in which the polymer composition (b2) layer was interposed between the E layer and the intermediate layer was manufactured. (3) A laminated structure consisting of five layers was prepared in the same manner as in the above (2) except that the thickness of the two polymer composition (b2) layers interposed between the PE layer and the PVDC layer was changed to 3 μm. Manufactured. (4) When the film-forming properties of the multilayer structure obtained in (2) and the multilayer structure obtained in (3) were evaluated by the above-described method, it was very good (（). . When the adhesive strength between the layers of the laminated structure obtained in the above (2) was measured by the method described above, the PE on both surfaces was measured.
The adhesive strength between the layer and the polymer composition (b2) layer inside the layer was 750 g / cm, indicating a high value. Further, in the laminated structure obtained in the above (2), the polymer composition (b)
2) The adhesion between the layer and the intermediate PVDC layer was very strong and could not be peeled off, so no measurement of the adhesion strength was made.

Example 3 [Production of a Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b1) / EVOH / Polymer Composition (b1) / PP] (1) Used in Example 1 PP, the polymer composition (b1) obtained in (1) of Example 1 and EVOH are supplied to each extruder using the same extrusion molding apparatus as described above, and the maximum temperature at the time of extrusion is set to 240. ° C, the polymer composition (b1) was set to 220 ° C, and the EVOH was set to 210 ° C.
/ Polymer composition (b1) (10 μm) / EVOH (50
μm) / polymer composition (b1) (10 μm) / PP (5
0 μm) and co-extrusion was performed so as to form a five-layer structure. Both surfaces were a PP layer, an intermediate layer was an EVOH layer, and a polymer composition (b1 )
A laminated structure consisting of five layers with each layer interposed was produced. (2) A laminated structure consisting of five layers was prepared in the same manner as (1) except that the thickness of the two polymer composition (b1) layers interposed between the PP layer and the EVOH layer was changed to 2 μm. Manufactured. (3) With respect to the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2), the film forming property was evaluated by the above-mentioned method, and was very good (（). . When the adhesive strength between the layers of the laminated structure obtained in the above (1) was measured by the above-described method, the adhesion between the PP layer on both surfaces and the polymer composition (b1) layer inside the PP layer was found. It was extremely strong and could not be peeled off, so that the measurement of the adhesive strength was not performed. In the laminated structure obtained in the above (1), the adhesive strength between the polymer composition (b1) layer and the intermediate EVOH layer was 920 g / cm, which was an extremely high value.

Example 4 [Production of a Laminated Structure Consisting of Five Layers of PE / Polymer Composition (b2) / EVOH / Polymer Composition (b2) / PE] (1) Used in Example 1 PE, the polymer composition (b2) obtained in (1) of Example 2 and EVOH were supplied to each extruder by using the same extrusion molding apparatus as described above, and the maximum temperature at the time of extrusion was 235. ° C, the polymer composition (b2) was set to 220 ° C, and the EVOH was set to 210 ° C.
/ Polymer composition (b2) (10 μm) / EVOH (50
μm) / polymer composition (b2) (10 μm) / PE (5
0 μm) and co-extrusion was performed so as to form a five-layer structure. Both surfaces were a PE layer, an intermediate layer was an EVOH layer, and a polymer composition (b2) was interposed between the PE layer and the intermediate layer. )
A laminated structure consisting of five layers with each layer interposed was produced. (2) A laminated structure consisting of five layers was prepared in the same manner as in the above (1) except that the thickness of the two polymer composition (b2) layers interposed between the PE layer and the EVOH layer was changed to 2 μm. Manufactured. (3) With respect to the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2), the film forming property was evaluated by the above-mentioned method, and was very good (（). . When the adhesive strength between the layers of the laminated structure obtained in the above (1) was measured by the above method, the adhesive strength between the PE layer on both surfaces and the polymer composition (b2) layer inside the PE layer was measured. Was 750 g / cm, which was a high value. In the laminated structure obtained in the above (1), the polymer composition (b)
2) The adhesion between the layer and the intermediate EVOH layer was so strong that it could not be peeled off, so that no measurement of the adhesion strength was made.

