JPH10259303A - Thermoplastic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polymer compsn. which is excellent in clarity, elasticity, etc., and exhibits a high fusibility and adhesiveness to a low- polarity polymer (e.g. a polyolefin), a high-polarity polymer (e.g. a saponified ethylene-vinyl acetate copolymer, polyvinylidene chloride, PVC, a polyamide, a polyester, a polycarbonate, an acrylic polymer, polyoxymethylene, or a copolymer of an arom. vinyl compd. with at least one monomer selected from among vinyl cyanide, conjugated dienes, and olefins), and other materials and to provide a molded item produced therefrom, a laminate having a layer formed from the same, and a bolt-melt adhesive. SOLUTION: This compsn. contains a thermoplastic polyurethane (A) and a block copolymer comprising an arom. vinyl polymer block and conjugated diene polymer block and/or hydrogenation product of the block copolymer (B) in a wt. ratio of A/B of (20/80)-(80/20). The polyurethane is a reaction product of a high-molecular polyol having a number average mol.wt. of 500-10,000, an org. diisocyanate, and a chain extender. The difference in refractive index between the polyurethane and the block copolymer or its hydrogenation product at 25 deg.C is 0.005 or lower. The compsn. has a melt viscosity ηa of 150-10,000 Pa.s (22 deg.C, a shear rate of 100 sec<-1> ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic polymer composition containing a specific thermoplastic polyurethane and a block copolymer, a molded article comprising the same, and a polymer layer comprising the thermoplastic polymer composition. The present invention relates to a laminated structure having the same, a method for producing the laminated structure, and a hot melt adhesive comprising the thermoplastic polymer composition. More specifically, the present invention, polyethylene, low-polarity polymers such as olefinic polymers such as polypropylene and styrene-based polymers, and saponified ethylene-vinyl acetate copolymer,
Vinylidene chloride polymer, vinyl chloride polymer, polyamide, polyester, polycarbonate, acrylic polymer, polyoxymethylene, and at least one selected from vinyl cyanide compounds, conjugated diene compounds and olefin compounds, and aromatic vinyl compounds A specific thermoplastic that adheres strongly to any highly polar polymer such as a copolymer with, and has high melt adhesion to other materials, and is also excellent in transparency A thermoplastic polymer composition containing a polyurethane and a block copolymer, a molded article comprising the same, a laminated structure having a polymer layer composed of the thermoplastic polymer composition, and a hot melt adhesive, The thermoplastic polymer composition of the present invention takes advantage of the above-mentioned excellent properties to make use of a variety of laminated structures, It can be effectively used in applications.

[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 the production of laminated films, 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. . Especially,
When laminating a saponified ethylene-vinyl acetate copolymer film, a polyvinylidene chloride film, a polyvinyl chloride film, a polyester film, a polycarbonate film, or an acrylic polymer film with another polymer film, a solvent-based adhesive has conventionally been used. Is widely used, but there is a problem 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-based 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. Further, in the production of a laminated film using a solvent type adhesive, ethylene-vinyl acetate copolymer saponified film, polyvinylidene chloride film,
A polyvinyl chloride film, a polyamide film, a polyester film, a polycarbonate film or an acrylic polymer film must be manufactured in advance and then laminated with another polymer film that has been manufactured in advance using a solvent-based adhesive. Therefore, the number of steps is extremely large, such as a step of manufacturing a film to be laminated in advance, a drying step for removing the solvent after bonding and laminating the films, and a step of collecting the solvent, and the work content becomes complicated,
Various problems have also arisen in that the manufacturing cost is high.

[0004] Further, it has been conventionally performed to carry out melt coextrusion molding using a hot melt type adhesive such as fatty acid-modified polyolefin or epoxy-modified polyolefin to produce a laminated film. However, the resulting laminated film has low adhesive strength between layers,
Delamination easily occurs, and its improvement is required. Furthermore, a plastic laminated structure, such as a laminated film for packaging materials, is often required to be transparent so that an object to be packaged or the like can be seen through from the outside. In this case, even if the plastics constituting the front and back layers are transparent, if the intermediate adhesive layer is opaque, a transparent laminated structure cannot be obtained. Therefore, a non-solvent type adhesive having excellent adhesive strength and excellent transparency is required.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to exhibit high melt adhesion to both low and high polarity polymers and to achieve high melt adhesion to other materials. It shows adhesiveness and is excellent in transparency, so that it can avoid environmental pollution, deterioration of working environment, and complication of the bonding process, etc. caused by using a solvent. It is an object of the present invention to provide a thermoplastic polymer composition which can be used, and a film, a sheet and other molded articles comprising the same. It is a further object of the present invention to provide a laminated structure having an adhesive layer comprising the above-mentioned thermoplastic polymer composition and a method for producing the same. In particular, a saponified ethylene-vinyl acetate copolymer having excellent gas barrier properties, a layer made of vinylidene chloride-based polymer or polyamide, and a vinyl chloride-based polymer having excellent transparency, chemical resistance, printability, and mechanical properties. layer,
Polyester layer with excellent chemical resistance and mechanical properties,
Polycarbonate layer with excellent transparency and impact resistance,
An acrylic polymer layer having excellent transparency, weather resistance, and printability; a polyoxymethylene layer having excellent mechanical properties and moldability; and at least one selected from a vinyl cyanide compound, a conjugated diene compound, and an olefin compound. Laminated structure having a layer of a copolymer of a seed and an aromatic vinyl compound, 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, and production thereof It is intended to provide a method. Then, an object of the present invention is to provide a hot melt adhesive comprising the above-mentioned thermoplastic polymer composition.

[0006]

The present inventor has made various studies in order to solve the above-mentioned problems. As a result, when a specific thermoplastic polyurethane, a block copolymer composed of an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block and / or a hydrogenated product of the block copolymer are blended at a specific ratio. The resulting thermoplastic polymer composition exhibits high melt adhesion to both low-polar and high-polar polymers, and also exhibits high melt adhesion to other materials. Showing,
Moreover, it is excellent in transparency, and therefore, the thermoplastic polymer composition is suitable for the production of various molded articles and various laminated structures including films and sheets, and further as a hot melt adhesive. Found to be effective. And the present inventors, using the thermoplastic polymer composition described above, saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide, polyester, polycarbonate, acrylic-based A polymer layer containing at least one of a polymer, polyoxymethylene, and a copolymer of an aromatic vinyl compound and at least one selected from a vinyl cyanide compound, a conjugated diene compound, and an olefin compound; At least one of a polymer and a styrenic polymer
When the polymer layer containing the seeds is melt-bonded, the interlayer bond strength is high and delamination does not occur, and a high-quality laminated structure excellent in transparency, without using a harmful organic solvent or the like, It should be obtained safely and with good processability and workability, and such a laminated structure should be obtained more smoothly by co-extrusion molding the above-mentioned polymer together with the above-mentioned thermoplastic polymer composition. The present invention has been completed based on the findings described above.

That is, the present invention relates to (i) a thermoplastic polyurethane, at least 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. A thermoplastic polymer composition containing one kind in a weight ratio of [thermoplastic polyurethane]: [block copolymer and / or hydrogenated product thereof] = 20: 80 to 80:20; (ii) The thermoplastic polyurethane has a number average molecular weight of 500
A thermoplastic polyurethane obtained by the reaction of a polymer polyol, an organic diisocyanate and a chain extender of from 10,000 to 10,000; (iii) a refractive index of the thermoplastic polyurethane measured at 25 ° C., and the above-mentioned block copolymer and / or Or the difference (Δn) from the refractive index of the hydrogenated product is 0.005 or less; and (iv) the melt viscosity ηa of the thermoplastic polymer composition (temperature 2
(Measured at 20 ° C. and a shear rate of 100 sec ⁻¹ ) is 150-1.
0000 Pa · s; a thermoplastic polymer composition characterized by the following:

[0008] The present invention is a molded article comprising the above-mentioned thermoplastic polymer composition. Further, the present invention is a laminated structure having a polymer layer made of the above-mentioned thermoplastic polymer composition and a layer made of another material. In particular, the present invention provides, as the above-described laminated structure,
(A) a polymer layer mainly composed of at least one of an olefin-based polymer and a styrene-based polymer; (B)
A polymer layer comprising the thermoplastic polymer composition described above; 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 polyoxymethylene, and a polymer layer mainly composed of at least one of a copolymer of an aromatic vinyl compound and at least one selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound;
Is the polymer layer (A) / polymer layer (B) / polymer layer (C)
As a preferred embodiment.

The present invention relates to (a) a polymer mainly composed of at least one of an olefin polymer and a styrene polymer; (b) the thermoplastic polymer composition described above; and (c) ethylene. -Selected from saponified vinyl acetate copolymer, vinylidene chloride polymer, vinyl chloride polymer, polyamide, polyester, polycarbonate, acrylic polymer, polyoxymethylene, and vinyl cyanide compound, conjugated diene compound and olefin compound. At least one polymer selected from the group consisting of at least one copolymer of at least one aromatic vinyl compound and an aromatic vinyl compound, between the layer of the polymer (a) and the layer of the polymer (c). This is a method for producing a laminated structure by co-extrusion molding with a layer of the composition (b) interposed therebetween.

Further, the present invention is a hot melt adhesive comprising the above-mentioned thermoplastic polymer composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The thermoplastic polymer composition of the present invention comprises a thermoplastic polyurethane, and a block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block (hereinafter referred to as “aromatic vinyl compound / conjugated diene block copolymer”). And a hydrogenated product of the aromatic vinyl compound / conjugated diene block copolymer.

[0012] The thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention is substantially a high molecular polyol,
It is a polyurethane obtained by reacting an organic diisocyanate and a chain extender.

Examples of the high molecular polyol which can be used for the production of thermoplastic polyurethane include polyester polyol, polycarbonate polyol, polyester polycarbonate polyol, polyether polyol and the like. Thermoplastic polyurethane is one of these high molecular polyols or It can be formed using two or more kinds.

The polyester polyol used in the production of the thermoplastic polyurethane is, for example, directly subjected to an ester reaction between a polyol component and a polycarboxylic acid component such as a polycarboxylic acid, an ester thereof, or an ester-forming derivative such as an anhydride according to a conventional method. Or by a transesterification reaction.

Examples of the polycarboxylic acid component which is a raw material for producing a polyester polyol used for producing a thermoplastic polyurethane include glutaric acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecane diacid. Acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecaneedioic acid, 3,7-dimethyldecaneedioic acid Aliphatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid;
Examples thereof include ester-forming derivatives thereof, and the polyester polyol can be formed using one or more of the above-described polycarboxylic acid components. Among them, polyester polyol is
As the polycarboxylic acid component, a product mainly composed of an aliphatic carboxylic acid or an ester-forming derivative thereof, and optionally containing a small amount of trifunctional or higher-functional polycarboxylic acid or an ester-forming derivative thereof. Is preferred.

The polyol component, which is a raw material for producing a polyester polyol used for producing a thermoplastic polyurethane, includes, for example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4- Butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-
Pentanediol, 1,6-hexanediol, 1,7
-Heptanediol, 1,8-octanediol, 2-
Aliphatic diols such as methyl-1,8-octanediol, 1,9-nonanediol and 1,10-decanediol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; glycerin, trimethylolpropane, butanetriol; Triols such as pentaerythritol can be used, and one or more of the above-mentioned polyol components can be used.
Among them, the polyester polyol is mainly composed of an aliphatic polyol, and further produced using a polyol component containing a small amount of a trifunctional or higher polyol.
It is preferable to use a polyester polyol as described below, in which the number of hydroxyl groups per molecule is slightly larger than 2.

