JP3497058B2 - Thermoplastic polymer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 above 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 is a polymer having low polarity such as polyethylene, olefin polymers such as polypropylene and styrene polymers, and saponified ethylene-vinyl acetate copolymers.
Vinylidene chloride polymer, vinyl chloride polymer, polyamide, polyester, polycarbonate, acrylic polymer, polyoxymethylene, and at least one selected from vinyl cyanide compound, conjugated diene compound and olefin compound and aromatic vinyl compound A specific thermoplastic resin that adheres strongly to any highly polar polymer such as a copolymer with and has high melt adhesion to other materials, and also has excellent transparency. A thermoplastic polymer composition containing a polyurethane and a block copolymer, a molded article made thereof, a laminated structure having a polymer layer made of the thermoplastic polymer composition, and a hot melt adhesive, The thermoplastic polymer composition of the present invention can be widely used in various laminated structures including various laminated structures by taking advantage of the above excellent properties. It can be effectively used in applications.

[0002]

2. Description of the Related Art Saponified film of ethylene-vinyl acetate copolymer, polyvinylidene chloride film, and polyamide film are excellent in gas barrier property. Laminated with a plastic film that has excellent heat sealability and other properties,
Widely used in packaging materials and other fields. Polyvinyl chloride film is excellent in its transparency, chemical resistance, printability, mechanical properties, etc., and polyester film is excellent in mechanical properties, chemical resistance, etc.,
Utilizing those characteristics, alone or polyethylene,
It is used in a wide range of applications by laminating it with polystyrene and other plastic films. Furthermore, the polycarbonate film is excellent in transparency and impact resistance, and the polymethylmethacrylate film is excellent in transparency, weather resistance, printability, and the like. Being tried.

In the production of a laminated film, a solvent type adhesive such as a polyurethane solution is used for adhering and laminating between plastic films, or laminating with a hot melt adhesive. . In particular,
When laminating an ethylene-vinyl acetate copolymer saponified 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 is conventionally used. However, there is a problem in terms of pollution of the natural environment, deterioration of working environment and safety due to the use of organic solvents, and there is a demand for a lamination technique that does not use a solvent-type adhesive. Moreover, among these films, a polycarbonate film, an acrylic polymer film and the like have poor solvent resistance, so that it is necessary to be careful in selecting a solvent. Further, in the production of a laminated film using a solvent-based adhesive, an 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 also been manufactured in advance using a solvent-based adhesive. Therefore, the number of steps is extremely large, such as the step of manufacturing the laminated film in advance, the drying step for removing the solvent after adhering / laminating the films to each other, the solvent recovery step, and the work content becomes complicated.
There are various problems in that the manufacturing cost becomes high.

Further, it has been conventionally practiced to carry out melt coextrusion molding using a hot-melt type adhesive such as a fatty acid-modified polyolefin or an epoxy-modified polyolefin to produce a laminated film. However, since the laminated film thus obtained has a small adhesive strength between layers,
Delamination is likely to occur, and improvement thereof is required. Further, in many cases, such as a laminated film for a packaging material, a plastic laminated structure is required to be transparent so that an object to be packaged or the like can be seen from the outside. In that case, even if the plastic constituting the front and back layers is transparent, if the intermediate adhesive layer is opaque, a transparent laminated structure cannot be obtained. Therefore, there is a demand for a non-solvent type adhesive having excellent adhesiveness and excellent transparency.

[0005]

The object of the present invention is to show high melt adhesion to both low-polarity polymers and high-polarity polymers, and also to high melting properties to other materials. It exhibits adhesiveness and excellent transparency, which can avoid environmental pollution, deterioration of working environment, and complicated adhesion process that occur when using a solvent, and see through the packaged item from the outside. The present invention provides a thermoplastic polymer composition, a film, a sheet, and other molded articles made of the thermoplastic polymer composition. Further, it is an object of the present invention to provide a laminated structure having an adhesive layer made of 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,
A layer of polycarbonate with excellent transparency and impact resistance,
At least one selected from an acrylic polymer layer having excellent transparency, weather resistance and printability, a polyoxymethylene layer having excellent mechanical properties and molding processability, and 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 polymer such as polyethylene or polypropylene having excellent heat sealability, and / or a layer of a styrene polymer, and the production thereof It is intended to provide a method. And the objective of this invention is to provide the hot-melt adhesive agent which consists of the above-mentioned thermoplastic polymer composition.

[0006]

The present inventor has made various studies in order to solve the above problems. As a result, when a specific thermoplastic polyurethane and 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 in a specific ratio, , The thermoplastic polymer composition thus obtained exhibits high melt adhesion to both low-polarity polymers and high-polarity polymers, and also to other materials. Showing,
Moreover, it is also excellent in transparency, and therefore the thermoplastic polymer composition is suitable for the production of various molded products such as films and sheets and various laminated structures, and further as a hot melt adhesive. It was found to be effective. Then, the present inventors use the above-mentioned thermoplastic polymer composition to saponify ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide, polyester, polycarbonate, acrylic-based. A polymer layer containing a polymer, polyoxymethylene, and at least one kind of a copolymer of an aromatic vinyl compound and at least one kind selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound, and an olefin system At least one of polymer and styrenic polymer
When a polymer layer containing a seed is melt-bonded, the interlayer adhesion strength is high and delamination does not occur, and a high-quality laminated structure having excellent transparency is obtained without using a harmful organic solvent or the like. It can be obtained safely and with good processability and workability, and such a laminated structure can be obtained more smoothly by coextrusion of the above-mentioned polymer with the above-mentioned thermoplastic polymer composition. The present invention has been completed based on the findings and those findings.

That is, the present invention provides (i) at least a thermoplastic polyurethane, a block copolymer composed of an aromatic vinyl compound polymer block and a conjugated diene 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) Thermoplastic polyurethane has a number average molecular weight of 500
A thermoplastic polyurethane obtained by the reaction of a high molecular weight polyol of 10000, an organic diisocyanate and a chain extender; (iii) the refractive index of the thermoplastic polyurethane measured at 25 ° C., and the 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 (temperature 2 of the thermoplastic polymer composition.
Measured at 20 ° C. and a shear rate of 100 sec ⁻¹ ) is 150 to ¹
It is 0000 Pa.s; It is a thermoplastic polymer composition characterized by the above.

The present invention is a molded article made of the above-mentioned thermoplastic polymer composition. Further, the present invention is a laminated structure characterized by having a polymer layer made of the above-mentioned thermoplastic polymer composition and a layer made of another material. In particular, the present invention, as the above-mentioned laminated structure,
(A) A polymer layer mainly composed of at least one of an olefin polymer and a styrene polymer; (B)
Polymer layer composed of the above-mentioned thermoplastic polymer composition; and (C) saponified ethylene-vinyl acetate copolymer, vinylidene chloride polymer, vinyl chloride polymer, polyamide, polyester, polycarbonate, acrylic polymer , A polyoxymethylene, and a polymer layer mainly composed of at least one kind of a copolymer of an aromatic vinyl compound and at least one kind selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound;
Is a polymer layer (A) / polymer layer (B) / polymer layer (C)
The preferred embodiment includes a laminated structure having at least a part of the laminated structure in the order of.

The present invention further comprises (a) a polymer mainly composed of at least one of an olefin polymer and a styrene polymer; (b) the above-mentioned thermoplastic polymer composition; and (c) ethylene. -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 A polymer mainly composed of at least one kind of copolymer of at least one kind of the aromatic vinyl compound and a polymer (a) layer and a polymer (c) layer. It is a method of producing a laminated structure by coextrusion molding with a layer of the composition (b) interposed.

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

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The thermoplastic polymer composition of the present invention is a thermoplastic polyurethane, and a block copolymer composed of 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 sometimes at least one hydrogenated aromatic vinyl compound / conjugated diene block copolymer.

The thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention is essentially a polymeric polyol,
It is a polyurethane obtained by reacting an organic diisocyanate and a chain extender.

As the polymer polyol which can be used for producing the thermoplastic polyurethane, polyester polyol, polycarbonate polyol, polyester polycarbonate polyol, polyether polyol and the like can be mentioned. The thermoplastic polyurethane is one of these polymer polyols or It can be formed by using two or more kinds.

The polyester polyol used for producing the thermoplastic polyurethane is obtained by, for example, subjecting a polycarboxylic acid component such as a polycarboxylic acid, an ester thereof, an ester-forming derivative such as an anhydride and the like to a direct ester reaction with a polyol component according to a conventional method. Alternatively, it can be obtained by transesterification.

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 dodecanedicarboxylic acid. Acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid Aliphatic dicarboxylic acids such as; terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid and other aromatic dicarboxylic acids; cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids; trimellitic acid and other tricarboxylic acids;
Examples thereof include ester-forming derivatives, and the polyester polyol can be formed by using one kind or two or more kinds of the above-mentioned polycarboxylic acid components. Among them, polyester polyol is
The polycarboxylic acid component is mainly produced by using an aliphatic carboxylic acid or an ester-forming derivative thereof, and optionally containing a small amount of trifunctional or higher polycarboxylic acid or an ester-forming derivative thereof. Is preferred.

Examples of the polyol component which is a raw material for producing a polyester polyol used for producing a thermoplastic polyurethane include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol and 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 mentioned, 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 by using a polyol component containing a small amount of a trifunctional or higher functional 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 two.

The polycarbonate polyol which can be used for producing the thermoplastic polyurethane is obtained, for example, by reacting a polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate or diaryl carbonate. As the polyol which is the current raw material for producing the polycarbonate polyol, the above-mentioned polyols which are the raw material 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 the polyester polycarbonate polyol which can be used for producing the thermoplastic polyurethane include those obtained by reacting a polyol, a polycarboxylic acid and a carbonate compound at the same time, and polyester polyester and polycarbonate polyol produced in advance. Examples thereof include those obtained by reacting with a carbonate compound and those obtained by reacting a polyol with a polycarboxylic acid.

Further, as an example of the polyether polyol which can be used in the production of the thermoplastic polyurethane, polyethylene glycol, polypropylene glycol, or poly (ethylene glycol) obtained by polymerizing a diol component is preferably present in the presence of a small amount of a trifunctional or higher functional polyol. Tetramethylene glycol and the like can be mentioned, and one or more of these can be used. Among them, it is preferable to use polytetramethylene glycol in which the number of hydroxyl groups per molecule is slightly higher than two.

Further, in the present invention, the number average molecular weight of the polymer polyol used for producing the thermoplastic polyurethane needs to be 500 to 10,000, and 700
Is preferably 5,000 to 5,000, more preferably 750 to 4,000. Number average molecular weight is 500 to 10
In the case of using a thermoplastic polyurethane produced by using a high molecular weight polyol outside the range of 000, melt moldability and coextrusion of a thermoplastic polymer composition containing the thermoplastic polyurethane and the block copolymer described above. sex,
Cold resistance and heat resistance tend to deteriorate. In addition,
The number average molecular weight as referred to in this specification is JIS K 1577.
The number average molecular weight calculated based on the hydroxyl value measured in accordance with

Further, the polymer polyol used for producing the thermoplastic polyurethane is preferably a polymer polyol having the number of hydroxyl groups 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. The number f of hydroxyl groups per molecule is 2.005 ≦
When the thermoplastic polyurethane obtained by using the polymer polyol in 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 high temperature is improved. It has good moldability when it is used to produce a laminated structure by co-melt extrusion molding with a thermoplastic polymer that needs to be melt-molded at high temperature (for example, polyester, polyamide, polycarbonate, etc.). Become.

