JP2004091796A - Polyurethane foam and laminate having polyurethane foam layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polyurethane foam in which fine cells of uniform size are evenly distributed inside the foam, which is excellent in appearance with the surface free of roughness or unevenness caused by cell fracture or dispersion of cell size, and excels in flexibility, mechanical strength, abrasion resistance and the like, and a laminate (particularly a leather-like laminate) having a layer of the foam, safely and at high productivity without employing organic solvents or chlorofluorocarbons foaming agents having problems on the environment, safety and so on. <P>SOLUTION: The thermoplastic polyurethane foam comprises an alkyl (meth)acrylate polymer having a number-average molecular weight of ≥200,000 in an amount of 1 to 30 pts.wt. to 100 pts.wt. thermoplastic polyurethane. The laminate has a layer of the foam. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a laminate and a composite material having a polyurethane foam and a polyurethane foam layer. ADVANTAGE OF THE INVENTION According to this invention, the fine air bubbles of uniform size are uniformly distributed inside the foam without unevenness, the surface condition is good, the appearance is excellent, and the flexibility, the mechanical properties, etc. are high quality. Can be provided smoothly and with high productivity without using an organic solvent or a chlorofluorocarbon blowing agent which is a major problem in terms of environment and safety. Furthermore, in the case of the present invention, a high-quality thermoplastic polyurethane foam layer-containing laminate having a foam layer having the above-mentioned excellent properties and having excellent peel strength between layers and abrasion resistance is also excellent. Body can be provided.

Conventionally, as a method for producing a polyurethane foam or a polyurethane porous body,
(1) A method for producing a polyurethane foam by adding water to a polyurethane raw material, generating carbon dioxide gas by reacting the isocyanate component in the raw material with water, and forming and foaming the polyurethane;
(2) A method of producing a polyurethane foam by adding a fluorine-based expanding agent such as Freon gas to a raw material for polyurethane to form and foam polyurethane.
(3) a method of adding a pyrolytic foaming agent to a thermoplastic polyurethane, heating and melting the polyurethane, decomposing the foaming agent to generate gas, and producing a foam;
(4) a method in which a polyurethane organic solvent solution is applied on a support, and wet-solidified in a polyurethane non-solvent to form a polyurethane porous body;
(5) a method of applying a polyurethane organic solvent solution on a support, drying and removing the solvent (dry coagulation) to form a polyurethane porous body;
Are generally adopted.

However, in the case of the above-mentioned conventional method (1), the degree of foaming is increased, and as a result, the foam film of the foam becomes thin, and therefore, there is a disadvantage that deformation due to collapse of the foam film easily occurs with a small compressive stress. If the foaming degree is reduced by reducing the amount of water added to prevent the collapse of the cell membrane, the size of the cells becomes non-uniform, and it is difficult to obtain a foam having good quality. In addition, in the case of the above-mentioned conventional method (2), the use of a fluorine-based expanding agent such as chlorofluorocarbon, whose use has been restricted in recent years in view of destruction of the global environment, has increased the regulations in recent years. ing.

Further, in the case of the conventional method (3), the melt viscosity of the thermoplastic polyurethane has a large temperature dependency, and at a temperature suitable for decomposing the foaming agent, the melt viscosity of the polyurethane becomes extremely low. The gas generated by the decomposition cannot be sufficiently retained, so that the bubble size becomes large or uneven, and the bubble film tends to burst. As a result, the resulting polyurethane foam is likely to be rough due to the occurrence of many irregularities on its surface, and the internal structure of the foam is also in a state in which coarse and uneven bubbles are unevenly distributed, and the mechanical characteristics Is also inferior. In addition, when a thin material such as a foamed film or a foamed sheet is manufactured by the melt extrusion foaming method according to the conventional method (3) using a pyrolytic foaming agent, the film or the sheet is particularly close to the die of the extruder. In many cases, extrusion foaming cannot be performed smoothly.
On the other hand, in the above-mentioned conventional method (3), if the melt molding temperature is set low for the purpose of preventing the melt viscosity of the thermoplastic polyurethane from lowering and easily retaining the decomposition gas of the foaming agent, the size of the bubbles becomes large. Although the rupture is suppressed, the density of the foam increases and the foam having the desired expansion ratio cannot be obtained. That is, in the case of the above-mentioned conventional method (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. There is a problem that it is difficult to form it inside, and it is particularly difficult to produce a thin foam film having a thickness of 0.5 mm or less.

In the case of a conventional method such as the wet coagulation method of (4) or the dry coagulation method of (5), when the thickness of the porous material layer is large (for example, 1 mm or more), coagulation is not performed. It takes a long time, which results in low productivity and high cost for manufacturing on an industrial scale. Further, in the case of the conventional method of (4) and the conventional method of (5), since the 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 terms of hygiene, and 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 obtained by laminating a polyurethane layer on a specific base material is often used. ing. 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, feel, feel, and the like. Or, they are widely used as artificial leather in applications such as footwear, clothing, bags and bags.

Conventionally, as a method for producing a leather-like polyurethane laminate,
(A) An organic solvent solution of polyurethane is applied on release paper and dried to form a polyurethane film, and then the polyurethane film is bonded to the surface of a fibrous base material made of a woven or nonwoven fabric with an adhesive. Method of peeling release paper from so-called (dry method);
(B) After applying an organic solvent solution of polyurethane to the surface of a fibrous base material made of a woven or nonwoven fabric, a porous polyurethane layer is formed by a wet coagulation method or a dry coagulation method, and a colorant is contained thereon. A method of forming a colored layer by applying and drying a polymer solution, and then forming an uneven pattern with an emboss roller;
Etc. are widely known.

Further, in addition to the conventional methods listed in the above (a) and (b), as a method for producing a leather-like laminate, for example,
(C) A method in which a synthetic resin is melt-extruded in the form of a film on the surface of a synthetic resin layer provided on a base material to laminate a skin layer, and the surface of the skin layer is embossed into a natural leather-like skin layer. (See Patent Document 1);
(D) A method of producing a leather-like sheet by laminating a thermoplastic polyurethane melt extruded from a T-die on a metal vapor-deposited layer formed on a substrate (see Patent Document 2);
(E) A silane coupling agent is preliminarily applied to the surface of the synthetic fiber cloth, and a thermoplastic resin is melt-extruded and pressed on the silane coupling agent to form a laminate having an improved adhesive strength between the cloth and the thermoplastic resin layer. Manufacturing method (see Patent Document 3);
And so on.

However, in the case of the above-mentioned conventional methods (a) and (b), as in the case of the above-mentioned conventional method for producing a porous body of (4) and (5), since the organic solvent solution of polyurethane is used, The use of organic solvents deteriorates the working environment, and poses problems in terms of safety and hygiene. In addition, processes and equipment for the recovery and treatment of the organic solvents used are required. The process is complicated and the cost is high. In addition, in the case of the above-mentioned conventional method (b), it takes a long time to solidify the polyurethane surface layer, so that the production speed cannot be increased, and as a result, the production cost must be increased. There's a problem.
Further, in the case of the above-mentioned conventional methods (c) to (e), when the obtained laminate product is pulled or bent, unevenness such as low-grade wrinkles appears on the surface, There are drawbacks such as easy peeling from the surface layer.

JP-A-53-62803 JP-A-62-282078 JP-A-2-307986

It is an object of the present invention to provide fine and uniform air bubbles uniformly distributed inside a foam without unevenness, a smooth surface, excellent appearance without rough or rough unevenness, flexibility, and mechanical properties. High-quality thermoplastic that can be produced smoothly and with good productivity without using organic solvents or chlorofluorocarbon blowing agents, which are a major problem in terms of environment and safety, etc. It is to provide a polyurethane foam.
An object of the present invention is to provide a layer of a thermoplastic polyurethane foam having the above-described excellent properties, and furthermore, to have no delamination between a substrate or a surface layer and a polyurethane foam layer, and to have good resistance. An object of the present invention is to provide a laminate having a thermoplastic polyurethane foam layer and a base material layer, which has abrasion properties, is excellent in durability, and has a high quality.
It is a further object of the present invention to provide a multilayer laminate having good properties very similar to natural leather, comprising a fibrous base material, a thermoplastic polyurethane foam layer and a thermoplastic elastomer non-porous layer. .

In order to achieve the above object, the present inventors have studied and found that the conventional method of (3) using a pyrolysis type foaming agent does not use environmentally deteriorating components such as organic solvents and chlorofluorocarbon gas, thereby improving productivity. In order to solve the above-mentioned various problems of the above-mentioned conventional method (3), various studies were further conducted from the viewpoints of a material surface, a molding surface, and the like, paying attention to the fact that the conventional method is high. As a result, when adding a pyrolytic foaming agent to the thermoplastic polyurethane and decomposing the foaming agent under heating and melting to produce a foam, without using the thermoplastic polyurethane alone, the thermoplastic polyurethane has a number average molecular weight of When a polyurethane composition containing a 200,000 or more alkyl (meth) acrylate polymer in a specific ratio is used, the melt viscosity of the polyurethane composition becomes extremely suitable for foaming, and the gas generated by thermal decomposition of the foaming agent is used. Is sufficiently and evenly held in the melt without unevenness, and fine and uniform bubbles are uniformly distributed throughout the foam. It has been found that a high-quality polyurethane foam having no unevenness due to uneven size of cells can be obtained. And the polyurethane foam obtained thereby has excellent mechanical properties and appearance due to such a good foamed structure, and is also extremely excellent in terms of flexibility and the like, making use of those various properties. It has been found that it can be used effectively in a wide range of fields.