The polycarbonate polyol which can be used for producing the thermoplastic polyurethane is obtained, for example, by reacting the polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate, diaryl carbonate and the like. As the polyol which is the current raw material for producing the polycarbonate polyol, the above-mentioned polyols which are the raw materials for producing the polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

Examples of polyester polycarbonate polyols that can be used for the production of thermoplastic polyurethane include, for example, those obtained by simultaneously reacting a polyol, a polycarboxylic acid and a carbonate compound, and a polyester polyol and a polycarbonate polyol that have been prepared in advance. Examples thereof include those obtained by reacting a carbonate compound and those obtained by reacting a polyol and a polycarboxylic acid.

Examples of polyether polyols that can be used in the production of thermoplastic polyurethanes include polyethylene glycol, polypropylene glycol, and poly (ethylene glycol) obtained by polymerizing a diol component, preferably in the presence of a small amount of a trifunctional or more functional polyol. One or more of these can be used. Among them, it is preferable to use polytetramethylene glycol having a slightly higher number of hydroxyl groups per molecule than 2 among them.

In the present invention, it is necessary that the number average molecular weight of the high molecular polyol used for producing the thermoplastic polyurethane is from 500 to 10,000.
It is preferably from 5,000 to 5,000, and more preferably from 750 to 4,000. Number average molecular weight of 500 to 10
When using a thermoplastic polyurethane produced using a high molecular polyol out of the range of 000, the melt moldability and co-extrusion molding of the thermoplastic polyurethane composition containing the thermoplastic polyurethane and the block copolymer described above. sex,
Cold resistance, heat resistance, etc. are likely to be reduced. In addition,
The number average molecular weight referred to in this specification is JIS K 1577.
Means the number average molecular weight calculated based on the hydroxyl value measured in accordance with

The high molecular polyol used for producing the thermoplastic polyurethane is preferably a high molecular polyol having a hydroxyl number f per molecule in the range of 2.005 ≦ f ≦ 2.1. .01 ≦ f ≦ 2.08
It is more preferable that the polymer polyol is in the range of The number of hydroxyl groups f per molecule is 2.005 ≦
When the thermoplastic polyurethane obtained using the polymer polyol having the range of f ≦ 2.10 is used in the thermoplastic polymer composition of the present invention, the melt moldability of the thermoplastic polymer composition at a high temperature is reduced. When the laminated structure is manufactured by co-melt extrusion molding with a thermoplastic polymer (eg, polyester, polyamide, polycarbonate, etc.) that needs to be melt-molded at a high temperature, the moldability is further improved. Become.

The type of the organic diisocyanate used in the production of the thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention is not particularly limited. 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,
And 4'-dicyclohexylmethane diisocyanate.
Species or two or more can be used. Among them, 4,4'-diphenylmethane diisocyanate is preferably used.

As the chain extender used for producing the thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention, any chain extender conventionally used for producing a thermoplastic polyurethane can be used. Among them, a low molecular weight compound having a molecular weight of 300 or less and having two or more active hydrogen atoms capable of reacting with an isocyanate group in a molecule is preferably used. Examples of such a chain extender include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, and 1,4-cyclohexanediol. , Bis- (β-hydroxyethyl)
Diols such as terephthalate and xylylene glycol; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, xylenediamine, diamines such as adipic dihydrazide and isophthalic dihydrazide Amino alcohols such as aminoethyl alcohol and aminopropyl alcohol; and one or more of these can be used. Among these, aliphatic diols having 2 to 10 carbon atoms are preferably used, and 1,4-butanediol is more preferably used.

In the thermoplastic polymer composition of the present invention, as a thermoplastic polyurethane, an aliphatic dicarboxylic acid component is reacted with a polyol component mainly composed of an aliphatic diol and containing a small amount of a trifunctional or more polyol. A high molecular polyol having a hydroxyl number f per molecule obtained in the above-mentioned range of 2.005 to 2.1,
Use of a thermoplastic polyurethane obtained by reacting with a chain extender comprising 4,4'-diphenylmethane diisocyanate and an aliphatic diol having 2 to 10 carbon atoms (particularly 1,4-butanediol) is a thermoplastic polymer. Mechanical properties of the composition, adhesion to other thermoplastic polymers, especially saponified ethylene-vinyl acetate copolymer, vinylidene chloride polymer, vinyl chloride polymer, polyamide, polyester, polycarbonate, acrylic polymer It is preferable because it has excellent adhesiveness to a thermoplastic polymer having a large polarity such as coalescence.

The thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention may have a number average molecular weight such that the equivalent ratio R of isocyanate group / hydroxyl group is in the range of 0.9 ≦ R ≦ 1.30. A thermoplastic polyurethane obtained by reacting a polymer polyol having a molecular weight of 500 to 10,000, an organic diisocyanate, and a chain extender is preferable from the viewpoint of improving the melt moldability of the thermoplastic polymer composition, and particularly, a film. Good film-forming stability is obtained when melt-molding into a shape. When the aromatic vinyl compound / conjugated diene block copolymer used in the thermoplastic polymer composition of the present invention and / or a hydrogenated product thereof has a hydroxyl group at a terminal, an equivalent ratio as a thermoplastic polyurethane is obtained. When the thermoplastic polyurethane obtained by reacting a polymer polyol, an organic diisocyanate and a chain extender such that R is in the range of 1.005 ≦ R ≦ 1.10. Is used, a thermoplastic polymer composition is obtained. Is preferable because the melt moldability, particularly the film-forming stability and the melt adhesiveness, are further improved.

The method for producing the thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention is not particularly limited. Utilizing, for example, can be produced by a prepolymer method or a one-shot method. Among them, the thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention is preferably produced by melt polymerization substantially in the absence of a solvent. It is preferable to produce by polymerization.

In the thermoplastic polymer composition of the present invention, a block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, which is another essential polymer component (aromatic vinyl compound / conjugated The diene block copolymer) includes a block copolymer having at least one aromatic vinyl compound-based polymer block and at least one conjugated diene-based polymer block, and a copolymer of the aromatic vinyl compound / conjugated diene block. At least one of the conjugated diene-based polymer blocks in the polymer in which unsaturated bonds are hydrogenated is used.
The hydrogenation rate in that case is 0 to 100 mol%, preferably 0 to 100 mol%.
It can be selected from the range of 95 mol%. When the hydrogenation rate of the unsaturated bond of the conjugated diene-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer is 50 mol% or more, particularly 80 mol% or more, the weather resistance and the thermal decomposition resistance are excellent. A thermoplastic polymer composition can be obtained.

The aromatic vinyl compound-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer is mainly composed of structural units derived from the aromatic vinyl compound, and may optionally contain a small amount of other unsaturated monomer. It is a polymer block having a derived structural unit. As the aromatic vinyl compound constituting the aromatic vinyl compound-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer, styrene, α-methylstyrene, o-,
m-, p-methylstyrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzyl Examples thereof include styrene and 4- (phenylbutyl) styrene, and the aromatic vinyl compound-based polymer block may have a structural unit composed of one or more of the above-described aromatic vinyl compounds. . Among them, the aromatic vinyl compound-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer is preferably mainly composed of a structural unit composed of styrene and / or α-methylstyrene.

The conjugated diene-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer includes 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. , 1,
A polymer block mainly formed from one or more conjugated diene compounds such as 6-hexadiene, and in a hydrogenated aromatic vinyl compound / conjugated diene block copolymer, the conjugated diene polymer block A part or all of the unsaturated bond part has become a saturated bond by hydrogenation. Among them, the aromatic vinyl compound / conjugated diene block copolymer used in the thermoplastic polymer composition of the present invention is a polymer in which the conjugated diene-based polymer block comprises 1,3-butadiene, isoprene or a mixture thereof. Coalesced blocks, more specifically isoprene polymer blocks, isoprene and butadiene copolymer blocks, butadiene polymer blocks and / or their hydrogenated polymer blocks,
It is preferable because the melt adhesion of the thermoplastic polymer composition is improved, and particularly the melt adhesion to the olefin polymer is excellent.

In particular, when it is desired to obtain a thermoplastic polymer composition having a large adhesive strength to polypropylene, the aromatic vinyl compound / conjugated diene block copolymer has a conjugated diene-based polymer block having 3,4-bonds. It is preferable to use an aromatic vinyl compound / conjugated diene block copolymer comprising an isoprene polymer block and / or a hydrogenated polymer block having a ratio of 30 mol% or more.

When the conjugated diene-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer is an isoprene / butadiene copolymer block or a hydrogenated copolymer block thereof, it is derived from butadiene. The arrangement of the structural units and the structural units derived from isoprene are random, block, tapered,
Alternatively, any form of 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 thermoplastic polymer composition of the present invention, as an aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof,
Diblock copolymer in which one aromatic vinyl compound polymer block and one conjugated diene polymer block are linearly bonded, aromatic vinyl compound polymer block-conjugated diene polymer block-aromatic vinyl compound A triblock copolymer in which three polymer blocks are linearly bonded in the order of the polymer blocks, and one or more hydrogenated products thereof are easily manufactured, easily available, It is preferably used in terms of 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 that the thermoplastic polymer composition has excellent melt adhesion, mechanical properties, and the like, and more preferably 10 to 90% by weight.

In particular, when it is desired to obtain a thermoplastic polymer composition having a high adhesive strength to an olefin polymer, it is derived from an aromatic vinyl compound in an aromatic vinyl compound / conjugated diene block copolymer and a hydrogenated product thereof. The content of the structural unit is preferably from 5 to 60% by weight, more preferably from 10 to 50% by weight. When it is desired to obtain a thermoplastic polymer composition having a high adhesive strength to a styrene-based polymer, an aromatic vinyl compound /
The content of the structural unit derived from the aromatic vinyl compound in the conjugated diene block copolymer and the hydrogenated product thereof is preferably from 40 to 90% by weight, more preferably from 50 to 90% by weight.

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 /
When the conjugated diene block copolymer and the hydrogenated product thereof have a hydroxyl group at the molecular terminal, the thermoplastic polymer composition of the present invention containing the same has remarkable film-forming stability during melt extrusion molding. As a result, the film can be stably formed even if 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 from 2,500 to 2,500.
50,000, and the number average molecular weight of the conjugated diene polymer block before hydrogenation is 10,000 to 10,000.
0, and the number average molecular weight of the entire aromatic vinyl compound / conjugated diene block copolymer is 15,000 to 150,000.
Is 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 a hydrogenated product thereof are not particularly limited, and the aromatic vinyl compound-based polymer block and the conjugated diene-based polymer block described above are not particularly limited. Any block copolymer can be used as long as it is an aromatic vinyl compound / conjugated diene block copolymer or a hydrogenated product thereof for the thermoplastic polymer composition of the present invention. May be used or obtained in other ways. Although not limited in any way, the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product used in the thermoplastic polymer composition of the present invention can be obtained, for example, by using an aromatic vinyl compound and a conjugated diene. It can be obtained by preparing a block copolymer by anionic polymerization, cationic polymerization, Ziegler polymerization, single-site polymerization, radical polymerization, or the like, and hydrogenating it if necessary.

The thermoplastic polymer composition of the present invention comprises the thermoplastic polyurethane described above, at least one of an aromatic vinyl compound / conjugated diene block copolymer and a hydrogenated product of the block copolymer. [Thermoplastic polyurethane] (If a plurality of thermoplastic polyurethanes are used, the sum thereof): [Aromatic vinyl compound / conjugated diene block copolymer and / or hydrogenated product thereof]
(When a plurality of aromatic vinyl compounds / conjugated diene block copolymers and / or hydrogenated products thereof are used, the total thereof is required) = 20: 80 to 80:20 in weight ratio. , Preferably in a weight ratio of 30:70 to 70:30, and 35:65 to 6
More preferably, it is contained in a weight ratio of 5:35.

