JP3532354B2 - Foamable polyurethane composition and method for producing foam - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a foamable polyurethane composition, and a foam using the foamable polyurethane composition.
And a method for producing a laminate . In the case of the present invention, fine cells of uniform size are evenly distributed inside the foam, the surface condition is good and the appearance is excellent, and the flexibility and mechanical properties are also high. The thermoplastic polyurethane foam can be provided smoothly and with high productivity without using an organic solvent or a CFC gas foaming agent, which is a big problem in terms of environment and safety. Further, in the case of the present invention, it has a foam layer having the above-mentioned excellent properties and is excellent in terms of peel strength between layers and abrasion resistance, and has a high-class feeling.
A thermoplastic polyurethane foam layer-containing laminate can be provided.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a polyurethane foam or a polyurethane porous body, (1) water is added to a polyurethane raw material, and a carbon dioxide gas is generated by a reaction between an isocyanate component in the raw material and water. (2) A method for producing a polyurethane foam by forming and foaming polyurethane by adding a fluorinated expanding agent such as CFC gas to a raw material for polyurethane. (3) A method of producing a foam by adding a pyrolytic foaming agent to thermoplastic polyurethane, heating and melting the polyurethane, and decomposing the foaming agent to generate gas; (4) adding an organic solvent solution of polyurethane. A method of forming a polyurethane porous body by coating on a support and wet-coagulating in a non-solvent of polyurethane to form a polyurethane porous body; ) An organic solvent solution of a polyurethane coated on a support, the solvent removed by drying (method dry coagulation) to form a polyurethane porous body; and is generally employed.

However, in the case of the above-mentioned conventional method (1), the degree of foaming becomes large, and as a result, the foam film of the foam becomes thin, so that there is a drawback that deformation due to collapse of the foam film easily occurs with a small compressive stress. is there. If the amount of water added is reduced to reduce the degree of foaming in order to prevent the collapse of the bubble film, the size of the bubbles becomes uneven, and it is difficult to obtain a good quality foam. Further, in the case of the conventional method of (2) above, due to the use of a fluorinated expander such as CFC gas, the use of which has been restricted in recent years from the viewpoint of the destruction of the global environment, etc., the regulation has become stronger in recent years. ing.

Further, in the case of the conventional method of (3) above,
The melt viscosity of thermoplastic polyurethane has a large temperature dependency, and at temperatures suitable for decomposing the foaming agent, the melt viscosity of the polyurethane becomes remarkably low, and the gas generated by the decomposition of the foaming agent cannot be sufficiently retained, resulting in bubbles. Enlargement of size, non-uniformity, and rupture of bubble film are likely to occur. As a result, the resulting polyurethane foam is likely to be rough with many irregularities on its surface, and the internal structure of the foam is also in a state in which coarse and uneven cells are unevenly distributed,
It also has poor mechanical properties. In addition, when a thin material such as a foamed film or a foamed sheet is manufactured by adopting the melt extrusion foaming method according to the conventional method of (3) using a thermal decomposition type foaming agent, especially, the film or sheet is near the die of the extruder. In many cases, breakage occurs, and extrusion foam molding cannot be performed smoothly. On the other hand, in the conventional method of (3), if the melt molding temperature is set low in order to prevent the melt viscosity of the thermoplastic polyurethane from decreasing and to easily hold the decomposed gas of the foaming agent, enormous bubbles and Although rupture is suppressed, the density of the foam becomes high, and it becomes impossible to obtain a foam having an intended expansion ratio. That is, according to the conventional method of (3), since the melting temperature range for obtaining a melt viscosity suitable for foaming is extremely narrow, it is extremely difficult to control the temperature during melt foaming, and moreover, uniform and fine bubbles are formed in the foam. It is difficult to form inside and the thickness is 0.
There is a problem that it is particularly difficult to manufacture a thin foam film having a thickness of 5 mm or less.

Further, in the case of the conventional method such as the wet coagulation method of (4) or the dry coagulation method of (5), when the porous body layer has a large thickness (for example, 1 mm or more) However, it takes a long time to solidify, which results in low productivity and high cost for manufacturing on an industrial scale. Also,
In both of the conventional method of (4) and the conventional method of (5) above, since an organic solvent solution of polyurethane is used, the working environment is deteriorated due to the use of the organic solvent.
There is a problem in safety and hygiene, and moreover, a process or facility for collecting and treating the used organic solvent is required, which complicates the manufacturing process and increases the cost.

By the way, thermoplastic polyurethane is widely used in various fields by utilizing its properties such as flexibility, elasticity and abrasion resistance, and a laminate formed by laminating a polyurethane layer on a specific base material is available. Many are used. Among the laminates having a polyurethane layer, a laminate obtained by laminating a thermoplastic polyurethane layer on a fibrous base material has a natural leather-like appearance, touch, feel, etc. Alternatively, it is widely used as artificial leather in the fields of footwear, clothing, bags, bags and the like.

As a method for producing a leather-like polyurethane laminate, (a) an organic solvent solution of polyurethane is coated on a release paper and dried to form a polyurethane film, and then the polyurethane film is knitted or woven. Or a method of adhering the release paper to the surface of a fibrous base material made of non-woven fabric with an adhesive (so-called dry method); (b) an organic solvent of polyurethane on the surface of a fibrous base material made of woven or non-woven fabric After applying the solution, a porous polyurethane layer is formed by a wet coagulation method or a dry coagulation method, and a polymer solution containing a coloring agent is applied and dried on the porous polyurethane layer to form a coloring layer, which is then embossed with an embossing roller. A method of forming a pattern; etc. are widely known.

In addition to the conventional methods described in (a) and (b) above, as a method for producing a leather-like laminate, for example, (c) on the surface of a synthetic resin layer provided on a substrate, A method of melt-extruding a synthetic resin into a film to laminate a skin layer and embossing the surface of the skin layer to form a natural leather-like skin layer (JP-A-53-62803); (d) Substrate A method for producing a leather-like sheet by laminating a thermoplastic polyurethane melt extruded from a T die on the metal vapor deposition layer formed above (JP-A-62-282078); (E) On the surface of a synthetic fiber cloth A method in which a silane coupling agent is applied in advance, and a thermoplastic resin is melt-extruded and pressure-bonded onto the silane coupling agent to produce a laminate having an improved adhesive strength between the cloth and the thermoplastic resin layer (JP-A-2-307986). No. gazette); Has been done.

However, in the case of the conventional methods of (a) and (b), as in the case of the conventional method of producing a porous body of (4) and (5), an organic solvent solution of polyurethane is used. In order to use it, there is a problem in terms of safety and hygiene due to the deterioration of the working environment associated with the use of organic solvents, and it is necessary to have a process and equipment for collecting and treating the used organic solvent. Therefore, the manufacturing process becomes complicated and the cost becomes high. Moreover, in the case of the above-mentioned conventional method (b), since it takes a long time to solidify the polyurethane surface layer, it is not possible to increase the production speed, resulting in a high production cost. There's a problem. Furthermore, in the case of the above-mentioned conventional methods (C) to (C), when the obtained laminated product is pulled or bent, unevenness such as low-quality wrinkles appears on the surface, and There are drawbacks such as easy separation from the surface layer.

[0010]

DISCLOSURE OF THE INVENTION The object of the present invention is that fine cells of uniform size are evenly distributed inside the foam, and the surface is smooth, and there is no roughness or rough unevenness and appearance. High-quality thermoplastic polyurethane foam that is excellent in flexibility, mechanical properties, etc., using organic solvents and CFC gas foaming agents, which are major problems in terms of environment and safety. It is an object of the present invention to provide a foamable polyurethane composition that can be produced smoothly and with good productivity. Another object of the present invention is, regardless of the thickness of the foam, to enable you to smoothly produce foams having excellent properties as described above, is to provide a method for producing a foam. Further, an object of the present invention is to have a layer of the thermoplastic polyurethane foam having the above-mentioned excellent properties, and yet to prevent delamination between the substrate or the surface layer and the polyurethane foam layer, and to have good resistance. It is an object of the present invention to provide a method for producing a laminate having a thermoplastic polyurethane foam layer and a base material layer, which has abrasion resistance, is excellent in durability, and is also rich in luxury. And an object of the present invention is to provide a fibrous base material,
It is an object of the present invention to provide a method for producing a multilayer laminate having a thermoplastic polyurethane foam layer and a thermoplastic elastomer non-porous layer and having good properties extremely close to those of natural leather.

[0011]

Means for Solving the Problems The inventors of the present invention conducted research to achieve the above object, and the conventional method (3) described above using a thermal decomposition type foaming agent was used to deteriorate the environment such as an organic solvent and CFC gas. In order to solve the above-mentioned various problems of the conventional method of (3), the material surface, molding surface, etc. From the aspect, various studies were repeated. As a result, in producing a foam by adding a pyrolytic foaming agent to the thermoplastic polyurethane and decomposing the foaming agent under heating and melting, the thermoplastic polyurethane is not used alone, but the thermoplastic polyurethane has a number average molecular weight of When a polyurethane composition in which an alkyl (meth) acrylate polymer of 200,000 or more is blended at a specific ratio is used, the melt viscosity becomes extremely suitable for foaming, and the gas generated by the thermal decomposition of the foaming agent. Is sufficiently and uniformly retained in the melt, and fine and uniform-sized cells are evenly distributed throughout the foam. It has been found that a high-quality polyurethane foam can be obtained in which unevenness due to uneven size of cells is not generated. The polyurethane foam obtained thereby has excellent mechanical properties and appearance due to such a good foam structure, and is also extremely excellent in terms of flexibility and the like. It has been found that it can be effectively used in a wide range of fields.

Further, the inventors of the present invention contain a thermoplastic polyurethane and a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more in a specific ratio and a thermal decomposition type foaming agent. When melt-foaming is performed using the above-described expandable polyurethane composition containing,
Depending on the application, etc., it can be smoothly produced from a thick foam to a thin foam as appropriate, and if its melt foaming is carried out by the melt extrusion foaming method, the extrudate is not damaged near the die of the extruder, For example, they have found that foamed molded products such as foamed films and foamed sheets can be produced with good processability and high productivity.

Furthermore, the present inventors have blended a thermoplastic polyurethane with a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more in a specific ratio and using a thermal decomposition type foaming agent. When a laminate comprising a layer of a foam obtained by heat-melt foaming the above-mentioned polyurethane composition contained and a substrate was produced, the thermoplastic polyurethane foam layer in the laminate obtained thereby was excellent in In addition to the characteristics, the laminate is strong in the bond between the base material layer and the polyurethane foam layer and does not cause peeling, and is also excellent in abrasion resistance, flexibility, touch and feel. I found that. In the laminate, a fibrous base material is used as a base material, a polyurethane foam layer is provided on the fibrous base material, and a non-porous layer made of a thermoplastic elastomer is further provided on the polyurethane foam layer. The laminated body provided with is more excellent in properties such as abrasion resistance, flexibility, touch, and feeling, and has good properties extremely similar to natural leather, and is various as synthetic leather or artificial leather. It has been found that it can be effectively used for other purposes.