Example 5 [Production of a Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b1) / PVC / Polymer Composition (b1) / PP] (1) Used in Example 1 The PP, the polymer composition (b1) obtained in (1) of Example 1 and PVC were supplied to each extruder by using the same extrusion molding apparatus as described above, and the maximum temperature at the time of extrusion was set to 240. ° C, the polymer composition (b
1) is set to 220 ° C. and PVC is set to 190 ° C., and PP (50 μm) / polymer composition (b1) (10 μm) / PVC (50 μm) /
Polymer composition (b1) (10 μm) / PP (50 μm)
Coextrusion molding is performed so as to form a five-layer structure in which layers are stacked in this order.
A laminated structure composed of five layers in which the polymer composition (b1) layer was interposed between the P layer and the intermediate layer was manufactured. (2) A laminated structure consisting of five layers was prepared in the same manner as in (1) except that the thickness of the two polymer composition (b1) layers interposed between the PP layer and the PVC layer was changed to 2 μm. Manufactured. (3) With respect to the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2), the film forming property was evaluated by the above-mentioned method, and was very good (（). . When the adhesion strength between the layers of the laminated structure obtained in the above (1) was measured by the above-mentioned method, it was found that between the PP layer on both surfaces and the polymer composition (b1) layer inside the PP layer, Further, the adhesion between the polymer composition (b1) layer and the intermediate PVC layer was extremely strong and could not be released, so that the measurement of the adhesion strength was not performed.

Example 6 Production of a Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b3) / NY-6 / Polymer Composition (b3) / PP [1] 100 parts by weight of the placed PU and 100 parts by weight of hydrogenated SIS-OH (2) were premixed, melt-kneaded at a temperature of 240 ° C. using a twin-screw extruder, and then extruded in a strand form and cut to produce pellets. . The pellets were heated and aged for 6 hours in a vacuum dryer at 80 ° C.
A polymer composition of U and hydrogenated SIS-OH (2) was obtained [referred to as "polymer composition (b3)"]. (2) Using the same extruder as used in Example 1, PP, the polymer composition (b3) obtained in (1) above, and PN-6 were supplied to each extruder, The maximum temperature at the time of extrusion was 240 ° C for PP, and the polymer composition (b
3) was set to 240 ° C. and NY-6 was set to 240 ° C., and PP (50 μm) / polymer composition (b3) (10 μm) / NY-6 (50 μm) was extruded from the die of the extrusion molding apparatus.
m) / polymer composition (b3) (10 μm) / PP (50
μm) and co-extrusion is performed so as to form a five-layer structure. Both surfaces are a PP layer, an intermediate layer is NY-6, and a polymer composition ( b3) A laminated structure composed of five layers each having a layer interposed was produced. (3) A laminated structure consisting of five layers in the same manner as in (2) above, except that the thickness of the two polymer composition (b3) layers interposed between the PP layer and the NY-6 layer was 2 μm. Body manufactured. (4) When the film-forming properties of the multilayer structure obtained in (2) and the multilayer structure obtained in (3) were evaluated by the above-described method, it was very good (（). . When the adhesive strength between the layers of the laminated structure obtained in the above (2) was measured by the method described above, the adhesion between the PP layer on both surfaces and the polymer composition (b3) layer inside the PP layer was found. It was extremely strong and could not be peeled off, so that the measurement of the adhesive strength was not performed. The polymer composition (b3) in the laminated structure obtained in the above (2) and the intermediate NY-6
The adhesive strength between the layers was 1400 g / cm, indicating a high value.

<< Example 7 >> [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b3) / PMMA / Polymer Composition (b3) / PP] (1) Used in Example 1 The PP, the polymer composition (b3) obtained in (1) of Example 6, and PMMA were supplied to each extruder using the same extrusion molding apparatus as described above. C., the polymer composition (b3) was set to 240.degree. C. and the PMMA was set to 250.degree.
/ Polymer composition (b3) (10 μm) / PMMA (50
μm) / Polymer composition (b3) (10 μm) / PP (5
0 μm), and co-extrusion was performed so as to form a five-layer structure. Both surfaces were a PP layer, an intermediate layer was a PMMA layer, and a polymer composition (b3) was interposed between the PP layer and the intermediate layer. )
A laminated structure consisting of five layers with each layer interposed was produced. (2) A laminated structure consisting of five layers was prepared in the same manner as in (1) except that the thickness of the two polymer composition (b3) layers interposed between the PP layer and the PMMA layer was changed to 2 μm. Manufactured. (3) With respect to the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2), the film forming property was evaluated by the above-mentioned method, and was very good (（). . Further, when the adhesive strength between the layers of the laminated structure obtained in the above (1) was measured by the above-mentioned method, it was found that the adhesive strength between the PP layer on both surfaces and the polymer composition (b3) layer inside the PP layer was measured. The adhesive strength was extremely strong and peeling was not possible, so that the adhesive strength was not measured. Further, in the laminate structure obtained in the above (1), the adhesive strength between the polymer composition (b3) layer and the intermediate PMMA layer was 810 g / cm, which was a high value.