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 (the block copolymer and / or the hydrogenated product thereof). An additive content of more than 80% by weight) and a highly polar polymer (for example, saponified ethylene-vinyl acetate copolymer,
At least one selected from a vinylidene chloride polymer, a vinyl chloride polymer, a polyamide, a polyester, a polycarbonate, an acrylic polymer, a polyoxymethylene, a vinyl cyanide compound, a conjugated diene compound and an olefin compound, and an aromatic vinyl compound; Copolymer)
The adhesiveness of the thermoplastic polymer composition to the polymer decreases. On the other hand, when the content of the thermoplastic polyurethane exceeds 80% by weight (the content of the block copolymer and / or its hydrogenated product is less than 20% by weight), a polymer having a small polarity (eg, an olefin polymer) , A styrene-based polymer, etc.).

Further, in the thermoplastic polymer composition of the present invention, the refractive index of the thermoplastic polyurethane contained in the thermoplastic polymer composition measured at a temperature of 25 ° C. and the aromatic vinyl compound / conjugated diene block copolymer It is important that the difference (refractive index difference) (Δn) between the coalescence and / or the hydrogenated product thereof and the refractive index measured at a temperature of 25 ° C. is 0.005 or less, and 0.002 or less. preferable. The difference between the refractive index of the thermoplastic polyurethane at 25 ° C and the refractive index of the aromatic vinyl compound / conjugated diene block copolymer and / or hydrogenated product thereof at 25 ° C (△
If n) is greater than 0.005, the transparency of the thermoplastic polymer composition will be impaired, making it unsuitable for applications requiring transparency. In general, in a molded article such as a film or a sheet obtained using a thermoplastic polymer composition or a laminated structure having a polymer layer made of the thermoplastic polymer composition, the transparency increases as the thickness increases. It tends to decrease. Therefore, in order to ensure the predetermined transparency, as the thickness increases, the refractive index of the thermoplastic polyurethane contained in the thermoplastic polymer composition and the aromatic vinyl compound / conjugated diene block copolymer and / or It is necessary to further reduce the difference (Δn) with the refractive index of the hydrogenated product. In addition, the refractive index difference (Δn) referred to in this specification
Was measured using an Appe refractometer at a temperature of 25 ° C and a thickness of 1
The refractive index of a thermoplastic polyurethane film having a thickness of 100 μm and the refractive index of an aromatic vinyl compound / conjugated diene block copolymer film having a thickness of 100 μm or a hydrogenated film thereof were measured. It refers to the value obtained by subtracting the smaller one, and the specific contents are as described in the following Examples.

Generally, the refractive index is temperature-dependent, and the refractive index changes as the temperature changes. And
The present inventor investigated that the temperature dependence of the refractive index of the thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention and the refractive index of the aromatic vinyl compound / conjugated diene block copolymer or its hydrogenated product Surprisingly have almost the same temperature-dependent characteristics, so that the difference in refractive index between the two when measured at a temperature of 25 ° C. (△
When n) was 0.005 or less, it was found that the refractive index difference (Δn) between the two was maintained at 0.005 or less even when the measurement temperature was changed. That is, the thermoplastic polymer composition of the present invention may be used in a temperature range where the thermoplastic polymer composition is generally used (usually -40 to 120 ° C.) as well as when the use temperature is 25 ° C. The difference (Δn) between the refractive index of the thermoplastic polyurethane contained in the polymer composition and the refractive index of the aromatic vinyl compound / conjugated diene block copolymer or a hydrogenated product thereof is 0.005 or less, Always has good transparency.

The refractive index of the thermoplastic polyurethane can be adjusted by the content of the hard segment in the thermoplastic polyurethane. Therefore, during the production of the thermoplastic polyurethane, for example, by adjusting the amount of the component used to form a hard segment such as aromatic diisocyanate or aromatic diol, the thermoplastic polyurethane having the desired refractive index Obtainable. The refractive index of the thermoplastic polyurethane can also be adjusted by the design of the soft segment in the thermoplastic polyurethane, when the soft segment is derived from, for example, polyester polyol,
By using an aromatic compound for part or all of the acid component and / or the polyol component in the polyester polyol and changing the content thereof, a thermoplastic polyurethane having a target refractive index can be obtained. The refractive index of the aromatic vinyl compound / conjugated diene block copolymer and / or the hydrogenated product thereof is determined by the content of the structural unit derived from the aromatic vinyl compound in the block copolymer, the conjugated diene-based polymer block. Can be adjusted according to the hydrogenation rate of the compound. Therefore, in the thermoplastic polymer composition of the present invention, by adjusting the refractive index of the thermoplastic polyurethane and the refractive index of the aromatic vinyl compound / conjugated diene block copolymer by the method described above, the heat at 25 ° C. The difference (Δn) between the refractive index of the plastic polyurethane and the refractive index of the aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof can be 0.005 or less.

It is important that the thermoplastic polymer composition of the present invention has a melt viscosity ηa of 150 to 10000 Pa · s measured at a temperature of 220 ° C. and a shear rate of 100 sec ⁻¹ . If the melt viscosity ηa of the thermoplastic polymer composition is out of the above range, the moldability will be poor. Moreover, the melt viscosity ηa of the thermoplastic polymer composition is 1
If it is less than 50 Pa · s, its mechanical properties are inferior. Incidentally, the specific contents of the method for measuring the melt viscosity ηa of the thermoplastic polymer composition referred to in the present specification,
This is as described in the following examples.

In order to set the melt viscosity ηa of the thermoplastic polymer composition in the range of 150 to 10000 Pa · s,
It can be achieved by adjusting the melt viscosity of the thermoplastic polyurethane, adjusting the melt viscosity of the aromatic vinyl compound / conjugated diene block copolymer, and mixing both polymers having such adjusted melt viscosities. . However, in that case, the transparency of the thermoplastic polymer composition should not be impaired, that is, the refractive index of the thermoplastic polyurethane in the thermoplastic polymer composition and the aromatic vinyl compound /
While maintaining the difference (Δn) from the refractive index of the conjugated diene block copolymer and / or the hydrogenated product thereof at 0.005 or less, the melt viscosity ηa of the thermoplastic polymer composition
However, it is important to keep the above range.

The melt viscosity of the thermoplastic polyurethane can be adjusted by the molecular weight and the urethane group concentration. However, when an aromatic diisocyanate is used as the organic diisocyanate, changing the urethane group concentration changes the refractive index of the thermoplastic polyurethane and may impair the transparency. Adjusting the melt viscosity is not a recommended measure. The molecular weight of the thermoplastic polyurethane can be adjusted by changing the concentration ratio between the hydroxyl group and the isocyanate group in the raw material components. However, when only the polymer diol is used, the adjustment range is limited. Therefore, in the case described above, the melt viscosity of the thermoplastic polyurethane can be smoothly adjusted by, for example, changing the number of hydroxyl groups f per molecule in the polymer polyol component used for producing the thermoplastic polyurethane. .

The melt viscosity of the aromatic vinyl compound / conjugated diene block copolymer and the hydrogenated product thereof can be generally adjusted by the molecular weight and the content of the structural unit derived from the aromatic vinyl compound. However, changing the content of the structural unit derived from the aromatic vinyl compound affects the refractive index of the aromatic vinyl compound / conjugated diene block copolymer, making it difficult to obtain a transparent thermoplastic polymer composition. Therefore, it is preferable to adjust the melt viscosity according to the molecular weight of the aromatic vinyl compound / conjugated diene block copolymer.

The thermoplastic polymer composition of the present invention may contain, if necessary, a heat stabilizer, a light stabilizer, an antioxidant, an antistatic agent, a coloring agent, as long as the object of the present invention is not hindered. And one or more additives such as a flame retardant, an ultraviolet absorber, a plasticizer, and a hydrolysis inhibitor.

The method for preparing the thermoplastic polymer composition of the present invention is not particularly limited, and any of the methods conventionally used for preparing a thermoplastic polymer composition can be employed. For example, pre-mixing using thermoplastic polyurethane, aromatic vinyl compound / conjugated diene block copolymer and other additives, if necessary, using a vertical or horizontal mixer generally used for mixing polymers. After that, the mixture can be kneaded under heating in a batch or continuous manner using a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer or the like. In particular, when heat kneading is performed using an extruder, the thermoplastic polymer composition may be extruded into a strand and then cut into an appropriate length to produce a granular thermoplastic polymer composition such as pellets. Further, for example, at the time of polymerization of the thermoplastic polyurethane, a thermoplastic polymer composition may be prepared by mixing an aromatic vinyl compound / conjugated diene block copolymer and additives as necessary. Further, for example, a thermoplastic polyurethane, an aromatic vinyl compound / conjugated diene block copolymer and, if necessary, an additive are dry-blended in advance, and the dry blend is directly used in a melt molding machine such as a direct extrusion molding machine. It may be supplied, melt-kneaded and melt-molded to produce sheets, films, laminated structures, and other molded products.

The thermoplastic polymer composition of the present invention has excellent transparency, is thermoplastic and has excellent melt moldability. Further, the thermoplastic polymer composition of the present invention is characterized in that both the thermoplastic polyurethane constituting the thermoplastic polymer composition and the aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof have elasticity. By having, good cushioning, impact resistance, cushioning,
It also has properties such as flexibility. Therefore, the thermoplastic polymer composition of the present invention, alone or in combination with other materials, a film, a sheet, a plate, a rod, a tubular,
Various molded articles such as molded articles and composite molded articles can be produced smoothly by melt molding. Therefore, the present invention relates to the above-mentioned various molded articles and composite molded articles comprising the thermoplastic polymer composition of the present invention. Are included in the scope of the present invention.

Further, the thermoplastic polymer composition of the present invention has high transparency and elasticity, as well as high melt adhesion to various materials, a low-polarity polymer and a low-polarity polymer. Shows high melt adhesion to high polymers and even other materials. Therefore, the thermoplastic polymer composition of the present invention is extremely effective in the production of various laminated structures, and therefore, the present invention provides a polymer layer comprising the above-described thermoplastic polymer composition of the present invention and other layers. A laminated structure in which a layer made of a material is laminated is included in the scope of the present invention.

The above-mentioned laminated structure having a polymer layer made of the thermoplastic polymer composition of the present invention is not particularly limited. One consisting of one polymer layer and another material
A two-layer structure in which two layers are laminated, and a three-layer structure in which a polymer layer made of the thermoplastic polymer composition of the present invention exists as an intermediate layer between two surface layers (front and back layers) made of other materials , A three-layer structure in which a polymer layer made of the thermoplastic polymer composition of the present invention is laminated on the front and back surfaces of one layer made of another material, a polymer layer made of the thermoplastic polymer composition of the present invention And a multilayer structure in which layers made of one or more other materials are alternately laminated in four or more layers, and any of those laminated structures is included in the scope of the present invention. . At that time, as the above-mentioned other material to be laminated with the polymer layer made of the thermoplastic polymer composition of the present invention, other various thermoplastic polymers other than the thermoplastic polymer composition of the present invention or the composition thereof Products, various thermosetting resins, rubber, paper, cloth, metal, wood, ceramics and the like.

The method for producing the above-mentioned laminated structure is not particularly limited. For example, a method for producing a laminated structure by melt-coating the above-mentioned other material with the thermoplastic polymer composition of the present invention, 2
A method for introducing and bonding the thermoplastic polymer composition of the present invention between two or more other materials under melting, and the method of the present invention in which other materials are placed (inserted) in a mold. A method in which the thermoplastic polymer composition is filled into a mold while being melted and bonded and integrated, and when the other material is thermoplastic, the thermoplastic polymer composition of the present invention and another material are co-extruded. A method of molding and bonding / integrating can be adopted.

In particular, the thermoplastic polymer composition of the present invention
Low-polarity polymers such as olefin polymers and styrene polymers such as polyethylene and polypropylene,
And saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide,
Polyester, polycarbonate, acrylic polymer,
Strongly adheres to any highly polar polymer such as a copolymer of at least one selected from polyoxymethylene, a vinyl cyanide compound, a conjugated diene compound and an olefin compound with an aromatic vinyl compound. A transparent laminated structure can be formed, and the resulting laminated structure can be effectively used for various applications. Therefore, the laminated structure of the present invention includes (A) a polymer layer mainly composed of at least one of an olefin-based polymer and a styrene-based polymer; (B) the thermoplastic polymer composition of the present invention described above. (C) saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide, polyester, polycarbonate, acrylic polymer, polyoxymethylene, and cyanide A polymer layer mainly composed of at least one of a copolymer of an aromatic vinyl compound and at least one selected from a vinyl compound, a conjugated diene compound and an olefin compound; a polymer layer (A) / polymer layer (B) / a polymer layer (C) in at least a part of a laminated structure (hereinafter referred to as “laminated”). Zotai (b) "hereinafter] is included as a preferred embodiment.