Further, the present inventors have blended a thermoplastic polyurethane with a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more at a specific ratio and contain a thermal decomposition type foaming agent. By performing a melt extrusion method using the foamable polyurethane composition described above, it was found that the above-mentioned laminate can be produced with good processability and high productivity, and the present invention was completed based on these various findings. did.

That is, in the present invention, the number average molecular weight is 200,00 per 100 parts by weight of the thermoplastic polyurethane.
A foamable polyurethane composition containing 0 or more (meth) acrylic acid alkyl ester-based polymer in a proportion of 1 to 30 parts by weight and a thermal decomposition type foaming agent.

The present invention also relates to thermoplastic polyurethane.
The number average molecular weight is 200,000 with respect to 100 parts by weight.
The above (meth) acrylic acid alkyl ester-based polymer
1 to 30 parts by weight and contains a thermal decomposition type foaming agent.
Melt foam molding using a foamable polyurethane composition having
Is a method for producing a foam .

By the above-mentioned method of the present invention, the thermoplastic resin is
The number average molecular weight is 20 per 100 parts by weight of polyurethane.
20,000 or more (meth) acrylic acid alkyl ester
Thermoplastic polymer containing 1 to 30 parts by weight of a polymer.
A foam made of a polyurethane composition is produced.

The present invention further comprises 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of the thermoplastic polyurethane , which is produced by the following method . It is a method for producing a laminate having a foam layer and a base material layer which are made of a thermoplastic polyurethane composition and are contained in proportion.

That is , the present invention provides the following (A) to
(C); (A) 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more per 100 parts by weight of the thermoplastic polyurethane, and is a thermal decomposition type A method of performing melt foam molding using a foaming polyurethane composition containing a foaming agent and simultaneously laminating the same with a substrate; (B) a number average molecular weight of 200,000 or more per 100 parts by weight of the thermoplastic polyurethane (meta. ) Melt foam molding is performed using a foamable polyurethane composition containing an acrylic acid alkyl ester polymer in a proportion of 1 to 30 parts by weight and a thermal decomposition type foaming agent, and then laminated with a substrate in a molten state. And (C) a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more relative to 100 parts by weight of the thermoplastic polyurethane. To 30 parts by weight and using a foamable polyurethane composition containing a pyrolytic foaming agent, melt-molding in an unfoamed state to produce a laminate with a substrate in a molten state, and then foaming A method for producing the above-mentioned laminate having a foam layer made of a thermoplastic polyurethane composition and a base material layer by any one of the above methods.

Further, the present invention comprises the following method :
Thermoplastic polyurethane composition containing, on a fibrous substrate, 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more relative to 100 parts by weight of the thermoplastic polyurethane. a foam layer made of things, a further method for producing a laminate having the formed of a thermoplastic elastomer onto the foam layer nonporous layer.

That is , the present invention provides (1) the following (a) to (c); (a) (meth) acrylic acid alkyl ester having a number average molecular weight of 200,000 or more relative to 100 parts by weight of the thermoplastic polyurethane. Of carrying out melt extrusion foaming using a foamable polyurethane composition containing 1 to 30 parts by weight of a base polymer and a thermal decomposition type foaming agent, and at the same time laminating the polyurethane foam with a fibrous base material (B) 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more per 100 parts by weight of the thermoplastic polyurethane, and a thermal decomposition type foaming agent. A method of melt-extruding and foaming using the foamable polyurethane composition contained, followed by laminating with a fibrous base material in a molten state; and (c) per 100 parts by weight of thermoplastic polyurethane Unexpanded using a foamable polyurethane composition containing 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more and a thermal decomposition type foaming agent. A step of producing a laminate comprising a polyurethane foam layer and a fibrous base material by any one of the following methods: melt extrusion in the state, laminating with a fibrous base material in the molten state, and then foaming; ) A step of laminating a melt extruded product of a thermoplastic elastomer in a film form on the expandable polyurethane composition layer or the polyurethane foam layer before, at the same time as, or after the manufacture of the laminate of (1) above. characterized in that it has, fibrous base material, manufacturing of the laminate described above thermoplastic polyurethane composition consisting foam layer and having a non-porous layer made of a thermoplastic elastomer It is a method.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the present invention, foam, or a thermoplastic polyurethane constituting the foam layer in the product Sotai, but any thermoplastic polyurethane capable of heating and melting it can be used. Among them, in the present invention, a thermoplastic polyurethane obtained by reacting a polymer diol having a number average molecular weight of 800 to 8000, an organic diisocyanate and a chain extender is preferably used as the thermoplastic polyurethane.

In particular, the number average molecular weight of the high molecular diol used for forming the thermoplastic polyurethane is 800 to 8 as described above.
000, preferably 900 to 6000, the thermoplastic polyurethane has good mechanical strength and moldability, and thus the foam of the present invention and the laminate having the foam layer have good mechanical strength. In addition, the moldability at the time of producing a foam or a laminate is improved. The number average molecular weight of the high molecular weight diols referred to in this specification is JIS
It means the number average molecular weight calculated based on the hydroxyl value measured according to K 1577.

Examples of the above-mentioned polymer diol used for forming the thermoplastic polyurethane preferably used in the present invention include polyester diol, polyether diol, polycarbonate diol, polyester polycarbonate diol, polyester polyether diol and the like. , 1 type, or 2 or more types thereof can be used. Among them, it is preferable to use polyester diol and / or polyether diol as the polymer diol.

The method for producing the above-mentioned polyester diol preferably used for forming the thermoplastic polyurethane is not particularly limited, and for example, a dicarboxylic acid component consisting of an ester-forming derivative such as dicarboxylic acid, its ester or anhydride can be prepared according to a conventional method. It can be produced by directly esterifying or transesterifying the low molecular weight diol component.

Examples of the dicarboxylic acid component used for forming the polyester diol include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 2-methylsuccinic acid,
2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-
Dimethyldecanedioic acid, 3.7-dimethyldecanedioic acid and other aliphatic dicarboxylic acids having 5 to 12 carbon atoms; terephthalic acid, isophthalic acid, orthophthalic acid and other aromatic dicarboxylic acids; or their ester forming derivatives, etc. Among these, 1 type (s) or 2 or more types can be used. Among them, as the dicarboxylic acid component, an aliphatic dicarboxylic acid having 5 to 12 carbon atoms or an ester-forming derivative thereof is preferably used from the viewpoint of the flexibility, abrasion resistance and mechanical properties of the foam obtained therefrom. In particular, adipic acid, azelaic acid, sebacic acid and / or their ester-forming derivatives are more preferably used.

The low molecular weight diol component used for forming the polyester diol includes, for example, ethylene glycol, 1,3-propanediol and 2-methyl-diol.
1,3-propanediol, 1,4-butanediol,
Neopentyl glycol, 1,5-pentanediol,
Aliphatic diols such as 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and 1,10-decanediol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol Among these, 1 type (s) or 2 or more types can be used. Among them, 3-
The content ratio of methyl-1,5-pentanediol is 50.
A low molecular weight diol component of not less than mol% is preferably used from the viewpoint of good flexibility and impact resilience of the foam obtained therefrom.

Further, as the above-mentioned polyether diol that can be used for forming the thermoplastic polyurethane, for example,
Polyethylene glycol, polypropylene glycol,
Examples thereof include polytetramethylene glycol, and one or more of these can be used. Among them, polytetramethylene glycol is preferably used because the foam obtained therefrom has excellent flexibility and hydrolysis resistance.

Further, examples of the above-mentioned polycarbonate diol that can be used for forming the thermoplastic polyurethane include a polycarbonate diol obtained by reacting a low molecular weight diol component with a carbonate compound such as dialkyl carbonate, alkylene carbonate and diaryl carbonate. be able to. As the low-molecular diol component at that time, those listed above as the low-molecular diol component that can be used for forming the polyester diol can be used. Examples of the above-mentioned 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.

As the above-mentioned polyester polycarbonate diol which can be used for forming the thermoplastic polyurethane, for example, a polyester polycarbonate diol obtained by simultaneously reacting the above-mentioned low molecular weight diol component, dicarboxylic acid component and carbonate compound; previously synthesized The previously prepared polyester diol and polycarbonate diol are combined with a carbonate compound,
A polyester polycarbonate diol obtained by reacting with a diol component and / or a dicarboxylic acid component can be used.

The type of organic diisocyanate used for producing the thermoplastic polyurethane is not particularly limited,
Any of the organic diisocyanates conventionally used in the production of polyurethanes can be used. Of which
As the organic diisocyanate, 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 one or more of these can be used. Among them, 4,4'-diphenylmethane diisocyanate is preferably used because the foam obtained from it has excellent mechanical properties. If necessary, a trifunctional or higher polyisocyanate such as triphenylmethane triisocyanate may be used in a small amount.

The type of the chain extender used for producing the thermoplastic polyurethane is not particularly limited, and any chain extender conventionally used for producing the thermoplastic polyurethane can be used. Among them, as the chain extender, 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-hydroxyethyl) benzene, 1,4-
Cyclohexanediol, bis - (beta-hydroxyethyl) terephthalate, diol such as xylylene glycol; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, adipic acid Examples thereof include diamines such as dihydrazine and dihydrazine isophthalate; amino alcohols such as aminoethyl alcohol and aminopropyl alcohol, and one or more of these can be used. Among them, carbon number 2-10
The aliphatic diol is preferably used from the viewpoint that the mechanical properties of the foam obtained therefrom are excellent, and particularly 1,4-butanediol is more preferably used.

In the present invention, the above-mentioned polymer diol, organic diisocyanate and chain extender are used as the thermoplastic polyurethane in the following numerical formula (1);

[0034]

0.99 ≦ e / (d + f) ≦ 1.08 (1) (where, d is the number of moles of the polymer diol, e is the number of moles of the organic diisocyanate, and f is the number of moles of the chain extender. Show.)

It is more preferable to use a thermoplastic polyurethane obtained by reacting at a ratio satisfying The thermoplastic polyurethane formed so as to satisfy the above mathematical formula (1) is excellent in melt-foaming property, particularly melt-extruding foaming property, mechanical properties, abrasion resistance, etc. The foamed state and mechanical properties, abrasion resistance and the like of the foam and foam layer obtained by using the plastic polyurethane are improved.

The method for producing the thermoplastic polyurethane is not particularly limited, and the above-mentioned polymer diol, organic diisocyanate, chain extender and, if necessary, other components are used,
It can be produced by a prepolymer method or a one-shot method by utilizing a known urethanization reaction technique. Among them, the method of melt polymerization in the substantial absence of a solvent, particularly the method of continuous melt polymerization using a multi-screw extruder is preferably used.

In the present invention, the hardness of the thermoplastic polyurethane is 55 to 9 as JIS-A hardness.
5, and more preferably in the range of 65 to 90, a foam having excellent mechanical strength and flexibility and a laminate having a foam layer are obtained, which is preferable.

Further, in the present invention, when a thermoplastic polyurethane having a logarithmic viscosity of 0.5 to 2.0 dl / g, more preferably 0.8 to 1.9 dl / g is used, a foamable polyurethane is obtained. It is possible to make the melt viscosity of the composition suitable for foaming, and to further improve the properties such as mechanical properties and abrasion resistance of the resulting foam and the laminate having the foam layer. it can. Here, the logarithmic viscosity of the thermoplastic polyurethane referred to in the present specification is n
-Value obtained by dissolving thermoplastic polyurethane in an N, N-dimethylformamide solution containing butylamine at a rate of 0.05 mol / liter so as to have a concentration of 0.05 g / dl and measuring at 30 ° C. Is.