Example 8 [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b4) / PET / Polymer Composition (b4) / PP] (1) Preliminarily dried 100 parts by weight of PU and 100 parts by weight of hydrogenated SIS-OH (2) were preliminarily mixed, melt-kneaded at a temperature of 250 ° C. using a twin-screw extruder, and then extruded in a strand form and cut to produce pellets. The pellets were heated and aged for 6 hours in a vacuum dryer at 80 ° C.
A polymer composition of U and hydrogenated SIS-OH (2) was obtained [referred to as "polymer composition (b4)"]. (2) Using the same extruder as used in Example 1, PP, the polymer composition (b4) obtained in (1) above, and PET were supplied to each extruder and extruded. The maximum temperature of PP is 240 ° C, polymer composition (b4)
Is set to 250 ° C. and PET to 270 ° C.
Five-layer structure in which PP (50 μm) / polymer composition (b4) (10 μm) / PET (50 μm) / polymer composition (b4) (10 μm) / PP (50 μm) are laminated in this order from the die of the extrusion molding apparatus. Coextrusion molding is performed so that both surfaces are a PP layer, an intermediate layer is a PET layer, and a polymer composition (b4) layer is interposed between the PP layer and the intermediate layer, respectively5. A laminated structure composed of layers was manufactured. (3) A laminated structure consisting of five layers was prepared in the same manner as in (2) except that the thickness of the two polymer composition (b4) layers interposed between the PP layer and the PET layer was set to 2 μm. Manufactured. (4) When the film-forming properties of the multilayer structure obtained in (2) and the multilayer structure obtained in (3) were evaluated by the above-described method, it was very good (（). . When the adhesive strength between the layers of the laminated structure obtained in the above (2) was measured by the above-mentioned method, the adhesion between the PP layer on both surfaces and the polymer composition (b4) layer inside the PP layer was found. It was extremely strong and could not be peeled off, so that the measurement of the adhesive strength was not performed. Further, the adhesive strength between the polymer composition (b4) and the intermediate PET layer in the laminated structure obtained in the above (2) was 1200 g / cm, which was a high value.

Example 9 Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b4) / PC / Polymer Composition (b3) / PP (1) Used in Example 1 PP, the polymer composition (b4) obtained in (1) of Example 8 and PC were supplied to each extruder using the same extrusion molding apparatus as described above, and the maximum temperature at the time of extrusion was set to 240. ° C, the polymer composition (b
4) is set to 240 ° C. and PC is set to 270 ° C., and the PP (50 μm) / polymer composition (b4) (10 μm) / PC (50 μm) / polymer composition is obtained from the die of the extrusion molding apparatus. (B4) Coextrusion molding is performed so as to form a five-layer structure in which (10 μm) / PP (50 μm) are laminated in this order. Both surfaces are a PP layer and an intermediate layer is a PC layer. A laminated structure composed of five layers with a polymer composition (b4) layer interposed therebetween was produced. (2) A laminated structure consisting of five layers was prepared in the same manner as in (1) except that the thickness of the two polymer composition (b4) layers interposed between the PP layer and the PC layer was set to 2 μm. Manufactured. (3) With respect to the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2), the film forming property was evaluated by the above-mentioned method, and was very good (（). . Further, when the adhesive strength between the layers of the laminated structure obtained in the above (1) was measured by the above-mentioned method, the adhesive strength between the PP layer on both surfaces and the polymer composition (b4) layer inside the PP layer was measured. The adhesive strength was extremely strong and peeling was not possible, so that the adhesive strength was not measured. In the laminated structure obtained in the above (1), the adhesive strength between the polymer composition (b4) layer and the intermediate PC layer is 870 g / cm,
It showed a high value.