Therefore, the above-described laminated structure (a), which is a preferred embodiment of the present invention, will be described below. The polymer layer (B) in the laminated structure (a) of the present invention is formed from the above-mentioned thermoplastic polymer composition. The polymer layer (A) in the laminated structure (A) of the present invention is mainly composed of 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), ethylene- Propylene copolymer, ethylene-propylene-diene copolymer,
Examples thereof include 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 polymer constituting the polymer layer (A), a polymer containing 10% by weight or more of a structural unit derived from a styrene monomer 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 contain, together with the structural units derived from the above-mentioned styrenic monomer, 90% by weight or less, preferably 50% by weight or less, of another 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.

As another rubbery polymer that can be contained in the styrene polymer constituting the polymer layer (A), acrylic rubber can be mentioned. 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) includes, 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 It is preferably a styrene-based polymer containing one or more of a polybutyl acrylate-based rubber and an 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 a heat stabilizer, a light stabilizer, an antioxidant, a coloring agent, a lubricant, an antistatic agent, if necessary, as long as it does not hinder its original properties. One or more of additives such as a release agent, a flame retardant, and an ultraviolet absorber may be contained.

The polymer layer (C) in the laminated structure (A) of the present invention comprises a saponified ethylene-vinyl acetate copolymer, a vinylidene chloride-based polymer, a vinyl chloride-based polymer, a polyamide, a polyester, and a polycarbonate. , An acrylic polymer, a polyoxymethylene, and at least one of a copolymer of an aromatic vinyl compound and at least one selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound.

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. In addition, saponified ethylene-vinyl acetate copolymer is available from ASTM D-1238-65T.
Melt index measured in accordance with 0.1 to 25
g / 10 minutes (measured at 190 ° C. under a load of 2160 g) is preferable from the viewpoint of moldability, and 0.3 to 20 g / min.
More preferably, it is 10 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 as 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; glutaric acid, adipic acid, pimelic acid,
Aliphatic dicarboxylic acids such as suberic acid, sebacic acid, azelaic acid, dodecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; tetrabromophthalate Halogen-containing dicarboxylic acids such as acids; 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, a carbonic acid diester or a 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 polyoxymethylene used in the polymer layer (C) is a high molecular compound having an oxymethylene group as a main structural unit.
A polymer composed of at least one species; ethylene oxide, propylene oxide, oxacyclobutane,
Copolymers of cyclic ethers such as 3-dioxolane; and copolymers of the monomers with cyclic esters such as β-propiolactone and γ-butyrolactone. Furthermore, in order to improve the heat resistance of polyoxymethylene, for example, a terminal-modified polyoxymethylene in which the terminal is acetylated with acetic anhydride or the like can be used.

The aromatic vinyl compound used in the copolymer of the aromatic vinyl compound and at least one selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound used in the polymer layer (C) is as follows. For example, styrene, α-methylstyrene, p-
Methyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, pt-butylstyrene,
Ethyl styrene, vinyl naphthalene and the like can be mentioned, and one or more of these are used. Of these, styrene is particularly preferred. Further, as the vinyl cyanide compound used in the copolymer,
For example, acrylonitrile, methacrylonitrile and the like can be mentioned. Examples of the conjugated diene compound used in the copolymer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-neopentyl-1. , 3
-Butadiene, 2-chloro-1,3-butadiene, 2-
Examples thereof include cyano-1,3-butadiene, substituted straight-chain conjugated petanedienes, straight-chain and side-chain conjugated hexadienes, and one or more of these can be used. Among them, 1,3-butadiene and 2-methyl-1,3-butadiene are particularly preferably used.
In addition, examples of the olefin compound used in the copolymer include ethylene and propylene. Preferred copolymers include styrene-
Acrylonitrile copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin),
An acrylonitrile-ethylene-propylene-styrene copolymer (AES resin) and the like can be mentioned.

The polymer layer (C) is composed of the above-mentioned saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer,
Of vinyl chloride polymers, polyamides, polyesters, polycarbonates, acrylic polymers, polyoxymethylene, and copolymers of at least one selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound with an aromatic vinyl compound. The polymer may be composed of only one kind, or may be composed of a mixture of two or more kinds. When composed of a mixture of two or more kinds, the compounding ratio of each polymer is not particularly limited.

Further, the polymer layer (C) is the same as 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, ethylene / propylene rubber, ethylene / propylene terpolymer, butadiene / acrylonitrile copolymer, ethylene-acetic acid) Vinyl copolymer),
Inorganic fine powder, organic lubricant, dispersant, dye / pigment, antistatic agent,
One or more kinds of antioxidants and the like may be contained.

In the laminated structure (A) of the present invention, the thickness of each layer is not particularly limited, and the kind of polymer constituting each layer, the total number of layers in the laminated structure (A), the laminated structure (A) )
In general, the thickness of the polymer layer (A) is 10 μm to 5 mm, the thickness of the polymer layer (B) is 1 μm to 1 mm, and the thickness of the polymer layer (C). 10 μm
The thickness is preferably set to 5 mm from the viewpoints of easiness of production of the laminated structure (A), interlayer adhesion, and the like.

The total number of layers in the laminated structure (A) of the present invention is not particularly limited, and the layers are laminated in the order of polymer layer (A) / polymer layer (B) / polymer layer (C). Any structure may be used as long as it is a laminated structure (a) having at least a part of the structure. Further, the laminated structure (A) of the present invention may be formed of only the three layers of the polymer layer (A), the polymer layer (B), and the polymer layer (C), or may be formed of the three types. A layer made of another material together with the layer (for example, another polymer,
Or one or more layers of paper, fabric, metal, ceramic, wood, etc.).

Although not particularly limited, examples of the laminated structure (a) of the present invention include a three-layer structure comprising a polymer layer (A) / polymer layer (B) / polymer layer (C). Structure;
(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 5-layer structure composed of a coalesced 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) / polymer layer ( B) / polymer layer (A) /
Seven-layer structure composed of (paper, cloth or metal); (paper, cloth or metal) / polymer layer (C) / polymer layer (B) / polymer layer (A) / polymer layer (B) / Polymer layer (C) /
(Paper, cloth or metal). When two or more polymer layers (A) are present in one laminated structure (A), the two or more polymer layers (A) are defined in the present invention. As long as the polymer is used, it may be composed of the same polymer or different polymers, which means that the laminated structure (A) has two or more polymer layers (B) and The same applies to the case where two or more polymer layers (C) are provided.

The method for producing the laminated structure (a) of the present invention is not limited at all. For example, (i) a polymer for the polymer layer (A) and a polymer for the polymer layer (B) The thermoplastic polymer composition of the present invention and the polymer layer (C)
A method for producing a laminated structure (a) by melt-coextrusion molding them and using them at least simultaneously with extrusion molding of each layer; (ii) forming a polymer layer (A). Film, sheet,
A plate or the like is manufactured in advance, and / or a molded product such as a film, a sheet, or a plate constituting the polymer layer (C) is manufactured in advance, and the thermoplastic resin of the present invention for the polymer layer (B) is used. If the polymer composition is melt-extruded, and if one of the polymer layer (A) and the polymer layer (C) is not preformed, it is also manufactured by melt extrusion. A method of manufacturing a laminated structure (a) by laminating and integrating the molded article for the polymer layer (A) and / or the molded article for the polymer layer (C), and (iii) the polymer layer ( A molded article such as a film, a sheet, and a plate constituting A) and a molded article such as a film, a sheet, and a plate constituting the polymer layer (C) are manufactured in advance, and further formed on the polymer layer (B). The polymer is also preliminarily formed into a film or a sheet, and the thermoplastic polymer composition of the present invention is prepared. The film or sheet for the polymer layer (B) is sandwiched between a molded article for the polymer layer (A) and a molded article for the polymer layer (C), and the polymer layer (B) is heated. A method for producing a laminated structure (a) by melting a film or sheet for use and bonding and integrating the polymer layer (A) and the polymer layer (C) via the polymer layer (B); iv) A molded article constituting the polymer layer (A) and a molded article constituting the polymer layer (C) are manufactured in advance, and the molded articles are arranged (inserted) in a mold in advance. A method in which the thermoplastic polymer composition of the present invention for the polymer layer (B) is filled in a molten state and bonded and integrated to produce a laminated structure (a).

In any of the above-mentioned methods (i) to (iv), 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 desired laminated structure (a) can be obtained without causing problems or trouble such as destruction of the natural environment, deterioration of the working environment, and recovery of the solvent due to the organic solvent. be able to. Among them, the method by the co-extrusion molding of the above (i) requires only a small number of steps, and has high productivity.
Moreover, it is most preferable because the laminated structure (A) having high adhesive strength between the polymer layer (A), the polymer layer (B) and the polymer layer (C) and free of delamination can be obtained.

When the laminated structure (a) of the present invention is manufactured by the coextrusion molding method, for example, three or more extruders are connected to one die according to the number of layers of the laminated structure (a). Thus, a plurality of polymers can be manufactured by laminating and integrating the polymer 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.

The laminated structure of the present invention, particularly the laminated structure (a), depends on the material and properties of the other material layers constituting the laminated structure, and particularly the laminated structure (a) is a polymer. Depending on the properties of the layer (A), the polymer layer (B), the polymer layer (C), etc., it can be used for various applications, and is not limited at all. For example, foods that dislike oxygen Packaging materials for medical and pharmaceutical agents; Packaging materials for clothing; Packaging materials for other products; Building materials such as wallpaper and decorative boards; Electrical insulating films; Adhesive films and base materials for tapes; Marking films; It can be used for various purposes such as films; for tableware, raincoats, umbrellas, curtains, covers, and other miscellaneous goods; and for lamination with metal plates and other materials. In particular, when the layer made of another material to be laminated with the polymer layer made of the thermoplastic polymer composition of the present invention is transparent, the layer made of the thermoplastic polymer composition of the present invention is transparent. Thus, a transparent laminated structure as a whole can be obtained.

Further, according to the present invention, the thermoplastic polymer composition of the present invention is stored as it is as a hot melt adhesive,
The hot melt adhesive may be used for the production of various products and various laminated structures as described above by using the hot melt adhesive when necessary, and therefore, the present invention provides the thermoplastic polymer of the present invention. Hot melt adhesives comprising the coalesced composition are included in the scope of the present invention. The form of the hot melt adhesive of the present invention is not particularly limited, and may be in any form such as a granular material such as a pellet, a rod, a film, a sheet, a plate, and the like.

[0090]

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 number of hydroxyl groups f per molecule of the polymer polyol (polyester polyol) used in the production of the thermoplastic polyurethane,
The refractive index of the thermoplastic polyurethane used to prepare the thermoplastic polymer composition, the refractive index of the block copolymer (hydrogenated block copolymer), and the refractive index difference between the two polymers (△
n), the melt viscosity ηa of the thermoplastic polymer composition, the transparency (haze value) and tensile strength of the film obtained from the thermoplastic polymer composition, and the lamination structure using the thermoplastic polymer composition. The evaluation of the film-forming property at the time of production and the adhesive strength of the laminated structure obtained thereby were measured or evaluated as follows.