In the present invention, the number average molecular weight of the (meth) acrylic acid alkyl ester polymer is 2
It is necessary to use one having a value of at least 0,000.
If the number average molecular weight of the (meth) acrylic acid alkyl ester-based polymer is less than 200,000, the melt viscosity (melt elasticity) of the foamable polyurethane composition will not be suitable for retaining bubbles, and the bubbles will be coarse. It becomes impossible to form a foam in which fine bubbles of uniform size are evenly distributed due to liquefaction or rupture, and moreover, the surface of the foam or foam layer becomes uneven or rough. The appearance becomes poor. In particular, in a thin foam film or foam layer, such unevenness or roughness of the surface becomes remarkable. The upper limit of the number average molecular weight of the (meth) acrylic acid alkyl ester-based polymer is not particularly limited, but in view of the uniformity of cells in the foam, compatibility with thermoplastic polyurethane, and the like,
It is preferably 50,000 or less.

In the present invention, the number average molecular weight is 200,00.
Any (meth) acrylic acid alkyl ester-based polymer having 0 or more can be used, but the number average molecular weight is 200,000 or more, preferably 250,000 or more, and (meth) acrylic acid The number of carbon atoms of the alkyl group forming the ester of the alkyl ester is 1 to 10
Those mainly composed of the acrylic acid alkyl ester and the methacrylic acid alkyl ester are preferably used.

Preferred examples of the (meth) acrylic acid alkyl ester constituting the (meth) acrylic acid alkyl ester polymer used in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate and isopropyl acrylate. Acrylic acid alkyl esters such as butyl acrylate, hexyl acrylate and 2-ethylhexyl acrylate; methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate and cyclohexyl methacrylate. Examples thereof include acid alkyl esters, and the (meth) acrylic acid alkyl ester-based polymer may be formed of one or more of the above-mentioned (meth) acrylic acid alkyl esters. Among them, the (meth) acrylic acid alkyl ester-based polymer is preferably a methyl methacrylate-based polymer, a butyl acrylate-based polymer, or a copolymer mainly composed of methyl methacrylate and butyl acrylate.

The (meth) acrylic acid alkyl ester-based polymer used in the present invention may be used together with the above-mentioned (meth) acrylic acid alkyl ester unit, if necessary, in a small amount (generally 25 mol% or less) of other copolymers. It may have a unit derived from a polyunsaturated monomer, and examples of such a copolymerizable unsaturated monomer include ethylene, butadiene, isoprene, styrene, α-methylstyrene, and acrylonitrile. It may have a unit composed of one or more of these copolymerizable unsaturated monomers.

The expandable polyurethane composition of the present invention contains 1 to 100 parts by weight of the above-mentioned thermoplastic polyurethane and 1 to 100 parts by weight of the above-mentioned (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more. It is necessary to contain at a ratio of 30 parts by weight, and 2 to 20
It is preferably contained in a ratio of parts by weight. When the content ratio of the (meth) acrylic acid alkyl ester polymer is less than 1 part by weight with respect to 100 parts by weight of the thermoplastic polyurethane, the melt viscosity (melt elasticity) of the expandable polyurethane composition becomes low, and the foaming agent is formed. The gas generated by the decomposition of can not be held well, causing the bubbles to become huge and break,
The foam structure inside the foam becomes defective, and the surface of the foam does not have a smooth surface due to coarse irregularities and roughness.
Further, the mechanical properties of the foam may be deteriorated, and the foam layer may be poorly adhered to another layer (for example, a non-porous layer) laminated thereon. Then, such deterioration of physical properties and quality is particularly remarkable in a thin foam such as a foam film or a laminated body having a thin foam layer. Also, in some cases, it is not possible to sufficiently hold the bubbles due to the decrease in melt viscosity,
The generated bubbles may escape to the outside, leading to a decrease in foaming ratio.

On the other hand, if the proportion of the (meth) acrylic acid alkyl ester polymer used is more than 30 parts by weight based on 100 parts by weight of the thermoplastic polyurethane, the melt viscosity of the foamable polyurethane composition will be too high. Expansion is suppressed and the expansion ratio is reduced, it is not possible to obtain a foam with the desired expansion ratio, and furthermore, the dispersion of the (meth) acrylic acid alkyl ester polymer in the thermoplastic polyurethane becomes poor and foaming occurs. Unmelted spots and the like are likely to occur on the body, the foam layer, and the surface thereof.

Further, in the present invention, a thermally decomposable foaming agent is further added to the above-mentioned thermoplastic polyurethane and (meth) acrylic acid alkyl ester-based polymer to prepare a foamable polyurethane composition, and the foamable polyurethane composition is prepared. An object is heated and melt-foamed to form a foam. As the foaming agent in this case, any conventionally known thermal decomposition type foaming agent can be used and is not particularly limited. Examples of the thermal decomposition type foaming agent that can be used in the present invention include azodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, azobisisobutyrodinitrile, azodiaminobenzene, azohexa Hydrobenzonitrile, barium azodicarboxylate, N, N'-dinitrosopentamethylenetetramine, N, N'-dinitroso-N, N'-dimethylterephthalamide, t-butylaminonitrile, p-toluenesulfonylacetonehydrazone, etc. Examples of the organic pyrolyzable foaming agent, inorganic foaming agents such as sodium bicarbonate and ammonium carbonate, and the like can be used, and one kind or two or more kinds thereof can be used.

Among them, in the present invention, the blowing agent such as azodicarbonamide is higher than the melting temperature of the polyurethane composition containing the thermoplastic polyurethane and the (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more. It has a decomposition temperature of 1, is excellent in handleability, generates a large amount of gas, and its decomposition behavior is suitable for melt molding of the thermoplastic polyurethane composition of the present invention. Further, among the above-mentioned foaming agents, for example, azodicarbonamide, 4,4 ′
-Oxybis (benzenesulfonyl hydrazide), p-
Toluenesulfonyl hydrazide, sodium bicarbonate, etc. have the effect of lowering the molecular weight of polyurethane,
On the other hand, N, N'-dinitrosopentamethylenetetramine has a function of promoting crosslinking of polyurethane. Therefore, when a foaming agent that causes a decrease in the molecular weight of polyurethane and a foaming agent that promotes cross-linking are used in combination, it is possible to suppress the decrease in melt viscosity while providing appropriate cross-linking to the polyurethane, and to improve mechanical properties and physical properties. It is possible to form a foam having good physical properties, chemical properties, and a foamed state.

The addition amount of the heat-decomposable foaming agent can be adjusted according to the density of the desired foam or foam layer (foaming ratio), the application of the foam or laminate, the gas generation amount of the foaming agent, and the like. Although it is possible, generally, it is preferably about 0.05 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane.
More preferably, it is 0.3 to 3.0 parts by weight.

Further, in the present invention, in producing a foam using the above-mentioned thermal decomposition type foaming agent, foaming is performed smoothly to obtain a foam having more uniform and fine cells. You may use together an auxiliary agent. As the foaming aid in that case, a foaming aid conventionally used for each thermal decomposition type foaming agent can be used. For example, for azo foaming agents such as azodicarbonamide, sodium bicarbonate, and hydrazide foaming agents, metal carboxylates, metal carbonates such as calcium carbonate, metal oxides such as silica and alumina, minerals such as talc. A foaming aid such as, for example, N, N′-dinitrosopentamethylenetetramine, and a foaming aid such as a urea compound or an organic acid can be used.

When a foaming aid is used, the amount of the foaming aid is appropriately determined according to the expansion ratio (specific gravity) of the foam or foam layer intended for production, the use of the foam, the gas generation amount of the foaming agent, and the like. Although it can be adjusted, it is usually about 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 100 parts by weight of the thermoplastic polyurethane. It is more preferable that the amount is 2 parts by weight. The ratio of the foaming aid to be used is preferably 0.1 to 1 part by weight with respect to 1 part by weight of the foaming agent.

Further, in the present invention , the foamable polyurethane composition, the foam, and the foam layer in the laminate may contain polyethylene, if necessary, in addition to the components described above, as long as they do not interfere with the purpose of the present invention. Polypropylene, ethylene
Olefin-based polymers such as vinyl acetate copolymer, polystyrene, acrylonitrile / styrene copolymer, ABS
It may contain a small amount of one or more kinds of other thermoplastic polymers such as resins and unhydrogenated styrene block copolymers.

Further, in the present invention , the foam layer in the expandable polyurethane composition, the foam, and the laminated body may contain other additives, for example, a cell regulator for forming uniform and fine cells in the foam. (Inorganic fine powder, etc.), filler, reinforcing material,
One or more additives such as pigments, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, hydrolysis inhibitors, lubricants, flame retardants and the like may be contained as required.

In preparing the foamable polyurethane composition of the present invention, the preparation method is not particularly limited, and the foaming ability of the foaming agent and the foaming aid when a foaming aid is used during the preparation of the foamable polyurethane composition. Any method can be adopted as long as the function as an agent is not lost. Although not limited, in the preparation of the expandable polyurethane composition of the present invention, for example, (1) a mixture of a thermoplastic polyurethane and a (meth) acrylic acid alkyl ester-based polymer is prepared in advance, and A method for preparing a foamable polyurethane composition by adding and mixing a foaming agent and optionally a foaming aid and other components; (2) thermoplastic polyurethane, (meth) acrylic acid alkyl ester-based polymer, foaming agent and case A foaming aid and other components are mixed at the same time to prepare a foamable polyurethane composition; (3) A foaming agent and optionally a foaming aid are thermoplastic polyurethane and / or (meth) acrylic acid alkyl ester-based polymer. Premix with a portion of the coalescence to form a masterbatch containing a blowing agent and optionally a blowing aid, Or the like can be adopted; Batchi remaining thermoplastic polyurethane and / or methods for preparing (meth) were mixed with other components optionally alkyl ester-based polymer and acrylic foamable polyurethane composition.

In the above-mentioned method for preparing the expandable polyurethane composition, the method for mixing the respective components and the mixing apparatus used are not particularly limited, and they have been conventionally used for preparing the expandable thermoplastic polymer composition. The same mixing method and mixing device as described above may be used. For example, a mixing device such as a kneader or a Banbury mixer, or a mixing device such as a single-screw or twin-screw extruder can be used. The expandable polyurethane composition obtained as described above can be used in the production of a foam in any form such as chips, pellets, sheets, and lumps according to a conventional method.

The expandable polyurethane composition of the present invention is generally thermoplastic, and generally about 160 to 250 ° C., although it depends on the type of thermoplastic polyurethane or (meth) acrylic acid alkyl ester polymer and the mixing ratio of both. It is melted by heating to the temperature. Therefore, the expandable polyurethane composition of the present invention can be melt-molded and heat-processed, and extrusion molding, injection molding, calender molding, cast molding,
By an arbitrary molding method such as press molding or casting, it can be molded into a foamed molded product or a foamable molded product (molded product before foaming) having various shapes and structures. Among them, when melt-foam molding is performed using the expandable polyurethane composition, the size is uniform and the fine bubbles are evenly distributed throughout the whole, and further, the mechanical properties, physical properties, and appearance are excellent. A foam can be obtained smoothly. At that time, particularly when the melt extrusion foam molding method is adopted, the foam film, the foam sheet, the foam plate, the laminate, and other foam extrudates having the above-mentioned excellent properties are protected from environmental pollution such as organic solvents and freon gas. It is preferable because it can be manufactured with good workability and high productivity without using materials.