The type of organic diisocyanate used in the production of the thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention is not particularly limited, and any of the organic diisocyanates conventionally used in the production of thermoplastic polyurethane can be used. Can be used. Among them, one or more of aromatic diisocyanates, alicyclic diisocyanates and aliphatic diisocyanates having a molecular weight of 500 or less are preferably used. Examples of such organic diisocyanates include 4,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,
4'-dicyclohexylmethane diisocyanate and the like can be mentioned, and 1 of these organic diisocyanates can be mentioned.
One kind or two or more kinds 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 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 the molecule is preferably used. Examples of such chain extenders include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol. , Bis- (β-hydroxyethyl)
Terephthalate, diols such as xylylene glycol; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, adipic dihydrazide, diamines such as isophthalic acid dihydrazide; amino Ethyl alcohol,
Examples thereof include amino alcohols such as aminopropyl alcohol, and one or more of these can be used. Of these, carbon numbers 2 to 1
An aliphatic diol of 0 is preferably used, and 1,4-butanediol is more preferably used.

In the thermoplastic polymer composition of the present invention, as the 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 higher functional polyol. The polymer polyol in which the number f of hydroxyl groups per molecule obtained in the above is in the above range of 2.005 to 2.1,
It is possible to use a thermoplastic polyurethane obtained by reacting with 4,4′-diphenylmethane diisocyanate and a chain extender composed of an aliphatic diol having 2 to 10 carbon atoms (particularly 1,4-butanediol). Mechanical properties of the composition, adhesiveness with 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 a coalescence.

Further, the thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention has a number average of the isocyanate group / hydroxyl group equivalent ratio R in the range of 0.9≤R≤1.30. A thermoplastic polyurethane obtained by reacting a high molecular weight polyol having a molecular weight of 500 to 10,000, an organic diisocyanate and a chain extender is preferable from the viewpoint of good melt moldability of the thermoplastic polymer composition, and particularly, a film. Good film-forming stability can be obtained when melt-molding into a shape. Then, when the aromatic vinyl compound / conjugated diene block copolymer and / or its hydrogenated product used in the thermoplastic polymer composition of the present invention has a hydroxyl group at the terminal, an equivalent ratio of thermoplastic polyurethane is obtained. When the above-mentioned 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. The melt moldability, especially the film forming stability, and the melt adhesion are further improved, which is preferable.

The method for producing the thermoplastic polyurethane used in the thermoplastic polymer composition of the present invention is not particularly limited, and a conventionally known urethanization reaction technique using the above-mentioned polymer polyol, organic diisocyanate and chain extender is used. Can be used, for example, 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, particularly continuous melting using a multi-screw extruder. It is preferably produced by polymerization.

A block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, which are the other essential polymer component in the thermoplastic polymer composition of the present invention (aromatic vinyl compound / conjugated As the diene block copolymer), a block copolymer having at least one aromatic vinyl compound-based polymer block and at least one conjugated diene-based polymer block, and the aromatic vinyl compound / conjugated diene block copolymer At least one of the polymers in which the unsaturated bond in the conjugated diene polymer block in the polymer is hydrogenated is used.
In that case, the hydrogenation rate is 0 to 100 mol%, preferably 0 to
It can be selected from the range of 95 mol%. When the hydrogenation rate of the unsaturated bond of the conjugated diene 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 be contained in a small amount of other unsaturated monomer in some cases. It is a polymer block having a structural unit derived from it. Examples of the aromatic vinyl compound constituting the aromatic vinyl compound-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer include styrene, α-methylstyrene, o
-, m-, p-methylstyrene emissions, 2, 4-dimethyl styrene, vinyl naphthalene, vinyl anthracene, 4-propyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene,
4- (phenylbutyl) styrene and the like can be mentioned, and the aromatic vinyl compound-based polymer block can have a structural unit composed of one or more of the above-mentioned aromatic vinyl compounds. Among them, the aromatic vinyl compound-based polymer block in the aromatic vinyl compound / conjugated diene block copolymer is styrene and / or
Alternatively, it is preferably composed mainly of a structural unit composed of α-methylstyrene.

The conjugated diene polymer block in the aromatic vinyl compound / conjugated diene block copolymer is 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene. , 1,
A polymer block mainly formed from one or more conjugated diene-based compounds such as 6-hexadiene. In a hydrogenated aromatic vinyl compound / conjugated diene block copolymer, the conjugated diene-based polymer block A part or all of the unsaturated bond portions are saturated bonds by hydrogenation. Among them, in the aromatic vinyl compound / conjugated diene block copolymer used in the thermoplastic polymer composition of the present invention, the conjugated diene polymer block is a heavy chain composed of 1,3-butadiene, isoprene or a mixture thereof. A coalescing block, more specifically an isoprene polymer block, an isoprene-butadiene copolymer block, a butadiene polymer block and / or their hydrogenated polymer blocks,
It is preferable in that the melt adhesion of the thermoplastic polymer composition becomes good, and particularly the melt adhesion to the olefin polymer becomes excellent.

In particular, when it is desired to obtain a thermoplastic polymer composition having a high adhesive strength to polypropylene, an aromatic vinyl compound / conjugated diene block copolymer is prepared, and the conjugated diene polymer block has 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 thereof in a proportion of 30 mol% or more.

When the conjugated diene polymer block in the aromatic vinyl compound / conjugated diene block copolymer is an isoprene / butadiene copolymer block or its hydrogenated copolymer block, it is derived from butadiene. The arrangement of the structural unit and the structural unit 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 is linear,
It may be branched, radial, or any combination thereof. Among them, in the thermoplastic polymer composition of the present invention, as the aromatic vinyl compound / conjugated diene block copolymer and / or its hydrogenated product,
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 The 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 easy to manufacture, easy to obtain, It is preferably used from the viewpoint of compatibility with thermoplastic polyurethane and mechanical properties.

In the aromatic vinyl compound / conjugated diene block copolymer and hydrogenated product thereof, 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. From the viewpoint that the melt adhesion and mechanical properties of the thermoplastic polymer composition are excellent, it is more preferably 10 to 90% by weight.

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

Further, the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product preferably have a hydroxyl group at the molecular end. In that 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 both ends thereof, and particularly at one end. It is preferable that Aromatic vinyl compound /
When the conjugated diene block copolymer and its hydrogenated product have a hydroxyl group at the molecular end, the thermoplastic polymer composition of the present invention containing it has a remarkable film-forming stability during melt extrusion molding. As a result, the film quality is improved and stable film formation can be achieved 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 2500 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.
And the number average molecular weight of the entire aromatic vinyl compound / conjugated diene block copolymer is 15,000 to 150,000.
Is preferable from the viewpoint of mechanical properties, moldability, and adhesiveness.

The method for producing or obtaining the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product is not particularly limited, and the aromatic vinyl compound-based polymer block and the conjugated diene-based polymer block as described above are used. Can be used as long as it is a block copolymer having an aromatic vinyl compound / conjugated diene block copolymer or a hydrogenated product thereof for the thermoplastic polymer composition of the present invention, and is commercially available. Available, or otherwise obtained. Although not limited thereto, the aromatic vinyl compound / conjugated diene block copolymer and hydrogenated product thereof used in the thermoplastic polymer composition of the present invention can be prepared, for example, by using an aromatic vinyl compound and a conjugated diene. It can be obtained by forming a block copolymer by an anionic polymerization method, a cationic polymerization method, a Ziegler polymerization method, a single-site polymerization method, a radical polymerization method, or the like, and hydrogenating it if necessary.

The thermoplastic polymer composition of the present invention comprises the above-mentioned thermoplastic polyurethane, 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, a total of them): [Aromatic vinyl compound / conjugated diene block copolymer and / or hydrogenated product thereof]
(A plurality of aromatic vinyl compounds / conjugated diene block copolymers and / or their hydrogenated products when used in total) = 20: 80 to 80:20 must be contained in a weight ratio. , 30:70 to 70:30 by weight, preferably 35:65 to 6
More preferably, it is contained in a weight ratio of 5:35.

The thermoplastic polyurethane content is less than 20% by weight, based on the total weight of the thermoplastic polyurethane and the block copolymer and / or its hydrogenated product (the block copolymer and / or its hydrogen). When the content of the additive exceeds 80% by weight, a polymer having a large polarity (for example, saponified ethylene-vinyl acetate copolymer,
At least one selected from vinylidene chloride polymers, vinyl chloride polymers, polyamides, polyesters, polycarbonates, acrylic polymers, polyoxymethylene, vinyl cyanide compounds, conjugated diene compounds and olefin compounds, and aromatic vinyl compounds. (Copolymer, etc.)
Adhesiveness of the thermoplastic polymer composition to the is reduced. On the other hand, when the content of the thermoplastic polyurethane exceeds 80% by weight (the content of the block copolymer and / or the hydrogenated product thereof is less than 20% by weight), a polymer having a small polarity (for example, an olefin polymer). , Styrene-based polymers, etc.) of the thermoplastic polymer composition is reduced.

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 coalesced product and / or its hydrogenated product and the refractive index measured at a temperature of 25 ° C. is 0.005 or less, and it is 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 its hydrogenated product at 25 ° C. (Δ
When n) is larger than 0.005, the transparency of the thermoplastic polymer composition is impaired, and the thermoplastic polymer composition is unsuitable for applications requiring transparency. Generally, in a molded article such as a film or a sheet obtained by 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 a predetermined transparency, the greater the thickness, the more the refractive index of the thermoplastic polyurethane contained in the thermoplastic polymer composition and the aromatic vinyl compound / conjugated diene block copolymer and / or its It is necessary to further reduce the difference (Δn) with the refractive index of the hydrogenated substance. The difference in refractive index (Δn) as used in this specification
Using an Appe refractometer, at a temperature of 25 ° C and a thickness of 1
The refractive index of the thermoplastic polyurethane film having a thickness of 00 μm and the refractive index of the aromatic vinyl compound / conjugated diene block copolymer film having a thickness of 100 μm or its hydrogenated film were measured, and the refractive index was measured from the larger refractive index. It means a value obtained by subtracting the smaller one, and the specific content thereof is as described in the following examples.

Generally, the refractive index is temperature-dependent, and the refractive index also changes as the temperature changes. And
As a result of investigation by the present inventors, 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, they have almost the same temperature dependence, so that the difference in refractive index (Δ) between the two when measured at a temperature of 25 ° C.
It was found that when n) is 0.005 or less, the refractive index difference (Δn) between the two is kept at 0.005 or less even if the measurement temperature changes. That is, the thermoplastic polymer composition of the present invention has a thermoplasticity not only in the case where the use temperature is 25 ° C., but also in the temperature range (usually −40 to 120 ° C.) in which the thermoplastic polymer composition is generally used. 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 its hydrogenated product is 0.005 or less, It 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, by adjusting the amount used by using a component forming a hard segment such as aromatic diisocyanate or aromatic diol, it is possible to obtain a thermoplastic polyurethane having a 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, and when the soft segment is derived from polyester polyol, for example,
By using an aromatic compound as a 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 desired refractive index can be obtained. The refractive index of the aromatic vinyl compound / conjugated diene block copolymer and / or its hydrogenated product is determined by the content of the structural unit derived from the aromatic vinyl compound in the block copolymer, the conjugated diene polymer block. It can be adjusted by the hydrogenation rate of 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 as described above, 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 its hydrogenated product can be 0.005 or less.

Further, it is important that the thermoplastic polymer composition of the present invention has a melt viscosity ηa of 150 to 10,000 Pa · s measured under the conditions of a temperature of 220 ° C. and a shear rate of 100 sec ⁻¹ . When the melt viscosity ηa of the thermoplastic polymer composition is out of the above range, the moldability becomes poor. Moreover, the melt viscosity ηa of the thermoplastic polymer composition is 1
If it is less than 50 Pa · s, the mechanical properties will be poor. The specific contents of the method for measuring the melt viscosity ηa of the thermoplastic polymer composition referred to in this specification are as follows.
As described in the examples below.

In order to bring the melt viscosity ηa of the thermoplastic polymer composition into the above range of 150 to 10,000 Pa · s,
Achieved by adjusting the melt viscosity of the thermoplastic polyurethane and adjusting the melt viscosity of the aromatic vinyl compound / conjugated diene block copolymer, and mixing both such melt viscosity adjusted polymers. . 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) with the refractive index of the conjugated diene block copolymer and / or its hydrogenated product to be 0.005 or less, the melt viscosity ηa of the thermoplastic polymer composition.
It is essential that the above range be set.

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, when the urethane group concentration is changed, the refractive index of the thermoplastic polyurethane changes, and the transparency may be impaired. Adjusting melt viscosity is not a recommended tool. Further, the molecular weight of the thermoplastic polyurethane can be adjusted by changing the concentration ratio of the hydroxyl group and the isocyanate group in the raw material component, but the adjustment range is limited when only the polymer diol is used. Therefore, in the above case, for example, the melt viscosity of the thermoplastic polyurethane can be smoothly adjusted by changing the number f of hydroxyl groups 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 its hydrogenated product can be generally adjusted by the molecular weight and the content of the structural unit derived from the aromatic vinyl compound. However, when the content of the structural unit derived from the aromatic vinyl compound is changed, the refractive index of the aromatic vinyl compound / conjugated diene block copolymer is affected, and it is difficult to obtain a transparent thermoplastic polymer composition. Therefore, it is preferable to adjust the melt viscosity of the aromatic vinyl compound / conjugated diene block copolymer depending on the molecular weight thereof.

The thermoplastic polymer composition of the present invention comprises, if necessary, a heat stabilizer, a light stabilizer, an antioxidant, an antistatic agent, a colorant, unless it interferes with the above-mentioned object of the present invention. , One or more additives such as flame retardants, ultraviolet absorbers, plasticizers, and hydrolysis inhibitors may be contained.

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 adopted. For example, a thermoplastic polyurethane, an aromatic vinyl compound / conjugated diene block copolymer and, if necessary, other additives, pre-mixing using a vertical or horizontal mixer that is usually used for mixing polymers. Then, it can be produced by kneading under heating in a batch type or a continuous type using a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer or the like. In particular, when the mixture is heated and kneaded by using an extruder, it may be extruded in a strand shape and then cut into an appropriate length to prepare a thermoplastic polymer composition in a granular form such as pellets. Further, for example, at the time of polymerization of the thermoplastic polyurethane, the aromatic vinyl compound / conjugated diene block copolymer and, if necessary, additives may be mixed to prepare the thermoplastic polymer composition. Furthermore, for example, thermoplastic polyurethane, an aromatic vinyl compound / conjugated diene block copolymer and, if necessary, additives are dry blended in advance, and the dry blended product is directly subjected to a melt molding machine such as an extrusion molding machine. Sheets, films, laminated structures, and other molded articles may be manufactured by supplying, melt-kneading, and melt-molding.

The thermoplastic polymer composition of the present invention is excellent in transparency, thermoplastic and excellent in melt moldability. Further, the thermoplastic polymer composition of the present invention has both elasticity of the thermoplastic polyurethane constituting the thermoplastic polymer composition and the aromatic vinyl compound / conjugated diene block copolymer and / or hydrogenation thereof. Good cushioning, impact resistance, cushioning,
It also has characteristics such as flexibility. Therefore, the thermoplastic polymer composition of the present invention, alone or in combination with other materials, film, sheet, plate-like body, rod-like body, tubular body,
Various molded products such as molded products and composite molded products can be smoothly produced by melt molding, and therefore the present invention provides various molded products and composite molded products comprising the thermoplastic polymer composition of the present invention. Within the scope of the present invention.

Furthermore, the thermoplastic polymer composition of the present invention has properties such as excellent transparency and elasticity, as well as high melt adhesion to various materials, a polymer having low polarity and a polymer having low polarity. It exhibits high melt adhesion to high polymers as well as 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 relates to a polymer layer comprising the above-mentioned 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, but for example, 1 made of the thermoplastic polymer composition of the present invention can be used. Consisting of one polymer layer and another material 1
Two-layer structure in which one layer is laminated, three-layer structure in which a polymer layer made of the thermoplastic polymer composition of the present invention is present as an intermediate layer between two surface layers made of other materials (front and back layers) Body, 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, and a polymer layer made of the thermoplastic polymer composition of the present invention And a multilayer structure in which four or more layers composed of one or more other materials are alternately laminated, and any of these 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, various thermoplastic polymers other than the thermoplastic polymer composition of the present invention or a composition thereof Materials, 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, and for example, a method for producing a laminated structure by melt coating the above-mentioned other materials with the thermoplastic polymer composition of the present invention, 2
A method of introducing the thermoplastic polymer composition of the present invention between two or more other materials under melting and adhering / integrating the same, and the method of the present invention in a state where other materials are placed (inserted) in a mold. Method of filling a thermoplastic polymer composition into a mold while melting and adhering / integrating it, and when the other material is thermoplastic, co-extruding the thermoplastic polymer composition of the present invention and the other material A method of molding and adhering / integrating can be adopted.

In particular, the thermoplastic polymer composition of the present invention comprises
Polymers with low polarity such as olefin polymers such as polyethylene and polypropylene and styrene polymers,
And ethylene-vinyl acetate copolymer saponified product, vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide,
Polyester, polycarbonate, acrylic polymer,
Strong adhesion to any highly polar polymer such as a copolymer of at least one selected from polyoxymethylene, vinyl cyanide compound, conjugated diene compound and olefin compound and aromatic vinyl compound A transparent laminated structure can be formed, and the laminated structure obtained thereby can be effectively used for various purposes. Therefore, in the laminated structure of the present invention, a polymer layer mainly composed of at least one of (A) an olefin polymer and a styrene polymer; (B) the above-mentioned thermoplastic polymer composition of the present invention. And (C) saponified ethylene-vinyl acetate copolymer, vinylidene chloride polymer, vinyl chloride polymer, polyamide, polyester, polycarbonate, acrylic polymer, polyoxymethylene, and cyanide Polymer layer (A) / polymer layer, which is mainly composed of at least one kind of copolymer of an aromatic vinyl compound and at least one kind selected from a vinyl compound, a conjugated diene compound and an olefin compound. A laminated structure having at least a part of the structure in which (B) / polymer layer (C) is laminated in this order (hereinafter referred to as “lamination”). Zotai (b) "hereinafter] is included as a preferred embodiment.

Therefore, the above-mentioned 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. And 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. In this case, the olefin polymer may be a homopolymer of olefin such as ethylene, propylene or butylene, an olefin copolymer composed of two or more of the above olefins, or one or more of the above olefins and others. And a copolymer with one or more kinds of the 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 vinyl acetate content is 5 to 30% by weight), ethylene-acrylic acid copolymer (preferably acrylic acid content is 5 to 30% by weight), ethylene- Propylene copolymer, ethylene-propylene-diene copolymer,
Examples thereof include ethylene-butylene copolymer. The polymer layer (A) can be formed from one kind or two or more kinds of the above-mentioned olefin homopolymer and olefin copolymer.

As the styrene-based polymer constituting the polymer layer (A), a polymer containing 10% by weight or more of the structural unit derived from the styrene-based monomer is preferably used, and 50% by weight or more is contained. The polymer to be used is more preferably used. In that case, as the styrene-based monomer, styrene, α-methylstyrene, p-methylstyrene, pt
-Butylstyrene, 3,4-dimethylstyrene and the like can be mentioned, and the styrene-based polymer has a structural unit derived from one or more of the above-mentioned styrene-based monomers.

The styrene-based polymer constituting the polymer layer (A) is not more than 90% by weight, preferably 50% by weight or less, together with the above-mentioned structural unit derived from the styrene-based monomer. It may have a structural unit derived from a monomer. Examples of other vinyl-based monomers in that case include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; methyl, ethyl, propyl, n-butyl, i-butyl of acrylic acid or methacrylic acid,
Hexyl, 2-ethylhexyl, dodecyl, octadecyl, and other alkyl esters having 1 to 18 carbon atoms; acrylic acid or methacrylic acid, such as ethylene glycol, propylene glycol, and butanediol; diol esters; acetic acid, propionic acid, and other carbon atoms 1 to 6 Vinyl ester of carboxylic acid; unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid; anhydride of unsaturated dicarboxylic acid such as maleic anhydride; acrylamide, methacrylamide, N, N-dimethylacrylamide, etc. ) Acrylamides; N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; 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 and acrylonitrile, methyl methacrylate, butyl acrylate, N-
A copolymer with phenylmaleimide, maleic anhydride, and one or more of butadiene is preferable from the viewpoint of mechanical properties and the like.

The styrene-based polymer constituting the polymer layer (A) may be a styrene-based 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 30% by weight or less of (meth) acrylic acid lower alkyl ester, polyisoprene, and polychloroprene.

As the other rubbery polymer which can be contained in the styrene-based 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 alkyl esters 1 to 8, in particular ethyl acrylate, butyl acrylate and / or ethylhexyl acrylate. The alkyl acrylate rubber may optionally have structural units derived from other monomers such as vinyl acetate, methyl methacrylate, styrene, acrylonitrile, vinyl ether in an amount of 30% by weight or less. In some cases, it may have a structural unit derived from a crosslinkable unsaturated monomer such as alkylene diol (meth) acrylate, divinylbenzene, triallyl cyanurate or the like in a proportion of 5% by weight or less. Further, the alkyl acrylate rubber is, for example, a cross-linked diene rubber obtained by cross-linking polybutadiene, butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, etc. as a core body, and the alkyl acrylate rubber is present in a sheath shape around the core. It may be a core-sheath type rubber.

As the rubbery polymer which can be contained in the styrene polymer constituting the polymer layer (A), in addition to the above,
For example, ethylene-propylene-ethylidene norbornene copolymer and other ethylene-propylene-non-conjugated diene copolymer rubber, styrene polymer block-butadiene polymer block block hydrogenated product, styrene Examples thereof include hydrogenated products of block copolymers composed of a polymer block-isoprene polymer block.

As the rubber-like polymer which can be contained in the styrene-based polymer constituting the polymer layer (A), various rubber-like polymers listed above can be used in addition to the styrene-based monomer and other various types. A graft copolymer obtained by graft-polymerizing an unsaturated monomer can be mentioned.

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

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

The polymer layer (A) may, if necessary, have a heat stabilizer, a light stabilizer, an antioxidant, a colorant, a lubricant, an antistatic agent, as long as it does not interfere with its original properties. You may contain the 1 type (s) or 2 or more types of additives, such as a mold release agent, a flame retardant, and an ultraviolet absorber.

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

As the saponified product of the ethylene-vinyl acetate copolymer in that case, ethylene having 20 to 60 mol%, preferably 25 to 60 mol% and a saponification degree of 95% or more is preferably used. In addition, saponified ethylene-vinyl acetate copolymer is ASTM D-1238-65T.
Melt index measured according to
g / 10 min (measured under a load of 190 ° C. and 2160 g) is preferable from the viewpoint of moldability, and 0.3 to 20 g /
More preferably, it is 10 minutes.

As the vinylidene chloride-based 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 proportion of 70 to 98% by weight is more preferably used. When the vinylidene chloride-based polymer is a copolymer of vinylidene chloride and other monomer, vinylidene chloride and other unsaturated monomers such as vinyl chloride, acrylonitrile, acrylic acid ester and acrylic acid can be used. A copolymer of one type or two or more types 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 polymerization degree of 400 to 5,000 are more preferably used.

The vinyl chloride polymer used in the polymer layer (C) is a vinyl chloride homopolymer,
A copolymer of vinyl chloride having a structural unit derived from vinyl chloride in a proportion of 70% by weight or more and another copolymerizable monomer, and one or more of chlorides 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. One or more copolymers are preferably used. The degree of polymerization of the vinyl chloride polymer is not particularly limited, but in general,
A polymerization degree of 100 to 10,000 is preferably used, and a polymerization degree of 400 to 5,000 is more preferably used.

As the polyamide used in the polymer layer (C), an amide bond (--CO--N) is added to the polymer main chain.
It is not particularly limited as long as it has H-) and can be melted by heating. 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, a polycondensation of a dibasic acid and a diamine. And the like. Examples thereof include polyamides and the like, 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 and
Examples thereof include enatractrum, capryllactam, lauryllactam, and α-pyrrolidone. Also,
Specific examples of the above-mentioned ω-amino acid which is a raw material for polyamide include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and the like.

Specific examples of the above-mentioned dibasic acid, which is a raw material 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, 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 '
-Aromatic dicarboxylic acids such as dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid and 4,4'-diphenyldicarboxylic acid can be mentioned.

Specific examples of the above-mentioned diamine which is a raw material for polyamide include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine and 1,9-nonanediamine. , 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2
4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-
Aliphatic diamines such as nonanediamine; alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, isophoronediamine; p-phenylenediamine, m-phenylenediamine, xylylenediamine, xylenediamine, 4,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfone, 4,4 '
Mention may be made of 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 the reaction of a dicarboxylic acid component and a diol component, a polyester (polylactone) obtained by ring-opening polymerization of a lactone, a hydroxycarboxylic acid or an ester-forming derivative thereof. The polyester obtained by the above can be mentioned, and one or more of these polyesters can be used. Among them, in the present invention, the polyester substantially formed from the dicarboxylic acid component and the 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, anthracene dicarboxylic acid, and 4 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 and dodecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; tetrabromophthal Halogen-containing dicarboxylic acids such as acids; and their ester-forming derivatives.

Specific examples of the above-mentioned diol component, which is a raw material for 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, 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 a trifunctional or higher functional compound such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid. The above may be contained in a small amount.

Examples of the polycarbonate used in the polymer layer (C) include a polycarbonate obtained by reacting a substantially dihydroxy compound with phosgene, a carbonic acid diester or a halogen formate. In that case, examples of the dihydroxy compound as a raw material include 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, and among these, bisphenol A is preferable. Polycarbonate may be 4,6-dimethyl-2,4, if necessary.
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) ) It may have a small amount of one type or two or more types of structural units derived from a trihydroxy or higher functional polyhydroxy compound such as ethane.

The acrylic polymer used in the polymer layer (C) may be an acrylic polymer mainly composed of structural units derived from (meth) acrylic acid ester. In that case, the proportion of the structural unit derived from the (meth) acrylic acid ester in the acrylic polymer is preferably 50% by weight or more, and more preferably 80% by weight or more. Examples of the (meth) acrylic acid ester that constitutes the acrylic polymer include, for example, methyl (meth) acrylate and (meth)
Examples thereof include alkyl esters of (meth) acrylic acid such as ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Acrylic polymers include these ( It can have a structural unit derived from one or more of (meth) acrylic acid esters. In addition, the acrylic polymer is a structural unit 1 derived from an unsaturated monomer other than the (meth) acrylic acid ester, if necessary.
You may have 1 type or 2 or more types. 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 and o-methylstyrene. , A structural unit derived from an aromatic vinyl compound such as m-methylstyrene, p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc., preferably in a proportion of 10% by weight or less. May be.

The polyoxymethylene used in the polymer layer (C) is a polymer compound having an oxymethylene group as a main structural unit, and for example, one of monomers such as formaldehyde, trioxane and tetraoxane can be used.
Polymer consisting of one or more species; the monomer and ethylene oxide, propylene oxide, oxacyclobutane, 1,
Examples thereof include a copolymer composed of a cyclic ether such as 3-dioxolane; a copolymer of the monomer and a cyclic ester such as β-propiolactone and γ-butyrolactone. Furthermore, in order to improve the heat resistance of polyoxymethylene, for example, a terminal-modified polyoxymethylene whose terminal is acetylated with acetic anhydride or the like can also be used.

The aromatic vinyl compound used in the copolymer of the aromatic vinyl compound and at least one selected from vinyl cyanide compounds, conjugated diene compounds and olefin compounds used in the polymer layer (C) is , Styrene, α-methylstyrene, p-
Methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, pt-butylstyrene,
Examples thereof include ethylstyrene and vinylnaphthalene, and one or more of these are used. Of these, styrene is particularly preferable. Further, as the vinyl cyanide compound used in the copolymer,
Examples thereof include acrylonitrile and methacrylonitrile. The conjugated diene compound used in the copolymer is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1. , 3
-Butadiene, 2-chloro-1,3-butadiene, 2-
Examples thereof include cyano-1,3-butadiene, substituted linear conjugated petanediene, linear and side chain conjugated hexadiene, and one or more of them can be used. Among them, 1,3-butadiene and 2-methyl-1,3-butadiene are particularly preferably used.
Examples of the olefin compound used in the copolymer include ethylene and propylene. A preferred copolymer is styrene-
Acrylonitrile copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin),
Examples thereof include acrylonitrile-ethylene-propylene-styrene copolymer (AES resin).

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

The polymer layer (C) is the polymer layer (C).
As long as the properties of the above are not impaired, a heat stabilizer (for example, metal soap, phosphorus compound, sulfur compound, phenol compound, L-ascorbic acid, epoxy compound, etc.), plasticizer (for example, aliphatic dibasic acid) may be used as necessary. Ester, hydroxy polycarboxylic acid ester, fatty acid ester, polyester compound, phosphoric acid ester, etc., impact resistance imparting agent (eg ethylene / propylene rubber, ethylene / propylene terpolymer, butadiene / acrylonitrile copolymer, ethylene / acetic acid) Vinyl copolymers, etc.),
Inorganic fine powder, organic lubricant, dispersant, dye / pigment, antistatic agent,
You may contain 1 type (s) or 2 or more types, such as antioxidant.

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) )
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) is adjustable. 10 μm
It is preferable to set the thickness to 5 mm from the viewpoint of the ease of manufacturing the laminated structure (a), the interlayer adhesive strength, 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 of them may be used as long as it is a laminated structure (a) having a structure having at least a part thereof. Further, the laminated structure (a) of the present invention may be formed from only three members of the polymer layer (A), the polymer layer (B) and the polymer layer (C), or may be formed of three kinds of them. Layers made of other materials (eg other polymers,
It may have one or two or more layers of paper, cloth, metal, ceramic, wood, etc.).

Although not limited thereto, examples of the laminated structure (a) of the present invention include three layers of a polymer layer (A) / polymer layer (B) / polymer layer (C). Structure;
(Paper, cloth or metal) / polymer layer (A) / polymer layer (B) / polymer layer (C) four-layer structure; polymer layer (A) / polymer layer (B) / weight Five-layer structure consisting of polymer layer (C) / polymer layer (B) / polymer layer (A); polymer layer (C) / polymer layer (B) / polymer layer (A) / polymer layer Five-layer structure consisting of (B) / polymer layer (C); (paper, cloth or metal) / polymer layer (A) / polymer layer (B) / polymer layer (C) / polymer layer ( B) / polymer layer (A) /
7-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) /
A seven-layer structure made of (paper, cloth or metal) may be mentioned. 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 a 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 of having at least two polymer layers (C).

The method for producing the laminated structure (a) of the present invention is not limited in any way. For example, (i) a polymer for the polymer layer (A) and a polymer for the polymer layer (B) Of the present invention, the thermoplastic polymer composition and the polymer layer (C)
A method for producing a laminated structure (a) by melt-coextruding at least the polymers for use in extrusion, and laminating them simultaneously with the extrusion molding of the respective layers; (ii) forming the polymer layer (A) Film, sheet,
The thermoplastic resin of the present invention for the polymer layer (B) is produced by previously producing a plate and / or a molded article such as a film, a sheet and a plate constituting the polymer layer (C). Preliminarily produced while melt-extruding the polymer composition and, if one of the polymer layer (A) and the polymer layer (C) is not preformed, also melt-extruding it. The polymer layer (A) molded article and / or the polymer layer (C) molded article that have been laminated are integrated by being integrated to produce a laminated structure (a); (iii) Polymer layer ( Molded products such as the film, sheet and plate constituting A) and molded products such as the film, sheet and plate constituting the polymer layer (C) are manufactured in advance and further prepared for the polymer layer (B). The polymer is also formed into a film or a sheet in advance, and the thermoplastic polymer composition of the present invention A polymer layer (B) film or sheet comprising the polymer layer (B) is sandwiched between the polymer layer (A) molded article and the polymer layer (C) molded article and the polymer layer (B) is heated. A method for producing a laminated structure (a) by melting a film or sheet for use in a polymer and adhering and integrating the polymer layer (A) and the polymer layer (C) via the polymer layer (B); iv) A molded article that constitutes the polymer layer (A) and a molded article that constitutes the polymer layer (C) are manufactured in advance, and these molded articles are placed (inserted) in the mold in advance, and And a method for producing a laminated structure (a) by filling the thermoplastic polymer composition of the present invention for the polymer layer (B) under melting and adhering and integrating the same.

In any of the above methods (i) to (iv), the polymer layer (A) and the polymer layer (C) are bonded to each other 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 troubles such as the destruction of the natural environment by the organic solvent, the deterioration of the working environment, and the recovery of the solvent. be able to. Among them, the above-mentioned method (i) by coextrusion molding has a small number of steps and has high productivity,
Moreover, the adhesive strength between the polymer layer (A), the polymer layer (B) and the polymer layer (C) is high, and the laminated structure (a) without delamination can be obtained, which is the most preferable.

When the laminated structure (a) of the present invention is produced by the coextrusion molding method, for example, three or more extruders are combined into one die depending on the number of layers of the laminated structure (a). Then, a plurality of polymers can be laminated and integrated inside or outside the die. As the die in this case, a T die, an annular die or the like can be used, and the shape and structure of the extruder and die are not particularly limited.

The laminated structure of the present invention, in particular the laminated structure (a), is a polymer especially in the laminated structure (a) depending on the materials and properties of the other material layers constituting the laminated structure. It can be used for various purposes depending on the properties of the layer (A), the polymer layer (B), the polymer layer (C), and the like, but is not limited thereto. For example, foods that dislike oxygen. Packaging materials for medicines and medicinal agents; Packaging materials for clothing; Packaging materials for other products; Building materials such as wallpaper and decorative boards; Films for electrical insulation; Base materials for adhesive films and tapes; Marking films; Agriculture The film can be used in various applications such as table cloths, raincoats, umbrellas, curtains, covers and other miscellaneous goods; laminating with metal plates and other materials. In particular, when the layer made of the other material 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. A transparent laminated structure can be obtained as a whole.

In the present invention, the thermoplastic polymer composition of the present invention is directly stored as a hot melt adhesive,
The hot melt adhesive may be distributed, sold, and used as needed to produce various products and various laminated structures as described above. Therefore, the present invention is based on the thermoplastic polymer of the present invention. Hot melt adhesives comprising the coalesced composition are included within the scope of the present invention. The form of the hot-melt adhesive of the present invention is not particularly limited, and may be any form such as pellets and other granular bodies, rod-shaped bodies, films, sheets, and plate-shaped bodies.

[0090]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the number f of hydroxyl groups per molecule of the polymer polyol (polyester polyol) used for producing 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 (Δ
n), the melt viscosity ηa of the thermoplastic polymer composition, the transparency (haze value) and the tensile strength of the film obtained from the thermoplastic polymer composition, and the laminated structure using the thermoplastic polymer composition. The evaluation of the film-forming property during production and the adhesive strength of the laminated structure thus obtained were measured or evaluated as follows.

[Number of hydroxyl groups f per molecule of polyester polyol] The polyester polyol was decomposed with a methanol solution of sodium methoxide, and then the hydroxyl groups of the decomposed product were silylated with a trimethylsilylating agent. The silylated sample was analyzed by gas chromatography to determine the molar ratio of the diol compound and the triol compound. Furthermore, the hydroxyl value of the polyester polyol was determined according to JIS K 1577, and the number f of hydroxyl groups per molecule of the polyester polyol was calculated from this hydroxyl value and the above molar ratio.

[Refractive Index of Thermoplastic Polyurethane and Hydrogenated Aromatic Vinyl Compound / Conjugated Diene Block Copolymer and Difference in Refractive Index 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 taken from the film,
The refractive index was measured at a temperature of 25 ° C. using an Appe refractometer. (2) The hydrogenated product of the 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's refractometer. (3) In each Example or Comparative Example, 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 two, the smaller value is subtracted from the larger value to obtain the difference in refractive index (Δ
n) was determined.

[Transparency of thermoplastic polymer composition (haze value)] The transparency was measured according to ASTM D 1003.

[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., using a Takashita type flow tester (manufactured by Shimadzu Corporation; Shimadzu Flow Tester CFT-500C), a measurement temperature of 220 ° C. and a preheating time of 360 seconds. , Die diameter 1mm,
Die thickness 10 mm, extrusion pressure 0.49 ~ 49MPa under different conditions shear rate is measured melt viscosity at several points,
A graph was prepared by plotting the melt viscosity against the shear rate, and the melt viscosity ηa when the shear rate corresponds to 100 sec ⁻¹ was determined from the graph.

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

[Film Forming Property in Manufacturing 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), a 5-layer laminated structure was produced, and the smoothness of the surface was visually observed. In addition, the thickness of the laminated structure was measured with a caliper at 10 positions along the length direction at intervals of 2 m, and the difference between the maximum thickness and the minimum thickness at that time was obtained. (2) The outermost layer (50 μm) / adhesive layer (2 μm) / intermediate layer (50 μm) / adhesive layer (2 μm) / outermost layer (50 μm) was similarly used except that the thickness of the two adhesive layers was changed to 2 μm.
m), a five-layer laminated structure is manufactured, the smoothness of the surface thereof is visually observed, and the thickness of the laminated structure is measured at 10 points at 2 m intervals along the length direction thereof. Then, the difference between the maximum thickness and the minimum thickness was calculated. (3) Based on the results obtained in (1) and (2) above, the film-forming property was evaluated according to the evaluation criteria shown in Table 1 below.

[0097]

[Table 1] [Evaluation Criteria for Film Formability] ⊚: In any of the above (1) and (2), the surface of the laminated structure is smooth, no unevenness or curvature is generated, and the maximum thickness and the minimum in the laminated structure of (1) above. The difference from the thickness is less than 5 μm and the difference between the maximum thickness and the minimum thickness in the laminated structure of the above (2) is less than 5 μm, and the film forming property is extremely good. ◯: In both cases of (1) and (2) above, the surface of the laminated structure was almost smooth and there were no irregularities or curves, and the maximum and minimum thicknesses of the laminated structure of (1) above Is 5 μm or more and less than 10 μm, and the difference between the maximum thickness and the minimum thickness in the laminated structure of (2) is 5 μm or more and less than 12 μm, and the film-forming property is almost good. X: In any of the above cases (1) and (2), whether the surface of the laminated structure is not smooth and has irregularities or curves, or the maximum thickness and the minimum thickness of the laminated structure of (1) above The difference is 10 μm or more and / or the difference between the maximum thickness and the minimum thickness in the laminated structure of (2) is 12 μm or more, and the film forming property is poor.

[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) / the outermost layer (50 μm) of a 5-layer laminated structure is cut into 1 cm (width direction of laminated structure) × 10 cm (longitudinal direction of laminated structure), and a cut is made 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 using an autograph manufactured by Shimadzu Corporation, according to JIS K 6854, 1
An 80 degree peel test was performed. However, when the adhesive strength at the interface was so high that peeling out was difficult with human power, the 180-degree peeling test could not be performed, and that fact is described in each example.

Thermoplastic polyurethanes, hydrogenated products of aromatic vinyl compounds / conjugated diene block copolymers (hereinafter referred to as "block copolymer hydrogenated products"), polypropylenes used in the following examples and / or comparative examples. Contents of polyethylene, polystyrene, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, polyamide, polycarbonate, vinylidene chloride copolymer, polymethylmethacrylate, polyethylene terephthalate, polyoxymethylene and acrylonitrile-butadiene-styrene copolymer, The abbreviations are shown below.

Thermoplastic polyurethane-1 (abbreviation: TP
U) : Polyester polyol having a number average molecular weight of 3500 and having a hydroxyl number f per molecule of 2.02 (polyester polyol produced by reacting 3-methyl-1,5-pentanediol, trimethylolpropane and adipic acid) , 4,4'-diphenylmethane diisocyanate and 1,4-butanediol 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 and having a hydroxyl number f per molecule of 2.02 (polyester polyol produced by reacting 3-methyl-1,5-pentanediol, trimethylolpropane and adipic acid) , 4,4'-diphenylmethane diisocyanate and 1,4-butanediol 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 having a number average molecular weight of 2,000, in which the number f of hydroxyl groups per molecule is 2.02 )
-Butanediol, trimethylolpropane and adipic acid produced by reacting a polyester polyol), 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 (1,4 having a number average molecular weight of 2,000 in which the number f of hydroxyl groups per molecule is 2.01 )
A polyester polyol produced by reacting butanediol, trimethylolpropane and adipic acid), 4,4′-diphenylmethane diisocyanate and 1,4-butanediol 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 and having a hydroxyl group number f per molecule of 2.06 (polyester polyol produced by reacting 3-methyl-1,5-pentanediol, trimethylolpropane and adipic acid) , 4,4'-diphenylmethane diisocyanate and 1,4-butanediol 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 and having a hydroxyl group number f of 2.00 per molecule (polyester polyol produced by reacting 3-methyl-1,5-pentanediol and adipic acid), 4, 4 '
-The thermoplastic polyurethane obtained by reacting diphenylmethane diisocyanate and 1,4-butanediol in a molar ratio of 1: 3.43: 2.43 (refractive index 1.51
1).

○ Thermoplastic polyurethane-7 (abbreviation: TP
U) : Polyester polyol having a number average molecular weight of 3500 and having a hydroxyl group number f of 2.00 per molecule (polyester polyol produced by reacting 3-methyl-1,5-pentanediol and adipic acid), 4, 4 '
-The 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 block copolymer-1 [Abbreviated]
No .: hydrogenated SBIS-OH (1)] : a triblock copolymer composed of hydrogenated polystyrene block having a hydroxyl group at the end / 1,3-butadiene and an isoprene copolymer block / polystyrene block (refractive index 1. 51
3): [Content: number average molecular weight of two polystyrene blocks =
7,000, 1,3-butadiene and isoprene copolymer block number average molecular weight = 26000, triblock copolymer number average molecular weight = 40,000, hydroxyl group is bonded to the end of one polystyrene block, average in triblock copolymer Hydroxyl content = 0.7 / molecule, 1,3-
1, in the butadiene and isoprene copolymer block
Molar ratio of 3-butadiene unit to isoprene unit = 1 /
Unsaturation degree in 1,1,3-butadiene and isoprene copolymer block = 5% (hydrogenation rate 95%); styrene unit content in triblock copolymer before hydrogenation =
35% by weight, 1,4-butadiene in hydrogenated 1,3-butadiene and 1,3-butadiene unit in isoprene copolymer block: 1,4-bond content = 95%, 1,2-bond content = 5%,
1,4-bond amount in isoprene unit = 95%, 3,
4-Amount of binding = 5%]

○Block copolymer hydrogenated product-2 [Omitted
No .: Hydrogenated SIS-OH (2)]: Water having a hydroxyl group at the end
Elementally added polystyrene block / polyisoprene
Triblock consisting of lock / polystyrene block
Polymer (refractive index 1.514); (Content: number average molecular weight of two polystyrene blocks =
6000, number average molecular weight of polyisoprene block = 2
8,000, number average molecular weight of triblock copolymer = 40
000, a hydroxyl group at the end of one polystyrene block
Average hydroxyl group content in bonding and triblock copolymers
= 0.7 / molecule, the difference in the polyisoprene block
Saturation = 15%, for triblock copolymer before hydrogenation
Styrene unit content = 30% by weight, before hydrogenation
1,4-bond amount in polyisoprene block = 45
%, 3,4-bond amount = 55%)

○Block copolymer hydrogenated product-3 [Omitted
No .: Hydrogenated SIS-OH (3)]: Water having a hydroxyl group at the end
Elementally added polystyrene block / polyisoprene
Triblock consisting of lock / polystyrene block
Polymer (refractive index 1.514); (Content: number average molecular weight of two polystyrene blocks =
10500, number average molecular weight of polyisoprene block =
49000, number average molecular weight of triblock copolymer = 7
0000, hydroxyl group at the end of one polystyrene block
Bonded, average hydroxyl group content in triblock copolymer
Amount = 0.7 / molecule, in polyisoprene block
Unsaturation = 15%, triblock copolymer before hydrogenation
Styrene unit content in 30% by weight, before hydrogenation
1,4-bond amount in the polyisoprene block = 4
5%, 3,4-bond amount = 55%)

Block copolymer hydrogenated product-4 [ Omitted]
No .: hydrogenated SBIS-OH (4)] : triblock copolymer (hydrogenated polystyrene block having a hydroxyl group at the end / 1,3-butadiene and isoprene copolymer block / polystyrene block (refractive index 1. 54
4): [Content: number average molecular weight of two polystyrene blocks =
19500, number average molecular weight of 1,3-butadiene and isoprene copolymer block = 21,000, number average molecular weight of triblock copolymer = 60,000, hydroxyl group is bonded to one polystyrene block end, average in triblock copolymer Hydroxyl content = 0.7 / molecule, 1,3
-The molar ratio of 1,3-butadiene units and isoprene units in the butadiene and isoprene copolymer block = 1
Unsaturation degree in 1,1,3-butadiene and isoprene copolymer block = 5% (hydrogenation rate 95%); styrene unit content in triblock copolymer before hydrogenation = 65% by weight, hydrogenation 1,4-bond content in the 1,3-butadiene unit in the previous 1,3-butadiene and isoprene copolymer block = 95%, 1,2-bond content = 5
%, 1,4-bond amount in isoprene unit = 95%,
3,4-bond amount = 5%]

Block copolymer hydrogenated product-5 [ Omitted]
No .: hydrogenated SBIS-OH (5)] : a triblock copolymer composed of hydrogenated polystyrene blocks having terminal hydroxyl groups / 1,3-butadiene and isoprene copolymer block / polystyrene block (refractive index 1. 51
3): [Content: number average molecular weight of two polystyrene blocks =
6100, number average molecular weight of 1,3-butadiene and isoprene copolymer block = 22800, number average molecular weight of triblock copolymer = 35,000, hydroxyl group bonded to one polystyrene block end, average in triblock copolymer Hydroxyl content = 0.7 / molecule, 1,3-
1, in the butadiene and isoprene copolymer block
Molar ratio of 3-butadiene unit to isoprene unit = 1 /
Unsaturation degree in 1,1,3-butadiene and isoprene copolymer block = 5% (hydrogenation rate 95%); styrene unit content in triblock copolymer before hydrogenation =
65% by weight, 1,3-butadiene before hydrogenation and 1,4-butadiene content in 1,3-butadiene unit in isoprene copolymer block = 95%, 1,2-bond content = 5%,
1,4-bond amount in isoprene unit = 95%, 3,
4-Amount of binding = 5%]

○ Polypropylene (abbreviation: PP) : "Mitsubishi Polypro EX6" manufactured by Mitsubishi Chemical Co., Ltd. ○ Polyethylene (abbreviation: PE) : "Mirason NEO23H" manufactured by Mitsui Petrochemical Co., Ltd. ○ Polystyrene (abbreviation: PS) : Sumitomo Chemical "SUMIPLITE M192" manufactured by Kogyo Co., Ltd. ○ Saponified ethylene-vinyl acetate copolymer (abbreviation: EV)
OH) : "Eval ES-F101" manufactured by Kuraray Co., Ltd. ○ Polyvinyl chloride (abbreviation: PVC) : "Shin-Etsu PVC CT-500" manufactured by Shin-Etsu Chemical Co., Ltd. ○ Polyamide ( abbreviation: PA) : "UBE" manufactured by Ube Industries, Ltd. Nylon 1013B ”○ Polycarbonate (abbreviation: PC) :“ Panlite L-1225 ”manufactured by Teijin Chemicals Ltd. ○ Vinylidene chloride copolymer (abbreviation: PVDC) : Copolymerization of 82% by weight vinylidene chloride and 18% by weight vinyl chloride A 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. ○ Polymethylmethacrylate (abbreviation: PMMA) : "Parapet EH" made by Kuraray Co., Ltd. ○ Polyethylene terephthalate (abbreviation: PET) : "Clapet KS760K" made by Kuraray Co., Ltd. ○ Polyoxymethylene (abbreviation: POM) : Polyplastics Co., Ltd. "Duracon M90-4
4 ”○ Acrylonitrile-butadiene-styrene copolymer
(Abbreviation: ABS) : "JSR ABS82" manufactured by Japan Synthetic Rubber Co., Ltd.

Example 1 [Production of Thermoplastic Polymer Composition (a)] (1) Pre-dried TPU (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 twin- screw extruder, melt-kneaded at 220 ° C., and then extruded in a strand form, A pellet of the thermoplastic polymer composition was produced by cutting, and the pellet was aged for 6 hours in a vacuum dryer at 80 ° C. to obtain a thermoplastic polymer composition [thermoplastic polymer composition (a)]. . (2) When the melt viscosity ηa of the thermoplastic polymer composition (a) obtained in (1) above was measured by the above method, it was as shown in Table 2 below. (3) The thermoplastic polymer composition (a) obtained in the above (1) is supplied to an extrusion molding device (a single-screw extruder with a T die bonded), and the maximum temperature during extrusion molding is 220. Extrusion molding is performed at a temperature of 100 ° C.
Film was manufactured. A test piece was sampled from the film and its haze value and tensile strength were measured by the methods described above. The results are 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 preliminarily drying each of the combined hydrogenated products, they were premixed in the ratios shown in Table 2, and the pellets of the thermoplastic polymer composition were produced in the same manner as in Example 1 using the premixed product. , Age it in a vacuum dryer at 80 ° C for 6 hours,
Each thermoplastic polymer composition was prepared [thermoplastic polymer composition (b)-(f)]. (2) The melt viscosity ηa of the thermoplastic polymer compositions (b) to (f) obtained in (1) above was measured by the above method, and was 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 extrusion molding device (a single-screw extruder with a T die bonded thereto) to perform extrusion molding. The maximum temperature at that time was set to 220 to 250 ° C., and extrusion molding was performed 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 above-mentioned methods.
It was as shown in.

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 preliminarily drying each of the combined hydrogenated products, they were premixed in the ratios shown in Table 2, and the pellets of the thermoplastic polymer composition were produced in the same manner as in Example 1 using the premixed product. , Age it 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 viscosity ηa of the thermoplastic polymer compositions (g) and (h) obtained in (1) above was measured by the above-mentioned method and was 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 extrusion molding device (a single-screw extruder with a T die bonded thereto) to perform extrusion molding. The maximum temperature at that time was set to 220 ° C., and extrusion molding was performed to produce a film having a thickness of 100 μm. A test piece was sampled from the film and its haze value and tensile strength were measured by the methods described above. The results are shown in Table 2 below.

[0116]

[Table 2]

As is clear from the results shown in Table 2 above, the hydrogenated product of the thermoplastic polyurethane and the aromatic vinyl compound / conjugated diene block copolymer was added at 20:80 to 80: 2.
It is contained in a weight ratio within the range of 0, and the difference (Δn) between the refractive index of the thermoplastic polyurethane and the hydrogenated product of the aromatic vinyl compound / conjugated diene block copolymer is 0.005.
And the melt viscosity ηa (measured at a temperature of 22 ° C. and a shear rate of 100 sec ⁻¹ ) is 150 to 10,000 Pa · s.
In the thermoplastic polymer compositions of Examples 1 to 6 which are within the range of 1 to 6, the haze value of the film obtained therefrom is extremely small and the transparency is excellent, and the film has high tensile strength and mechanical properties. Also proves to be excellent.

On the other hand, even a thermoplastic polymer composition comprising a thermoplastic polyurethane and a hydrogenated product of 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 scope of the invention, the melt moldability was poor and holes were formed during the production of the film, and the film obtained therefrom had a haze value of Example 1 Greater than 6 and poorer in transparency,
Furthermore, it can be seen that the tensile strength is extremely low and the mechanical properties are inferior.

Further, even a thermoplastic polymer composition comprising a thermoplastic polyurethane and a hydrogenated product of an aromatic vinyl compound / conjugated diene block copolymer has a small melt viscosity ηa of 120 Pa · s, and the present invention. Out of the above range, 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, the range of the present invention In the thermoplastic polymer composition of Comparative Example 2 which is out of the range, the haze value of the film obtained therefrom is extremely large and the transparency is poor, and the tensile strength is extremely low and the mechanical properties are also significantly poor. Recognize.

Example 7 Production of Laminated Structure Consisting of 5 Layers of PP / Polymer Composition (a) / PVDC / Polymer Composition (a) / PP] (1) Three extruders were used. Using an extrusion molding apparatus connected to one die, PP, the polymer composition (a) obtained in Example 1 and PVDC were fed to each extruder, and the maximum temperature at the time of extrusion was 240 ° C. for PP. The polymer composition (a) was set to 220 ° C. and the PVDC was set to 200 ° C., and PP (50 μm) /
Polymer composition (a) (10 μm) / PVDC (50 μm
m) / polymer composition (a) (10 μm) / PP (50 μm
m) was laminated in the order of 5 to form a five-layer structure and coextrusion was carried out to form a PP layer on both surfaces and a PVDC layer in the middle, and the polymer composition (a) was placed between the PP layer and the intermediate layer. A laminated structure consisting of 5 layers with each layer interposed was manufactured. (2) A laminated structure composed of 5 layers was formed 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 (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (a) layer on the inside was extremely strong and peeling could not be performed, and therefore the adhesive strength was not measured. In addition, the polymer composition (a) layer and the intermediate PVDC in the laminated structure obtained in (1) above.
The adhesive strength between the layers was 820 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) have excellent transparency, and the contents can be satisfactorily improved when packaged using the laminated structure. I could see through.

Example 8 [Production of laminated structure consisting of 5 layers of PP / polymer composition (b) / PVDC / polymer composition (b) / PP] (1) Used in Example 7. PP, the thermoplastic polymer composition (b) obtained in Example 2 and PVDC were fed to the respective extruders using the same extrusion molding apparatus as in the above, and the maximum temperature at the time of extrusion was 240 ° C. for PP, The polymer composition (b) was set to 220 ° C. and PVDC to 200 ° C., and PP (50 μm) /
Polymer composition (b) (10 μm) / PVDC (50 μm
m) / polymer composition (b) (10 μm) / PP (50 μm
m) was laminated in the order of 5 to form a five-layer structure and subjected to coextrusion molding to form a PP layer on both surfaces and a PVDC layer on the intermediate layer. ) A laminated structure consisting of 5 layers with each layer interposed was produced. (2) A laminated structure composed of 5 layers was formed 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 (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (b) layer on the inside was extremely strong and peeling could not be carried out, and therefore the adhesive strength was not measured. In addition, the polymer composition (b) layer and the intermediate PVDC in the laminated structure obtained in the above (1)
The adhesive strength between the layers was 870 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) have excellent transparency, and the contents can be satisfactorily improved when packaged using the laminated structure. I could see through.

Example 9 Production of Laminated Structure Comprising 5 Layers of PP / Polymer Composition (d) / PVC / Polymer Composition (d) / PP (1) Used in Example 7 PP, the thermoplastic polymer composition (d) obtained in Example 4 and PVC were fed to the respective extruders using the same extrusion molding apparatus as in the above, and the maximum temperature at the time of 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) were laminated in this order from the die of the extrusion molding apparatus. Co-extrusion molding is performed so that
A laminated structure having 5 layers in which both surfaces were PP layers, the intermediate layer was a PVC layer, and the polymer composition (d) layer was interposed between the PP layer and the intermediate layer was produced. (2) A laminated structure composed of 5 layers was formed 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 2 μm. Manufactured. (3) With respect to the laminated structure obtained in (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (d) layer inside thereof was so strong that peeling-out was not possible, and therefore the adhesive strength was not measured. Further, the adhesive strength between the polymer composition (d) layer and the intermediate PVC layer in the laminated structure obtained in (1) above was 950 g / cm, which was a high value. Further, both the laminated structure obtained in (1) above and the laminated structure obtained in (2) above are excellent in transparency, and when the laminated structure is packaged, the contents are I was able to see through well.

Example 10 Production of Laminated Structure Comprising 5 Layers of PP / Polymer Composition (b) / EVOH / Polymer Composition (b) / PP (1) Used in Example 7 PP, the thermoplastic polymer composition (b) obtained in Example 2 and EVOH were fed to the respective extruders using the same extruder as described above, and the maximum temperature during extrusion was PP of 240 ° C., The polymer composition (b) was set to 220 ° C. and the EVOH was set to 220 ° C., and PP (50 μm) /
Polymer composition (b) (10 μm) / EVOH (50 μm
m) / polymer composition (b) (10 μm) / PP (50 μm
m) were laminated in this order to form a five-layer structure, and coextrusion molding was performed to form a PP layer on both surfaces and an EVOH layer on the intermediate layer. ) A laminated structure consisting of 5 layers with each layer interposed was produced. (2) A laminated structure composed of 5 layers was formed 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 EVOH layer was 2 μm. Manufactured. (3) With respect to the laminated structure obtained in (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (b) layer on the inside was extremely strong and peeling could not be carried out, and therefore the adhesive strength was not measured. Further, the polymer composition (b) layer and the intermediate EVOH in the laminated structure obtained in (1) above.
The adhesive strength between the layers was 840 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) have excellent transparency, and the contents can be clearly seen when packaged using the laminated structure. We were able to.

Example 11 Production of Laminated Structure Comprising 5 Layers of PP / Polymer Composition (c) / PET / Polymer Composition (c) / PP (1) Used in Example 7 PP, the thermoplastic polymer composition (c) obtained in Example 3 and PET were fed to the respective extruders using the same extrusion molding apparatus as in the above, and the maximum temperature during extrusion was 240 ° C. for PP, Polymer composition (c)
Is set to 245 ° C and PET 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) were laminated in this order from the die of the extrusion molding apparatus. Co-extrusion molding is performed so that
A laminated structure having 5 layers in which both surfaces were PP layers, the intermediate layer was a PET layer, and the polymer composition (c) layer was interposed between the PP layer and the intermediate layer was produced. (2) A laminated structure composed of 5 layers was formed 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 (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer on the inside thereof was extremely strong and could not be peeled off, and therefore the adhesive 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 (1) above was 1050 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) have excellent transparency, and the contents can be clearly seen when packaged using the laminated structure. We were able to.

Example 12 [Production of laminated structure consisting of 5 layers of PP / polymer composition (c) / PA / polymer composition (c) / PP] (1) Used in Example 7 PP, the thermoplastic polymer composition (c) obtained in Example 3 and PA were fed to the respective extruders using the same extrusion molding apparatus as described above, and the maximum temperature at the time of extrusion was 240 ° C. for PP, The polymer composition (c) was set to 245 ° C. and the PA was set to 255 ° C., and PP (50 μm) / polymer composition (c) (10 μm) / PA (50 μm) was fed from the die of the extrusion molding apparatus. / Polymer composition (c) (10 μm) / PP (50 μm) are laminated in this order to form a five-layer structure, and coextrusion molding is performed to form a PP layer on both surfaces and a PA layer on the intermediate layer. From 5 layers in which the polymer composition (c) layer is respectively interposed between the layer and the intermediate layer Was manufactured. (2) A laminated structure composed of 5 layers was formed 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 PA layer was 2 μm. Manufactured. (3) With respect to the laminated structure obtained in (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer on the inside thereof was extremely strong and could not be peeled off, and therefore the adhesive 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 (1) above was 1540 g / cm, which was an extremely high value. Further, both the laminated structure obtained in (1) above and the laminated structure obtained in (2) above are excellent in transparency, and the contents can be well seen through when packaged using the laminated structure. I was able to.

Example 13 [Production of Laminated Structure Composed of 5 Layers of PP / Polymer Composition (c) / PMMA / Polymer Composition (c) / PP] (1) Used in Example 7 PP, the thermoplastic polymer composition (c) obtained in Example 3 and PMMA were fed to the respective extruders using the same extrusion molding apparatus as described above, and the maximum temperature at the time of extrusion was 240 ° C. for PP, The polymer composition (c) was set to 245 ° C. and the PMMA was set to 250 ° C., and PP (50 μm) /
Polymer composition (c) (10 μm) / PMMA (50 μm
m) / polymer composition (c) (10 μm) / PP (50 μm
m) are laminated in this order to form a five-layer structure, and coextrusion molding is performed to form a PP layer on both surfaces and a PMMA layer on the intermediate layer. The polymer composition (c ) A laminated structure consisting of 5 layers with each layer interposed was produced. (2) A laminated structure consisting of 5 layers was formed 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 (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer on the inside thereof was extremely strong and could not be peeled off, and therefore the adhesive 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, which was a high value. Further, both the laminated structure obtained in (1) above and the laminated structure obtained in (2) above are excellent in transparency, and the contents can be well seen through when packaged using the laminated structure. I was able to.

Example 14 [Production of Laminated Structure Comprising 5 Layers of PP / Polymer Composition (c) / PC / Polymer Composition (c) / PP] (1) Used in Example 7 PP, the thermoplastic polymer composition (c) obtained in Example 3 and PC were supplied to the respective extruders using the same extrusion molding apparatus as described in No. 1, and the maximum temperature during extrusion was 240 ° C. for PP, The polymer composition (c) was set to 250 ° C. and the PC was set to 270 ° C., and PP (50 μm) / polymer composition (c) (10 μm) / PC (50 μm) was fed from the die of the extrusion molding apparatus. / Polymer composition (c) (10 μm) / PP (50 μm) are laminated in this order to form a five-layer structure, and coextrusion molding is performed to form a PP layer on both surfaces and a PC layer on the intermediate layer. From 5 layers in which the polymer composition (c) layer is respectively interposed between the layer and the intermediate layer Was manufactured. (2) A laminated structure composed of 5 layers was formed 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 PC layer was 2 μm. Manufactured. (3) With respect to the laminated structure obtained in (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer on the inside thereof was extremely strong and could not be peeled off, and therefore the adhesive 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 (1) above 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) have excellent transparency, and the contents can be satisfactorily improved when packaged using the laminated structure. I could see through.

Example 15 [Production of Laminated Structure Consisting of 5 Layers of PVC / Polymer Composition (e) / PS / Polymer Composition (e) / PVC] (1) Used in Example 7 Using the same extrusion molding apparatus as in No. 1, PVC, the thermoplastic polymer composition (e) obtained in Example 5 and PS were fed to each extruder, and the maximum temperature at the time of extrusion was 190 ° C for PVC, The polymer composition (e) was set to 225 ° C. and the PS was set to 240 ° C., and PVC (50 μm) / polymer composition (e) (10 μm) / PS (50 μm) was obtained from the die of the extrusion molding apparatus. / Polymer composition (e) (10 μm) / PVC (50 μm) are laminated in this order to form a five-layer structure, and coextrusion molding is performed to form a PVC layer on both surfaces and a PS layer on the intermediate layer.
A laminated structure consisting of 5 layers in which the polymer composition (e) layer was interposed between the C layer and the intermediate layer was produced. (2) A laminated structure composed of 5 layers was formed 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 (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PV on both surfaces was measured.
The adhesive strength between the C layer and the polymer composition (e) layer inside thereof was 920 g / cm, which was a high value. Further, in the laminated structure obtained in the above (1), the adhesion between the polymer composition (e) layer and the intermediate PS layer is so strong that peeling cannot be performed, and therefore the adhesion strength can be measured. Didn't do it. Furthermore, both the laminated structure obtained in the above (1) and the laminated structure obtained in the above (2) have excellent transparency, and the contents can be satisfactorily improved when packaged using the laminated structure. I could see through.

Example 16 [Production of laminated structure consisting of 5 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 fed to the respective extruders using the same extrusion molding apparatus as in the above, and the maximum temperature at the time of extrusion was 240 ° C. for PP, 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) are laminated in this order to form a five-layer structure, and coextrusion molding is performed. Both surfaces are PP layers, the intermediate layer is a PVDC layer, and the polymer composition (f) is formed between the PP layer and the intermediate layer. ) A laminated structure consisting of 5 layers with each layer interposed was produced. (2) A laminated structure composed of 5 layers was formed in the same manner as in (1) above 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 (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (f) layer on the inside thereof was extremely strong and could not be peeled off, and therefore the adhesive strength was not measured. In addition, the polymer composition (f) layer and the intermediate PVDC 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) have excellent transparency, and the contents can be clearly seen when packaged using the laminated structure. We were able to.

Example 17 [Production of Laminated Structure Comprising 5 Layers of PP / Polymer Composition (b) / POM / Polymer Composition (b) / PP] (1) Used in Example 7 PP, the thermoplastic polymer composition (b) obtained in Example 2 and POM were fed to the respective extruders using the same extruder as described above, and the maximum temperature during extrusion was PP = 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) were laminated in this order from the die of the extrusion molding apparatus. Co-extrusion molding is performed so that
A laminated structure having 5 layers in which both surfaces were PP layers, the intermediate layer was a POM layer, and the polymer composition (b) layer was interposed between the PP layer and the intermediate layer was produced. (2) A laminated structure composed of 5 layers was formed 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 POM layer was 2 μm. Manufactured. (3) With respect to the laminated structure obtained in (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (b) layer on the inside was extremely strong and peeling could not be carried out, and therefore the adhesive 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 (1) above was 1500 g / cm, which was a high value.

Example 18 Production of Laminated Structure Comprising 5 Layers of PP / Polymer Composition (c) / ABS / Polymer Composition (c) / PP (1) Used in Example 7 PP, the thermoplastic polymer composition (c) obtained in Example 3 and ABS were fed to the respective extruders using the same extrusion molding apparatus as in the above, and the maximum temperature at the time of extrusion was 240 ° C. for PP, 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) were laminated in this order from the die of the extrusion molding apparatus. Co-extrusion molding is performed so that
A laminated structure having 5 layers in which both surfaces were PP layers, the intermediate layer was an ABS layer, and the polymer composition (c) layer was interposed between the PP layer and the intermediate layer was produced. (2) A laminated structure composed of 5 layers was formed 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 ABS layer was 2 μm. Manufactured. (3) With respect to the laminated structure obtained in (1) above and the laminated structure obtained in (2) above, the film-forming property was evaluated by the above-mentioned method, and was very good (⊚). . Moreover, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, PP on both surfaces was measured.
The adhesion between the layer and the polymer composition (c) layer on the inside thereof was extremely strong and could not be peeled off, and therefore the adhesive strength was not measured. The adhesive strength between the polymer composition (c) layer and the intermediate ABS layer in the laminated structure obtained in (1) above was 1200 g / cm, which was a high value.

Comparative Example 3 [Manufacture of Laminated Structure Consisting of 5 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 were fed to the extruder, and the maximum temperature during extrusion was PE 23
5 ° C, TPU is 220 ° C, EVOH is 210 ° C, and PE (50
μm) / TPU (10 μm) / EVOH (50 μm)
/ TPU (10 μm) / PE (50 μm) are laminated in this order to form a five-layer structure, and coextrusion molding is performed to form a PE layer on both surfaces and an EVOH layer on both surfaces. A laminated structure consisting of 5 layers with TPUs in between was produced. (2) When the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the method described above, the adhesive strength between the PE layers on both surfaces and the TPU layer on the inside was 20 g / m 2.
Which was a very low value.

Comparative Example 4 PE / hydrogenated SBIS-OH (1) / PVDC / hydrogenated S
Production of Laminated Structure Consisting of 5 Layers of BIS-OH (1) / PE] (1) Using the same extrusion molding apparatus used in Example 7, PE was used for each extruder and hydrogenated SBIS described above. −
OH (1) and PVDC were supplied, and the maximum temperature during extrusion was 235 ° C. for PE and 2 for hydrogenated SBIS-OH (1).
20 ° C, PVDC is set to 200 ° C, PE (50 μm) / hydrogenated SBI is obtained from the die of the extrusion molding device.
S-OH (1) (10 μm) / PVDC (50 μm) /
Hydrogenated SBIS-OH (1) (10 μm) / PE (50 μm
m) is laminated in this order to form a five-layer structure and coextrusion molding is performed. Both surfaces are PE layers, the intermediate layer is a PVDC layer, and hydrogenated SBIS-OH (between the PE layer and the intermediate layer is used. 1)
A laminated structure consisting of 5 layers with each layer interposed was manufactured. (2) With respect to the laminated structure obtained in (1) above, its film-forming property was evaluated by the above-described method.
Met. Further, when the adhesive strength between layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, hydrogenation S
The adhesive strength between the BIS-OH (1) layer and the PVDC layer inside the layer was as low as 10 g / cm.

Comparative Example 5 [Production of Laminated Structure Comprising 5 Layers of PP / Polymer Composition (g) / PVDC / Polymer Composition (g) / PP] (1) Used in Example 7 PP, the thermoplastic polymer composition (g) obtained in Comparative Example 1 and PVDC were fed to the respective extruders using the same extrusion molding apparatus as in No. 1, and the maximum temperature during extrusion was 240 ° C. for PP, The polymer composition (g) was set to 220 ° C. and PVDC 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) is laminated in this order so as to form a five-layer structure, and a co-extrusion molding is carried out to form a PP layer on both surfaces and a PVDC layer on the intermediate layer, and the polymer composition (g ) A laminated structure consisting of 5 layers with each layer interposed was produced. (2) With respect to the laminated structure obtained in (1) above, when the film-forming property was evaluated by the above-described method, the surface was severely roughened and was defective (x). Further, when the adhesive strength between the layers of the laminated structure obtained in (1) above was measured by the above-mentioned method, the adhesion between the PP layers on both surfaces and the polymer composition (g) layer inside thereof was found to be high. It was strong and could not be peeled off, so 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 (1) above is 670.
It was g / cm. Furthermore, the laminated structure obtained from the laminated structure obtained in (1) above was not sufficiently transparent, and the contents could not be seen through when packaged with the laminated structure.

Comparative Example 6 [Production of Laminated Structure Comprising 5 Layers of PP / Polymer Composition (g) / PA / Polymer Composition (g) / PP] (1) Used in Example 7 PP, the thermoplastic polymer composition (g) obtained in Comparative Example 1 and PA were supplied to the respective extruders using the same extrusion molding apparatus as in No. 1, and the maximum temperature at the time of 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 fed from the die of the extrusion molding apparatus. / Polymer composition (g) (10 μm) / PP (50 μm) was co-extruded in such a manner that a five-layer structure was formed, and both surfaces were a PP layer and an intermediate layer was a PA layer. The polymer composition (g) layer is interposed between the layer and the intermediate layer. To produce a laminated structure. (2) With respect to the laminated structure obtained in (1) above, when the film-forming property was evaluated by the above-mentioned method, the surface was extremely rough and markedly defective (x), and a test piece suitable for a peel test. However, the peeling test was not conducted. The laminated structure obtained in (1) above was opaque.

Comparative Example 7 [Production of Laminated Structure Comprising 5 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 the respective extruders using the same extrusion molding apparatus as in No. 2, and the maximum temperature during extrusion was 240 ° C. for PP, 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) were laminated in this order from the die of the extrusion molding apparatus. Co-extrusion molding is performed so that
A laminated structure having 5 layers in which both surfaces were PP layers, the intermediate layer was a PET layer, and the polymer composition (h) layer was interposed between the PP layer and the intermediate layer was produced. (2) With respect to the laminated structure obtained in (1) above, when the film-forming property was evaluated by the above-mentioned method, the surface was extremely rough and markedly defective (x), and a test piece suitable for a peel test. However, the peeling test was not conducted. The laminated structure obtained in (1) above was opaque.

[0137]

INDUSTRIAL APPLICABILITY The thermoplastic polymer composition of the present invention exhibits high melt adhesion to both low-polarity polymers and high-polarity polymers, and also high to other materials. Shows melt adhesion. Therefore, when using the thermoplastic polymer composition of the present invention, various laminated structures can be formed without causing problems such as environmental pollution in conventional solvent-based adhesives, deterioration of working environment, and complicated adhesion process. The melt-adhesion method enables safe and excellent workability with high productivity. 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, No problems such as peeling occur. 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 through from the outside, and moreover, a transparent material is bonded by using the thermoplastic polymer composition of the present invention as an adhesive. In the laminated structure obtained in this way, due to its excellent transparency, it is possible to easily see through an object to be packaged or the like packaged by the laminated structure from the outside. Furthermore, since the thermoplastic polymer composition of the present invention is excellent in melt moldability, various molded articles and laminated structures are adopted as conventional thermoplastic polymers with good workability and good finish. It can be smoothly produced with high productivity by various melt molding methods.

In particular, the thermoplastic polymer composition of the present invention comprises
Saponified ethylene-vinyl acetate copolymer with excellent gas barrier properties, vinylidene chloride-based polymers and polyamides, vinyl chloride-based polymers with excellent transparency, chemical resistance, printability, mechanical properties, chemical resistance and mechanical properties. Polyester with excellent physical properties, polycarbonate with excellent transparency and impact resistance, acrylic polymer with excellent transparency, weather resistance and printability, polyoxymethylene, vinyl cyanide compound with excellent mechanical properties and molding processability , A copolymer of at least one selected from a conjugated diene compound and an olefin compound and an aromatic vinyl compound, an olefin polymer such as polyethylene and polypropylene having excellent heat-sealing properties, a styrene polymer having excellent transparency and rigidity High melt adhesion to any of the above.

Therefore, taking advantage of the above-mentioned characteristics, the thermoplastic polymer composition of the present invention is a polymer layer mainly composed of at least one of (A) an olefin polymer and a styrene polymer; ) A polymer layer comprising the thermoplastic polymer composition of the present invention; and (C) saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide, polyester, polycarbonate, acrylic-based Polymer, polyoxymethylene,
And a polymer layer mainly composed of at least one kind of a copolymer of at least one kind selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound and an aromatic vinyl compound is a 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 in which the combined layer (B) / polymer layer (C) are laminated in this order. The above-mentioned laminated structure (a) is used as a packaging material for foods and medical agents that dislike oxygen, packaging material for clothing, packaging material for other products, building materials such as wallpaper and decorative board, and electrical insulation. Film, adhesive film and tape substrate, marking film, agricultural film, table cloth, raincoat, umbrella, curtain,
It can be effectively used in various applications such as for general goods such as covers and for laminating with metal plates and other materials. Then, by performing a melt molding lamination method such as melt coextrusion 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 productivity. It can be manufactured smoothly.

Further, the thermoplastic polymer composition of the present invention comprises
By utilizing the above-mentioned excellent melt adhesiveness, it can be effectively used alone as a hot melt adhesive. Furthermore, since 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, Since the plastic polymer composition as a whole has good elasticity, it can be effectively used for various applications in which properties such as elasticity, cushioning property, cushioning property and impact resistance are required.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI C09J 175/04 C09J 175/04 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 75/04-75/16 C08L 53/02

Claims (11)

(57) [Claims] 1. (i) A thermoplastic polyurethane, and a block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, and at least one hydrogenated compound of the block copolymer, [Thermoplastic polyurethane]: [block copolymer and / or hydrogenated product thereof] = a thermoplastic polymer composition containing in a weight ratio of 20:80 to 80:20; (ii) the thermoplastic polyurethane , Number average molecular weight 500
A thermoplastic polyurethane obtained by the reaction of a high molecular weight polyol of 10000, an organic diisocyanate and a chain extender; (iii) the refractive index of the thermoplastic polyurethane measured at 25 ° C., and the 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 (temperature 2 of the thermoplastic polymer composition.
Measured at 20 ° C. and a shear rate of 100 sec ⁻¹ ) is 150 to ¹
The thermoplastic polymer composition is characterized in that it is 0000 Pa · s. 2. The thermoplastic polyurethane comprises a polymer polyol having a number average molecular weight of 500 to 10,000 and having a number f of hydroxyl groups per molecule in the range of 2.005 ≦ f ≦ 2.1, an organic diisocyanate and chain extension. The thermoplastic polymer composition according to claim 1, which is a thermoplastic polyurethane obtained by a reaction with an agent. 3. The thermoplastic polyurethane has an isocyanate group / hydroxyl group equivalent ratio R of 0.9 ≦ R ≦ 1.30.
Number average molecular weight of 500 to 100
The thermoplastic polymer composition according to claim 1 or 2, which is a thermoplastic polyurethane obtained by reacting a high molecular weight polyol of 00 with an organic diisocyanate and a chain extender. 4. The block copolymer comprising the aromatic vinyl compound polymer block and the conjugated diene polymer block and / or the hydrogenated product of the block copolymer has a hydroxyl group at the terminal. The thermoplastic polymer composition according to claim 1. 5. The block copolymer comprising the aromatic vinyl compound polymer block and the conjugated diene polymer block and / or the hydrogenated product of the block copolymer, wherein the conjugated diene polymer block 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 made of 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. A polymer layer mainly composed of at least one of (A) an olefin polymer and a styrene polymer; (B) a thermoplastic polymer composition according to any one of claims 1 to 5. And a polymer layer (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 polyoxymethylene and at least one kind of a copolymer of an aromatic vinyl compound and at least one kind selected from a vinyl cyanide compound, a conjugated diene compound and an olefin compound. 8. A structure in which at least a part of (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 coextrusion molding. 10. (a) A polymer mainly composed of at least one of an olefin polymer and a styrene polymer; (b) a thermoplastic polymer composition according to any one of claims 1 to 5; And (c) saponified ethylene-vinyl acetate copolymer, vinylidene chloride-based polymer, vinyl chloride-based polymer, polyamide, polyester, polycarbonate, acrylic polymer, polyoxymethylene, vinyl cyanide compound, conjugated diene compound And at least one polymer selected from the group consisting of at least one copolymer selected from olefin compounds and an aromatic vinyl compound, and using at least the polymer (a) layer and the polymer (c) layer. Coextrusion molding is carried out such that the layer of the polymer composition (b) is interposed between the layers.
A method for manufacturing a laminated structure. 11. A hot melt adhesive comprising the thermoplastic polymer composition according to claim 1.