Further, the present inventors contain the thermoplastic polyurethane and the (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more in a specific ratio, and further contain a pyrolytic foaming agent. When melt foaming is performed using the foamable polyurethane composition thus obtained, it is possible to appropriately produce a thick foam to a thin foam depending on the application and the like, and when the melt foaming is performed by a melt extrusion foaming method, an extruder is used. It was found that a foam molded article such as a foam film or a foam sheet can be produced with good processability and high productivity without causing breakage of the extrudate near the die.

In addition, the present inventors have blended a thermoplastic polyurethane with a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more at a specific ratio, and contain a pyrolytic foaming agent. When a laminate comprising a foam layer obtained by heating and melt-foaming the obtained polyurethane composition and a substrate was produced, the thermoplastic polyurethane foam layer in the laminate obtained thereby has the above-described excellent properties. In addition, in the laminate, the bonding between the base material layer and the polyurethane foam layer is strong and no peeling occurs, and it is also found that the laminate is excellent in terms of abrasion resistance, flexibility, touch feeling, feeling, and the like. Was. 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 formed on the polyurethane foam layer. The laminate provided with is further excellent in properties such as abrasion resistance, flexibility, tactile sensation, feeling, and has excellent properties very similar to natural leather, and is variously used as synthetic leather or artificial leather. Have been found to be able to be used effectively in applications.
Further, the present inventors have found that the above-mentioned laminate is obtained by mixing a thermoplastic polyurethane with a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more at a specific ratio, and using a pyrolytic foaming agent. It has been found that by performing a melt extrusion method using the above-mentioned expandable polyurethane composition containing the compound, it can be manufactured with good processability and high productivity, and the present invention has been completed based on those various findings.

That is, the present invention relates to a thermoplastic polyurethane composition containing 1 to 30 parts by weight of an alkyl (meth) acrylate-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of a thermoplastic polyurethane. It is a foam made of an object.

Further, the present invention provides a thermoplastic polyurethane composition containing 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of a thermoplastic polyurethane. A laminate comprising a foam layer made of a product and a base material layer.

Further, the present invention provides a method for preparing a fibrous base material in which a number average molecular weight of 200,000 or more and an alkyl (meth) acrylate-based polymer having a molecular weight of 200,000 or more are contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of a thermoplastic polyurethane. A foamed layer made of a thermoplastic polyurethane composition contained in the above, and a non-porous layer made of a thermoplastic elastomer on the foamed layer.

According to the present invention, fine bubbles having a uniform size are uniformly distributed without unevenness inside the foam, and the surface state is good without roughness or unevenness due to breakage of bubbles or unevenness of bubble diameter on the surface. Offers high-quality thermoplastic polyurethane foam, and composites and laminates composed of polyurethane foam and base material that are excellent in mechanical properties such as flexibility, mechanical strength, and abrasion resistance. Is done.
In the three-layer structure laminate of the present invention comprising the fibrous base material layer / thermoplastic polyurethane foam layer / thermoplastic elastomer nonporous layer, the flexibility and elasticity of each layer are fully utilized. Excellent in properties such as resistance, abrasion resistance, and mechanical strength, there is no delamination, no low-grade wrinkles or irregularities when pulled or bent, and a high-quality appearance similar to natural leather , Feeling, touch, etc.
Furthermore, the thermoplastic polyurethane foam and the laminate of the present invention can be used without adding an organic solvent or a chlorofluorocarbon blowing agent, which is a major problem in terms of environment and safety, to 100 parts by weight of the thermoplastic polyurethane. On the other hand, a foamable thermoplastic polyurethane composition containing a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more in a proportion of 1 to 30 parts by weight and containing a pyrolytic foaming agent is used. Therefore, it can be manufactured safely and with high productivity.

Hereinafter, the present invention will be described in detail.
In the foam of the present invention and the foam layer of the laminate of the present invention, any thermoplastic polyurethane can be used as long as it can be heated and melted. 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, when the number average molecular weight of the high molecular weight diol used for forming the thermoplastic polyurethane is 800 to 8000, preferably 900 to 6000, the mechanical strength and moldability of the thermoplastic polyurethane are improved, and the present invention is further improved. The foam and the laminate having the foam layer have good mechanical strength, and also have good moldability when producing the foam and the laminate. In addition, the number average molecular weight of the high molecular weight diol referred to in this specification means a number average molecular weight calculated based on a hydroxyl value measured according to JIS @ K1577.

Examples of the above-mentioned polymer diol used for forming the thermoplastic polyurethane preferably used in the present invention include, for example, polyester diol, polyether diol, polycarbonate diol, polyester polycarbonate diol, polyester polyether diol, and the like. One or more kinds 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 polyester diol preferably used in forming the thermoplastic polyurethane is not particularly limited.For example, a dicarboxylic acid component composed of an ester-forming derivative such as a dicarboxylic acid, an ester thereof, and an anhydride, and a low molecular It can be produced by directly esterifying or transesterifying a diol component.

Examples of the dicarboxylic acid component used for forming the polyester diol include, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 2-methylsuccinic acid, 2-methyladipic acid, and 3-methyladipate. Aliphatic dicarboxylic acids having 5 to 12 carbon atoms such as methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecandioic acid, and 3.7-dimethyldecandioic acid; terephthalic acid And aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid; and their ester-forming derivatives. One or more of these 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 excellent flexibility, abrasion resistance and mechanical properties of a foam obtained therefrom. In particular, adipic acid, azelaic acid, sebacic acid and / or their ester-forming derivatives are more preferably used.

Examples of the low molecular weight diol component used for forming the polyester diol include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, and the like. Aliphatic diols such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and 1,10-decanediol; cyclohexanedimethanol, cyclohexanediol And the like, and one or more of these can be used. Among them, a low molecular weight diol component having a content ratio of 3-methyl-1,5-pentanediol of 50 mol% or more is preferably used from the viewpoint of good flexibility and rebound resilience of a foam obtained therefrom.

Examples of the polyether diol that can be used for forming the thermoplastic polyurethane include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and one or more of these may be used. Can be. 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 a thermoplastic polyurethane include, for example, a polycarbonate diol obtained by reacting a low-molecular diol component with a carbonate compound such as a dialkyl carbonate, an alkylene carbonate, or a diaryl carbonate. . As the low molecular weight diol component at that time, those mentioned above as the low molecular weight diol component that can be used for forming the polyester diol can be used. The above-mentioned dialkyl carbonate includes dimethyl carbonate, diethyl carbonate and the like, the alkylene carbonate includes ethylene carbonate, and the diaryl carbonate includes diphenyl carbonate.

Examples of the above-mentioned polyester polycarbonate diol that can be used for forming a thermoplastic polyurethane include, for example, a polyester polycarbonate diol obtained by simultaneously reacting the above-mentioned low-molecular diol component, dicarboxylic acid component and carbonate compound; For example, polyester polycarbonate diol obtained by reacting a polyester diol and a polycarbonate diol with a carbonate compound, a diol component and / or a dicarboxylic acid component can be used.

The type of the organic diisocyanate used for forming the thermoplastic polyurethane is not particularly limited, and any organic diisocyanate conventionally used for producing polyurethane can be used. Among them, as the organic diisocyanate, one or more of aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate having a molecular weight of 500 or less are preferably used. Examples of such organic diisocyanates include 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4 ' -Dicyclohexylmethane diisocyanate, etc., and one or more of these can be used. Among them, 4,4'-diphenylmethane diisocyanate is preferably used because the foam obtained therefrom has excellent mechanical properties. If necessary, a small amount of trifunctional or higher polyisocyanate such as triphenylmethane triisocyanate may be used.

The type of the chain extender used for forming the thermoplastic polyurethane is not particularly limited, and any of the chain extenders conventionally used in the production of 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 a 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 And diols such as bis- (β-hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, dihydrazine adipate; Diamines such as dihydrazine isophthalate; amino alcohols such as aminoethyl alcohol and aminopropyl alcohol; and one or more of these can be used.
Among them, aliphatic diols having 2 to 10 carbon atoms are preferably used from the viewpoint of excellent mechanical properties of a foam obtained therefrom, and 1,4-butanediol is particularly 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 formula (1);
0.99 ≦ e / (d + f) ≦ 1.08 (1)
(In the formula, d indicates the number of moles of the polymer diol, e indicates the number of moles of the organic diisocyanate, and f indicates the number of moles of the chain extender.)
It is more preferable to use a thermoplastic polyurethane obtained by reacting at a ratio satisfying the following.

The thermoplastic polyurethane formed so as to satisfy the above formula (1) is excellent in melt foaming properties, particularly in melt extrusion foaming properties, mechanical properties, abrasion resistance, and the like. The foamed state and mechanical properties, abrasion resistance, and the like of the foam and the foam layer obtained using the plastic polyurethane are improved.

The production method of the thermoplastic polyurethane is not particularly limited, and the above-mentioned polymer diol, organic diisocyanate, chain extender and, if necessary, other components are used, utilizing a known urethane-forming reaction technique, to obtain a prepolymer method. Alternatively, it can be manufactured by a one-shot method. Among them, a method of performing melt polymerization substantially in the absence of a solvent, particularly a method of performing continuous melt polymerization using a multi-screw extruder is preferably used.

In the present invention, when a thermoplastic polyurethane having a hardness in the range of 55 to 95, more preferably 65 to 90 as JIS-A hardness is used as the thermoplastic polyurethane, a foam having excellent mechanical strength and excellent flexibility can be obtained. This is preferable because a laminate having a body and a foam layer is obtained.

Furthermore, 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, The melt viscosity can be made suitable for foaming, and furthermore, the properties such as mechanical properties and abrasion resistance of the obtained foam and the laminate having the foam layer can be further improved.
Here, the logarithmic viscosity of the thermoplastic polyurethane referred to in the specification of the present application is such that the concentration of the thermoplastic polyurethane is 0.05 g in a N, N-dimethylformamide solution containing n-butylamine at a ratio of 0.05 mol / liter. / Dl and measured at 30 ° C.

In the present invention, it is necessary to use a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more. 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 holding bubbles, and the foam will be coarse. It becomes impossible to form a foam in which fine bubbles of uniform size are distributed without unevenness, and irregularities and roughness occur on the surface of the foam and the foam layer. Bad appearance. In particular, in the case of a thin foam film or a thin foam layer, such surface irregularities and roughness are significantly generated.
The upper limit of the number average molecular weight of the alkyl (meth) acrylate polymer is not particularly limited, but is 5,000,000 or less from the viewpoints of uniformity of cells in the foam, compatibility with the thermoplastic polyurethane, and the like. Is preferred.

In the present invention, any alkyl (meth) acrylate-based polymer having a number average molecular weight of 200,000 or more can be used, but the number average molecular weight is 200,000 or more, preferably 250,000 or more. And those mainly comprising alkyl acrylates and alkyl methacrylates in which the alkyl group forming the ester of the alkyl (meth) acrylate has 1 to 10 carbon atoms.

Preferred examples of the alkyl (meth) acrylate constituting the alkyl (meth) acrylate-based polymer used in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and acrylic acid. Alkyl acrylates such as butyl, hexyl acrylate, and 2-ethylhexyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate And the like. The alkyl (meth) acrylate-based polymer can be formed from one or more of the above-mentioned alkyl (meth) acrylates.
Among them, the alkyl (meth) acrylate-based polymer is preferably a copolymer mainly composed of methyl methacrylate-based polymer, butyl acrylate-based polymer, or methyl methacrylate and butyl acrylate.

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

The thermoplastic polyurethane composition constituting the foam of the present invention is obtained by adding the above-mentioned alkyl (meth) acrylate polymer having a number average molecular weight of 200,000 or more to 100 parts by weight of the above-mentioned thermoplastic polyurethane. It is necessary to contain it in a proportion of 1 to 30 parts by weight, and it is preferable to contain it in a proportion of 2 to 20 parts by weight.

The foam of the present invention and the foam layer in the laminate of the present invention contain thermoplastic polyurethane, a (meth) alkyl acrylate polymer having a number average molecular weight of 200,000 or more, and a pyrolytic foaming agent. The foamable polyurethane composition can be produced by heating and foaming.
In the foamable polyurethane composition used for producing the foam and laminate of the present invention, the content of the alkyl (meth) acrylate-based polymer is less than 1 part by weight based on 100 parts by weight of the thermoplastic polyurethane. If there is, the melt viscosity (melt elasticity) of the foamable polyurethane composition becomes low, and the gas generated by the decomposition of the foaming agent cannot be held well, and the bubbles become large or torn, and the bubble structure inside the foam is generated. Becomes bad. In addition, the surface of the foam obtained does not have a rough surface due to coarse irregularities and roughness, and furthermore, the mechanical properties of the foam are deteriorated, and the foam layer and another layer (for example, Poor adhesion to the porous layer). Such deterioration in physical properties and quality is particularly prominent in a thin foam such as a foam film or a laminate having a thin foam layer. In some cases, bubbles may not be sufficiently retained due to a decrease in melt viscosity, and the generated bubbles may escape to the outside, resulting in a decrease in expansion ratio.

On the other hand, in the foamable polyurethane composition described above, when the use ratio of the alkyl (meth) acrylate polymer exceeds 30 parts by weight with respect to 100 parts by weight of the thermoplastic polyurethane, the melt viscosity of the foamable polyurethane composition is increased. Is too high, expansion is suppressed and the expansion ratio is reduced, so that a foam having a desired expansion ratio cannot be obtained. In addition, the dispersion of the alkyl (meth) acrylate polymer in the thermoplastic polyurethane Becomes unsatisfactory, and unmelted bumps and the like easily occur on the foam, the foam layer, and their surfaces.

As the pyrolytic foaming agent contained in the foamable polyurethane composition used for producing the thermoplastic polyurethane foam and laminate of the present invention, any of conventionally known pyrolytic foaming agents can be used. Yes, there is no particular limitation.
Examples of the thermal decomposition type foaming agent that can be used in the present invention include azodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, azobisisobutyronitrile, azodiaminobenzene, and azohexaamine. Hydrobenzonitrile, barium azodicarboxylate, N, N'-dinitrosopentamethylenetetramine, N, N'-dinitroso-N, N'-dimethylterephthalamide, t-butylaminonitrile, p-toluenesulfonylacetonehydrazone, etc. And an inorganic foaming agent such as sodium bicarbonate and ammonium carbonate. One or more of these can be used.

Among them, a blowing agent such as azodicarbonamide has a decomposition temperature higher than the melting temperature of a polyurethane composition containing a thermoplastic polyurethane and a (meth) acrylic acid alkyl ester polymer having a number average molecular weight of 200,000 or more. It is preferably used because it has excellent 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 foaming agents, for example, azodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, sodium bicarbonate and the like have an effect of causing a decrease in the molecular weight of the polyurethane. , N, N'-dinitrosopentamethylenetetramine and the like have an action of accelerating the crosslinking of polyurethane. Therefore, when a foaming agent that causes a decrease in the molecular weight of the polyurethane and a foaming agent that promotes the crosslinking are used in combination, it is possible to suppress the decrease in the melt viscosity while providing appropriate crosslinking to the polyurethane, and to improve the mechanical properties and physical properties. A foam having good physical properties, chemical properties and foaming state can be formed.

The amount of the pyrolytic foaming agent to be added can be adjusted according to the desired density of the foam or foam layer (expansion ratio), the use of the foam or laminate, the amount of gas generated from the foaming agent, and the like. In general, the amount is preferably about 0.05 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight, and more preferably 0.3 to 3.0 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane. More preferably, it is parts by weight.

Further, in producing a foam using the above-described pyrolytic foaming agent, in order to make foaming smooth, and to obtain a foam having more uniform and fine bubbles, a foaming aid may be used in combination. Good. In this case, as the foaming auxiliary, a foaming auxiliary conventionally used for each of the pyrolytic foaming agents can be used.
For example, azo-based blowing agents such as azodicarbonamide, sodium bicarbonate, and hydrazide-based blowing agents include metal carboxylate, metal carbonate such as calcium carbonate, metal oxide such as silica and alumina, and minerals such as talc. For example, for N, N'-dinitrosopentamethylenetetramine, a foaming aid such as a urea compound or an organic acid can be used.

When a foaming aid is used, its amount should be appropriately adjusted according to the expansion ratio (specific gravity) of the foam or foam layer to be manufactured, the use of the foam, and the amount of gas generated by the foaming agent. Usually, it is preferably about 0.005 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane. Is more preferable. Further, as a usage ratio to the foaming agent, it is preferable that the foaming aid is 0.1 to 1 part by weight based on 1 part by weight of the foaming agent.

Further, the foam of the present invention, and the foam layer in the laminate, other than the above-described components, as long as the object of the present invention is not hindered, if necessary, polyethylene, polypropylene, ethylene-vinyl acetate copolymer A small amount of one or more of other thermoplastic polymers such as olefin-based polymers such as polystyrene, acrylonitrile / styrene copolymer, ABS resin, and unhydrogenated styrene-based block copolymer. Is also good.

Further, the foam of the present invention and the foam layer in the laminate may contain other additives such as a cell regulator (such as an inorganic fine powder) for forming uniform and fine cells in the foam, and a filler. And one or more additives such as reinforcing materials, pigments, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, hydrolysis inhibitors, lubricants, flame retardants, etc., if necessary. Is also good.

The method for preparing the foamable polyurethane composition used in the production of the foam and laminate of the present invention is not particularly limited, and the foaming ability of the foaming agent when the foamable polyurethane composition is prepared, Any method can be adopted as long as the function as an auxiliary agent is not lost.
Although not limited, in preparing the foamable polyurethane composition, for example,
(1) A mixture of a thermoplastic polyurethane and an alkyl (meth) acrylate-based polymer is prepared in advance, and a foaming agent, and optionally a foaming aid and other components are added to and mixed with the mixture, and the foamable polyurethane composition is prepared. A method for preparing
(2) a method for preparing a foamable polyurethane composition by simultaneously mixing a thermoplastic polyurethane, an alkyl (meth) acrylate polymer, a foaming agent, and optionally a foaming aid, and other components;
(3) A masterbatch containing a foaming agent and optionally a foaming aid is prepared by previously mixing the foaming agent and optionally a foaming aid with a portion of the thermoplastic polyurethane and / or the alkyl (meth) acrylate-based polymer. A method of preparing a foamable polyurethane composition by mixing the masterbatch with the remaining thermoplastic polyurethane and / or alkyl (meth) acrylate-based polymer and optionally other components;
Etc. can be adopted.

In the method for preparing the expandable polyurethane composition described above, the method of mixing the components and the mixing apparatus to be used are not particularly limited, and the mixing method used in the preparation of the expandable thermoplastic polymer composition has been generally used. The same mixing method and mixing apparatus as described above may be used. For example, a mixing apparatus such as a kneader or a Banbury mixer, or a mixing apparatus such as a single screw or twin screw extruder can be used.
The foamable polyurethane composition obtained as described above can be used in the production of a foam in an arbitrary form such as a chip, a pellet, a sheet, or a lump according to a conventional method.

The foamable polyurethane composition used for producing the foam and the laminate of the present invention is thermoplastic, and it depends on the type of the thermoplastic polyurethane and the alkyl (meth) acrylate-based polymer, the mixing ratio of both, and the like. , Generally by heating to a temperature of about 160-250 ° C. Therefore, the foamable polyurethane composition can be melt-molded or heat-processed, and can be formed into various shapes and structures by any molding method such as extrusion molding, injection molding, calendar molding, cast molding, press molding, and casting. Can be molded into a foamed molded article or a foamed molded article (a molded article before foaming).
Among them, when melt-foam molding is performed using the foamable polyurethane composition, the uniform size and fine bubbles are uniformly distributed throughout, and the mechanical properties, physical properties, and appearance are excellent. A foam can be obtained smoothly. In this case, especially when the melt extrusion foam molding method is adopted, the foamed film, foamed sheet, foamed board, laminated body, and other foamed extruded products having the above-mentioned excellent characteristics can be subjected to environmental pollution such as organic solvent and CFC gas. It is preferable because it can be manufactured with good workability and high productivity without using materials.

Here, when foaming is performed simultaneously with molding and processing using the expandable polyurethane composition, at least at a certain stage of molding and processing, a temperature higher than the decomposition temperature of the foaming agent is employed, and molding and processing are performed. Good. The foaming temperature may vary depending on the type of the foaming agent and the type of the foaming auxiliary used in combination. However, since the above-described pyrolytic foaming agent generally decomposes in a range of about 100 to 250 ° C, the foaming agent is used. In order to produce a foam by decomposing it, it is preferred to heat and foam at a temperature of 100 to 250 ° C. or higher, depending on the type of the foaming agent or foaming auxiliary used.

When an unfoamed sheet, film, plate, tube, laminate, or other molded article is once manufactured using the foamable polyurethane composition and then heated to foam, the foamable polyurethane composition is used as the foamable polyurethane composition. The composition is molded and processed at a temperature at which the composition can be molded and at a temperature at which the foaming agent does not decompose to produce an unfoamed molded article, and then the unfoamed molded article, etc. , A foam molded article can be obtained.
Further, in the production of the foam and the laminate of the present invention, the thermoplastic polyurethane, the above-mentioned alkyl (meth) acrylate polymer, the thermal decomposition type foam, and the foamable polyurethane composition are not prepared in advance. The agent and, if necessary, other components may be supplied directly to, for example, a melt extrusion foaming apparatus or another melt foam molding apparatus to produce a foam.

The foam obtained as described above may be used as it is, or may be used as a composite material by using another material as a base material and laminating it with the base material, or combining with the base material by a method other than lamination. You may. In this case, the other base material used to form the composite material is not particularly limited, and can be appropriately selected according to the purpose of use and the form of use of the foam.
Although not limited, examples of the substrate that can be used in combination with the foam include, for example, a fibrous substrate such as a woven fabric, a knitted fabric, or a nonwoven fabric made of natural fibers, synthetic fibers, semi-synthetic fibers, and inorganic fibers. Paper; plastic, rubber films, sheets, plates, and other shapes; metal foils, sheets, plates, and other shapes; wood; ceramics;

In producing a composite material comprising a foam and a substrate, even if the foam is integrally formed with the substrate after the foam is produced, the foamable thermoplastic polymer composition is simultaneously foamed with the substrate. Or foaming may be carried out after foaming.
In the composite integration of the foam or the foamable polyurethane composition and the substrate, depending on the affinity between them, the adhesiveness, etc., for example, while the foam or the foamable polyurethane composition is in a molten state A method of bonding with a substrate, a method of bonding with an adhesive, a method of welding using a solvent, a method of melting a bonding surface of a foam after the production of the foam, and bonding with the substrate can be employed.

Among composite materials composed of a foam and a substrate, a laminate obtained by laminating a foam and a substrate in a layered form can be widely used in various fields. Therefore, the present invention relates to such a laminate. Preferred embodiments are included in the scope of the present invention. The laminate of the present invention composed of a foam layer and a base material layer has, for example, a three-layer structure having a base material on both sides of a foam even if it has a two-layer structure of one foam layer and one base material. It may be a structure (sandwich structure), a multilayer structure of four or more layers in which foams and other materials are alternately laminated, or a laminated structure of other layers. In the case of a multi-layer structure, each layer may be made of the same material or different materials.

The method for producing the laminate of the present invention comprising a foam layer and a substrate is not particularly limited,
(A) 1 to 30 parts by weight of an alkyl (meth) acrylate-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of a thermoplastic polyurethane and a pyrolytic foaming agent A method of performing melt-foam molding using the expandable polyurethane composition to be performed and simultaneously laminating it with a substrate;
(B) 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of a thermoplastic polyurethane, and a pyrolytic foaming agent A method of performing melt-foaming molding using the expandable polyurethane composition to be performed and then laminating with a substrate in a molten state; and
(C) 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of a thermoplastic polyurethane and a pyrolytic foaming agent Melt molding in an unfoamed state using the expandable polyurethane composition to be produced, and producing a laminate with a base material in a molten state, followed by foaming;
When the laminate is manufactured by using any one of the methods described above, the foam layer and the base material can be formed without using an adhesive, and without performing reheating for bonding after manufacturing the foam. It is preferable because the laminate of the present invention can be produced smoothly.

When the laminate is manufactured by the method (A), (B) or (C), the melt foaming of the expandable polyurethane composition in the method (A) or (B) is performed by melt extrusion foaming. When the melt molding in the non-foamed state in the method (C) is performed by melt extrusion molding, the laminate of the foam layer and the base material can be formed in a simple process with good productivity. Can be manufactured. The conditions for foam molding such as the melt foaming temperature in the above method (A) or (B) may be the same or similar to those described above for the production of 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 layer made of a thermoplastic elastomer is further formed on the foam layer. The formed laminate has the three layers described above, such as the toughness of the fibrous base material, the flexibility and appropriate elasticity of the foam layer, and the supple feel and touch of the nonporous thermoplastic elastomer layer on the surface. Is exhibited in a complex manner, and has a good feeling, appearance, touch, and the like very similar to natural leather, and therefore can be effectively used as synthetic leather or artificial leather. Also encompasses the body.

Hereinafter, the laminate of the present invention having a fibrous base material layer, a foam layer, and a nonporous layer made of a thermoplastic elastomer (hereinafter, this may be referred to as a “three-layer laminate”) will be described.
In the three-layer structure laminate of the present invention, any fibrous base material having an appropriate thickness and a sense of fulfillment and having a soft feel can be used as the fibrous base material. Various types of fibrous base materials used in the production of leather-like laminates can be used. Although not limited, as the fibrous base material, for example, formed using ultrafine fibers or bundled fibers thereof, special porous fibers, ordinary synthetic fibers, semi-synthetic fibers, natural fibers, inorganic fibers, and the like A fibrous sheet such as an entangled nonwoven sheet or a knitted woven sheet; a fibrous sheet obtained by impregnating or otherwise containing a polymer material such as polyurethane in the above fibrous sheet; A fibrous sheet or the like 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 using ultrafine fibers or ultrafine fiber bundles is preferably used, and from the viewpoint of the feeling of the three-layer structure laminate obtained in that case. The single fiber fineness of the ultrafine fibers is preferably 0.5 denier or less, and more preferably 0.1 denier or less. When the fibrous base material is formed from the ultrafine fiber bundle, the total denier of the ultrafine fiber bundle is preferably 0.5 to 10 denier from the viewpoint of the feeling of the obtained three-layer structure laminate. Further, it is preferable that the ultrafine fibers constituting the fibrous base material be formed from polyester fibers and / or nylon fibers from the viewpoints of strength, feel, cost and the like of the obtained laminate.

In particular, when a fibrous sheet formed of a nonwoven fabric of the above-mentioned ultrafine fiber bundle and containing a polymer material in the nonwoven fabric is used as the fibrous base material, a good wind more similar to natural leather can be obtained. It is preferable because a three-layer structure laminate having a joint feeling and a touch feeling can be obtained. In this case, the polymer material to be contained in the nonwoven fabric includes a polyurethane polymer, a polyamide polymer, a vinyl chloride polymer, a polyvinyl butyral polymer, an acrylic polymer, a polyamino acid polymer, and a silicon polymer. These polymers may be used alone or in combination of two or more.
Among them, when a fibrous sheet impregnated with a polyurethane-based polymer by other methods is used as a fibrous base material, a foam layer laminated on the fibrous base material (that is, This is particularly preferable because it has a high affinity for the formed foam layer) and the adhesion between the fibrous base material layer and the foam layer becomes strong. When a fibrous base material made of a fibrous sheet containing a polymer material is used, the content of the polymer material in the fibrous base material is determined by the weight of the fibrous sheet before containing the polymer material. Is preferably about 10 to 70% by weight, based on

Further, 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 high affinity with the foam layer is formed on the surface of the fibrous base material. In this case, the thickness of the coating layer is preferably 5 μm or less. When the thickness of the coating layer is large, it is difficult to obtain a laminate composed of a fibrous base material layer / a foam layer / a thermoplastic elastomer nonporous layer having a feeling of flexibility and unity.

The thickness of the above-mentioned fibrous base material layer in the three-layer structure laminate can be determined according to the use of the obtained laminate, and the like. From the viewpoint of balance with the thickness of the thermoplastic elastomer nonporous layer of the body layer, the thickness of the fibrous base material is preferably about 0.3 to 3 mm, and is about 0.5 to 2.0 mm. Is more preferred.

Further, in order to obtain a three-layer laminate having a soft feel and a moderate resilience and a feeling of stiffness, the apparent specific gravity of the fibrous base material should be 0.25 to 0.5 g / cm ³ . Preferably, it is 0.3 to 0.35 g / cm ³ . If the apparent specific gravity of the fibrous base material is too large, it tends to have a rubber-like texture, while if the apparent specific gravity of the fibrous base material is too small, it has a resilience and a waist-free feel, which is also similar to natural leather. It is difficult to obtain.

The foam layer laminated on the fibrous base material layer is formed by foaming using the foamable polyurethane composition described above. The thickness of the foam layer in the three-layer structure laminate can be selected according to the application and the like, but is generally 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 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 in the above range, the laminate has flexibility and moderate elasticity, and does not have low-grade wrinkles or unevenness on the surface when the laminate is pulled or bent, and has a luxurious feeling. This gives rise to a leather-like laminate with high bonding strength between the fibrous base material layer and the foam layer, and does not cause delamination or the like.

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, etc. Any thermoplastic elastomer which has an affinity for is usable. Examples of the thermoplastic elastomer forming the non-porous layer include: (1) thermoplastic polyurethane; (2) a crystalline aromatic polyester such as polyethylene terephthalate, polypropylene terephthalate, or polybutylene terephthalate as a hard segment, and a glass transition temperature. Polyester elastomer having a soft segment of aliphatic polyether, aliphatic polyester, aliphatic polycarbonate, aliphatic polyester polycarbonate or the like having a low content; (3) polyamide such as 6-nylon, 6,6-nylon or 12-nylon being a hard segment A polyamide elastomer having an aliphatic polyether, an aliphatic polyester, an aliphatic polyester ether or the like as a soft segment; (4) a polystyrene as a hard segment comprising a styrene-based polymer; Styrene-based elastomer having soft segments of styrene, polybutadiene, hydrogenated polyisoprene, hydrogenated polybutadiene, etc .; (5) silicone-based elastomer; (6) non-crystalline having crystalline polyvinyl chloride and / or crystalline polyethylene as hard segments (7) A chlorinated polymer elastomer having a soft segment of polyvinyl chloride and / or amorphous chlorinated polyethylene; (7) a polyolefin elastomer having a hard segment of polypropylene and a soft segment of ethylene propylene rubber or partially cross-linked ethylene propylene rubber; (8) A fluoropolymer elastomer having a fluorine resin as a hard segment and a fluorine rubber as a soft segment; (9) a crystalline 1,2-polybutadiene having a hard segment and 1,2 1,2-butadiene polymer elastomer having polybutadiene as a soft segment; (10) urethane / vinyl chloride elastomer; (11) ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid- Ethylene copolymers such as a sodium acrylate terpolymer and the like can be mentioned, and a non-porous layer can be formed by using one or more of these.

In the three-layer structure laminate of the present invention, the non-porous layer is formed of thermoplastic polyurethane or a mixture of thermoplastic polyurethane and another thermoplastic elastomer among the thermoplastic elastomers described above. 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 are similar, and the foam layer and the non-porous layer Due to the high affinity between the non-porous layer and the foam layer, the adhesive strength between the non-porous layer and the foam layer is increased so that 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 a thermoplastic polyurethane or a mixture of a thermoplastic polyurethane and another thermoplastic elastomer, the thermoplastic polyurethane forming the non-porous layer is used for preparing a foamable polyurethane composition. Various thermoplastic polyurethanes similar to those described above can be used. In that case, the thermoplastic polyurethane constituting the foam layer of the three-layer laminate and the thermoplastic polyurethane constituting the nonporous layer may be the same or different. In general, when the thermoplastic polyurethane constituting the non-porous layer has a somewhat higher hardness than the thermoplastic polyurethane used for forming the foam layer, the wear resistance of the three-layer structure laminate is reduced. It can be further improved.

The thickness of the non-porous layer can be adjusted according to 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 about 30 to 200 μm, from the viewpoint of imparting surface strength, adhesion strength to the foam layer, durability against bending, and the like. Is more preferred. 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 is reduced, resulting in a rubber-like inferior hand and a tendency to lose the leather-like hand. It is necessary that the non-porous layer contains substantially no air bubbles. If air bubbles are present, the abrasion resistance, strength, and smoothness of the surface of the three-layer structure laminate are reduced, and color unevenness and the like are reduced. It is easy to occur.

Further, in the three-layer structure laminate of the present invention, the surface of the non-porous layer may be subjected to an embossed pattern, a textured pattern or the like and / or a mirror-finished processing. Then, when the surface of the nonporous layer is subjected to unevenness processing, an embossed pattern, a grain pattern, or the like that is more similar to natural leather can appear on the surface of the three-layer structure laminate.
On the other hand, when the surface of the nonporous layer is mirror-finished, a glossy surface having an enamel tone is imparted to the three-layer structure laminate.
In the three-layer structure laminate of the present invention, the surface of the non-porous layer may be subjected to both unevenness processing and mirror-finished processing. In that case, the unevenness pattern is further applied to the glossy enamel surface. It will be in the state that was done.

The method for producing the three-layer structure laminate is not particularly limited, and a method for producing a laminate structure comprising a fibrous base material layer / a foam layer / a non-porous layer smoothly without delamination between the layers. If it is, you may manufacture with any method.
Among them, the production of the three-layer structure laminate by the following method, namely,
(1) (a) 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of a thermoplastic polyurethane, and pyrolytic foaming Melt extrusion foaming using the foamable polyurethane composition containing the agent, and simultaneously laminating the polyurethane foam with the 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 based on 100 parts by weight of a thermoplastic polyurethane, and a pyrolytic foaming agent A method of laminating with a fibrous base material in a molten state after melt-extrusion and foaming using the expandable polyurethane composition;
(C) 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of a thermoplastic polyurethane and a pyrolytic foaming agent A method of foaming after laminating with a fibrous base material in a molten state by performing melt extrusion in an unfoamed state using a foamable polyurethane composition to be made;
Producing a laminate comprising a polyurethane foam layer and a fibrous base material by any of the methods described above;
(2) A step of laminating a melt-extruded thermoplastic elastomer on the foamable polyurethane composition layer or polyurethane foam layer before, simultaneously with, or after the production of the laminate of (1) above. ;
When manufactured by the method having a high quality, there is no delamination between layers, and a high-quality three-layer structure laminate that fully utilizes the characteristics of each layer using harmful components such as an organic solvent and a CFC gas expanding agent. It is preferable because it can be manufactured smoothly with good productivity.

In the step (1) for producing a three-layer structure laminate, the molding conditions such as the foaming temperature during melt extrusion foaming in the method (a) or (b) are as described above for the production of foam. This can be performed under the same or similar conditions as those described above.

In performing the step (2) of laminating the thermoplastic elastomer, for example,
(I) Foamable polyurethane of a laminate comprising a fibrous substrate layer and a foam layer, or a laminate comprising a fibrous substrate layer and an unfoamed foamable polyurethane composition layer A method in which a thermoplastic elastomer is directly melt-extruded and laminated on the composition layer, and the laminate is pressed between a roll and a back roll facing the roll;
(Ii) After the thermoplastic elastomer is melt-extruded onto a roll, a laminate comprising a fibrous base material layer and a foam layer, or a fibrous base material layer is provided between the roll and a back roll opposed thereto. A laminate comprising an unfoamed foamable polyurethane composition layer is supplied, and a thermoplastic elastomer layer is transferred and laminated on the foam layer of the laminate or on the unfoamed foamable polyurethane composition and pressed. Method;
(Iii) A roll is arranged on the foam layer side of a laminate comprising a fibrous base material layer and a foam layer, or a laminate comprising a fibrous base material layer and an unfoamed foamable polyurethane composition layer. In advance, the thermoplastic elastomer is directly melt-extruded into the gap between the foam layer and the roll, and further a laminate comprising a fibrous base material and a foam layer, or a fibrous base material and an unfoamed foamable polyurethane composition A method in which a back roll is disposed on the back side (the fibrous base material side) of the layered body composed of layers, and the layers are laminated while pressing;
Etc. can be adopted.
In that case, if the intermediate layer in the laminate in which the nonporous layer is laminated has not been foamed yet and is in the state of the foamable polyurethane composition layer, it is contained in the intermediate foamable polyurethane composition layer. It is preferable that the foaming is carried out by heating at a temperature not lower than the decomposition temperature of the thermal decomposition type foaming agent and the melting temperature of the polyurethane composition.
In addition, as long as the thermoplastic elastomer has fluidity, a desired three-layer structure laminate can be smoothly obtained by any of the above-described methods (i) to (iii). Can be.

Further, in the case where the surface of the nonporous layer of the three-layer structure laminate is further subjected to unevenness processing and / or mirror finishing, the method of the unevenness processing and / or mirror finishing is not particularly limited.
(1) In performing any of the methods (i) to (iii) in the above step (2), the surface of the roll disposed on the foam layer side is subjected to unevenness processing and / or mirror finishing. A method in which a nonporous layer in a molten state made of a thermoplastic elastomer is pressed and laminated on a foam layer, and at the same time, the surface of the nonporous layer made of a thermoplastic elastomer is textured and / or mirror-finished;
(2) After forming a non-porous layer made of a thermoplastic elastomer on a foam layer, while the non-porous layer is still in a plasticized state capable of shaping, it is used for unevenness processing and / or mirror finishing. A method of subjecting the surface of the non-porous layer to unevenness and / or mirror finishing using the above roll;
It can be performed by such as.
Among them, the method (1) is preferable because the number of steps is small and the productivity is high.
When the method (1) is employed, the pressing force provided by the roll and the back roll is set to a gauge pressure of 490 to 1470 kPa (5 to 15 kg / cm ² ), and the foam layer and the foam layer are formed. Adhesion of the non-porous layer and unevenness and / or mirror finishing on the surface of the non-porous layer can be performed smoothly.

In performing the concavo-convex and / or mirror-finished processing on the surface of the non-porous layer, for example, a roll that has been subjected to the concavo-convex processing and / or mirror-finished processing is brought into direct contact with the surface of the non-porous layer, and A method of forming unevenness and / or a mirror surface on a surface, a releasable processed sheet having been subjected to unevenness and / or mirror surface processing is brought into contact with the surface of the non-porous layer, and pressed from the back of the processed sheet by a roll or the like. For example, a method of forming unevenness and / or a mirror surface on the surface of the non-porous layer may be employed.
When the latter method using a releasable processed sheet is adopted, an arbitrary concavo-convex pattern and / or a mirror surface state can be formed on the surface of the nonporous layer simply by replacing the processed sheet. , Convenient.

In any of the above-described methods, the non-porous layer no longer flows through a surface processing roll or a release processing sheet for forming irregularities and / or mirror surfaces on the surface of the non-porous layer. From the non-porous layer. If this is not done and the non-porous layer is still fluid, if the surface processing roll or release-treated sheet is peeled from the non-porous layer surface, it will be formed on the non-porous layer surface. The unevenness and / or mirror surface may be destroyed or lost due to the fluidity of the non-porous layer, and clear unevenness or a mirror surface excellent in gloss may not be obtained.
As a surface processing roll for forming irregularities and / or a mirror surface on the surface of the non-porous layer or a pressing roll disposed on the back of a releasable processing sheet, a type in which a coolant is circulated is adopted. Or a method of forcibly sending cold air to the vicinity of performing the concavo-convex processing and / or mirror finishing to actively cool the vicinity of the separation point of the surface processing roll or the releasable processed sheet from the non-porous layer. Adopting this method is preferable because the non-porous layer subjected to the unevenness processing and / or the mirror-finished processing is rapidly cooled, and the surface processing roll and the releasable processed sheet can be separated 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, it is used by directly contacting the non-porous layer. In general, a metal roll is preferably used. Further, as the back roll used without directly contacting the non-porous layer, or as the roll used on the back of the releasable surface-treated sheet, any of a metal roll, an elastic roll, and the like can be used. Among them, it is preferable to use an elastic roll because pressing can be stably performed.

In the three-layer structure laminate of the present invention, the surface of the nonporous layer is further subjected to a surface finish or a coloring agent for the purpose of improving abrasion resistance, preventing dirt, and imparting a deep color tone. You may keep it.

Although it is not limited at all, when the step (a) of the above (1) and the step (i) of the above (2) are adopted, and the nonporous layer is laminated on the surface of the foam layer, In the case where a three-layer structure laminate in which the unevenness is formed on the surface of the non-porous layer by simultaneously performing the lamination and the concavo-convex processing on the surface of the non-porous layer, A three-layer structure laminate can be manufactured.
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, and 6 is a fibrous base material layer. A laminate composed of 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 a three-layer laminate.

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

[Logarithmic viscosity of thermoplastic polyurethane]
In a N, N-dimethylformamide solution containing n-butylamine at a rate of 0.05 mol / liter, a thermoplastic polyurethane was dissolved to a concentration of 0.5 g / dl, and the solution was dissolved using an Ubbelohde viscometer. The flow time of the thermoplastic polyurethane solution at a temperature of 30 ° C. was measured, and the logarithmic viscosity was determined by the following equation.

Logarithmic viscosity of thermoplastic polyurethane = {ln (t / t ₀ )} / c
[In the formula, t represents the flow time (second) of the thermoplastic polyurethane solution, t ₀ represents the flow time of the solvent (second), and c represents the concentration (g / dl) of the thermoplastic polyurethane solution. ]

[Hardness of thermoplastic polyurethane]
Injection molding of thermoplastic polyurethane (cylinder temperature 180-200 ° C., mold temperature 30 ° C.) to produce a disc-shaped test piece having a diameter of 120 mm and a thickness of 2 mm, and using two superposed test pieces, Shore hardness A was measured according to JIS K6301.

[Apparent specific gravity of foam film]
According to JIS K6767, the apparent specific gravity of the foamed film obtained in the following Examples or Comparative Examples was measured.

[Tensile strength of foam film]
In accordance with JIS K 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 foam film]
By visually observing the surface state of the foamed film obtained in the following Examples or Comparative Examples, the surface of the foamed film has no irregularities or roughness due to breakage of bubbles or unevenness of the bubble diameter and the like. If the foamed film is smooth and covered with a thin skin layer, it is regarded as good (○). If the foam film has irregularities or roughness due to the breakage of bubbles and unevenness of the bubble diameter, it is regarded as defective (×). evaluated.

[Abrasion resistance of the surface of the three-layer structure laminate]
According to JIS L 1096 6.17.3 using a tapered rotary abrasion device (with a dust absorbing unit) (“Rotary Ablation Tester” manufactured by Toyo Seiki Co., Ltd.), non-porous three-layer laminated body The amount of wear reduction on the surface of the layer was measured.

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

<< Example 1 >>
(1) Polyester diol (PMPA) (number average molecular weight 1500) obtained by a condensation reaction between 3-methyl-1,5-pentanediol and adipic acid is used as a polymer diol, and 1,4-butanediol ( BD) and 4,4′-diphenylmethane diisocyanate (MDI) heated and melted at 50 ° C. are further used in a molar ratio of PMPA: BD: MDI = 1: 1.4: 2.4 and their total supply The amount was set to 300 g / min, and continuously supplied to a twin-screw extruder (30 mmφ, L / D = 36, cylinder temperature 75 to 260 ° C.) coaxially rotated by a metering pump to carry out continuous melt polymerization. To produce a thermoplastic polyurethane. The resulting thermoplastic polyurethane melt is extruded into water in the form of a strand, then cut into pellets with a pelletizer, and the pellets are dehumidified and dried at 80 ° C. for 5 hours to obtain the logarithmic viscosity and the viscosity shown in Table 2 below. A thermoplastic polyurethane having hardness was produced.

(2) 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: 20% by weight) Of polyethylene pellets) and 1 part by weight of an azodicarbonamide-based blowing agent ("Vinihome AC # 3" manufactured by Eiwa Chemical Co., Ltd.) and melt-kneaded at 150 to 160 ° C. using a twin-screw extruder. Thereafter, the mixture was extruded into water and cut with a pelletizer to produce foamable polyurethane composition pellets.
(3) The foamable polyurethane composition pellets obtained in the above (2) are charged into a single screw extruder (25 mmφ), and a T-die (lip width 0) is set at a melting zone temperature of 180 to 210 ° C and a die temperature of 180 ° C. (2 mm, die width: 350 mm) was subjected to melt extrusion foaming into a film shape to produce a foam film having a thickness of 255 μm and a width of 300 mm. The apparent specific gravity, tensile strength and appearance of the obtained foamed film were measured or evaluated by the above-mentioned methods, and the results were as shown in Table 3 below.

<< Examples 2-4 >>
(1) Using the same polyester diol as used in Example 1, 1,4-butanediol and 4,4′-diphenylmethane diisocyanate heated and melted at 50 ° C. were used in a molar ratio shown in Table 2 below. And then subjected to continuous melt polymerization in the same manner as in Example 1 (1) to produce a thermoplastic polyurethane, which was pelletized and dehumidified and dried in the same manner as in Example 1 (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) 5 parts by weight or 10 parts by weight of the (meth) acrylate copolymer shown in Table 2 below with respect to 100 parts by weight of the thermoplastic polyurethane obtained in (1) above, 5 parts by weight of the same black pigment pellets as used in (2) and 1 or 2 parts by weight of the same azodicarbonamide-based blowing agent as used in (2) of Example 1 were mixed. In the same manner as (2) of Example 1, pellets of the foamable polyurethane composition were produced.
(3) Using the foamable polyurethane composition pellets obtained in the above (2), melt extrusion foaming was performed in the form of a film in the same manner as in (3) of Example 1, and the results are shown in Table 3 below. A foam film having a thickness 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 the results were as shown in Table 3 below.

<< Examples 5-6 >>
(1) Polytetramethylene ether glycol (number average molecular weight 1000)) was used as the polymer diol, and 1,4-butanediol and 4,4′-diphenylmethane diisocyanate heated and melted at 50 ° C. were added to the following table. 2 and then subjected to continuous melt polymerization in the same manner as in Example 1 (1) to produce a thermoplastic polyurethane, which was pelletized in the same manner as in Example 1 (1). The resulting mixture was dehumidified and dried to produce a thermoplastic polyurethane. The logarithmic viscosity and hardness of the thermoplastic polyurethane obtained as a result were measured by the methods described above, and were as shown in Table 2 below.
(2) 5 parts by weight of the (meth) acrylate copolymer shown in Table 2 below with respect to 100 parts by weight of the thermoplastic polyurethane obtained in (1) above, 5 parts by weight of the same black pigment pellets as used, and 1 part by weight of the same azodicarbonamide-based blowing agent as used in (2) of Example 1, were mixed at a ratio of 1 part by weight. In the same manner as in the above, foamable polyurethane composition pellets were produced.
(3) Using the foamable polyurethane composition pellets obtained in the above (2), melt extrusion foaming was performed in the form of a film in the same manner as in (3) of Example 1, and the results are shown in Table 3 below. A foam film having a thickness 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 the results were as shown in Table 3 below.

<< Comparative Example 1 >>
For 100 parts by weight of the same thermoplastic polyurethane obtained in (1) of Example 1, 5 parts by weight of the same black pigment pellets used in (2) of Example 1 and The same azodicarbonamide-based blowing agent as used in (2) was mixed at a ratio of 1 part by weight to produce a foamable polyurethane composition pellet in the same manner as in (2) of Example 1, and this pellet was used. In the same manner as in Example 1 (3), melt extrusion foaming was performed into a film to produce a foamed film having a thickness shown in Table 3 below. The apparent specific gravity, tensile strength and appearance of the obtained foamed film were measured or evaluated by the above-mentioned methods, and the results were as shown in Table 3 below.

<< Comparative Example 2 >>
Based on 100 parts by weight of the same thermoplastic polyurethane obtained in (1) of Example 1, 35 parts by weight of the (meth) acrylic acid alkyl ester-based polymer shown in Table 2 below was used. 5) and the same azodicarbonamide-based blowing agent as used in (2) of Example 1 were mixed at a ratio of 2 parts by weight. A foamable polyurethane composition pellet was produced in the same manner as in 2), and the pellet was subjected to melt extrusion foaming in the form of a film in the same manner as in (3) of Example 1 and shown in Table 3 below. A foam film having a thickness 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 the results were as shown in Table 3 below.

<< Comparative Example 3 >>
For 100 parts by weight of the same thermoplastic polyurethane obtained in (1) of Example 5, 5 parts by weight of the same black pigment pellets used in (2) of Example 1 and The same azodicarbonamide-based blowing agent as used in (2) was mixed at a ratio of 1 part by weight to produce a foamable polyurethane composition pellet in the same manner as in (2) of Example 1, and this pellet was used. In the same manner as in Example 1 (3), melt extrusion foaming was performed into a film to produce a foamed film having a thickness shown in Table 3 below. The apparent specific gravity, tensile strength and appearance of the obtained foamed film were measured or evaluated by the above-mentioned methods, and the results were as shown in Table 3 below.

<< Comparative Example 4 >>
Based on 100 parts by weight of the same thermoplastic polyurethane as obtained in (1) of Example 5, 35 parts by weight of a (meth) acrylic acid alkyl ester-based polymer shown in Table 2 below was used. 5) and the same azodicarbonamide foaming agent as used in (2) of Example 1 were mixed at a ratio of 5 parts by weight of the same black pigment pellets used in (1), and 3 parts by weight of (1) in Example 1. A foamable polyurethane composition pellet was produced in the same manner as in 2), and the pellet was subjected to melt extrusion foaming in the form of a film in the same manner as in (3) of Example 1 and shown in Table 3 below. A foam film having a thickness 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 the results were as shown in Table 3 below.

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

From the results in Tables 2 and 3, the number average molecular weight of the alkyl (meth) acrylate polymer having a number average molecular weight of 200,000 or more is in the range of 1 to 30 parts by weight based on 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 amounts described above, a foamed film having excellent tensile strength, smoothness and good appearance can be obtained.
In contrast, in the case of Comparative Examples 1 and 3 using a foamable polyurethane composition containing no alkyl (meth) acrylate polymer, the melt viscosity was too low to be suitable for foaming. The foamed sheet obtained by melt extrusion foaming has a poor appearance due to irregularities and roughness due to the breakage of bubbles and unevenness of the bubble diameter, and has a poor tensile strength and poor mechanical properties. You can see that it is.
Further, in the case of Comparative Examples 2 and 4 using a foamable polyurethane composition in which an alkyl (meth) acrylate-based polymer exceeding 30 parts by weight was blended with respect to 100 parts by weight of the thermoplastic polyurethane, the melt viscosity was Is too high, the gas generated by the decomposition of the azodicarbonamide-based foaming agent does not sufficiently swell, the apparent specific gravity of the foamed sheet becomes high, and the appearance becomes poor.

<< Example 7 >>
(1) An entangled non-woven fabric (having a basis weight of 360 g / m ² ) manufactured using polyester fiber having a single fiber fineness of 2.5 deniers is coated with a polyurethane elastic body (“Kuramilon U2195” manufactured by Kuraray Co., Ltd., logarithmic viscosity 1.05 dl / g, An N, N-dimethylformamide solution having a Shore A hardness of 95) was impregnated and dried to prepare a fibrous base material having a thickness of 1.3 mm and a basis weight of 455 g / m ² (polyester fiber entanglement in the fibrous base material). The weight ratio of nonwoven fabric: polyurethane elastic body = 8: 2).

(2) {Polymer diol (PMPA) (number average molecular weight 1500) obtained by condensation reaction of 3-methyl-1,5-pentanediol and adipic acid as a polymer diol, and 1,4-butanediol (BD) is used. And 4,4′-diphenylmethane diisocyanate (MDI) heated and melted at 50 ° C. in a molar ratio of PMPA: BD: MDI = 1: 1.4: 2.4, and their total supply was 300 g / The mixture was continuously supplied to a twin-screw extruder (30 mmφ, L / D = 36, cylinder temperature 75 to 260 ° C.) coaxially rotated by a metering pump to perform continuous melt polymerization. The resulting thermoplastic polyurethane melt is extruded into water in the form of a strand, then cut into pellets with a pelletizer, and the pellets are dehumidified and dried at 80 ° C. for 5 hours to obtain a logarithmic viscosity of 1.07 dl / g. A thermoplastic polyurethane having a Shore hardness A of 75 (hereinafter sometimes referred to as “PU-1”) was produced.

(3) The same (meth) acrylate-based copolymer used in Example 1 (Mitsubishi Rayon Co., Ltd.) with respect to 100 parts by weight of the thermoplastic polyurethane (PU-1) obtained in (2) above. (“METABLEN P530”), 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 were mixed. After melt-kneading at 150 to 160 ° C. using a screw extruder, the mixture was extruded into water and cut with a pelletizer to produce pellets of an expandable polyurethane composition.

(4) As shown in FIG. 1, the fibrous base material 1 prepared in the above (1) is supplied between the mirror-finished metal roll 2 and the elastic back roller 3 and supplied. Between the metal roller 2 and the fibrous base material 1, pellets of the foamable polyurethane composition obtained in the above (3) were charged into a single screw extruder (25 mmφ) 4 and the melting zone temperature was 180 to 190 ° C. At a die temperature of 180 ° C., a melt-extruded and foamed film is supplied from a T-die (lip width 0.2 mm, die width 350 mm) in a fluid state, and is cold-pressed at a gauge pressure of 784 kPa (8 kg / cm ² ). Thus, a laminate 6 having a 150 μm thick foam layer 5 formed on the surface of the fibrous base material layer was manufactured. The expansion ratio of the foam layer 5 in the laminate 6 was 2.0 times.

(5) Apart from the above (2), a polyester diol (PMPA) (number average molecular weight 1500) obtained by a condensation reaction of 3-methyl-1,5-pentanediol and adipic acid is used as a polymer diol, 1,4-butanediol (BD) and 4,4′-diphenylmethane diisocyanate (MDI) heated and melted at 50 ° C. in a molar ratio of PMPA: BD: MDI = 1: 2.1: 3.1. Then, continuous melt polymerization is carried out in the same manner as in (2) above to produce a thermoplastic polyurethane, pelletized and dried to produce a thermoplastic polyurethane having a logarithmic viscosity of 1.09 dl / g and a Shore hardness A of 85. (Hereinafter sometimes referred to as “PU-2”).
(6) To 100 parts by weight of the thermoplastic polyurethane (PU-2) obtained in the above (5), 5 parts by weight of the same black pigment pellets as 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 pellets of a polyurethane composition for a nonporous layer.

(7) A laminate 6 comprising the fibrous base material layer 1 and the foam layer 5 obtained in the above (4) is processed into a metal embossing roll 7 which has been subjected to pore-like unevenness and an elastic back roller. 8 and between the metal embossing roller 7 and the surface of the foam layer 5 of the laminate 6, the polyurethane composition for the nonporous layer obtained in (6) above. The product pellets were charged into a single screw extruder (25 mmφ) 9 and melt-extruded into a film from a T-die (lip width 0.2 mm, die width 350 mm) at a melting zone temperature of 190 to 210 ° C. and a die temperature of 220 ° C. The foamed material layer is supplied in a fluidized state, cold pressed at a gauge pressure of 980 kPa (10 kg / cm ² ), and a fibrous base material layer / foamed layer having a nonporous layer 10 having a thickness of 100 μm on the surface of the foamed layer 5 / Production of a three-layer laminate 11 composed of a non-porous layer It was. The three-layered structure 11 could be stably manufactured at a line speed of 30 m / min.
(8) The three-layer structure laminate 11 obtained in the above (7) has a high pore strength, is excellent in flexibility, and has an excellent pore-like grain pattern very close in appearance to a pore grain product of natural leather. The surface was free from low-grade unevenness or wrinkles on the surface when pulled or bent, was extremely excellent in appearance, feeling, touch, and the like, and was a leather-like laminate having a high-quality feel. Further, the peel strength of the three-layered structure 11 was measured by the above-mentioned method and found to be as high as 15 kg / 25 mm, while the abrasion loss was as small as 7 mg and excellent in abrasion resistance.

<< Embodiment 8 >>
(1) Ultrafine nylon fiber entangled nonwoven fabric (basis weight: 300 g / m ² ) manufactured by using an ultrafine fiber bundle in which about 300 ultrafine nylon fibers having a single fiber fineness of 0.007 denier are converged, and a polyurethane elastic body (manufactured by Kuraray Co., Ltd.) "Kuramilon U9198", inherent viscosity 1.05 dl / g, Shore a hardness 98) of N, impregnated with N- dimethylformamide, dried, thickness 1.3 mm, the fibrous base material having a basis weight of 442 g / m ² Was prepared (weight ratio of ultrafine nylon fiber entangled nonwoven fabric: polyurethane elastic body in the fibrous base material = 6: 4).

(2) Polytetramethylene ether glycol (PTG) (number average molecular weight: 1000) was used as the polymer diol, 1,4-butanediol (BD) was added thereto, and 4,4′-diphenylmethane diisocyanate heated and melted at 50 ° C. Using (MDI) in a molar ratio of PTG: 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 a thermoplastic polyurethane. A thermoplastic polyurethane pellet was produced and dried to produce a thermoplastic polyurethane having a logarithmic viscosity of 1.02 dl / g and a Shore hardness A of 75 (hereinafter sometimes referred to as “PU-3”).
(3) With respect to 100 parts by weight of the thermoplastic polyurethane (PU-3) obtained in the above (2), the same (meth) acrylate-based copolymer used in Example 3 (Mitsubishi Rayon Co., Ltd.) (“METABLEN L1000”), 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 were mixed. After melt-kneading at 150 to 160 ° C. using a screw extruder, the mixture was extruded into water and cut with a pelletizer to produce pellets of an expandable polyurethane composition.

(4) As shown in FIG. 1, the fibrous base material 1 prepared in the above (1) is supplied between the mirror-finished metal roll 2 and the elastic back roller 3 and supplied. Between the metal roller 2 and the fibrous base material 1, the foamable polyurethane composition pellets obtained in the above (3) were charged into a single screw extruder (25 mmφ) 4 and the melting zone temperature was 180 to 190 ° C. At a die temperature of 180 ° C., a melt-extruded and foamed film formed from a T-die (lip width 0.2 mm, die width 350 mm) is supplied in a flowing state, and cold-pressed at a gauge pressure of 784 kPa (8 kg / cm ² ). Thus, a laminate 6 having a 200 μm-thick foam layer 5 formed on the surface of the fibrous base material layer 1 was manufactured. The expansion ratio of the foam layer in the laminate 6 was 2.2 times.

(5) Apart from the above (2), polytetramethylene ether glycol (PTG) (number average molecular weight 1000) is used as a high molecular diol, and 1,4-butanediol (BD) is heated and melted at 50 ° C. Using 4,4′-diphenylmethane diisocyanate (MDI) in a molar ratio of PTG: BD: MDI = 1: 1.2: 2.2, continuous melt polymerization was carried out in the same manner as in (2) above, and The production of thermoplastic polyurethane, the production and drying of pellets of thermoplastic polyurethane were carried out to produce a thermoplastic polyurethane having a logarithmic 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 as 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 a polyurethane composition pellet for a nonporous layer.

(7) A laminate 6 comprising the fibrous base material layer 1 and the foam layer 5 obtained in the above (4) is embossed with a metal embossing roll 7 and an elastic back roller 8 which have been subjected to a pore-like unevenness process. And between the metal embossing roller 7 and the surface of the foam layer 5 of the laminate 6, the polyurethane composition for a nonporous layer obtained in (6) above. The pellets were charged into a single screw extruder (25 mmφ) 9 and melt-extruded into a film from a T-die (lip width 0.2 mm, die width 350 mm) at a melting zone temperature of 190 to 210 ° C and a die temperature of 220 ° C. Is supplied in a fluidized state, and is cold-pressed at a gauge pressure of 980 kPa (10 kg / cm ² ), and further has a non-porous layer 10 having a thickness of 100 μm on the surface of the foam layer 5. Three-layer laminate 11 composed of layer / nonporous layer It was produced. The three-layered structure 11 could be stably manufactured at a line speed of 30 m / min.
(8) The three-layer structure laminate 11 obtained in the above (7) has a high pore strength, is excellent in flexibility, and has an excellent pore-like grain pattern very close in appearance to a pore grain product of natural leather. It was a high-quality leather-like laminate having excellent appearance, feeling, touch, and the like without causing low-grade uneven wrinkles on the surface when pulled or bent. Further, the peel strength of the three-layer structure laminate 11 was measured by the method described above, and was a high value of 13 kg / 25 mm. On the other hand, the wear reduction was as small as 9 mg, and the wear resistance was excellent.

<< Example 9 >>
Example 7 was repeated except that, in (3) of Example 7, a foamable polyurethane composition was produced using “METABLEN L1000” instead of “METABLEN P530” as the (meth) acrylic acid alkyl ester-based polymer. A three-layer laminate comprising a fibrous base material layer / a foam layer / a nonporous layer was produced in exactly the same manner. The resulting three-layered laminate has a large surface strength, is excellent in flexibility, has a good pore-like grain pattern that is very close in appearance to the pore texture of natural leather, and is pulled or bent. When this was done, low-grade uneven wrinkles and the like were not generated on the surface, and the appearance, feeling, and feel were extremely excellent, and the leather-like laminate had a luxurious feel. When the peel strength of the three-layered structure was measured by the above-described method, the peel strength was as high as 14 kg / 25 mm, while the abrasion loss was as small as 7 mg, and the abrasion resistance was excellent.

<< Comparative Example 5 >>
In (3) of Example 7, a fibrous base material layer / foam layer was made in exactly the same manner as in Example 7, except that the alkyl (meth) acrylate-based polymer (“METABLEN P530”) was not used. / A three-layer laminate having a nonporous layer was produced at a line speed of 30 m / min.
As a result, when producing a laminate composed of the fibrous base material layer and the foam layer, the foam viscosity of the foamable polyurethane composition is low, so that immediately after the extrusion, the bubbles become enlarged, crushed, burst, etc. The surface of the foam layer was rough with large irregularities. Also in the finally obtained three-layer structure laminate, the surface of the non-porous layer is affected by the poor surface condition of the foam layer under the non-porous layer, and the surface of the non-porous layer has pores formed by embossing rolls. The grain pattern was not sufficiently formed, and the corners of the projections flowed (collapsed), resulting in unclear and grainy flows. In addition, the laminate had a poor sense of unity and had a hard feel lacking in flexibility. When the peel strength of the three-layer structure laminate was measured by the above-described method, the peel strength was as low as 5 kg / 25 mm, while the abrasion reduction was as large as 20 mg, and the abrasion resistance was poor.

<< Comparative Example 6 >>
The fibrous base material layer / foam layer in exactly the same manner as in Example 8 except that the (meth) acrylic acid alkyl ester-based polymer ("METABLEN L1000") was not used in (3) of Example 8. / A three-layer laminate having a nonporous layer was produced at a line speed of 30 m / min.
As a result, when producing a laminate composed of the fibrous base material layer and the foam layer, the foam viscosity of the foamable polyurethane composition is low, so that immediately after the extrusion, the bubbles become enlarged, crushed, burst, etc. The surface of the foam layer was rough with large irregularities. Also in the finally obtained three-layer structure laminate, the surface of the non-porous layer is affected by the poor surface condition of the foam layer under the non-porous layer, and the surface of the non-porous layer has pores formed by embossing rolls. The grain pattern was not sufficiently formed, and the corners of the projections flowed (collapsed), resulting in unclear and grainy flows. In addition, the laminate had a poor sense of unity and had a hard feel lacking in flexibility. When the peel strength of the three-layer structure laminate was measured by the above-described method, the peel strength was as low as 5 kg / 25 mm, while the abrasion reduction was as large as 20 mg, and the abrasion resistance was poor.

Foam of the present invention, composite material comprising foam and other substrate, laminate comprising foam layer and substrate layer, three layers having fibrous substrate layer / foam layer / nonporous layer Structural laminates, etc. utilize their excellent flexibility, elasticity, abrasion resistance, mechanical properties, cushioning, cushioning, feel, etc. Effectively used in a wide range of applications, such as chairs and other furniture, vehicle seats, vehicle interior materials, footwear, bags, bags, clothing, clothing miscellaneous goods, gloves, cushioning materials, heat insulating materials, cushioning materials, belts, etc. can do. In particular, the above-mentioned three-layer laminate comprising a fibrous base material layer / a foam layer / a non-porous layer is used as a substitute for natural leather, for example, clothing such as coats, blazers, skirts, and shoes and boots. It can be used effectively for bags, bags, camera cases, purses and other bags and bags, clothing-related items such as belts, and sports equipment such as volleyball and basketball.

It is a figure which shows an example of the manufacturing process preferably employ | adopted for manufacture of the three-layer structure laminated body of this invention which consists of a fibrous base material layer / a foam layer / a nonporous thermoplastic elastomer layer.

Explanation of reference numerals

Reference Signs List 1 fibrous base material 2 mirror-finished metal roll 3 elastic back roller 4 extruder 5 foam layer 6 laminate composed of fibrous base layer and foam layer 7 metal emboss roll 8 elastic back roller 9 Extruder 10 Non-porous layer 11 Three-layered laminate

Claims (9)

(4) A foam comprising a thermoplastic polyurethane composition containing 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of the thermoplastic polyurethane. The foam according to claim 1, which is a film, a sheet or a plate. Foaming containing an alkyl (meth) acrylate polymer having a number average molecular weight of 200,000 or more in an amount of 1 to 30 parts by weight and a pyrolytic foaming agent based on 100 parts by weight of a thermoplastic polyurethane. The foam according to claim 1, wherein the foam is formed by heating and foaming the conductive polyurethane composition. Foam layer composed of a thermoplastic polyurethane composition containing 1 to 30 parts by weight of an alkyl (meth) acrylate polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of the thermoplastic polyurethane And a laminate having a base material layer. A thermoplastic polyurethane containing, on a fibrous substrate, 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of the thermoplastic polyurethane. A laminate comprising: a foam layer made of a composition; and a non-porous layer made of a thermoplastic elastomer on the foam layer. The laminate according to claim 5, wherein the thermoplastic elastomer constituting the nonporous layer is a thermoplastic polyurethane elastomer. (7) The laminate according to the above (5) or (6), wherein the surface of the nonporous layer is subjected to unevenness processing and / or mirror finish processing. The foam layer contains 1 to 30 parts by weight of a (meth) acrylic acid alkyl ester-based polymer having a number average molecular weight of 200,000 or more based on 100 parts by weight of the thermoplastic polyurethane, and a pyrolytic foaming agent The laminate according to any one of claims 5 to 7, comprising a foam formed by heating and foaming a foamable polyurethane composition containing A composite material comprising the foam according to claim 1 and another material.

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