Example 10 Production of Laminated Structure Consisting of Five Layers of PVC / Polymer Composition (b5) / PS / Polymer Composition (b5) / PVC (1) Preliminarily dried 100 parts by weight of PU and 100 parts by weight of hydrogenated SBIS-OH (2) were preliminarily mixed, melt-kneaded at a temperature of 220 ° C. using a twin-screw extruder, and then extruded in a strand form and cut to produce pellets. The pellets were heated and aged in a vacuum dryer at 80 ° C. for 6 hours,
A polymer composition of PU and hydrogenated SBIS-OH (2) was obtained [referred to as "polymer composition (b5)"]. (2) Using the same extruder as used in Example 1, PVC, the polymer composition (b5) obtained in (1) above, and PS were supplied to each extruder and extruded. The maximum temperature of PVC is 190 ° C, and the polymer composition (b
5) was set to 220 ° C. and PS was set to 240 ° C., and the PVC (50 μm) / polymer composition (b5) (10 μm) / PS (50 μm) /
Polymer composition (b5) (10 μm) / PVC (50 μm)
m), a co-extrusion molding was performed so as to form a five-layer structure, and both surfaces were a PVC layer, an intermediate layer was a PS layer, and a polymer composition (b5) was interposed between the PVC layer and the intermediate layer. ) A laminated structure composed of five layers, each layer being interposed, was produced. (3) A laminated structure consisting of five layers was prepared in the same manner as in the above (2) except that the thickness of the two polymer composition (b5) layers interposed between the PVC layer and the PS layer was changed to 2 μm. Manufactured. (4) When the film-forming properties of the multilayer structure obtained in (2) and the multilayer structure obtained in (3) were evaluated by the above-described method, it was very good (（). . When the adhesive strength between the layers of the laminated structure obtained in the above (2) was measured by the above method, the adhesive strength between the PVC layers on both surfaces and the polymer composition (b5) layer inside the PVC layers was measured. Was 820 g / cm, which was a high value. Further, the polymer composition (b) in the laminated structure obtained in the above (2)
The adhesion between 5) and the intermediate PS layer was extremely strong, and peeling was not possible. Therefore, the measurement of the adhesive strength was not performed.

<< Comparative Example 1 >> [Production of Laminated Structure Consisting of Five Layers of PE / PU / EVOH / PU / PE] (1) Using the same extrusion molding apparatus as used in Example 1, PE, PU and EVOH are supplied to the extruder, and the maximum temperature during extrusion is 235 ° C.
Are set to 220 ° C. and EVOH to 210 ° C., and PE (50 μm) / PU
(10 μm) / EVOH (50 μm) / PU (10
μm) / PE (50 μm) and co-extrusion is performed so as to form a five-layer structure. Both surfaces are a PE layer, an intermediate layer is an EVOH layer, and a PU is provided between the PE layer and the intermediate layer.
A laminated structure consisting of five layers with each layer interposed was produced. (2) The multilayer structure obtained in the above (1) was evaluated for the film forming property by the above-mentioned method, and was almost good (（). However, the PE layers on both surfaces of the multilayer structure and the 20 g / cm adhesive strength between the inner PU layer
However, the value was extremely low, and a practically usable laminated structure could not be obtained.

Comparative Example 2 [PE / hydrogenated SBIS-OH (1) / PVDC / hydrogenated SB
Production of Laminated Structure Consisting of Five Layers of IS-OH (1) / PE] (1) Using the same extrusion molding apparatus used in Example 1, PE and hydrogenated SBIS-OH were used for each extruder. (1)
And PVDC are supplied, and the maximum temperature during extrusion is set to PE
235 ° C, hydrogenated SBIS-OH (1) at 210 ° C, PV
DC was set to 200 ° C., and PE (50 μm) / hydrogenated SBIS-OH (1) was passed through the die of the extrusion molding apparatus.
(10 μm) / PVDC (50 μm) / hydrogenated SBIS-
OH (1) (10 μm) / PE (50 μm) were laminated in this order to form a five-layer structure and co-extrusion was performed. Both surfaces were a PE layer, an intermediate layer was a PVDC layer, and a PE layer and an And a laminated structure composed of five layers in which a hydrogenated SBIS-OH (1) layer was interposed. (2) The multilayer structure obtained in the above (1) was evaluated for the film-forming property by the above-mentioned method, and was almost good (）). However, hydrogenation S on both surfaces of the multilayer structure was evaluated.
The adhesive strength between BIS-OH (1) and the intermediate PVDC layer was 40 g / cm, a very low value, and a practically usable laminated structure could not be obtained.

<< Comparative Example 3 >> [Production of Laminated Structure Consisting of Five Layers of PP / PU / NY-6 / PU / PP] (1) Using the same extrusion molding apparatus as used in Example 1, PP, PU and NY-6 are supplied to each extruder, and the maximum temperature during extrusion is 240 ° C.
Is set at 240 ° C. and NY-6 is set at 240 ° C., and PP (50 μm) / PU
(10 μm) / NY-6 (50 μm) / PU (10
μm) / PP (50 μm) and co-extrusion is performed so as to form a five-layer structure. Both surfaces are a PP layer and an intermediate layer is an NY-6 layer. To PU
A laminated structure consisting of five layers with each layer interposed was produced. (2) The multilayer structure obtained in the above (1) was evaluated for film forming properties by the above-mentioned method. As a result, the unevenness of the surface of the multilayer structure was severe and poor (x). Furthermore, the adhesive strength between the PP layers on both surfaces of the laminated structure and the PU layer on the inner side thereof was 20 g / cm, which was a very low value, and a practically usable laminated structure could not be obtained.