[Number of hydroxyl groups per molecule of polyester polyol f] Polyester polyol was decomposed with a methanol solution of sodium methoxide, and the hydroxyl group of the decomposition product was silylated with a trimethylsilylating agent. The silylated sample was analyzed by gas chromatography to determine the molar ratio between the diol compound and the triol compound. Further, the hydroxyl value of the polyester polyol was determined in accordance with JIS K 1577, and the number f of hydroxyl groups per molecule of the polyester polyol was calculated from the hydroxyl value and the molar ratio.

[Refractive Index of Hydrogenated Product of Thermoplastic Polyurethane and Aromatic Vinyl Compound / Conjugated Diene Block Copolymer and Refractive Index Difference Between Both (Δn)] (1) Used in the following Examples and Comparative Examples. A thermoplastic polyurethane is melt-extruded at a temperature of 200 to 230 ° C. to produce a film having a thickness of 100 μm, and a test piece (size: 10 mm × 10 mm) is collected from the film.
The refractive index was measured at a temperature of 25 ° C. using an Appe refractometer. (2) The hydrogenated aromatic vinyl compound / conjugated diene block copolymer used in the following Examples and Comparative Examples was melt-extruded at a temperature of 200 to 230 ° C. to a thickness of 100.
A μm film was manufactured, and a test piece (size: 10 mm × 10 mm) was sampled from the film, and the refractive index was measured at a temperature of 25 ° C. using an Appe refractometer. (3) In each of Examples and Comparative Examples, the refractive index of the thermoplastic polyurethane measured in (1) above and the refractive index of the hydrogenated aromatic vinyl compound / conjugated diene block copolymer measured in (2) above Of the larger values, the smaller value is subtracted from the larger value to obtain the difference between the refractive indices (△
n) was determined.

[Transparency (Haze Value) of Thermoplastic Polymer Composition] Measured according to ASTM D1003.

[Melt Viscosity ηa of Thermoplastic Polymer Composition]
After drying the pellets of the thermoplastic polymer composition under reduced pressure at a temperature of 90 ° C., a measuring temperature of 220 ° C. and a preheating time of 360 seconds were measured using a height type flow tester (Shimadzu Flow Tester CFT-500C). , Die diameter 1mm,
The melt viscosity was measured at several points by changing the shear rate under the conditions of a die thickness of 10 mm and an extrusion pressure of 0.49 to 49 MPa,
A graph was prepared in which the melt viscosity was plotted against the shear rate, and the melt viscosity ηa when the shear rate was equal to 100 sec ^-1 was determined from the graph.

[Tensile Strength of Thermoplastic Polymer Composition (Film)] The thermoplastic polymer composition of the following Examples or Comparative Examples was extruded at a temperature of 200 to 230 ° C. to a thickness of 100 μm. Was manufactured, and a test piece was sampled from this film, and the tensile strength was measured according to JIS K7311.

[Film Forming Property During Production of Laminated Structure] (1) In the following Examples or Comparative Examples, the outermost layer (50 μm) / adhesive layer (10 μm) / intermediate layer (50 μm)
m) / adhesive layer (10 μm) / outermost layer (50 μm) to produce 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) The outermost layer (50 μm) / adhesive layer (2 μm) / intermediate layer (50 μm) / adhesive layer (2 μm) / outermost layer (50 μm) except that the thickness of the two adhesive layers was changed to 2 μm.
m) to produce a five-layer laminated structure, observing the surface smoothness with the naked eye, and measuring the thickness of the laminated structure at two locations at 2 m intervals along its length direction. 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.

[0097]

[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 both 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 (1) were large. Is not less than 5 μm and less than 10 μm, and the difference between the maximum thickness and the minimum thickness in the laminated structure of the above (2) is not less than 5 μm and less than 12 μm, and the film forming property is almost good. ×: In either of the above cases (1) and (2), the surface of the laminated structure is not smooth and has irregularities or curvature, or the maximum thickness and the minimum thickness of the laminated structure of the above (1) are not satisfied. 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 in Laminated Structure] Outermost layer (50 μm) / adhesive layer (10 μm) / intermediate layer (50 μm) / adhesive layer (10 μm) manufactured in the following examples or comparative examples.
m) / Laminated structure composed of the outermost layer (50 μm) is cut out to 1 cm (width direction of the laminated structure) × 10 cm (length direction of the laminated structure), and cut out from the outermost layer with a cutter knife. Then, the interface between the outermost layer and the adhesive layer and the interface between the adhesive layer and the intermediate layer were peeled off, and 1 was applied according to JIS K 6854 using an autograph manufactured by Shimadzu Corporation.
An 80 degree peel test was performed. However, in the case where the adhesive strength at the interface was very high and peeling-out was difficult with human power, a 180-degree peeling test could not be performed, and this fact is described in each example.

In the following Examples and / or Comparative Examples, thermoplastic polyurethanes, hydrogenated aromatic vinyl compound / conjugated diene block copolymers (hereinafter referred to as “hydrogenated block copolymers”), polypropylene, Polyethylene, polystyrene, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, polyamide, polycarbonate, vinylidene chloride copolymer, polymethyl methacrylate, polyethylene terephthalate, polyoxymethylene and acrylonitrile-butadiene-styrene copolymer content, Abbreviations are shown below.

○ Thermoplastic polyurethane-1 (abbreviation: TP
U) : Polyester polyol having a number-average molecular weight of 3500 having a hydroxyl number f of 2.02 per molecule (polyester polyol produced by reacting 3-methyl-1,5-pentanediol, trimethylolpropane and adipic acid) , 4,4'-diphenylmethane diisocyanate and 1,4-butanediol at 1: 3.50
Thermoplastic polyurethane (refractive index 1.512) obtained by reacting at a molar ratio of 9: 2.43.

○ Thermoplastic polyurethane-2 (abbreviation: TP
U) : Polyester polyol having a number-average molecular weight of 3500 having a hydroxyl number f of 2.02 per molecule (polyester polyol produced by reacting 3-methyl-1,5-pentanediol, trimethylolpropane and adipic acid) , 4,4'-diphenylmethane diisocyanate and 1,4-butanediol in a ratio of 1: 4.09
Thermoplastic polyurethane (refractive index 1.516) obtained by reacting at a molar ratio of 0: 3.0.

○ Thermoplastic polyurethane-3 (abbreviation: TP
U) : A polyester polyol (1,4
-Polyester polyol prepared by reacting butanediol, trimethylolpropane and adipic acid), 4,4'-diphenylmethane diisocyanate and 1,4-butanediol at 1: 1.948: 0.9.
Thermoplastic polyurethane obtained by reacting at a molar ratio of
(Refractive index 1.511).

○ Thermoplastic polyurethane-4 (abbreviation: TP
U) : A polyester polyol having a number average molecular weight of 2000 and having a hydroxyl number f per molecule of 2.01 (1,4
-Polyester polyol prepared by reacting butanediol, trimethylolpropane and adipic acid), 4,4'-diphenylmethane diisocyanate and 1,4-butanediol at 1: 4.284: 3.2.
Thermoplastic polyurethane obtained by reacting at a molar ratio of
(Refractive index 1.542).

○ Thermoplastic polyurethane-5 (abbreviation: TP
U) : Polyester polyol having a number-average molecular weight of 3500 having a hydroxyl number f of 2.06 per molecule (polyester polyol produced by reacting 3-methyl-1,5-pentanediol, trimethylolpropane and adipic acid) , 4,4'-diphenylmethane diisocyanate and 1,4-butanediol in 1: 3.52
Thermoplastic polyurethane (refractive index 1.512) obtained by reacting at a molar ratio of 9: 2.43.

○ Thermoplastic polyurethane-6 (abbreviation: TP
U) : Polyester polyol having a number-average molecular weight of 3500 having a hydroxyl number f of 2.00 per molecule (polyester polyol produced by reacting 3-methyl-1,5-pentanediol and adipic acid), 4,4 '
Thermoplastic polyurethane obtained by reacting diphenylmethane diisocyanate and 1,4-butanediol at a molar ratio of 1: 3.43: 2.43 (refractive index 1.51
1).

O Thermoplastic polyurethane-7 (abbreviation: TP
U) : Polyester polyol having a number-average molecular weight of 3500 having a hydroxyl number f of 2.00 per molecule (polyester polyol produced by reacting 3-methyl-1,5-pentanediol and adipic acid), 4,4 '
Thermoplastic polyurethane obtained by reacting diphenylmethane diisocyanate and 1,4-butanediol in a molar ratio of 1: 5.17: 4.17 (refractive index 1.52
3).

○ Hydrogenated product of block copolymer-1 [abbreviated]
No .: hydrogenated SBIS-OH (1)] : triblock copolymer consisting of a hydrogenated polystyrene block having a terminal hydroxyl group / 1,3-butadiene and an isoprene copolymer block / polystyrene block (refractive index: 1. 51
3): [Contents: Number average molecular weight of two polystyrene blocks =
7000, number average molecular weight of 1,3-butadiene and isoprene copolymer block = 26,000, number average molecular weight of triblock copolymer = 40000, hydroxyl group bonded to terminal of one polystyrene block, average in triblock copolymer Hydroxyl group content = 0.7 / molecule, 1,3-
1,1 in butadiene and isoprene copolymer block
The molar ratio of 3-butadiene units to isoprene units = 1 /
Unsaturation in 1,1,3-butadiene / isoprene copolymer block = 5% (95% hydrogenation); Styrene unit content in triblock copolymer before hydrogenation =
35% by weight, the amount of 1,4-bond in the 1,3-butadiene unit in the 1,3-butadiene-isoprene copolymer block before hydrogenation = 95%, the amount of 1,2-bond = 5%,
1,4-bond amount in isoprene unit = 95%, 3,
4-bond amount = 5%]

○ Block copolymer hydrogenated product-2 [abbreviated]
No .: hydrogenated SIS-OH (2)] : triblock copolymer composed of hydrogenated polystyrene block / polyisoprene block / polystyrene block having a hydroxyl group at a terminal (refractive index 1.514); Number average molecular weight of polystyrene block =
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, degree of unsaturation 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%)

○ Block copolymer hydrogenated product-3 [abbreviated]
No .: hydrogenated SIS-OH (3)] : a triblock copolymer composed of a hydrogenated polystyrene block / polyisoprene block / polystyrene block having a hydroxyl group at a terminal (refractive index: 1.514); Number average molecular weight of polystyrene block =
10500, number average molecular weight of polyisoprene block =
49000, number average molecular weight of triblock copolymer = 7
0000, hydroxyl group bonded to the end of one polystyrene block, average hydroxyl group content in triblock copolymer = 0.7 / molecule, degree of unsaturation in polyisoprene block = 15%, triblock copolymerization before hydrogenation Styrene unit content in the coalesced unit = 30% by weight, 1,4-bond amount in the polyisoprene block before hydrogenation = 4
(5%, 3,4-bond amount = 55%)

O Hydrogenated product of block copolymer-4 [abbreviated]
No .: hydrogenated SBIS-OH (4)] : a triblock copolymer composed of a hydrogenated polystyrene block / 1,3-butadiene / isoprene copolymer block / polystyrene block having a hydroxyl group at the terminal (refractive index: 1. 54
4): [Contents: Number average molecular weight of two polystyrene blocks =
19500, number average molecular weight of 1,3-butadiene / isoprene copolymer block = 21000, number average molecular weight of triblock copolymer = 60000, hydroxyl group bonded to terminal of one polystyrene block, average in triblock copolymer Hydroxyl content = 0.7 / molecule, 1,3
The molar ratio of 1,3-butadiene units to isoprene units in the butadiene / isoprene copolymer block = 1
/ 1, unsaturation in 1,3-butadiene and 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 and isoprene copolymer block
%, 1,4-bond amount in isoprene unit = 95%,
3,4-bond amount = 5%]

O Hydrogenated product of block copolymer-5 [approximately
No .: hydrogenated SBIS-OH (5)] : triblock copolymer composed of hydrogenated polystyrene block / 1,3-butadiene / isoprene copolymer block / polystyrene block having a hydroxyl group at the terminal (refractive index: 1. 51
3): [Contents: Number average molecular weight of two polystyrene blocks =
6100, number average molecular weight of 1,3-butadiene and isoprene copolymer block = 22,800, number average molecular weight of triblock copolymer = 35,000, hydroxyl group bonded to terminal of one polystyrene block, average in triblock copolymer Hydroxyl group content = 0.7 / molecule, 1,3-
1,1 in butadiene and isoprene copolymer block
The molar ratio of 3-butadiene units to isoprene units = 1 /
Unsaturation in 1,1,3-butadiene / isoprene copolymer block = 5% (95% hydrogenation); Styrene unit content in triblock copolymer before hydrogenation =
65% by weight, 1,4-bond amount = 95%, 1,2-bond amount = 5% in 1,3-butadiene and 1,3-butadiene units in the isoprene copolymer block before hydrogenation,
1,4-bond amount in isoprene unit = 95%, 3,
4-bond amount = 5%]

○ Polypropylene (abbreviation: PP) : “Mitsubishi Polypro EX6” manufactured by Mitsubishi Chemical Corporation ○ Polyethylene (abbreviation: PE) : “Mirason NEO23H” manufactured by Mitsui Petrochemical Industries, Ltd. ○ Polystyrene (abbreviation: PS) : Sumitomo Chemical "Sumiprite M192" manufactured by Kogyo Co., Ltd. ○ Ethylene-vinyl acetate copolymer (abbreviation: EVOH) :
"EVAL ES-F101" manufactured by Kuraray Co., Ltd. ○ Polyvinyl chloride (abbreviation: PVC) : "Shin-Etsu PVCTK-500" manufactured by Shin-Etsu Chemical Co., Ltd. ○ Polyamide ( abbreviation: PA) : "U" manufactured by Ube Industries, Ltd.
BE Nylon 1013B "○ Polycarbonate (abbreviation: PC) :“ Panlite L-1225 ”manufactured by Teijin Chemicals Limited ○ Vinylidene chloride copolymer (abbreviation: PVDC) : Copolymer of 82% by weight of vinylidene chloride and 18% by weight of vinyl chloride A polymerized resin containing 1.7 parts by weight of dibutyl sebacate as a plasticizer and 1.0 part by weight of epoxidized soybean oil with respect to 100 parts by weight of the copolymer resin. ○ Polymethyl methacrylate (abbreviation: PMMA) : “Parapet EH” manufactured by Kuraray Co., Ltd. ○ Polyethylene terephthalate (abbreviation: PET) : “Kurapet KS760K” manufactured by Kuraray Co., Ltd. ○ Polyoxymethylene (abbreviation: POM) : manufactured by Polyplastics Co., Ltd. "Duracon M90-44" ○ Acrylonitrile-butadiene-styrene copolymer
(Abbreviation: ABS) : "JSR" manufactured by Nippon Synthetic Rubber Co., Ltd.
ABS82 "

Example 1 [Production of Thermoplastic Polymer Composition (a)] (1) TPU previously dried (refractive index 1.51)
2) 50 parts by weight and 50 parts by weight of hydrogenated SBIS-OH (1) (refractive index 1.513) are premixed, supplied to a two extruder, melt-kneaded at 220 ° C., extruded into a strand, and cut. Thus, a pellet of the thermoplastic polymer composition was produced, and the pellet was aged for 6 hours in a vacuum drier at 80 ° C. to obtain a thermoplastic polymer composition [Thermoplastic polymer composition (a)]. (2) The melt viscosity ηa of the thermoplastic polymer composition (a) obtained in the above (1) was measured by the method described above, and was as shown in Table 2 below. (3) The thermoplastic polymer composition (a) obtained in the above (1) is supplied to an extruder (a single-screw extruder with a T-die), and the maximum temperature during extrusion is 220 Extrusion molding at a temperature of 100 ° C.
Was manufactured. A test piece was taken from the film, and its haze value and tensile strength were measured by the methods described above. The results were as shown in Table 2 below.

Examples 2 to 6 [Production of Thermoplastic Polymer Compositions (b) to (f)] (1) Thermoplastic polyurethane and aromatic vinyl compound / conjugated diene block copolymer shown in Table 2 below After each of the combined hydrogenated products was dried in advance, they were premixed in the proportions shown in Table 2, and pellets of the thermoplastic polymer composition were produced in the same manner as in Example 1 using the premixed mixture. , And aged in a vacuum dryer at 80 ° C for 6 hours.
Each thermoplastic polymer composition was prepared [Thermoplastic polymer compositions (b) to (f)]. (2) The melt viscosities ηa of the thermoplastic polymer compositions (b) to (f) obtained in the above (1) were measured by the above-mentioned method, and were as shown in Table 2 below. (3) Each of the thermoplastic polymer compositions (b) to (f) obtained in the above (1) is supplied to an extruder (one in which a T-die is connected to a single-screw extruder) and is extruded. Extrusion was performed at a maximum temperature of 220 to 250 ° C. to produce a film having a thickness of 100 μm. A test piece was taken from the film, and its haze value and tensile strength were measured by the methods described above.
Was as shown in FIG.

<< Comparative Examples 1 and 2 >> [Production of thermoplastic polymer compositions (g) and (h)] (1) Thermoplastic polyurethane and aromatic vinyl compound / conjugated diene block copolymer shown in Table 2 below After each of the combined hydrogenated products was previously dried, they were premixed in the proportions shown in Table 2, and pellets of the thermoplastic polymer composition were produced using the premixed materials in the same manner as in Example 1. , And aged in a vacuum dryer at 80 ° C for 6 hours.
The respective thermoplastic polymer compositions were obtained [Thermoplastic polymer compositions (g) and (h)]. (2) The melt viscosities ηa of the thermoplastic polymer compositions (g) and (h) obtained in the above (1) were measured by the method described above, and were as shown in Table 2 below. (3) Each of the thermoplastic polymer compositions (g) and (h) obtained in the above (1) is supplied to an extruder (one in which a T-die is connected to a single-screw extruder) and is extruded. Extrusion was performed with the maximum temperature set at 220 ° C. to produce a film having a thickness of 100 μm. A test piece was taken from the film, and its haze value and tensile strength were measured by the methods described above. The results were as shown in Table 2 below.

[0116]

[Table 2]

As is clear from the results in Table 2 above, the hydrogenated product of the thermoplastic polyurethane and the aromatic vinyl compound / conjugated diene block copolymer was prepared in a ratio of 20:80 to 80: 2.
And a difference (Δn) between the refractive index of the thermoplastic polyurethane and the hydrogenated product of the aromatic vinyl compound / conjugated diene block copolymer (Δn) is 0.005.
And a melt viscosity ηa (measured at a temperature of 22 ° C. and a shear rate of 100 sec ⁻¹ ) of 150 to 10000 Pa · s
In the thermoplastic polymer compositions of Examples 1 to 6 in the range of, the film obtained therefrom has an extremely small haze value and excellent transparency, and the film has high tensile strength and mechanical properties. It can be seen that is also excellent.

On the other hand, even a thermoplastic polymer composition comprising a hydrogenated product of a thermoplastic polyurethane and an aromatic vinyl compound / conjugated diene block copolymer has a small melt viscosity ηa of 100 Pa · s. In the case of the thermoplastic polymer composition of Comparative Example 1 which is out of the range of the invention, the melt moldability is inferior and holes are produced during the production of the film. Further, the film obtained therefrom has a haze value of Example 1. That the transparency is inferior to that of ~ 6,
Further, it can be seen that the tensile strength is extremely low and the mechanical properties are inferior.

Further, even in the case of a thermoplastic polymer composition comprising a hydrogenated product of a thermoplastic polyurethane and an aromatic vinyl compound / conjugated diene block copolymer, the melt viscosity .eta. And the difference (Δn) between the refractive index of the thermoplastic polyurethane and the refractive index of the hydrogenated product of the aromatic vinyl compound / conjugated diene block copolymer is larger than 0.005 and is within the range of the present invention. In the thermoplastic polymer composition of Comparative Example 2, the haze value of the film obtained therefrom is extremely large and the transparency is inferior, and the tensile strength is extremely low and the mechanical properties are greatly inferior. Recognize.

Example 7 [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (a) / PVDC / Polymer Composition (a) / PP] (1) Three extruders were used. PP, the polymer composition (a) obtained in Example 1 and PVDC are supplied to each extruder using an extruder connected to one die, and the maximum temperature at the time of extrusion is 240 ° C. The polymer composition (a) was set at 220 ° C. and the PVDC at 200 ° C., and the PP (50 μm) /
Polymer composition (a) (10 μm) / PVDC (50 μm)
m) / polymer composition (a) (10 μm) / PP (50 μm)
m), a co-extrusion molding was carried out so as to form a five-layer structure, and both surfaces were a PP layer and a middle was a PVDC layer, and a polymer composition (a) was provided between the PP layer and the middle 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) above, except that the thickness of the two polymer composition (a) layers interposed between the PP layer and the PVDC layer was 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (a) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. Further, PVDC intermediate between the polymer composition (a) layer and the layered structure obtained in the above (1).
The adhesive strength between the layers was 820 g / cm, indicating a high value. Further, the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are both excellent in transparency, and when the packaging is carried out using the laminated structure, the contents are excellent. I could see through.

Example 8 [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b) / PVDC / Polymer Composition (b) / PP] (1) Used in Example 7 Using the same extrusion molding apparatus as above, PP, the thermoplastic polymer composition (b) obtained in Example 2 and PVDC were supplied to each extruder, and the maximum temperature during extrusion was 240 ° C for PP, The polymer composition (b) was set to 220 ° C. and the PVDC to 200 ° C., and the PP (50 μm) /
Polymer composition (b) (10 μm) / PVDC (50 μm)
m) / polymer composition (b) (10 μm) / PP (50 μm)
m), a co-extrusion molding was carried out so as to form a five-layer structure in which the polymer composition (b) was formed between the PP layer and the intermediate layer. ) A laminated structure composed of five layers, each layer being interposed, was produced. (2) A laminated structure composed of five layers was prepared in the same manner as in (1) above, except that the thickness of the two polymer composition (b) layers interposed between the PP layer and the PVDC layer was 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (b) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. Further, PVDC intermediate between the polymer composition (b) layer and the intermediate layer in the laminated structure obtained in (1) above.
The adhesive strength between the layers was 870 g / cm, indicating a high value. Further, the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are both excellent in transparency, and when the packaging is carried out using the laminated structure, the contents are excellent. I could see through.

Example 9 Production of a Laminated Structure Consisting of Five Layers of PP / Polymer Composition (d) / PVC / Polymer Composition (d) / PP (1) Used in Example 7 Using the same extrusion molding apparatus as above, PP, the thermoplastic polymer composition (d) obtained in Example 4 and PVC were supplied to each extruder, and the maximum temperature during extrusion was 240 ° C. for PP, Polymer composition (d)
Is set to 220 ° C and PVC to 190 ° C.
Five-layer structure in which PP (50 μm) / polymer composition (d) (10 μm) / PVC (50 μm) / polymer composition (d) (10 μm) / PP (50 μm) are laminated in this order from the die of the extrusion molding apparatus. And co-extrusion molding
A laminated structure composed of five layers in which both surfaces were a PP layer and an intermediate layer was a PVC layer, and a polymer composition (d) layer was interposed between the PP layer and the intermediate layer, respectively. (2) A laminated structure composed of five layers was prepared in the same manner as in (1) above, except that the thickness of the two polymer composition (d) 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 adhesive strength between the layers of the laminated structure obtained in the above (1) was measured by the method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (d) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. In addition, the adhesive strength between the polymer composition (d) layer and the intermediate PVC layer in the laminated structure obtained in the above (1) was 950 g / cm, which was a high value. Furthermore, the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are both excellent in transparency, and the contents are clarified when packaged using the laminated structure. It was possible to see through well.

Example 10 Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b) / EVOH / Polymer Composition (b) / PP (1) Used in Example 7 Using the same extruder as above, PP, the thermoplastic polymer composition (b) obtained in Example 2 and EVOH were supplied to each extruder, and the maximum temperature during extrusion was 240 ° C. for PP, The polymer composition (b) was set at 220 ° C. and the EVOH was set at 220 ° C., and the PP (50 μm) /
Polymer composition (b) (10 μm) / EVOH (50 μm)
m) / polymer composition (b) (10 μm) / PP (50 μm)
m), and co-extrusion is performed so as to form a five-layer structure. Both surfaces are a PP layer, an intermediate layer is an EVOH layer, and a polymer composition (b) is provided between the PP layer and the intermediate layer. ) A laminated structure composed of five layers, each layer being 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 (b) layers interposed between the PP layer and the EVOH layer was 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (b) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. Further, the polymer composition (b) layer and the intermediate EVOH in the laminate structure obtained in (1) above
The adhesive strength between the layers was 840 g / cm, indicating a high value. Furthermore, both the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are excellent in transparency, and when the packaging is carried out using the laminated structure, the contents can be seen well. We were able to.

Example 11 [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (c) / PET / Polymer Composition (c) / PP] (1) Used in Example 7 Using the same extrusion molding apparatus as above, PP, the thermoplastic polymer composition (c) obtained in Example 3 and PET were supplied to each extruder, and the maximum temperature during extrusion was 240 ° C. for PP, Polymer composition (c)
Is set to 245 ° C and PET is set to 270 ° C.
Five-layer structure in which PP (50 μm) / polymer composition (c) (10 μm) / PET (50 μm) / polymer composition (c) (10 μm) / PP (50 μm) are laminated in this order from the die of the extrusion molding apparatus. And co-extrusion molding
A laminated structure composed of five layers in which both surfaces were a PP layer and an intermediate layer was a PET layer, and a polymer composition (c) layer was interposed between the PP layer and the intermediate layer, respectively. (2) A laminated structure consisting of five layers was prepared in the same manner as in (1) above, except that the thickness of the two polymer composition (c) layers interposed between the PP layer and the PET layer was 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. Further, the adhesive strength between the polymer composition (c) layer and the intermediate PET layer in the laminated structure obtained in the above (1) was 1,050 g / cm, which was an extremely high value. Furthermore, the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are both excellent in transparency, so that the contents can be seen well when packaged using the laminated structure. We were able to.

Example 12 Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (c) / PA / Polymer Composition (c) / PP (1) Used in Example 7 Using the same extrusion molding apparatus as above, PP, the thermoplastic polymer composition (c) obtained in Example 3, and PA were supplied to each extruder, and the maximum temperature during extrusion was 240 ° C. The polymer composition (c) was set at 245 ° C. and the PA was set at 255 ° C., and PP (50 μm) / polymer composition (c) (10 μm) / PA (50 μm) were passed through a die of an extrusion molding apparatus. / Polymer composition (c) (10 μm) / PP (50 μm) and co-extrusion was performed so as to form a five-layer structure, both surfaces being a PP layer, an intermediate layer being a PA layer, 5 layers each having a polymer composition (c) layer interposed between the layer and the intermediate layer Was manufactured. (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 (c) layers interposed between the PP layer and the PA layer was 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. Further, the adhesive strength between the polymer composition (c) layer and the intermediate PA layer in the laminated structure obtained in the above (1) was 1540 g / cm, which was an extremely high value. Furthermore, both the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are excellent in transparency, and when the packaging is carried out using the laminated structure, the contents are well seen through. I was able to.

Example 13 Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (c) / PMMA / Polymer Composition (c) / PP (1) Used in Example 7 Using the same extrusion molding apparatus as above, PP, the thermoplastic polymer composition (c) obtained in Example 3, and PMMA were supplied to each extruder, and the maximum temperature at the time of extrusion was 240 ° C. The polymer composition (c) was set to 245 ° C. and the PMMA was set to 250 ° C., and the PP (50 μm) /
Polymer composition (c) (10 μm) / PMMA (50 μm)
m) / polymer composition (c) (10 μm) / PP (50 μm)
m), a co-extrusion molding was carried out so as to form a five-layer structure, and both surfaces were a PP layer and an intermediate layer was a PMMA layer, and a polymer composition (c) was provided between the PP layer and the intermediate layer. ) A laminated structure composed of five layers, each layer being interposed, was produced. (2) A laminated structure consisting of five layers was prepared in the same manner as in (1) above, except that the thickness of the two polymer composition (c) layers interposed between the PP layer and the PMMA layer was 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. In addition, the polymer composition (c) layer and the intermediate PMMA in the laminated structure obtained in (1) above
The adhesive strength between the layers was 760 g / cm, indicating a high value. Furthermore, both the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are excellent in transparency, and when the packaging is carried out using the laminated structure, the contents are well seen through. I was able to.

Example 14 Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (c) / PC / Polymer Composition (c) / PP [1] Used in Example 7 Using the same extruder as above, PP, the thermoplastic polymer composition (c) obtained in Example 3 and PC were supplied to each extruder, and the maximum temperature during extrusion was 240 ° C for PP, The polymer composition (c) was set to 250 ° C. and the PC to 270 ° C., and PP (50 μm) / polymer composition (c) (10 μm) / PC (50 μm) was passed through a die of an extrusion molding apparatus. / Polymer composition (c) (10 μm) / PP (50 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 PC layer, and PP 5 layers each having a polymer composition (c) layer interposed between the layer and the intermediate layer Was manufactured. (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 (c) layers interposed between the PP layer and the PC layer was 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. Further, the adhesive strength between the polymer composition (c) layer and the intermediate PC layer in the laminated structure obtained in the above (1) was 920 g / cm, which was a high value. Furthermore, both the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are excellent in transparency, and when the packaging is carried out using the laminated structure, the contents can be improved. I could see through.

Example 15 Production of Laminated Structure Consisting of Five Layers of PVC / Polymer Composition (e) / PS / Polymer Composition (e) / PVC (1) Used in Example 7 Using the same extrusion molding apparatus as above, PVC, the thermoplastic polymer composition (e) obtained in Example 5, and PS were supplied to each extruder, and the maximum temperature during extrusion was 190 ° C. The polymer composition (e) was set at 225 ° C. and the PS was set at 240 ° C., and PVC (50 μm) / polymer composition (e) (10 μm) / PS (50 μm) was passed through a die of an extrusion molding apparatus. / Polymer composition (e) (10 μm) / PVC (50 μm) and co-extrusion molding was performed in a five-layer structure, both surfaces were a PVC layer, an intermediate layer was a PS layer, and PV
A five-layer laminated structure in which the polymer composition (e) layer was interposed between the C layer and the intermediate layer was manufactured. (2) A laminated structure consisting of five layers was prepared in the same manner as in (1) above, except that the thickness of the two polymer composition (e) layers interposed between the PVC layer and the PS layer was 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 PV of both surfaces was measured.
The adhesive strength between the layer C and the polymer composition (e) layer inside the layer C was 920 g / cm, indicating a high value. In addition, the adhesion between the polymer composition (e) layer and the intermediate PS layer in the laminated structure obtained in the above (1) is extremely strong, so that peeling cannot be performed. Did not do. Furthermore, both the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are excellent in transparency, and when the packaging is carried out using the laminated structure, the contents can be improved. I could see through.

Example 16 Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (f) / PVDC / Polymer Composition (f) / PP (1) Used in Example 7 PP, the thermoplastic polymer composition (f) obtained in Example 6 and PVDC were supplied to each extruder using the same extrusion molding apparatus as above, and the maximum temperature during extrusion was 240 ° C. The polymer composition (f) was set to 220 ° C. and PVDC to 200 ° C., and PP (50 μm) /
Polymer composition (f) (10 μm) / PVDC (50 μm)
m) / polymer composition (f) (10 μm) / PP (50 μm)
m), a co-extrusion molding was carried out so as to form a five-layer structure in which the two layers were a PP layer and an intermediate layer was a PVDC layer, and the polymer composition (f) was interposed between the PP layer and the intermediate layer. ) A laminated structure composed of five layers, each layer being 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 (f) layers interposed between the PP layer and the PVDC layer was 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (f) layer inside the layer was extremely strong and could not be released, and therefore, the measurement of the adhesion strength was not performed. Further, PVDC intermediate between the polymer composition (f) layer and the intermediate layer in the laminated structure obtained in (1) above.
The adhesive strength between the layers was 1040 g / cm, which was a high value. Furthermore, both the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) are excellent in transparency, and when the packaging is carried out using the laminated structure, the contents can be seen well. We were able to.

Example 17 Production of a Laminated Structure Consisting of Five Layers of PP / Polymer Composition (b) / POM / Polymer Composition (b) / PP (1) Used in Example 7 Using the same extrusion molding apparatus as above, PP, the thermoplastic polymer composition (b) obtained in Example 2 and POM were supplied to each extruder, and the maximum temperature at the time of extrusion was 240 ° C. Polymer composition (b)
Is set to 220 ° C. and POM to 200 ° C.
Five-layer structure in which PP (50 μm) / polymer composition (b) (10 μm) / POM (50 μm) / polymer composition (b) (10 μm) / PP (50 μm) are stacked in this order from the die of the extrusion molding apparatus. And co-extrusion molding
A laminated structure composed of five layers in which both surfaces were a PP layer and an intermediate layer was a POM layer, and a polymer composition (b) layer was interposed between the PP layer and the intermediate layer, respectively. (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 (b) layers interposed between the PP layer and the POM 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (b) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. Further, the adhesive strength between the polymer composition (b) layer and the intermediate POM layer in the laminated structure obtained in the above (1) was 1500 g / cm, which was a high value.

<< Example 18 >> [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (c) / ABS / Polymer Composition (c) / PP] (1) Used in Example 7 The PP, the thermoplastic polymer composition (c) obtained in Example 3 and ABS were supplied to each extruder using the same extrusion molding apparatus as described above, and the maximum temperature at the time of extrusion was 240 ° C. Polymer composition (c)
Is set to 250 ° C and ABS to 260 ° C.
Five-layer structure in which PP (50 μm) / polymer composition (c) (10 μm) / ABS (50 μm) / polymer composition (c) (10 μm) / PP (50 μm) are laminated in this order from the die of the extrusion molding apparatus. And co-extrusion molding
A laminated structure composed of five layers in which both surfaces were a PP layer and an intermediate layer was an ABS layer, and a polymer composition (c) layer was interposed between the PP layer and the intermediate layer, respectively. (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 (c) layers interposed between the PP layer and the ABS 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 method described above, the PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer inside the layer was extremely strong and could not be peeled off, so that the adhesion strength was not measured. Further, the adhesive strength between the polymer composition (c) layer and the intermediate ABS layer in the laminated structure obtained in the above (1) was 1200 g / cm, which was a high value.

<< Comparative Example 3 >> [Production of Laminated Structure Consisting of Five Layers of PE / TPU / EVOH / TPU / PE] (1) Using the same extrusion molding apparatus as used in Example 7, PE, the above-mentioned TPU and EVOH are supplied to an extruder, and the maximum temperature during extrusion is adjusted to 23
5 ° C., TPU at 220 ° C., EVOH at 210 ° C., and PE (50
μm) / TPU (10 μm) / EVOH (50 μm)
/ TPU (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 and an intermediate layer was an EVOH layer. A laminated structure composed of five layers with a TPU interposed therebetween was manufactured. (2) 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 PE layer on both surfaces and the TPU layer on the inner side was 20 g / m.
And showed a very low value.

Comparative Example 4 [PE / hydrogenated SBIS-OH (1) / PVDC / hydrogenated S
Production of Laminated Structure Consisting of Five Layers of BIS-OH (1) / PE] (1) Using the same extrusion molding apparatus as used in Example 7, PE was used for each extruder, and hydrogenated SBIS described above was used. −
OH (1) and PVDC are supplied, and the maximum temperature at the time of extrusion is 235 ° C. for PE and 2 for hydrogenated SBIS-OH (1).
20 ° C., PVDC was set to 200 ° C., and PE (50 μm) / hydrogenated SBI was passed through the die of the extrusion molding apparatus.
S-OH (1) (10 μm) / PVDC (50 μm) /
Hydrogenated SBIS-OH (1) (10 μm) / PE (50 μm)
m), co-extrusion was performed so as to form a five-layer structure, both surfaces were a PE layer, an intermediate layer was a PVDC layer, and hydrogenated SBIS-OH ( 1)
A laminated structure consisting of five layers with each layer interposed was produced. (2) The laminated structure obtained in the above (1) was evaluated for its film formability by the above-mentioned method.
Met. When the adhesive strength between the layers of the laminated structure obtained in the above (1) was measured by the above-mentioned method, the hydrogenated S
The adhesive strength between the BIS-OH (1) layer and the PVDC layer inside it was as low as 10 g / cm.

Comparative Example 5 [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (g) / PVDC / Polymer Composition (g) / PP] (1) Used in Example 7 Using the same extruder as above, PP, the thermoplastic polymer composition (g) obtained in Comparative Example 1 and PVDC were supplied to each extruder, and the maximum temperature during extrusion was 240 ° C. for PP, The polymer composition (g) was set to 220 ° C. and the PVDC was set to 200 ° C., and PP (50 μm) /
Polymer composition (g) (10 μm) / PVDC (50 μm)
m) / polymer composition (g) (10 μm) / PP (50 μm)
m), a co-extrusion molding was carried out so as to form a five-layer structure in which the two layers were a PP layer and an intermediate layer was a PVDC layer, and a polymer composition (g) was provided between the PP layer and the intermediate layer. ) A laminated structure composed of five layers, each layer being interposed, was produced. (2) The multilayer structure obtained in the above (1) was evaluated for film forming properties by the above-described method. As a result, the surface was severely roughened and was poor (x). 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 (g) layer inside the PP layer was found. The adhesive was so strong that it could not be peeled off, so that the adhesive strength was not measured. Further, the adhesive strength between the polymer composition (g) layer and the intermediate PVDC layer in the laminated structure obtained in the above (1) is 670.
g / cm. Furthermore, the laminated structure obtained from the laminated structure obtained in the above (1) was not sufficiently transparent, and the contents could not be seen through when the package was packaged using the laminated structure.

<< Comparative Example 6 >> [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (g) / PA / Polymer Composition (g) / PP] (1) Used in Example 7 Using the same extruder as above, PP, the thermoplastic polymer composition (g) obtained in Comparative Example 1 and PA were supplied to each extruder, and the maximum temperature during extrusion was 240 ° C. for PP, The polymer composition (g) was set to 240 ° C. and the PA was set to 240 ° C., and PP (50 μm) / polymer composition (g) (10 μm) / PA (50 μm) was passed through a die of an extrusion molding apparatus. / Polymer composition (g) (10 μm) / PP (50 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 PA layer, and PP was A polymer composition (g) layer between the layer and the intermediate layer. A laminated structure was manufactured. (2) When the laminated structure obtained in the above (1) was evaluated for film forming properties by the above-described method, the surface roughness was extremely severe and extremely poor (×), and a test piece suitable for a peel test. Could not be collected, and the peel test was not performed. Further, the laminated structure obtained in the above (1) was opaque.

<< Comparative Example 7 >> [Production of Laminated Structure Consisting of Five Layers of PP / Polymer Composition (h) / PET / Polymer Composition (h) / PP] (1) Used in Example 7 PP, the thermoplastic polymer composition (h) obtained in Comparative Example 2 and PET were supplied to each extruder using the same extrusion molding apparatus as described above, and the maximum temperature during extrusion was 240 ° C. Polymer composition (h)
Is set to 250 ° C. and PET to 270 ° C.
Five-layer structure in which PP (50 μm) / polymer composition (h) (10 μm) / PET (50 μm) / polymer composition (h) (10 μm) / PP (50 μm) are laminated in this order from the die of the extrusion molding apparatus. And co-extrusion molding
A laminated structure composed of five layers in which both surfaces were a PP layer and an intermediate layer was a PET layer, and a polymer composition (h) layer was interposed between the PP layer and the intermediate layer, respectively. (2) When the laminated structure obtained in the above (1) was evaluated for its film forming property by the above-described method, the surface roughness was extremely severe and was extremely poor (x), and the test piece was suitable for a peel test. Could not be collected, and the peel test was not performed. In addition, the laminated structure obtained in the above (1) was opaque.

[0137]

The thermoplastic polymer composition of the present invention exhibits high melt adhesion to both low-polarity polymers and high-polarity polymers, and also has a high degree of adhesion to other materials. Shows melt adhesion. Therefore, when the thermoplastic polymer composition of the present invention is used, various laminated structures can be formed without causing problems such as environmental pollution, deterioration of the working environment, and complication of the bonding process in the conventional solvent-based adhesive. It can be manufactured safely and with good workability and high productivity by the melt bonding method. Moreover, since the thermoplastic polymer composition of the present invention has high adhesive strength to various materials as described above, the laminated structure obtained by using the thermoplastic polymer composition of the present invention has high durability, There is no problem such as peeling. Moreover, the thermoplastic polymer composition of the present invention has excellent transparency. Therefore, various molded articles obtained by using the thermoplastic polymer composition of the present invention can be seen from the outside, and a transparent material is bonded by using the thermoplastic polymer composition of the present invention as an adhesive. In the laminated structure obtained as described above, an object to be packaged and the like packaged by the laminated structure can be easily seen through from the outside due to its excellent transparency. Furthermore, since the thermoplastic polymer composition of the present invention is excellent in melt moldability, various molded articles and laminated structures can be employed in conventional thermoplastic polymers with good workability and good finish. It can be produced smoothly and with good productivity by the various melt molding methods used.

In particular, the thermoplastic polymer composition of the present invention
Saponified ethylene-vinyl acetate copolymer, vinylidene chloride polymer and polyamide with excellent gas barrier properties, vinyl chloride polymer with excellent transparency, chemical resistance, printability, mechanical properties, etc., chemical resistance and machinery Polyester with excellent mechanical properties, polycarbonate with excellent transparency and impact resistance, acrylic polymer with excellent transparency, weather resistance and printability, polyoxymethylene and vinyl cyanide compounds with excellent mechanical properties and moldability , Copolymers of at least one selected from conjugated diene compounds and olefin compounds with aromatic vinyl compounds, olefin polymers such as polyethylene and polypropylene having excellent heat sealing properties, and styrene polymers having excellent transparency and rigidity Shows high melt adhesion to any of them.

Therefore, taking advantage of the above-mentioned properties, the thermoplastic polymer composition of the present invention comprises (A) a polymer layer mainly composed of at least one of an olefin polymer and a styrene polymer; A) a polymer layer comprising the thermoplastic polymer composition of the present invention; 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-based material. Polymer, polyoxymethylene,
And a polymer layer mainly composed of at least one of a copolymer of an aromatic vinyl compound and at least one selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound, wherein the polymer layer (A) / It is particularly suitable for the production of the laminated structure (A) of the present invention, which has at least a part of the structure laminated in the order of the united layer (B) / polymer layer (C). The above-mentioned laminated structure (a) is used for 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, and electrical insulation. Film, adhesive film and tape base material, marking film, agricultural film, table cloth, raincoat, umbrella, curtain,
It can be effectively used for various purposes such as miscellaneous goods such as covers, and lamination with metal plates and other materials. Then, by performing a melt-molded lamination method such as melt co-extrusion molding using the thermoplastic polymer composition of the present invention, various laminated structures having high adhesive strength between layers can be produced with a small number of steps and with high productivity. It can be manufactured well and smoothly.

The thermoplastic polymer composition of the present invention comprises
Taking advantage of the above excellent melt adhesion, it can be effectively used alone as a hot melt adhesive. Further, the thermoplastic polymer composition of the present invention comprises a thermoplastic polyurethane having excellent elasticity and an aromatic vinyl compound / conjugated diene block copolymer having excellent elasticity and / or a hydrogenated product thereof. The plastic polymer composition has good elasticity as a whole, and therefore can be effectively used for various applications requiring characteristics such as elasticity, cushioning, cushioning, and impact resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 175/04 C09J 175/04

Claims (11)

[Claims] (I) A thermoplastic polyurethane, at least one of 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, [Thermoplastic polyurethane]: a thermoplastic polymer composition containing [block copolymer and / or hydrogenated product thereof] in a weight ratio of 20:80 to 80:20; (ii) thermoplastic polyurethane , Number average molecular weight 500
A thermoplastic polyurethane obtained by the reaction of a polymer polyol, an organic diisocyanate and a chain extender of from 10,000 to 10,000; (iii) a refractive index of the thermoplastic polyurethane measured at 25 ° C., and the above-mentioned block copolymer and / or Or the difference (Δn) from the refractive index of the hydrogenated product is 0.005 or less; and (iv) the melt viscosity ηa of the thermoplastic polymer composition (temperature 2
(Measured at 20 ° C. and a shear rate of 100 sec ⁻¹ ) is 150-1.
0000 Pa · s; a thermoplastic polymer composition, 2. The thermoplastic polyurethane comprises a polymer polyol having a number average molecular weight of 500 to 10,000 having a hydroxyl number f per molecule in the range of 2.005 ≦ f ≦ 2.1, an organic diisocyanate and a chain elongation. The thermoplastic polymer composition according to claim 1, which is a thermoplastic polyurethane obtained by reaction with an agent. 3. The thermoplastic polyurethane has an isocyanate group / hydroxyl group equivalent ratio R of 0.9 ≦ R ≦ 1.30.
So that the number average molecular weight is 500 to 100.
3. The thermoplastic polymer composition according to claim 1, which is a thermoplastic polyurethane obtained by reacting a high molecular polyol, an organic diisocyanate, and a chain extender. 4. 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. The thermoplastic polymer composition according to claim 1. 5. The conjugated diene-based polymer block in the block copolymer composed of the aromatic vinyl compound-based polymer block and the conjugated diene-based polymer block and / or a hydrogenated product of the block copolymer is isoprene. The thermoplastic polymer composition according to any one of claims 1 to 4, which is a polymer block, a copolymer block of isoprene and butadiene and / or a hydrogenated polymer block thereof. 6. A molded article comprising the thermoplastic polymer composition according to claim 1. 7. A laminated structure comprising a polymer layer made of the thermoplastic polymer composition according to claim 1 and a layer made of another material. 8. The thermoplastic polymer composition according to claim 1, wherein (A) a polymer layer mainly composed of at least one of an olefin polymer and a styrene polymer; and (B) the thermoplastic polymer composition according to any one of claims 1 to 5. (C) saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide,
Polyester, polycarbonate, acrylic polymer,
A polymer layer mainly composed of at least one of polyoxymethylene and a copolymer of an aromatic vinyl compound and at least one selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound; 8. A structure having at least a part of a structure in which (A) / polymer layer (B) / polymer layer (C) are laminated in this order.
Laminated structure. 9. The laminated structure according to claim 8, which is manufactured by co-extrusion molding. 10. A polymer mainly composed of at least one of an olefin polymer and a styrene polymer; (b) the thermoplastic polymer composition according to any one of claims 1 to 5; And (c) saponified ethylene-vinyl acetate copolymer, vinylidene chloride polymer, vinyl chloride polymer, polyamide, polyester, polycarbonate, acrylic polymer, polyoxymethylene, vinyl cyanide compound, conjugated diene compound A layer of a polymer (a) and a layer of a polymer (c) using at least a polymer mainly composed of at least one of copolymers of an aromatic vinyl compound and at least one selected from olefin compounds. 10. Co-extrusion molding with a layer of the polymer composition (b) interposed therebetween.
A method for producing a laminated structure. 11. A hot melt adhesive comprising the thermoplastic polymer composition according to claim 1.