Here, when the foaming polyurethane composition is used to perform foaming at the same time as molding and processing, at a certain stage of molding and processing, a temperature not lower than the decomposition temperature of the foaming agent is used to perform molding and processing. Should be done. The foaming temperature may vary depending on the type of the foaming agent and the type of the foaming auxiliary agent used in combination. However, since the thermal decomposition type foaming agent as described above generally decomposes in the range of about 100 to 250 ° C. In order to produce a foam by decomposing it, it is advisable to employ a temperature of 100 to 250 ° C. or higher for heat foaming, depending on the type of the foaming agent or foaming aid used.

When an unfoamed sheet, film, plate, tube, laminate or other molded article is once produced using the expandable polyurethane composition and then heated to be foamed, the expandable polyurethane composition The product is molded and processed at a temperature at which the composition can be molded and processed and at a temperature at which the foaming agent does not decompose to produce an unfoamed molded article or the like. A foam-molded article can be obtained by heating above the decomposition temperature. Furthermore, in the present invention, against the production of such foams and laminates, side dish previously prepared foamable polyurethane composition, the thermoplastic polyurethane, the above-mentioned (meth) acrylic acid alkyl ester-based polymer, thermal decomposition Mold blowing agent and other ingredients as needed,
For example, the foam may be produced by directly supplying it to a melt extrusion foaming device or other melt foam molding device.

The foam obtained as described above may be used as it is, or may be laminated with another material as a base material, or may be combined with the base material by a method other than lamination,
It may be used as a composite material. In that case, the other base material used for forming the composite material is not particularly limited, and can be appropriately selected depending on the purpose of use of the foam and the usage form. The base material that can be used in combination with the foam is not limited, and examples thereof include woven fabric and knitted fabric made of natural fibers, synthetic fibers, semi-synthetic fibers, inorganic fibers, and the like.
Examples thereof include fibrous substrates such as non-woven fabrics; paper; films, sheets, plates and other shapes made of plastics and rubber; foils, sheets, plates and other shapes made of metal; wood; ceramics and the like.

In producing a composite material comprising a foam and a substrate, even when the foam is produced and then integrated with the substrate, the foamable thermoplastic polymer composition is foamed. At the same time, it may be integrally compounded with the substrate, or may be integrally compounded with the substrate before foaming and then foamed. In the composite integration of the foam or the expandable polyurethane composition and the substrate, for example, while the foam or the expandable polyurethane composition is in a molten state, depending on the affinity, adhesion, etc. between them. A method of joining with a base material, a method of adhering with an adhesive, a welding method with a solvent, a method of melting the joining surface of the foam and joining it with the base material after the production of the foam can be adopted.

Among composite materials composed of a foam and a base material, a laminate formed by laminating the foam and the base material in layers can be widely used in various fields. A laminated body is included in the scope of the present invention as a preferred embodiment. The laminated body of the present invention comprising a foam layer and a base material layer has, for example, a three-layer structure having base materials on both sides of the foam even if it has a two-layer structure of one foam layer and one base material. It may have a structure (sandwich structure), a multilayer structure of four or more layers in which foam and another material are alternately laminated, or a laminated structure other than that, and two or more base materials. In the case of the multi-layer structure having, each layer may be made of the same material or different materials.

The method for producing a laminate comprising a foam layer and a base material is not particularly limited, but (A) the foamable polyurethane composition of the present invention is melt-foam molded and simultaneously laminated with the base material. Or (C) a method in which the foamable polyurethane composition of the present invention is melt-foamed and then laminated with a substrate in a molten state; or (C) the foamable polyurethane composition of the present invention. When a laminate is manufactured by adopting a method of producing a laminate with a base material in a molten state by performing melt molding in a non-foamed state using a material; It is preferable that the laminated body of the present invention comprising the foam layer and the base material can be smoothly produced without reheating for adhesion after the production of the above.

Then, the above (A), (B) or (C)
In the case of producing a laminate by the method (1), the melt-foam molding of the expandable polyurethane composition in the method (A) or (B) is performed by melt extrusion foam molding, and in the method (C). When the melt molding in the unfoamed state is carried out by adopting the melt extrusion molding, the laminate of the foam layer and the base material can be manufactured with high productivity in a simple process. The conditions for foam molding such as the melt foaming temperature in the method (A) or (B) may be the same as or similar to those described above for the production of the foam. it can.

Further, among the above-mentioned laminates, a fibrous base material is used as a base material, the above-mentioned foam layer is formed thereon, and a non-porous material made of a thermoplastic elastomer is further formed on the foam layer. The laminate formed with the porous layer has a toughness of the fibrous base material, flexibility and moderate elasticity of the foam layer, and a supple texture and touch of the nonporous thermoplastic elastomer layer on the surface,
The properties of the three layers described above are exhibited in a composite manner, and have a good feeling, appearance, and touch that are extremely similar to those of natural leather. Therefore, it can be effectively used as synthetic leather or artificial leather. .

The following is a description of the present invention having a fibrous base material layer, a foam layer and a non-porous layer made of a thermoplastic elastomer.
A laminate manufactured by the method (hereinafter, this may be referred to as a “three-layer structure laminate”) will be described. 3-layer structure
In the laminated body , the fibrous base material can be any sheet-like fibrous base material having an appropriate thickness and a sense of fulfillment and having a soft texture, and has been a leather-like laminated body. Various fibrous base materials used in the production of the above can be used. Although not limited, the fibrous base material is formed by using, for example, ultrafine fibers or bundled fibers thereof, special porous fibers, ordinary synthetic fibers, semi-synthetic fibers, natural fibers, inorganic fibers, etc. A fibrous sheet such as an entangled non-woven sheet or a knitted woven sheet; a fibrous sheet obtained by impregnating or otherwise containing a polymer material such as polyurethane in the fibrous sheet described above; A fibrous sheet in which a porous coating layer of a polymer material is further formed on the surface of the sheet can be used.

Among the above, as the fibrous base material,
A fibrous sheet formed by using ultrafine fibers or an ultrafine fiber bundle is preferably used, and in view of the texture of the three-layer structure laminate obtained in that case, the single fiber fineness of the ultrafine fibers is 0.5 denier. It is preferably not more than 0.1, more preferably not more than 0.1 denier. When the fibrous base material is formed of an ultrafine fiber bundle, it is preferable that the total denier of the ultrafine fiber bundle is 0.5 to 10 denier from the viewpoint of the texture of the obtained three-layer structure laminate. Further, the ultrafine fibers constituting the fibrous base material are formed of polyester fibers and / or nylon fibers,
It is preferable in terms of strength, feel, cost, etc. of the obtained laminate.

In particular, when a fibrous sheet formed of a non-woven fabric of the ultrafine fiber bundle as described above and containing a polymer material in the non-woven fabric is used as the fibrous base material, it is more similar to natural leather. It is preferable because a three-layer structure laminate having a good feel and touch can be obtained.
In that case, as the polymer material to be contained in the nonwoven fabric,
Examples thereof include polyurethane-based polymers, polyamide-based polymers, vinyl chloride-based polymers, polyvinyl butyral-based polymers, acrylic-based polymers, polyamino acid-based polymers, silicon-based polymers, and the like. Or may be used in combination of two or more kinds. Among them, when a fibrous sheet impregnated with a polyurethane-based polymer or other method is used as a fibrous base material, a foam layer laminated on the fibrous base material (that is, from the foamable polyurethane composition described above) It is particularly preferable because it has a high affinity with the formed foam layer and the adhesion between the fibrous base material layer and the foam layer is strong. When a fibrous base material composed of a fibrous sheet containing a polymeric material is used, the content of the polymeric material in the fibrous base material is the weight of the fibrous sheet before containing the polymeric material. It is preferably about 10 to 70% by weight based on

In order to improve the adhesion between the fibrous base material and the foam layer, a coating layer of a surface treatment agent containing a polymer having a high affinity for the foam layer is formed on the surface of the fibrous base material. The thickness of the coating layer in that case is preferably 5 μm or less. When the thickness of the coating layer is large, it becomes difficult to obtain a laminate including a fibrous base material layer / foam layer / thermoplastic elastomer non-porous layer having a soft and cohesive feeling.

The thickness of the above-mentioned fibrous base material layer in the three-layer structure laminate can be determined according to the application of the obtained laminate, and the like. The foam layer to be laminated on the fibrous base material, Further, from the viewpoint of the balance with the thickness of the thermoplastic elastomer non-porous layer of the foam layer, the thickness of the fibrous base material is 0.
It is preferably about 3 to 3 mm, and 0.5 to 2.0 m
It is more preferably about m.

Further, in order to obtain a three-layer structure laminate having a soft texture and having a suitable resilience and a feeling of softness,
The apparent specific gravity of the fibrous base material is 0.25 to 0.5 g / cm ³
Is preferable, and 0.3 to 0.35 g / cm ³ is more preferable. If the apparent specific gravity of the fibrous base material is too large, it tends to give a rubber-like feel, while if the apparent specific gravity of the fibrous base material is too small, it will have a repulsive and stiff feel, and a feel similar to that of natural leather. It becomes difficult to obtain.

The foam layer laminated on the fibrous base material layer is formed by foaming the foamable polyurethane composition of the present invention. The thickness of the foam layer in the three-layer structure laminate can be selected according to the application etc., but generally it is preferably about 50 to 500 μm, and more preferably about 50 to 300 μm. preferable. The expansion ratio of the foam layer [(specific gravity of the foamable polyurethane composition before foaming) / (apparent specific gravity of foam)] is preferably about 1.5 to 4 times.
When the expansion ratio of the foam layer is within the above range, the foam layer has flexibility and appropriate elasticity, and when the laminate is pulled or bent, low-grade wrinkles or irregularities do not occur on the surface and a high-class feeling is obtained. It becomes a leather-like laminated body with a certain degree, and the bonding strength between the fibrous base material layer and the foam layer is increased, and delamination does not occur.

The thermoplastic elastomer forming the non-porous layer on the foam layer is excellent in flexibility, elasticity, abrasion resistance, mechanical strength, weather resistance, hydrolysis resistance and the like. Any thermoplastic elastomer that is compatible with the foam layer can be used. Examples of the thermoplastic elastomer forming the non-porous layer include (1) thermoplastic polyurethane; (2) crystalline aromatic polyester such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate as a hard segment, and a glass transition temperature. (3) 6-nylon, which has a low segment of aliphatic polyether, aliphatic polyester, aliphatic polycarbonate, aliphatic polyester polycarbonate, or the like as a soft segment;
Polyamide elastomer having polyamide such as 6,6-nylon or 12-nylon as a hard segment and an aliphatic polyether, aliphatic polyester or aliphatic polyester ether as a soft segment; (4) Styrene-based polymer as a hard segment , Polyisoprene, polybutadiene, hydrogenated polyisoprene, hydrogenated polybutadiene, etc. as a soft segment styrene elastomer; (5) silicone elastomer;
(6) Chlorinated polymer elastomer containing crystalline polyvinyl chloride and / or crystalline polyethylene as a hard segment and amorphous polyvinyl chloride and / or amorphous chlorinated polyethylene as a soft segment; (7) Polypropylene as a hard segment Polyolefin elastomers with soft segments such as ethylene propylene rubber and partially cross-linked ethylene propylene rubber as segments;
(8) A fluoropolymer elastomer having a fluororesin as a hard segment and a fluororubber as a soft segment; (9) a crystalline 1,2-polybutadiene as a hard segment and a 1,2-polybutadiene as a soft segment 1, 2-Butadiene polymer elastomer; (1
0) urethane / vinyl chloride elastomer; (11) ethylene copolymer such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid-sodium acrylate terpolymer The non-porous layer can be formed by using one or two or more of these.

In the three- layer structure laminate, the non-porous layer is formed of the above-mentioned thermoplastic elastomers from thermoplastic polyurethane or a mixture of thermoplastic polyurethane and another thermoplastic elastomer. preferable. And in that case, the material of the polymer forming the non-porous layer and the material of the foam layer formed from the foamable polyurethane composition described above become similar, and the foam layer and the non-porous layer are Since the affinity between the two is large, the adhesive strength between the non-porous layer and the foam layer is increased and peeling between the two layers does not occur, and a three-layer structure laminate having extremely excellent physical properties can be obtained. . In forming the non-porous layer from thermoplastic polyurethane, or a mixture of thermoplastic polyurethane and other thermoplastic elastomer,
As the thermoplastic polyurethane forming the non-porous layer, the above-mentioned various thermoplastic polyurethanes similar to those used for preparing the foamable polyurethane composition can be used. In that case, the thermoplastic polyurethane forming the foam layer of the three-layer structure laminate and the thermoplastic polyurethane forming the non-porous layer may be the same or different. Generally, if a thermoplastic polyurethane having a hardness slightly higher than that of the thermoplastic polyurethane used for forming the foam layer is used as the thermoplastic polyurethane forming the non-porous layer, the abrasion resistance of the three-layer structure laminate is improved. It can be further improved.

The thickness of the non-porous layer can be adjusted depending on the type of the thermoplastic elastomer forming the non-porous layer, the use of the three-layer structure laminate, and the like. The thickness of the non-porous layer is preferably about 10 to 400 μm, and more preferably 30 to 200 μm, from the viewpoint that it can be imparted to the laminate and can also impart surface strength, adhesive strength with the foam layer, durability against bending and the like. It is more preferable that the degree is. If the non-porous layer is too thin, the abrasion resistance of the surface of the obtained leather-like laminate tends to decrease. On the other hand, if the non-porous layer is too thick, the flexibility of the three-layer structure laminate is deteriorated, resulting in a rubber-like poor texture and a leather-like texture tending to be lost. It is necessary that the non-porous layer contains substantially no bubbles, and when bubbles are present, the wear resistance of the surface of the three-layer structure laminate,
The strength and smoothness are lowered, and color spots are likely to occur.

Furthermore , in the three- layer structure laminate, the surface of the non-porous layer may be subjected to unevenness processing such as embossed pattern or textured pattern and / or mirror surface processing. And
When the surface of the non-porous layer is processed to have an uneven surface, an embossed pattern or a textured pattern that more closely resembles natural leather can appear on the surface of the three-layer structure laminate. On the other hand, when the surface of the non-porous layer is mirror-finished, a glossy enamel surface is imparted to the three-layer structure laminate. In the case of a three- layer structure laminate, the surface of the non-porous layer may be subjected to both concavo-convex processing and mirror surface processing, in which case a state in which a concavo-convex pattern is further provided on the glossy enamel surface. become.

The method for producing a three-layer structure laminate is not particularly limited, and a laminate structure comprising a fibrous base material layer / foam layer / non-porous layer can be smoothly produced without peeling between the layers. Any method may be used as long as it can be produced. Among them, the three-layer structure laminate is produced by the following method, that is, (1) (a) melt extrusion foaming is performed using the foamable polyurethane composition of the present invention and at the same time, the polyurethane foam is formed into a fibrous base material. A method of laminating with a material; (b) a method of laminating with a fibrous base material in a molten state after melt extrusion foaming using the foamable polyurethane composition of the present invention described above; and (c) foaming of the present invention described above. A method of melt-extruding a polyurethane composition in an unfoamed state, laminating it in a molten state with a fibrous base material, and then foaming the same, wherein the polyurethane foam layer and the fibrous base material are laminated. And (2) before, at the same time as, or after the production of the laminate of (1) above, on the expandable polyurethane composition layer or on a foamed polyurethane foam layer. And a step of laminating a melt extruded product of a thermoplastic elastomer in a film shape; there is no peeling between layers, and a high quality three-layer structure laminated body that fully utilizes the characteristics of each layer is obtained. It is preferable because it can be manufactured with good productivity and smoothly without using harmful components such as an organic solvent and a CFC gas swelling agent.

In the step (1) for producing the three-layer structure laminate, the molding conditions such as the foaming temperature at the time of the melt extrusion foaming in the method (a) or (b) are set as follows. Manufacture can be carried out using the same or similar conditions as described above.

In carrying out the step (2) of laminating the thermoplastic elastomer, for example, (i) on the foam layer of the laminate comprising the fibrous base material layer and the foam layer, or On the expandable polyurethane composition layer of the laminate comprising the base material layer and the foamable polyurethane composition layer in the unfoamed state, the thermoplastic elastomer is directly melt-extruded and laminated, and the laminate is provided with a roll and a back facing the roll. A method of pressing through a roll; (ii) A thermoplastic elastomer is melt-extruded onto a roll, and then a laminate including a fibrous base material layer and a foam layer is formed between the roll and a back roll facing the roll. Body, or a laminate comprising a fibrous base material layer and an unfoamed foamable polyurethane composition layer, and is provided on the foam layer of the laminate or in the unfoamed foamable polyurethane composition layer. Laminate of (iii) and fibrous substrate layer and the foam layer; a method of pressing and transferring laminating a thermoplastic elastomer layer Tan composition
Alternatively, a roll is placed on the foam layer side of a laminate composed of a fibrous base material layer and an unfoamed expandable polyurethane composition layer, and the thermoplastic elastomer is directly placed in the gap between the foam layer and the roll. Melt extrusion, and a back roll on the back side (fibrous base material side) of the laminate composed of the fibrous base material and the foam layer, or the laminated body composed of the fibrous base material and the foamable polyurethane composition layer in the unfoamed state. And a method of stacking them while pressing them, and the like can be adopted. In that case, when the intermediate layer in the laminate in which the non-porous layer is laminated is not yet foamed and is in the state of the foamable polyurethane composition layer,
It is preferable to heat the foamable polyurethane composition layer at a temperature not lower than the decomposition temperature of the thermal decomposition type foaming agent contained therein and not lower than the melting temperature of the polyurethane composition for foaming.
And, as long as the thermoplastic elastomer has fluidity, the desired three-layer structure laminate can be obtained smoothly by adopting any of the above methods (i) to (iii). You can

Further, when the surface of the non-porous layer of the three-layer structure laminate is further subjected to unevenness processing and / or mirror surface processing,
The method of unevenness processing and / or mirror surface processing is not particularly limited, but, for example, (1) when performing any one of the methods (i) to (iii) of the above-mentioned step (2), the method of arranging on the foam layer side, The surface of the roll is subjected to unevenness processing and / or mirror surface processing, and at the same time a molten non-porous layer made of a thermoplastic elastomer is pressure-laminated on the foam layer and at the same time a non-porous material made of a thermoplastic elastomer is formed. A method of subjecting the surface of the layer to unevenness processing and / or mirror surface processing; (2) After forming a non-porous layer made of a thermoplastic elastomer on the foam layer, the non-porous layer can still be shaped It can be carried out by a method of subjecting the surface of the non-porous layer to the concavo-convex processing and / or the specular processing while using the above-mentioned rolls for the concavo-convex processing and / or the specular processing while in the activated state. Among them, the method (1) is preferable because the number of steps is small and the productivity is high. When the method (1) is adopted, if the pressing force provided by the roll and the back roll is set to a gauge pressure of 5 to 15 kg / cm ² , the foam layer and the non-porous layer are Adhesion and unevenness processing and / or mirror surface processing on the surface of the non-porous layer can be smoothly performed.

In performing the unevenness processing and / or the mirror surface processing on the surface of the non-porous layer, for example, a roll having the uneven processing and / or the mirror surface processing is directly brought into contact with the surface of the non-porous layer to form the non-porous surface. Method of forming unevenness and / or mirror surface on the surface of the porous layer, release-processed sheet that has been subjected to unevenness processing and / or mirror surface processing is brought into contact with the surface of the non-porous layer, and roll etc. from the back of the processed sheet It is possible to employ a method of pressing to form unevenness and / or a mirror surface on the surface of the non-porous layer. Then, when the latter method using a releasable processed sheet is adopted, any concavo-convex pattern and / or mirror surface state can be formed on the surface of the non-porous layer simply by replacing the processed sheet. It's convenient.

In any of the above methods, the non-porous layer is no longer flowable through the surface-processing roll for forming irregularities and / or mirror surface on the surface of the non-porous layer or the release-processed sheet. It is preferable to peel it from the non-porous layer after it has stopped. If this is not done and the non-porous layer is still fluid and the surface processing roll or release processing sheet is peeled from the non-porous layer surface, it will be formed on the non-porous layer surface. The unevenness and / or the mirror surface may be broken or disappear due to the fluidity of the non-porous layer, and there is a risk that a sharp unevenness and a mirror surface having excellent gloss cannot be obtained. As the surface processing roll for forming unevenness and / or mirror surface on the surface of the non-porous layer and the pressing roll arranged at the back of the mold release processing sheet, the type in which the cooling liquid is circulated inside is adopted. Alternatively, a method of positively cooling the surface processing roll or the peeling point from the non-porous layer of the releasable processed sheet by forcing cold air to the vicinity of the unevenness processing and / or mirror surface processing, etc. It is preferable to employ it, because the non-porous layer that has been unevenly processed and / or mirror-finished is quickly cooled, and the surface processing roll and the release-processed sheet can be peeled off at an early stage.

As a roll for forming a non-porous layer on the foam layer and / or a roll for performing unevenness processing and / or mirror-finishing on the surface of the non-porous layer, direct contact with the non-porous layer In the case of the rolls used by being used, generally, metal rolls are preferably used. Further, the back roll used without directly contacting the non-porous layer, as the roll used for the back of the releasable surface-treated sheet, any of metal rolls, elastic rolls, etc. can be used, Among them, it is preferable to use the elastic roll because stable pressing can be performed.

In the three- layer structure laminate, the surface of the non-porous layer is further provided with a surface finishing agent or a coloring agent for the purpose of improving abrasion resistance, preventing stains, and imparting a deep color tone. You may keep it.

Although not limited thereto, the step (a) of the above (1) and the step (i) of the above (2) are adopted, and a non-porous layer is formed on the surface of the foam layer. In the case of producing a three-layer structure laminate in which the surface of the non-porous layer is provided with a concavo-convex pattern by carrying out the lamination and the concavo-convex processing on the surface of the non-porous layer at the same time when laminating, for example, A three-layer structure laminated body can be manufactured by various steps. In FIG. 1, 1 is a fibrous base material, 2 is a mirror-finished metal roll, 3 is an elastic back roller, 4 is an extruder, 5
Is a foam layer, 6 is a laminate comprising a fibrous base material layer and a foam layer, 7 is a metal embossing roll, 8 is an elastic back roller, 9 is an extruder, 10 is a non-porous layer, and 11 is 3 Each of the layer structure laminates is shown.

Foams produced by the present invention, composite materials comprising foams and other substrates, laminates comprising foam layers and substrate layers, fibrous substrate layers / foam layers / non-porous The three-layer structure laminate having a quality layer has excellent flexibility, elasticity,
Taking advantage of properties such as abrasion resistance, mechanical properties, cushioning properties, cushioning properties, and feel, building materials such as artificial leather, wall materials and floor materials, furniture such as chairs and vehicle seats, interior materials for vehicles, etc. It can be effectively used for a wide range of applications as footwear, bags, bags, clothes, clothing miscellaneous goods, gloves, cushioning materials, heat insulating materials, cushioning materials, belts and the like. In particular, the above-mentioned three-layer structure laminate comprising a fibrous base material layer / foam layer / non-porous layer is a substitute material for natural leather, for example, clothing such as coats, blazer, skirts, shoes and boots. footwear,
It can be effectively used for bags and camera cases, bags and bags such as wallets, clothing-related products such as belts, and sports equipment such as volleyball and basketball.

[0084]

[Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. In the following examples, measurement of various physical properties and evaluation of physical properties of the obtained foam or three-layer structure laminate were carried out as follows.

[Logarithmic viscosity of thermoplastic polyurethane] n-
A thermoplastic polyurethane was dissolved in an N, N-dimethylformamide solution containing butylamine in a proportion of 0.05 mol / liter so that the concentration was 0.5 g / dl, and the thermoplasticity was measured using an Ubbelohde viscometer. The flow-down time of the polyurethane solution at a temperature of 30 ° C. was measured, and the logarithmic viscosity was determined by the following mathematical formula.

[0086]

## EQU00002 ## Logarithmic viscosity of thermoplastic polyurethane = {ln (t
/ T ₀ )} / c [wherein t is the flow-down time (second) of the thermoplastic polyurethane solution, t ₀ is the flow-down time (second) of the solvent, and c is the concentration (g / dl) of the thermoplastic polyurethane solution. Show. ]

[Hardness of Thermoplastic Polyurethane] Thermoplastic polyurethane is injection-molded (cylinder temperature: 180 to 20).
0 ℃, mold temperature 30 ℃), diameter 120mm, thickness 2m
A disc-shaped test piece of m was produced, and the Shore hardness A was measured according to JIS K 6301 using two pieces of the test piece that were superposed.

[Apparent Specific Gravity of Foamed Film] JIS K
According to 6767, the apparent specific gravity of the foamed film obtained in the following Examples or Comparative Examples was measured.

[Tensile Strength of Foamed Film] JIS K
According to 6767, the tensile strength in the length direction (extrusion direction: MD) of the foamed film obtained in the following Examples or Comparative Examples was measured.

[Appearance of Foamed Film] The surface condition of the foamed films obtained in the following Examples or Comparative Examples was visually observed to confirm that the surface of the foamed films had irregularities due to the breakage of bubbles or the unevenness of bubble diameters. If the surface is not rough and the surface is covered with a thin skin layer of foam and is smooth, it is considered good (○), and the surface of the foam film has irregularities and roughness due to bubble breakage and uneven bubble diameter. What is bad (×)
Evaluated as.

[Abrasion resistance of surface of three-layer structure laminate] Tapered rotary abrader device (with dust suction unit)
(Rotation Ablation Tester, manufactured by Toyo Seiki Co., Ltd.), JIS L 109667.17.3
The amount of wear reduction on the surface of the non-porous layer of the three-layer structure laminate was measured in accordance with.

[Peeling strength of three-layer structure laminate] The non-porous layer of the three-layer structure laminate was adhered to a support using a two-component urethane adhesive and left at 25 ° C and 65% RH for 24 hours. After that, the 180-degree peel strength was measured according to JIS K6301.

Example 1 (1) Polyester diol (PMPA) obtained by a condensation reaction of 3-methyl-1,5-pentanediol and adipic acid as a polymer diol (number average molecular weight 15
00) and 1,4-butanediol (B
D) and 4,4′-diphenylmethane diisocyanate (MDI) heated and melted at 50 ° C. were added to PMPA: B.
A twin-screw extruder (30 mmφ) that is further used in a molar ratio of D: MDI = 1: 1.4: 2.4 and has a total feed amount of 300 g / min and is coaxially rotated by a metering pump. , L / D = 36, cylinder temperature 75-2
(60 ° C.) and continuously melt-polymerized to produce thermoplastic polyurethane. The resulting thermoplastic polyurethane melt was extruded into water in a strand form, then shredded into pellets with a pelletizer, and the pellets were dehumidified and dried at 80 ° C. for 5 hours to give the following Table 2
A thermoplastic polyurethane having a logarithmic viscosity and hardness shown in Table 1 was produced.

(2) With respect to 100 parts by weight of the thermoplastic polyurethane obtained in (1) above, 5 parts by weight of a (meth) acrylate copolymer shown in Table 2 below, black pigment pellets (pigment concentration: 5 parts by weight of 20% by weight of polyethylene pellets) and 1 part by weight of an azodicarbonamide-based foaming agent (“Vinhome AC # 3” manufactured by Eiwa Kasei Co., Ltd.) are mixed, and the mixture is mixed at 150 to 160 ° C. using a twin-screw extruder. After melt-kneading, the mixture was extruded into water and cut with a pelletizer to produce expandable polyurethane composition pellets. (3) The expandable polyurethane composition pellets obtained in (2) above were charged into a single-screw extruder (25 mmφ), and the melt zone temperature was 180 to 210 ° C., the die temperature was 180 ° C., and the T
Melt extrusion foam molding was performed in a film form from a die (lip width 0.2 mm, die width 350 mm) to a thickness of 255 μm and a width of 3
A 00 mm foam film was produced. The apparent specific gravity, tensile strength and appearance of the obtained foamed film were measured or evaluated by the above-mentioned methods and were as shown in Table 3 below.

Examples 2 to 4 (1) The same polyester diol as that used in Example 1 was used, and 1,4-butanediol and 5 were used.
4,4′-diphenylmethane diisocyanate heated and melted at 0 ° C. was mixed in a molar ratio shown in Table 2 below, and continuous melt polymerization was carried out in the same manner as in (1) of Example 1 to produce a thermoplastic polyurethane. Then, it was pelletized and dehumidified and dried in the same manner as in (1) of Example 1 to produce thermoplastic polyurethane pellets. The logarithmic viscosity and hardness of the resulting thermoplastic polyurethane pellets were measured by the methods described above and were as shown in Table 2 below. (2) Thermoplastic polyurethane 1 obtained in (1) above
5 parts by weight or 10 parts by weight of the (meth) acrylic acid ester-based copolymer shown in Table 2 below relative to 00 parts by weight,
5 parts by weight of the same black pigment pellets used in (2) of Example 1 and 1 or 2 parts by weight of the same azodicarbonamide-based blowing agent used in (2) of Example 1 Mix in a ratio, and in the same manner as in (2) of Example 1,
A pellet of the expandable polyurethane composition was produced. (3) Using the expandable polyurethane composition pellet obtained in (2) above, in the same manner as in (3) of Example 1,
The film was subjected to melt extrusion foam molding to produce a foam film having a thickness shown in Table 3 below. The apparent specific gravity, tensile strength and appearance of the resulting foamed film were measured or evaluated by the methods described above, and the results are shown in Table 3 below.

Examples 5 to 6 (1) Polytetramethylene ether glycol (number average molecular weight 1000) was used as a polymer diol, 1,4-butanediol, and heat-melted at 50 ° C. 4, 4'-diphenylmethane diisocyanate,
Mixing in the molar ratio shown in Table 2 below, (1) of Example 1
Continuous melt polymerization was carried out in the same manner as above to produce a thermoplastic polyurethane, which was pelletized and dehumidified and dried in the same manner as in (1) of Example 1 to produce a thermoplastic polyurethane. The logarithmic viscosity and hardness of the resulting thermoplastic polyurethane were measured by the methods described above, and were as shown in Table 2 below. (2) Thermoplastic polyurethane 1 obtained in (1) above
5 parts by weight of the (meth) acrylic acid ester-based copolymer shown in Table 2 below, based on 00 parts by weight, (2) of Example 1
5 parts by weight of the same black pigment pellets used in (1) and 1 part by weight of the same azodicarbonamide-based foaming agent used in (2) of Example 1 were mixed, The expandable polyurethane composition pellets were manufactured similarly to the above. (3) Using the expandable polyurethane composition pellet obtained in (2) above, in the same manner as in (3) of Example 1,
The film was subjected to melt extrusion foam molding to produce a foam film having a thickness shown in Table 3 below. The apparent specific gravity, tensile strength and appearance of the resulting foamed film were measured or evaluated by the methods described above, and the results are shown in Table 3 below.

Comparative Example 1 With respect to 100 parts by weight of the same thermoplastic polyurethane as obtained in Example 1 (1),
5 parts by weight of the same black pigment pellets used in (2) of Example 1 and 1 part by weight of the same azodicarbonamide-based blowing agent used in (2) of Example 1 were mixed. Then, expandable polyurethane composition pellets were produced in the same manner as in Example 1 (2), and the pellets were subjected to melt extrusion foam molding in a film form in the same manner as in Example 1 (3). A foamed film having a thickness shown in Table 3 below was manufactured. The apparent specific gravity, tensile strength and appearance of the resulting foamed film were measured or evaluated by the methods described above, and the results are shown in Table 3 below.

Comparative Example 2 With respect to 100 parts by weight of the same thermoplastic polyurethane obtained in (1) of Example 1,
In 35 parts by weight of a (meth) acrylic acid alkyl ester-based polymer shown in Table 2 below, 5 parts by weight of the same black pigment pellets used in (2) of Example 1, and (2) of Example 1 were used. The same azodicarbonamide-based foaming agent as used was mixed at a ratio of 2 parts by weight to produce a foamable polyurethane composition pellet in the same manner as in (2) of Example 1, and using this pellet, Example 1 was used. Melt extrusion foam molding was carried out in the same manner as in (3) above to produce a foam film having a thickness shown in Table 3 below. The apparent specific gravity, tensile strength and appearance of the resulting foamed film were measured or evaluated by the methods described above, and the results are shown in Table 3 below.

Comparative Example 3 With respect to 100 parts by weight of the same thermoplastic polyurethane as obtained in (1) of Example 5,
5 parts by weight of the same black pigment pellets used in (2) of Example 1 and 1 part by weight of the same azodicarbonamide-based blowing agent used in (2) of Example 1 were mixed. Then, expandable polyurethane composition pellets were produced in the same manner as in Example 1 (2), and the pellets were subjected to melt extrusion foam molding in a film form in the same manner as in Example 1 (3). A foamed film having a thickness shown in Table 3 below was manufactured. The apparent specific gravity, tensile strength and appearance of the resulting foamed film were measured or evaluated by the methods described above, and the results are shown in Table 3 below.

Comparative Example 4 With respect to 100 parts by weight of the same thermoplastic polyurethane as that obtained in (1) of Example 5,
In 35 parts by weight of a (meth) acrylic acid alkyl ester-based polymer shown in Table 2 below, 5 parts by weight of the same black pigment pellets used in (2) of Example 1, and (2) of Example 1 were used. The same azodicarbonamide-based foaming agent as used was mixed at a ratio of 3 parts by weight to produce expandable polyurethane composition pellets in the same manner as in (2) of Example 1, and the pellets were used in Example 1 Melt extrusion foam molding was carried out in the same manner as in (3) above to produce a foam film having a thickness shown in Table 3 below. The apparent specific gravity, tensile strength and appearance of the resulting foamed film were measured or evaluated by the methods described above, and the results are shown in Table 3 below.

The contents of the abbreviations used in Table 2 below are as shown in Table 1 below.

[0102]

[Table 1] Abbreviation: Contents BD: 1,4-butanediol MDI: 4,4'-diphenylmethane diisocyanate PMPA: Polymethyl diol consisting of 3-methyl-1,5-pentanediol and adipic acid (number average molecular weight 1,500) PTG: Polytetramethylene ether glycol ( Number average molecular weight 1,000) ADCA: Azodicarbonamide-based foaming agent ("Vinform AC # 3" manufactured by Eiwa Chemical Co., Ltd.) PMMA-1: Methyl methacrylate / butyl acrylate (75/25 weight ratio) Copolymer ( Mitsubishi Rayon Co., Ltd. "Metaprene P530", number average molecular weight 3,100,000) PMMA-2: methyl methacrylate / butyl acrylate (50/50 weight ratio) Copolymer ("Metaprene L1000", Mitsubishi Rayon Co., Ltd., number average molecular weight 300,000)

[0103]

[Table 2]

[0104]

[Table 3] Examples of physical properties of foam film Thickness Apparent specific gravity Tensile strength Appearance (μm) (kg / cm ² ) Example 1 255 0.75 300 300 Example 2 260 0.73 280 ○ Example 3 245 0.78 290 ○ Example 4 250 0.70 330 ○ Example 5 255 0.73 280 ○ Example 6 240 0.75 300 ○ Comparative Example 1 290 0.60 190 × Comparative Example 2 250 0.98 290 × Comparative Example 3 275 0 .63 180 x Comparative Example 4 250 1.02 285 x

From the results shown in Tables 2 and 3 above, 1 to 30 parts by weight of the (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more is used with respect to 100 parts by weight of the thermoplastic polyurethane. It can be seen that when the foamable polyurethane compositions of Examples 1 to 6 blended in the amount within the range are used, a foamed film having excellent tensile strength, smoothness and good appearance can be obtained. On the other hand, in the cases of Comparative Examples 1 and 3 using the expandable polyurethane composition containing no (meth) acrylic acid alkyl ester-based polymer, the melt viscosity was too low to be suitable for foaming. The foamed sheet obtained by melt extrusion foam molding has a poor appearance due to unevenness or roughness on the surface due to bubble breakage or unevenness of bubble diameter, and also has low tensile strength and poor mechanical properties. You can see that Further, in the case of Comparative Examples 2 and 4 using the expandable polyurethane composition in which the amount of the (meth) acrylic acid alkyl ester polymer exceeds 30 parts by weight with respect to 100 parts by weight of the thermoplastic polyurethane, the melt viscosity is Is too high, the gas generated by decomposition of the azodicarbonamide-based foaming agent does not swell sufficiently, and the apparent specific gravity of the foamed sheet becomes high, and the appearance also becomes poor.

Example 7 (1) A polyurethane elastic body (“Kuramiron U” manufactured by Kuraray Co., Ltd.) was added to an entangled nonwoven fabric (unit weight: 360 g / m ² ) produced by using a polyester fiber having a single fiber fineness of 2.5 denier.
2195 ", logarithmic viscosity 1.05 dl / g, Shore A hardness 95) is impregnated with N, N-dimethylformamide solution and dried to prepare a fibrous base material having a thickness of 1.3 mm and a basis weight of 455 g / m ^2. (Weight ratio of polyester fiber entangled nonwoven fabric in the fibrous base material: polyurethane elastic body = 8:
2).

(2) Polyester diol (PMPA) (number average molecular weight 1500) obtained by condensation reaction of 3-methyl-1,5-pentanediol and adipic acid was used as the high molecular diol, and 1,4-butanediol was used. (BD) and 4,4′-diphenylmethane diisocyanate (MDI) heated and melted at 50 ° C.
A: BD: MDI = 1: 1.4: 2.4 molar ratio, and the total feed amount thereof was 300 g / min, and the twin-screw extruder (30 mmφ) rotating coaxially with a metering pump. , L / D = 36, cylinder temperature 75-2
(60 ° C.) for continuous melt polymerization.
The resulting thermoplastic polyurethane melt was extruded into water in a strand form, then shredded into pellets with a pelletizer, and the pellets were dehumidified and dried at 80 ° C. for 5 hours to give a logarithmic viscosity of 1.07 dl / g and Thermoplastic polyurethane with Shore hardness A of 75 (hereinafter "PU-1"
That is) produced.

(3) With respect to 100 parts by weight of the thermoplastic polyurethane (PU-1) obtained in (2) above, the same (meth) acrylate copolymer as used in Example 1 (Mitsubishi Rayon Co., Ltd. "Metaprene P53
0 ") 8 parts by weight, 5 parts by weight of the same black pigment pellets as used in Example 1 and 1 part by weight of the same azodicarbonamide-based blowing agent as used in Example 1 are mixed and mixed in a twin-screw extruder. Was melt-kneaded at 150 to 160 ° C., extruded into water, and cut with a pelletizer to produce pellets of the expandable polyurethane composition.

(4) As shown in FIG. 1, the fibrous base material 1 prepared in the above (1) is fed through between a mirror-finished metal roll 2 and an elastic back roller 3. At the same time, between the metal roller 2 and the fibrous base material 1, pellets of the expandable polyurethane composition obtained in (3) above were charged in a single-screw extruder (25 mmφ) 4 and the melting zone temperature 180 ~ 190 ℃, die temperature 180 ℃, T
A film (lip width 0.2 mm, die width 350 mm) was melt-extruded and foamed into a film form, which was supplied in a fluid state and cold-pressed at a gauge pressure of 8 kg / cm ² to obtain a thick fibrous base layer surface. A laminate 6 having a foam layer 5 having a thickness of 150 μm was manufactured. The expansion ratio of the foam layer 5 in this laminate 6 was 2.0.

(5) In addition to the above ( 2 ), polyester diol (PMPA) (number average molecular weight 1500) obtained by condensation reaction of 3-methyl-1,5-pentanediol and adipic acid was used as a polymer diol. 1,4-butanediol (BD) and 4,4′-diphenylmethane diisocyanate (MDI) heated and melted at 50 ° C. were used, and PMPA: BD: MDI = 1: 2.
Using a molar ratio of 1: 3.1, continuous melt polymerization was carried out in the same manner as in ( 2 ) above to produce a thermoplastic polyurethane, pelletization and drying were carried out to obtain a logarithmic viscosity of 1.09 dl.
/ G and a Shore hardness A of 85 were produced (hereinafter sometimes referred to as "PU-2"). (6) To 100 parts by weight of the thermoplastic polyurethane (PU-2) obtained in (5) above, 5 parts by weight of the same black pigment pellet as used in Example 1 was mixed, and a twin screw extruder was used. After melt-kneading at 180 to 200 ° C, the mixture was extruded into water and cut with a pelletizer to produce pellets of the polyurethane composition for a non-porous layer.

(7) The laminate 6 composed of the fibrous base material layer 1 and the foam layer 5 obtained in the above (4) is elastically combined with a metal embossing roll 7 which has a textured pore-like texture. The non-porous layer obtained in (6) above is supplied between the body back roller 8 and the metal embossing roller 7 and the surface of the foam layer 5 of the laminate 6. The polyurethane composition pellets in Example 1 were charged into a single-screw extruder (25 mmφ) 9, and the melt zone temperature was 190 to 210 ° C., and the die temperature was 22.
At 0 ℃, T die (lip width 0.2mm, die width 350m
m) is melt-extruded in a film form and supplied in a fluid state, and cold pressed at a gauge pressure of 10 kg / cm ² ,
A three-layer structure laminate 11 comprising a fibrous base material layer / foam layer / nonporous layer having a nonporous layer 10 having a thickness of 100 μm on the surface of the foam layer 5 was produced. This three-layer structure laminate 11 has three
Stable production was possible at a line speed of 0 m / min. (8) The three-layer structure laminate 11 obtained in (7) above is
Its surface strength is great, its flexibility is excellent, and its appearance has a good pore-like grain pattern that is very close to that of natural leather, and when it is pulled or bent, it has low-grade irregularities or wrinkles. It was a leather-like laminate having a high quality appearance, which was extremely excellent in appearance, texture, and touch. When the peel strength of the three-layer structure laminate 11 was measured by the above-mentioned method, it was a high value of 15 kg / 25 mm, on the other hand, the wear reduction amount was as small as 7 mg, and the wear resistance was excellent.

Example 8 (1) An ultrafine nylon fiber entangled nonwoven fabric (weight per unit area: 300 g / m ² ) produced by using an ultrafine fiber bundle in which about 300 ultrafine nylon fibers each having a single fiber fineness of 0.007 denier are converged. Polyurethane elastic (Kuraray Co., Ltd. “Kuramiron U
9198 ", logarithmic viscosity 1.05 dl / g, Shore A hardness 98) is impregnated with N, N-dimethylformamide solution and dried to prepare a fibrous base material having a thickness of 1.3 mm and a basis weight of 442 g / m ^2. (Weight ratio of ultrafine nylon fiber entangled nonwoven fabric: polyurethane elastic body in fibrous base material = 6:
4).

(2) Polytetramethylene ether glycol (PTG) (number average molecular weight 1000) was used as the high molecular diol, 1,4-butanediol (BD), and 4,4 'were heated and melted at 50 ° C. -Diphenylmethane diisocyanate (MDI), PTG:
Using a molar ratio of BD: MDI = 1: 0.6: 1.6,
Continuous melt polymerization was carried out in the same manner as in ( 2 ) of Example 7 to produce thermoplastic polyurethane, pellets of thermoplastic polyurethane and drying were performed to obtain a logarithmic viscosity of 1.02.
A thermoplastic polyurethane having a dl / g and a Shore hardness A of 75 was produced (hereinafter sometimes referred to as "PU-3"). (3) With respect to 100 parts by weight of the thermoplastic polyurethane (PU-3) obtained in (2) above, the same (meth) acrylate copolymer as used in Example 3 (Mitsubishi Rayon Co., Ltd.) Manufactured by "Metaprene L1000") 5 parts by weight, the same black pigment pellet 5 as used in Example 1
Parts by weight and 1 part by weight of the same azodicarbonamide-based blowing agent used in Example 1 are mixed and melt-kneaded at 150 to 160 ° C. using a twin-screw extruder, then extruded into water and cut with a pelletizer. To produce pellets of the expandable polyurethane composition.

(4) As shown in FIG. 1, the fibrous base material 1 prepared in the above (1) is supplied by passing it between a mirror-finished metal roll 2 and an elastic back roller 3. In addition, between the metal roller 2 and the fibrous base material 1, the expandable polyurethane composition pellets obtained in (3) above were charged into a single-screw extruder (25 mmφ) 4, and the melting zone temperature was 180 to At 190 ° C, the die temperature is 180 ° C, a T-die (lip width: 0.2 mm, die width: 350 mm) is melt-extruded and foamed into a film form and supplied in a fluid state, and cold pressed at a gauge pressure of 8 kg / cm ^2. Thus, a laminate 6 in which the foam layer 5 having a thickness of 200 μm was formed on the surface of the fibrous base material layer 1 was manufactured. The expansion ratio of the foam layer in this laminate 6 was 2.2 times.

(5) In addition to the above ( 2 ), polytetramethylene ether glycol (P
TG) (number average molecular weight 1000) was used and 1,4
-Butanediol (BD), and 4,4'-diphenylmethane diisocyanate (MD) heated and melted at 50 ° C.
I) is used in a molar ratio of PTG: BD: MDI = 1: 1.2: 2.2 to carry out continuous melt polymerization in the same manner as in ( 2 ) above to produce a thermoplastic polyurethane. Pellets were produced and dried to produce a thermoplastic polyurethane having an inherent viscosity of 1.03 dl / g and a Shore hardness A of 85 (hereinafter sometimes referred to as "PU-4"). (6) To 100 parts by weight of the thermoplastic polyurethane (PU-4) obtained in (5) above, 5 parts by weight of the same black pigment pellets used in Example 1 were mixed, and a twin screw extruder was used. After melt-kneading at 180 to 200 ° C., the mixture was extruded into water and cut with a pelletizer to produce polyurethane composition pellets for a non-porous layer.

(7) A metal embossing roll 7 and an elastic body obtained by subjecting a laminate 6 comprising the fibrous base material layer 1 and the foam layer 5 obtained in the above (4) to a textured texture of pores. The non-porous layer obtained in (6) above is supplied between the metal embossing roller 7 and the surface of the foam layer 5 of the laminate 6 while being supplied through the back roller 8. The polyurethane composition pellets were charged into a single-screw extruder (25 mmφ) 9, and the melt zone temperature was 190 to 210 ° C and the die temperature was 220 ° C.
And T-die (lip width 0.2 mm, die width 350 mm)
A melt-extruded film-like material is supplied in a fluid state and cold-pressed at a gauge pressure of 10 kg / cm ² to further have a non-porous layer 10 having a thickness of 100 μm on the surface of the foam layer 5. A three-layer structure laminate 11 including a base material layer / foam layer / non-porous layer was produced. This three-layer structure laminate 11 could be stably manufactured at a line speed of 30 m / min. (8) The three-layer structure laminate 11 obtained in (7) above is
Its surface strength is large, it has excellent flexibility, and the appearance has a good pore-like grain pattern that is very close to that of natural leather with pores. It did not occur, was extremely excellent in appearance, feel, touch, etc., and was a leather-like laminate having a high-grade feeling. When the peel strength of the three-layer structure laminate 11 was measured by the above method, it was a high value of 13 kg / 25 mm, while the wear reduction amount was as small as 9 mg, and the wear resistance was excellent.

<< Embodiment 9 >> In (3) of Embodiment 7,
Instead of “metaprene P530” as the (meth) acrylic acid alkyl ester-based polymer, “metaprene L1
A three-layer structure laminate comprising a fibrous base material layer / foam layer / nonporous layer was produced in exactly the same manner as in Example 7, except that the expandable polyurethane composition was produced using "000".
The three-layer structure laminate obtained as a result has a large surface strength, excellent flexibility, and has a good pore-like texture pattern that is very similar in appearance to the pore-textured product of natural leather, and can be pulled or bent. It was a leather-like laminate with a high-quality appearance, which was excellent in appearance, feel, and touch, without the occurrence of low-quality uneven wrinkles on the surface. Also, part 3
When the peel strength of the layer structure laminate was measured by the above-mentioned method, it was a high value of 14 kg / 25 mm, while the wear reduction amount was as small as 7 mg, and the wear resistance was excellent.

Comparative Example 5 In (3) of Example 7,
Three layers consisting of fibrous base material layer / foam layer / non-porous layer, exactly as in Example 7, except that the (meth) acrylic acid alkyl ester polymer (“methaprene P530”) was not used. The structural laminate was produced at a line speed of 30 m / min. As a result, when a laminate comprising a fibrous base material layer and a foam layer is produced, due to the low melt viscosity of the expandable polyurethane composition, enormous bubbles, crushing, and rupture of the cells occur immediately after extrusion. The surface of the foam layer was rough with large irregularities. Also in the finally obtained three-layer structure laminate, due to the influence of the poor surface state of the foam layer below the non-porous layer, the surface of the non-porous layer is formed into pores by embossing rolls. The wrinkle pattern was not sufficiently formed, the corners of the protrusions flowed (collapsed) and became unclear, and the wrinkle flow occurred. In addition, the laminate had a poor sense of unity and had a hard texture lacking in flexibility. When the peel strength of the three-layer structure laminate was measured by the above-mentioned method, it was a low value of 5 kg / 25 mm, while the wear reduction amount was as large as 20 mg and the wear resistance was poor.

<< Comparative Example 6 >> In (3) of Example 8,
Example 8 except that the (meth) acrylic acid alkyl ester polymer (“metaprene L1000”) was not used.
In exactly the same manner as above, a three-layer structure laminate comprising a fibrous base material layer / foam layer / non-porous layer was produced at a line speed of 30 m / min. As a result, when a laminate comprising a fibrous base material layer and a foam layer is produced, due to the low melt viscosity of the expandable polyurethane composition, enormous bubbles, crushing, and rupture of the cells occur immediately after extrusion. The surface of the foam layer was rough with large irregularities. Also in the finally obtained three-layer structure laminate, due to the influence of the poor surface state of the foam layer below the non-porous layer, the surface of the non-porous layer is formed into pores by embossing rolls. The wrinkle pattern was not sufficiently formed, the corners of the protrusions flowed (collapsed) and became unclear, and the wrinkle flow occurred. In addition, the laminate had a poor sense of unity and had a hard texture lacking in flexibility. When the peel strength of the three-layer structure laminate was measured by the above-mentioned method, it was a low value of 5 kg / 25 mm, while the wear reduction amount was as large as 20 mg and the wear resistance was poor.

[0120]

In the case of the present invention, fine bubbles of uniform size are evenly distributed inside the foam, and the surface is rough or uneven due to breakage of bubbles or unevenness of bubble diameter. High-quality thermoplastic polyurethane foam, which is excellent in mechanical properties such as flexibility, mechanical strength, and abrasion resistance, and has a good surface condition, and a composite consisting of a polyurethane foam and a substrate. Materials and laminates are provided. Then, consisting fibrous base material layer / thermoplastic polyurethane foam layer / thermoplastic elastomer nonporous layer, manufactured according to the present invention
The three-layer structure laminate to be produced is excellent in various properties such as flexibility, elasticity, abrasion resistance and mechanical strength, in which the properties of each layer are fully utilized, and there is no delamination, pulling, It has a high-quality appearance, texture, and touch that is similar to natural leather and does not cause low-quality wrinkles or unevenness when folded. Further, the expandable polyurethane composition of the present invention is used to produce the above-mentioned thermoplastic polyurethane foam, a composite or laminate of the same and another substrate, and the above three-layer structure laminate by the method of the present invention. If you do, without using an organic solvent or CFC gas blowing agent, which is a big problem in terms of environment and safety,
The above-mentioned high quality product can be smoothly manufactured with high productivity.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a production process that is preferably adopted for producing a three-layer structure laminate of the present invention including a fibrous base material layer / foam layer / thermoplastic elastomer non-porous layer.

[Explanation of symbols]

1 fibrous base material 2 Metallic roll with mirror finish 3 Elastic back roller 4 extruder 5 foam layer 6 Laminate composed of fibrous base material layer and foam layer 7 Metal embossing roll 8 Elastic back roller 9 extruder 10 Non-porous layer 11 Three-layer structure laminate

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08J 9/04 C08L 75/04 B32B 5/18

Claims (8)

(57) [Claims] 1. A heat-decomposable type containing 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of thermoplastic polyurethane. A foamable polyurethane composition comprising a foaming agent. 2. A method for producing a foam, which comprises subjecting the foamable polyurethane composition of claim 1 to melt-foam molding. 3. The production method according to claim 2 , wherein the foam is produced by melt extrusion foam molding. 4. The manufacturing method according to claim 3 , wherein a foamed film, a sheet or a plate is manufactured. 5. The following (A) to (C); (A) A method of performing melt foam molding using the foamable polyurethane composition of claim 1 and simultaneously laminating it with a substrate; (B) 1. Melt-foaming using the foamable polyurethane composition described in 1 above, and then laminating with a substrate in a melted state; the method of foaming after producing the laminate of the substrate in performs a molten state; by any method, thermoplastic polyurethane 10
Number average molecular weight of 200,000 or more relative to 0 part by weight
1- (meth) acrylic acid alkyl ester polymer
Thermoplastic polyurethane composition containing 30 parts by weight
A method for producing a laminate having a foam layer and a base material layer made of a material . 6. (1) The following (a) to (c); (a) Melt extrusion foaming using the foamable polyurethane composition of claim 1, and simultaneously laminating the polyurethane foam with a fibrous base material. A method of: (b) melt extrusion foaming using the expandable polyurethane composition of claim 1 and then laminating it with a fibrous base material in a molten state; and (c) adding the expandable polyurethane composition of claim 1. A method of producing a laminate comprising a polyurethane foam layer and a fibrous base material by any one of the following methods: melt extrusion in an unfoamed state, laminating with a fibrous base material in a molten state, and then foaming; And (2) laminating a melt extruded product of a thermoplastic elastomer into a film on the expandable polyurethane composition layer or the polyurethane foam layer before, at the same time as, or after the manufacture of the laminate of (1) above. Let Step; and having a, in the fibrous base material, thermoplastic
The number average molecular weight is 2 with respect to 100 parts by weight of polyurethane.
Alkyl ester of (meth) acrylate with a value of over 100,000
Thermoplastic polymer containing 1 to 30 parts by weight of a polymer
A polyurethane composition having a foam layer,
Non-porous layer made of thermoplastic elastomer on the foam layer
A method for manufacturing the laminated body having . 7. The laminate according to claim 6 , which comprises subjecting the surface of the non-porous layer made of a thermoplastic elastomer to unevenness and / or mirror finishing while the non-porous layer is in a molten or plasticized state. Body manufacturing method. 8. The thermoplastic elastomer constituting the non-porous layer is a thermoplastic polyurethane elastomer according to claim 6
Alternatively, the method for manufacturing a laminated body according to 7 .