[0092]

The laminated structure of the present invention has a very high adhesive strength between layers, so that no delamination occurs between layers, and the food is a food which dislikes oxygen depending on the characteristics of the organic polymer constituting the laminated structure. Packaging materials for medicines and medicines; packaging materials for clothing; packaging materials for other products; for building materials such as wallpaper and decorative boards;
Film for electrical insulation; Adhesive film and base material for tape; Marking film; Agricultural film;
For miscellaneous goods such as raincoats, umbrellas, curtains and covers;
It can be effectively used for various uses such as lamination with metal plates and other materials. Furthermore, in the laminated structure of the present invention, the polymer layer (B) interposed between the polymer layer (A) and the polymer layer (C) is a polymer layer (A) in a molten state.
Functions as an adhesive for firmly bonding the polymer layer (C) with the polymer layer, and does not use an organic solvent in the production of the laminated structure. No safety, excellent processability and workability. In particular, when the laminated structure of the present invention is produced by melt co-extrusion molding, a laminated structure having a small number of steps and high adhesive strength between layers can be produced smoothly with good productivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 175/04 C09J 175/04 // (C08L 75/04 53:02) (C09J 175/04 153: 02)

Claims (9)

[Claims] (A) a polymer layer mainly composed of at least one of an olefin polymer and a styrene polymer; (B) a thermoplastic polyurethane, and an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer layer. At least one kind of a block copolymer composed of a polymer block and a hydrogenated product of the block copolymer was used as [thermoplastic polyurethane]: [block copolymer and / or hydrogenated product thereof] = 20 to 80:80. (C) a saponified ethylene-vinyl acetate copolymer, a vinylidene chloride-based polymer, a vinyl chloride-based polymer, a polyamide,
A polymer layer mainly composed of at least one of polyester, polycarbonate and acrylic polymer;
Is the polymer layer (A) / polymer layer (B) / polymer layer (C)
Characterized in that at least a part of the laminated structure has a structure laminated in this order. 2. A block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block and / or a hydrogenated product of the block copolymer in the polymer layer (B) has a terminal hydroxyl group. The laminated structure according to claim 1, which has: 3. The polymer layer (A) is a polypropylene layer, and the polymer layer (B) is a thermoplastic polyurethane or an aromatic vinyl compound-based polymer block having not less than 30 mol% of 3,4-bonds. 3. The laminated structure according to claim 1, comprising a block copolymer comprising isoprene polymer blocks and / or a polymer composition containing a hydrogenated product thereof. 4. The laminated structure according to claim 1, which is produced by co-extrusion molding. 5. A polymer mainly composed of at least one of an olefin-based polymer and a styrene-based polymer; (b) a thermoplastic polyurethane, and an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer. At least one of a block copolymer composed of united blocks and a hydrogenated product of the block copolymer was prepared by using [thermoplastic polyurethane]: [block copolymer and / or hydrogenated product thereof] = 20 to 80:80 to 20% by weight of a polymer composition; and (c) a saponified ethylene-vinyl acetate copolymer, a vinylidene chloride-based polymer, a vinyl chloride-based polymer, a polyamide, a polyester, a polycarbonate, and an acrylic polymer. A layer of the polymer (a) and a layer of the polymer (c) using at least a polymer mainly composed of at least one of the following. The method for producing a laminated structure according to claim 1, wherein the co-extrusion molding is performed so that a layer of the polymer composition (b) is interposed therebetween. 6. A thermoplastic polyurethane, at least one of a block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, and a hydrogenated product of the block copolymer. Polyurethane]: A hot melt adhesive comprising a polymer composition containing [block copolymer and / or hydrogenated product thereof] = 20 to 80:80 to 20 by weight. 7. The hot melt adhesive according to claim 6, which is for coextrusion lamination molding. 8. The block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block and / or a hydrogenated product of the block copolymer has a terminal hydroxyl group. Or 7 hot melt adhesive. 9. A block copolymer comprising a thermoplastic polyurethane, an isoprene polymer block having an aromatic vinyl compound polymer block and a 3,4-bond in a proportion of 30 mol% or more and / or a hydrogenated product thereof. The hot melt adhesive according to any one of claims 6 to 8, comprising a polymer composition containing: