JP2000143969A - Polyurethane composition having forming property and foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a polyurethane composition capable of imparting foam at high productivity which has very fine bubbles in a uniformly distributed state and is excellent in outer appearance, softness or the like by including both a thermoplastic polyurethane having excessive isocyanate groups and a thermoplastic polyurethane having excessive hydroxides. SOLUTION: This polyurethane composition is prepared by including both (A) a thermoplastic polyurethane including (a1) a polyol having 2-2.08 hydroxy groups and 800-8,000 number average molecular weight, (b1) an organic diisocyanate and (c1) a chain extender in a ratio of formula I [wherein, (a1)-(c1) are mole numbers of components (a1)-(c1) respectively], (B) a thermoplastic polyurethane including (a1) a polyol having 2-2.08 hydroxy groups and 800-8,000 number average molecular weight, (b1) an organic diisocyanate and (c1) a chain extender in a ratio of formula II [wherein, (a2)-(c2) are mole numbers of components (a2)-(c2) respectively] and (C) a thermally decomposable foaming agent. The content ratio of the ingredient A to the ingredient B meets the formula III [wherein, (a), (b) and (c) are the total mole numbers of the components (a1)+(a2), the components (b1)+(b2) and the components (c1)+(c2) respectively] and the weight ratio of the total of the ingredients A and B to the ingredient C is (100:0.05)-(100:10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a foamable polyurethane composition, a foam obtained from the foamable polyurethane composition and a method for producing the same, and a laminate having the foam layer and a method for producing the same. The foam obtained from the foamable polyurethane composition of the present invention has uniform and fine bubbles uniformly distributed inside the foam without unevenness, has a good surface condition, has an excellent appearance, and has flexibility. Since it is excellent in mechanical properties and the like, it is useful as a foam layer constituting a foam film, a foam sheet, and a natural leather-like laminate.

[0002]

2. Description of the Related Art Conventionally, polyurethane foams or polyurethane porous materials have been prepared by (1) adding water to a polyurethane raw material and reacting the isocyanate component in the raw material with water to generate carbon dioxide gas. (2) A method for producing a polyurethane foam by adding a fluorine-based expanding agent such as Freon gas to a raw material for polyurethane and forming and foaming a 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 of dissolving the polyurethane in an organic solvent. A method of coating on a support and wet-coagulating in a non-solvent of polyurethane to form a porous polyurethane; (5) A solution of polyurethane dissolved in an organic solvent is applied on the support, and the solvent is dried and removed In general, a method of forming a polyurethane porous layer by using such a method is employed.

However, in the conventional method (1),
Since the degree of foaming is increased, and as a result, the cell membrane of the foam becomes thinner, there is a disadvantage that the cell membrane collapses with a small compressive stress and deformation is likely to occur. When the foaming degree is reduced by reducing the amount of water added in order to prevent the collapse of the cell membrane, the size of the cells becomes uneven, and it is difficult to obtain a foam having good quality. In the conventional method (2), a fluorine-based expanding agent such as chlorofluorocarbon gas whose use has been restricted in recent years in view of destruction of the global environment is used. In the conventional method (3), the polyurethane has a very low melt viscosity at a temperature suitable for decomposing the pyrolytic foaming agent.
The gas generated by the decomposition of the thermal decomposition type foaming agent cannot be sufficiently retained, and the cell size is likely to be enlarged or non-uniform, and the cell membrane is likely to burst. As a result, the resulting polyurethane foam tends to be rough due to the appearance of many irregularities on its surface, and the internal structure of the foam is coarse and uneven, and the bubbles are unevenly distributed. It is also inferior. In particular, when manufacturing thin materials such as foamed films and foamed sheets by melt extrusion foaming, the film or sheet often breaks near the die of the extruder,
Extrusion foaming cannot be performed smoothly. The above (4)
In the case of the wet solidification method of the above or the dry solidification method of the above (5), when the thickness of the porous material layer is large (for example, 1 mm or more), a long time is required for the solidification, and therefore, the productivity is high. Costly to manufacture on an industrial scale. Furthermore, in the above-mentioned conventional methods (4) and (5), since a solution in which polyurethane is dissolved in an organic solvent is used, the working environment is deteriorated due to the use of the organic solvent.
There are safety and hygiene issues. In addition, steps and facilities for collecting and treating the used organic solvent are required, which complicates the manufacturing process and increases the cost.

[0004] By the way, thermoplastic polyurethanes are widely used in various fields by utilizing their properties such as flexibility, elasticity and abrasion resistance. It is often used as a body. 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, it is widely used as artificial leather in applications such as footwear, clothing, bags and bags.

Conventionally, as a method for producing a natural leather-like thermoplastic polyurethane laminate, (a) a solution obtained by dissolving a thermoplastic polyurethane in an organic solvent was applied to release paper and dried to form a polyurethane film. Then, the film is bonded to the surface of a fibrous base material made of a woven or nonwoven fabric with an adhesive, and then the release paper is peeled off (dry method); After applying a thermoplastic polyurethane solution to the surface, a porous thermoplastic polyurethane layer is formed by a wet coagulation method or a dry coagulation method, and a resin solution containing a colorant is applied thereon and dried to form a colored layer. After that, a method of forming a concavo-convex pattern with an embossing roll is widely known. Further, in addition to the conventional methods listed in (a) and (b) above,
As a method for producing a synthetic leather-like laminate, for example, (c)
A method in which a synthetic resin is melt-extruded in the form of a film on a 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 to form a natural leather-like skin layer (Japanese Patent Application Laid-Open (JP-A) No. 2002-110572). (D) A method of producing a leather-like sheet by laminating a thermoplastic polyurethane melt extruded from a T-die on a metal deposition layer formed on a substrate (Japanese Patent Laid-Open No. Sho 62-803). No. 282078);
(E) A laminate in which the surface of a synthetic fiber cloth has been subjected to a treatment with a silane coupling agent in advance, and a thermoplastic resin is melt-extruded and pressed thereon to improve the adhesive strength between the cloth and the thermoplastic resin layer. (Japanese Patent Application Laid-Open No. 2-3079)
No. 86 gazette) has been proposed.

However, in the case of the above-mentioned conventional methods (a) and (b), the polyurethane is dissolved in an organic solvent in the same manner as in the case of the above-mentioned conventional methods for producing a porous body (4) and (5). The use of the solution is accompanied by the deterioration of the working environment due to the use of the organic solvent, and there is a problem in terms of safety and hygiene. Further, steps and equipment for collecting and treating the used organic solvent are required, which complicates the manufacturing process and increases the cost. 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. In the case of the above conventional methods (c) to (e), when the obtained laminate is pulled or bent, an uneven pattern such as a low-grade wrinkle appears on the surface, peeling of the skin layer, There are drawbacks such as easy separation of the substrate and the surface layer.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide fine and uniform air bubbles uniformly distributed inside a foam, a good surface condition, excellent appearance, and flexibility. An object of the present invention is to provide a foamable polyurethane composition which can produce a thermoplastic polyurethane foam excellent in mechanical properties and the like smoothly and with high productivity without using a chlorofluorocarbon gas, an organic solvent or the like. An object of the present invention is to provide the above-mentioned high-grade thermoplastic polyurethane foam and a method for producing the same. Further, an object of the present invention is to provide a fibrous base material layer, a thermoplastic polyurethane foam layer and a thermoplastic elastomer nonporous layer having the above-mentioned excellent properties, and a fibrous base material layer and a nonporous layer. Laminate having no delamination between polyurethane and polyurethane foam layer and having good abrasion resistance and excellent durability, and in addition, having a high-grade silver surface layer which is particularly rich in flexibility and its production Is to provide a way.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted studies to achieve the above object, and as a result of repeated studies, have added a pyrolytic foaming agent to thermoplastic polyurethane and added the foaming agent under heating and melting. When a thermoplastic polyurethane having an excess of isocyanate groups and a thermoplastic polyurethane having an excess of hydroxyl groups are used together in producing a foam by decomposing the same, the melt elasticity and the melt elongation during foaming during heating and melting cause foaming. It becomes extremely suitable, the gas generated by the foaming agent is sufficiently and uniformly 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 can be obtained without rupture of a cell membrane or occurrence of an uneven pattern due to cell size unevenness inside and on the surface of the foam. And the resulting polyurethane foam has excellent mechanical properties and appearance due to its good foam structure, and is also extremely excellent in terms of flexibility, etc., making effective use of these properties in a wide range of fields. I found that it can be used.

Further, the present inventor has found that when melt-extrusion foam molding is performed using the above-mentioned foamable polyurethane composition, the extrudate does not break near the die of the extruder, and the like.
It has been found that foams such as foamed films and foamed sheets can be produced with good processability and good productivity by appropriately and smoothly producing thick foams to thin foams depending on the application.

Further, the present inventors have provided a foam layer obtained from the above foamable polyurethane composition on the surface of a fibrous base material layer, and further provided on the foam layer a nonporous thermoplastic elastomer comprising a thermoplastic elastomer. The laminated body provided with layers is excellent in properties such as abrasion resistance, flexibility, tactile sensation, feeling, and has properties very similar to natural leather, and is used in various applications as synthetic leather or artificial leather. It was found that it can be used effectively.

Furthermore, the present inventor has found that the above-mentioned laminate can be produced with good processability and high productivity by melt-extrusion foam molding using the above-mentioned foamable polyurethane composition. The present invention has been completed based on various findings.

That is, the present invention provides a number average molecular weight of 800 to 2.08 hydroxyl groups per molecule.
８8,000 polymer polyol (a ₁ ), organic diisocyanate (b ₁ ) and chain extender (c ₁ ), comprising polymer polyol (a ₁ ), organic diisocyanate (b ₁ ) and chain extender ( The ratio of c ₁ ) is the following equation (1): 0.92 ≦ b ₁ / (a ₁ + c ₁ ) ≦ 0.97 (1) (where a ₁ is the number of moles of the polymer polyol (a ₁ )) , B ₁
Represents the number of moles of the organic diisocyanate (b ₁ ), and c ₁ represents the number of moles of the chain extender (c ₁ ). Thermoplastic polyurethane (I) satisfying the above condition), the number of hydroxyl groups per molecule is 2.00.
～2.08 or a number-average molecular weight 800～8,000 of polymer polyol is (a _2), is composed of an organic diisocyanate (b ₂₎ and a chain extender (c _2), polymer polyol (a _2), the organic diisocyanate (b ₂₎ and a chain extender formula proportion of the following _{(c 2) (2):} 1.03 ≦ b 2 / (a 2 + c 2) ≦ 1.08 (2) ( wherein, a ₂ Is the number of moles of the polymer polyol (a ₂ ), b ₂
Represents the number of moles of the organic diisocyanate (b ₂ ), and c ₂ represents the number of moles of the chain extender (c ₂ ). A foamable polyurethane composition comprising a thermoplastic polyurethane (II) satisfying the above-mentioned (1) and a pyrolytic foaming agent (III); The ratio of the organic diisocyanate and the chain extender is represented by the following formula (3): 0.99 ≦ b / (a + c) ≦ 1.02 (3) (where a is a polymer polyol (a ₁ ) and a polymer The total number of moles of the polyol (a ₂ ), b is the total number of moles of the organic diisocyanate (b ₁ ) and the organic diisocyanate (b ₂ ), c is the total number of moles of the chain extender (c ₁ ) and the chain extender (c ₂ ) The ratio of the total weight of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) to the weight of the pyrolytic foaming agent (III) is 100: 0.0.
5 to 100: 10;

Further, the present invention provides a compound having a number average molecular weight of 800 to 2.08 in which the number of hydroxyl groups per molecule is 2.00 to 2.08.
8,000 high molecular polyols (a ₁ ), an organic diisocyanate (b ₁ ) and a chain extender (c ₁ )
The ratio of the polymer polyol (a ₁ ), the organic diisocyanate (b ₁ ) and the chain extender (c ₁ ) is represented by the following formula (1): 0.92 ≦ b ₁ / (a ₁ + c ₁ ) ≦ 0.97 ( 1) (where a ₁ is the number of moles of the polymer polyol (a ₁ ), b ₁
Represents the number of moles of the organic diisocyanate (b ₁ ), and c ₁ represents the number of moles of the chain extender (c ₁ ). A) a thermoplastic polyurethane (I) that satisfies)), and a number average molecular weight of 800 to 8, in which the number of hydroxyl groups per molecule is 2.00 to 2.08.
000, a polymer polyol (a ₂ ), an organic diisocyanate (b ₂ ) and a chain extender (c ₂ ). The polymer polyol (a ₂ ), the organic diisocyanate (b ₂ ) and the chain extender (c ₂ ) Is the following formula (2): 1.03 ≦ b ₂ / (a ₂ + c ₂ ) ≦ 1.08 (2) (where a ₂ is the number of moles of the polymer polyol (a ₂ ) and b ₂
Represents the number of moles of the organic diisocyanate (b ₂ ), and c ₂ represents the number of moles of the chain extender (c ₂ ). A) a foam comprising a thermoplastic polyurethane (II) satisfying the following: the proportion of the polymer polyol, the organic diisocyanate and the chain extender constituting the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) is as follows: Formula (3): 0.99 ≦ b / (a + c) ≦ 1.02 (3) (where a is the total number of moles of the polymer polyol (a ₁ ) and the polymer polyol (a ₂ ), and b is an organic The total number of moles of the diisocyanate (b ₁ ) and the organic diisocyanate (b ₂ ), and c represents the total number of moles of the chain extender (c ₁ ) and the chain extender (c ₂ ). The foam to be made.

Further, the present invention relates to a method for producing a foam by melt-extruding and foaming the foamable polyurethane composition.

The present invention has a foam layer (B) made of the above foam on the surface of the fibrous base material layer (A), and a nonporous layer (C) made of a thermoplastic elastomer thereon. And a surface of the non-porous layer (C) having been subjected to unevenness processing and / or mirror finish processing.

The present invention further provides a foam layer (B) obtained by melt-extruding and foaming the foamable polyurethane composition into a film.
Is formed, and while the foam layer (B) has fluidity, the foam layer (B) is pressed against and adhered to the surface of the fibrous substrate layer (A), whereby the fibrous substrate layer is formed. After laminating the foam layer (B) on the surface of (A), the thermoplastic elastomer is melt-extruded into a film and foamed while the thermoplastic elastomer has fluidity. By pressing and bonding to the surface of the body layer (B), the nonporous layer (C) made of a thermoplastic elastomer is laminated on the surface of the foam layer (B), and the nonporous layer (C) flows. The present invention relates to a method for producing a laminate in which the surface of a non-porous layer (C) is embossed while it has properties, and is subjected to unevenness processing and / or mirror finishing.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) used in the foamable polyurethane composition of the present invention have a number of hydroxyl groups per molecule of 2.00 to 2.08. A certain number average molecular weight of 800 to
It is a thermoplastic polyurethane obtained by reacting 8,000 high molecular polyols, organic diisocyanates and chain extenders.

The polymer polyol (a ₁ ) used for the production of the thermoplastic polyurethane (I) and the polymer polyol (a) used for the production of the thermoplastic polyurethane (II)
₂ ) The number average molecular weight is in the range of 800 to 8,000, preferably in the range of 900 to 6,000.
When a polymer polyol having such a number average molecular weight is used, the mechanical strength and moldability of the obtained thermoplastic polyurethane are improved, and thus the moldability of the foam obtained from the expandable polyurethane composition of the present invention, and The mechanical strength of the laminate having the foam layer becomes better. In addition, the number average molecular weight of the high molecular polyol referred to in the present specification means a number average molecular weight calculated based on a hydroxyl value measured according to JIS K1557.

The number of hydroxyl groups per molecule of the polymer polyol (a ₁ ) and the polymer polyol (a ₂ ) is 2.0
It is in the range of 0 to 2.08, and preferably in the range of 2.01 to 2.06. When the number of hydroxyl groups per molecule of the high molecular polyol is less than 2.00, the molecular weight of the obtained polyurethane does not increase, so that the melt viscosity and the melt elasticity of the foamable polyurethane composition are suitable for retaining cells. It is impossible to form a foam in which fine bubbles of uniform size are distributed without unevenness due to coarsening and bursting of the bubbles, and the surface of the foam or the foam layer The surface becomes poor due to uneven patterns and roughness. In particular, in the case of a thin foam film or foam layer, the occurrence of such irregularities and roughness on the surface tends to be remarkable. On the other hand, when the number of hydroxyl groups per molecule is larger than 2.08, the melt viscosity of the obtained thermoplastic polyurethane becomes high, so that the kneadability with other compounding components is inferior, and the melt extrusion foaming moldability is deteriorated. . As a method for controlling the number of hydroxyl groups per molecule of the polymer polyol (a ₁ ) and the polymer polyol (a ₂ ) to be in the range of 2.00 to 2.08, for example, (1) As a low molecular polyol component to constitute, a low molecular diol component having two primary hydroxyl groups in one molecule and a low molecular polyol component having three or more hydroxyl groups in one molecule, (2) a high molecular weight diol having two hydroxyl groups per molecule and a high molecular weight polyol having more than two hydroxyl groups per molecule; Can be used in a desired ratio so that the number of hydroxyl groups per molecule of the polymer polyol falls within the above range.

As the polymer polyol (a ₁ ) and the polymer polyol (a ₂ ), it is preferable to use, for example, a polyester polyol or a polyether polyol.

The polyester polyol is produced, for example, by directly subjecting a dicarboxylic acid component composed of an ester-forming derivative such as a dicarboxylic acid, an ester, and an anhydride thereof to a low-molecular-weight polyol component by an esterification reaction or a transesterification reaction. Can be.

The dicarboxylic acid component used in the production of the polyester polyol includes, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, 2-methylsuccinic acid, 2-methyladipic acid Aliphatic dicarboxylic acids having 5 to 12 carbon atoms such as, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecandioic acid, and 3,7-dimethyldecandioic acid Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and orthophthalic acid;
These ester-forming derivatives can be mentioned, and one or more of these can be used. As the dicarboxylic acid component, an aliphatic dicarboxylic acid having 5 to 12 carbon atoms is preferably used from the viewpoint of excellent flexibility and mechanical properties of the obtained foam and a laminate having the foam layer, and adipic acid and azelaine. Acids and sebacic acid are more preferably used.

Examples of the low molecular weight polyol component used for producing the polyester polyol include ethylene glycol, 1,3-propanediol, 2-methyl-
1,3-propanediol, 1,4-butanediol,
Neopentyl glycol, 1,5-pentanediol,
3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc. A low molecular weight aliphatic diol containing two primary hydroxyl groups in one molecule of glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, methylglycoxide, etc. containing three or more hydroxyl groups in one molecule Low molecular polyols and the like can be mentioned, and one or more of these can be used. Among them,
When the content ratio of 3-methyl-1,5-pentanediol is 5
A low-molecular-weight diol component of 0 mol% or more is preferred because the obtained foam and the laminate having the foam layer have good flexibility and rebound resilience. Furthermore, it is preferable to use a trifunctional trimethylolpropane in combination, since melt elasticity and melt elongation suitable for foaming can be obtained.

Examples of the above polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol obtained by polymerizing a low molecular weight diol component in the presence of a small amount of a trimolecular or higher functional low molecular weight polyol component. And one or more of these can be used. Among them, polytetramethylene glycol is preferred because the resulting foam and the laminate having the foam layer have good flexibility and hydrolysis resistance.

The type of the organic diisocyanate (b ₁ ) used in the production of the thermoplastic polyurethane (I) and the organic diisocyanate (b ₂ ) used in the production of the thermoplastic polyurethane (II) are not particularly limited. Any of the organic diisocyanates conventionally used for production can be used. Among them, one or more of aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate having a molecular weight of 500 or less are preferably used. Examples of the organic diisocyanate include 4,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate,
Examples thereof include 4′-dicyclohexylmethane diisocyanate, and one or more of these can be used. Among them, 4,4′-diphenylmethane diisocyanate is preferably used because the mechanical properties of the obtained foam and the laminate having the foam layer are improved.

The chain extender (c ₁ ) used in the production of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (I)
The type of the chain extender (c ₂ ) used in the production of I) is not particularly limited, and any chain extender conventionally used in the production of a thermoplastic polyurethane can be used. Among them, as a chain extender, a molecular weight of 300 or more having two or more active hydrogen atoms capable of reacting with an isocyanate group in a molecule.
The following low molecular weight compounds are preferably used. Examples of such chain extenders include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanedi methanol,
Diols such as bis- (β-hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, diadipate Diamines such as hydrazine and dihydrazine isophthalate; aminoethyl alcohol;
Examples thereof include amino alcohols such as aminopropyl alcohol, and one or more of these can be used. Among them, from the viewpoint that the mechanical properties of the foam and the laminate having the foam layer become better,
-10 aliphatic diols are preferably used,
Butanediol is more preferably used.

In the foamable polyurethane composition of the present invention, the thermoplastic polyurethane (I) comprises the above-mentioned polymer polyol (a ₁ ), organic diisocyanate (b ₁ ) and a chain extender (c ₁ ). The ratio of the polymer polyol (a ₁ ), the organic diisocyanate (b ₁ ) and the chain extender (c ₁ ) is represented by the following formula (1): 0.92 ≦ b ₁ / (a ₁ + c ₁ ) ≦ 0.97 (1) (where a ₁ is the number of moles of the polymer polyol (a ₁ ), b ₁
Represents the number of moles of the organic diisocyanate (b ₁ ), and c ₁ represents the number of moles of the chain extender (c ₁ ). ), That is, a thermoplastic polyurethane having an excess of isocyanate groups, the thermoplastic polyurethane (I
As I), the above-mentioned polymer polyol (a ₂ ), organic diisocyanate (b ₂ ) and chain extender (c ₂ ) are comprised, and polymer polyol (a ₂ ), organic diisocyanate (b ₂ ) and chain extender The ratio of (c ₂ ) is the following formula (2): 1.03 ≦ b ₂ / (a ₂ + c ₂ ) ≦ 1.08 (2) (where a ₂ is a mole of the polymer polyol (a ₂ )) Number, b ₂
Represents the number of moles of the organic diisocyanate (b ₂ ), and c ₂ represents the number of moles of the chain extender (c ₂ ). ), That is, a thermoplastic polyurethane having an excess of hydroxyl groups. Such a thermoplastic polyurethane (I) and a thermoplastic polyurethane (II) do not increase in molecular weight and do not require a high temperature for melting during melt-kneading. In addition, a foamable polyurethane composition which can be stably melt-kneaded at a temperature lower than the thermal decomposition temperature of the thermal decomposition type foaming agent and has excellent melt foamability, especially excellent melt extrusion foamability.

In the foamable polyurethane composition of the present invention, the ratio of the polymer polyol, organic diisocyanate and chain extender constituting the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) is represented by the following formula (3): 0.99 ≦ b / (a + c) ≦ 1.02 (3) (where a is the total mole number of the polymer polyol (a ₁ ) and the polymer polyol (a ₂ ), and b is the organic diisocyanate (b ₁₎ ) And the total number of moles of the organic diisocyanate (b ₂ ), and c represents the total number of moles of the chain extender (c ₁ ) and the chain extender (c ₂ ). It contains thermoplastic polyurethane (II). When the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) are blended so as to satisfy the above formula (3), the molecular weight of the thermoplastic polyurethane increases, and the foamable polyurethane containing such a thermoplastic polyurethane is used. The foam obtained from the composition has a good foaming state and is excellent in mechanical properties, abrasion resistance and the like.

The method for producing the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) is not particularly limited, and the above-mentioned polymer polyol, organic diisocyanate and chain extender are used, and a known urethanation reaction technique is used. And can be produced by a prepolymer method or 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.

The hardness (JIS-A hardness) of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) is preferably in the range of 55 to 85, and is preferably in the range of 60 to 8
More preferably, it is within the range of 0. When a thermoplastic polyurethane having such hardness is used, a foam having excellent mechanical strength and flexibility and a laminate having a foam layer can be obtained.

As the pyrolytic foaming agent (III) contained in the foamable polyurethane composition of the present invention, any of the conventionally known pyrolytic foaming agents can be used and is not particularly limited. Examples of the pyrolytic foaming agent that can be used in the present invention include azodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, azobisisobutyronitrile,
Azodiaminobenzene, azohexahydrobenzodinitrile, barium azodicarboxylate, N, N′-dinitrosopentamethylenetetramine, N, N′-dinitroso-N, N′-dimethylterephthalamide, t-butylaminonitrile, Organic thermal decomposition type foaming agents such as p-toluenesulfonylacetone hydrazone, inorganic thermal decomposition type foaming agents such as sodium bicarbonate and ammonium carbonate and the like can be used, and one or more of these can be used. Can be. Examples of the pyrolytic foaming agent include thermoplastic polyurethane (I) and thermoplastic polyurethane (I).
It has a decomposition temperature equal to or higher than the melting temperature of I), is excellent in handleability, generates a large amount of gas, and its decomposition behavior is suitable for melt molding of an expandable polyurethane composition. Azodicarbonamide is preferably used. Further, among the above-mentioned pyrolytic foaming agents, for example, azodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide), p-toluenesulfonylhydrazide, sodium bicarbonate, and the like have an effect of reducing the molecular weight of polyurethane. On the other hand, 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, the polyurethane is appropriately crosslinked, and a decrease in the melt viscosity can be suppressed, and the mechanical properties and physical properties can be suppressed. A foam having excellent properties and chemical properties and a good foaming state can be formed.

The amount of the pyrolytic foaming agent (III) to be added depends on the desired expansion ratio (apparent specific gravity) of the foam or foam layer, the use of the foam or laminate, and the amount of gas generated by the foaming agent. The amount is adjusted depending on the amount of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II).
The range is from 0.05 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, and more preferably from 0.3 to 3 parts by weight.

Further, in the present invention, in producing a foam using the above-mentioned pyrolytic foaming agent (III), foaming is carried out smoothly to obtain a foam having more uniform and fine cells. In addition, a foaming aid may be used in combination. As the foaming aid in that case, a foaming aid conventionally used for each of the pyrolytic foaming agents can be used. For example, for azo foaming agents, sodium bicarbonate, hydrazine foaming agents, metal carboxylate, metal carbonates such as calcium carbonate, silica, metal oxides such as alumina, and minerals such as talc as foaming aids. A urea-based compound or an organic acid can be used as a foaming aid for N, N'-dinitrosopentamethylenetetramine.

When a foaming aid is used, the amount used is
Foaming ratio (apparent specific gravity) of the desired foam or foam layer,
It can be appropriately adjusted depending on the use of the foam or the laminate, the amount of gas generated from the foaming agent, and the like. Usually, the total amount of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) is 100 parts by weight. It is preferably in the range of 0.005 to 10 parts by weight, more preferably in the range of 0.01 to 5 parts by weight, and even more preferably in the range of 0.1 to 2 parts by weight. In addition, pyrolytic foaming agent (III)
The use ratio of the thermal decomposition type foaming agent (III) 1
It is preferable that the foaming aid be in the range of 0.1 to 1 part by weight based on part by weight.

The foamable polyurethane composition of the present invention is added to at least one block copolymer selected from the group consisting of a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene polymer block and a hydrogenated product thereof. Polymer (IV) [Hereinafter, this may be referred to as block copolymer (IV). ] Can be suitably retained during melt foaming, and a foam having a high expansion ratio can be obtained. As the block copolymer (IV), a block copolymer having at least one, preferably at least two, polymer blocks composed of aromatic vinyl compound units and having at least one polymer block composed of conjugated diene units is used. At least one of a coalesced copolymer and a copolymer obtained by hydrogenating unsaturated bonds in the block copolymer is used. In this case, the hydrogenation rate is in the range of 0 to 100 mol%, preferably 0 to 100 mol%.
It can be selected from the range of ~ 95 mol%.

The aromatic vinyl compound units constituting the block copolymer (IV) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene and p-methylstyrene.
Derived from methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, etc. And one or more of these units can be used. Of the above, units derived from styrene are preferred.

The conjugated diene units constituting the block copolymer (IV) include 1,3-butadiene, isoprene and
Examples include units derived from 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, and the like. Two or more can be used. Of the above, units derived from 1,3-butadiene and isoprene are particularly preferred.

The molecular structure of the block copolymer (IV) may be linear, branched, radial, or any combination thereof. Among them, a diblock copolymer in which one aromatic vinyl compound polymer block and one conjugated diene polymer block are linearly bonded, an aromatic vinyl compound polymer block-a conjugated diene polymer block- A triblock copolymer in which three polymer blocks are linearly bonded in the order of an aromatic vinyl compound polymer block, and a hydrogenated product thereof are easily manufactured, easily available, and thermoplastic polyurethane. Compatibility with,
It is preferably used in terms of mechanical characteristics and the like.

In the block copolymer (IV), the number average molecular weight of the aromatic vinyl compound polymer block is from 2,500 to
5,000, and the number average molecular weight of the conjugated diene polymer block before hydrogenation is 10,000 to 10
It is preferable that the number average molecular weight of the block copolymer is in the range of 12,500 to 150,000.

The content of the aromatic vinyl compound unit in the block copolymer (IV) is preferably in the range of 5 to 30% by weight based on the total weight of the block copolymer. When the content of the aromatic vinyl compound unit is less than 5% by weight, the flexibility and surface smoothness of the foam tend to be poor. On the other hand, if the content of the aromatic vinyl compound unit exceeds 30% by weight, the compatibility with the thermoplastic polyurethane tends to decrease, and the resulting foam tends to have a poor appearance, They tend to be less flexible.

The hardness of the block copolymer (IV) (JIS-
(A hardness) is preferably in the range of 30 to 45 in view of the flexibility and surface smoothness of the obtained foam.

When the block copolymer (IV) is blended with the foamable polyurethane composition, the proportion of the block copolymer (IV) is determined from the viewpoint that the foam can be favorably retained and a foam having a high expansion ratio can be obtained. The ratio of the total weight of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) to the weight of the block copolymer (IV) is preferably in the range of 60:40 to 95: 5, and more preferably 70:30 to 95: 5. More preferably, it is within the range of 95: 5. The blending ratio of the block copolymer (IV) is determined by the total weight of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) and the block copolymer (I).
When the ratio to the weight of V) is more than 60:40, the compatibility with the thermoplastic polyurethane decreases, and the flexibility of the obtained foam tends to deteriorate.

The amount of the pyrolytic foaming agent (III) to be added depends on the desired expansion ratio (apparent specific gravity) of the foam or foam layer, the use of the foam or laminate, and the amount of gas generated by the foaming agent. The content is adjusted within the range of 0.05 to 10 parts by weight based on 100 parts by weight of the total of the thermoplastic polyurethane (I), the thermoplastic polyurethane (II) and the block copolymer (IV). 0.1 to 5 parts by weight,
More preferably, it is in the range of 0.3 to 3 parts by weight.

When a foaming aid is used, the amount used is
Foaming ratio (apparent specific gravity) of the desired foam or foam layer,
It can be appropriately adjusted depending on the use of the foam or the laminate, the gas generation amount of the foaming agent, and the like. Usually, the thermoplastic polyurethane (I), the thermoplastic polyurethane (II), and the block copolymer (IV) are used. With respect to 100 parts by weight in total, 0.
It is preferably in the range of 005 to 10 parts by weight.
It is more preferably in the range of from 0.01 to 5 parts by weight,
More preferably, it is in the range of 1 to 2 parts by weight. The proportion of the foaming aid to the thermal decomposition type foaming agent (III) is preferably in the range of 0.1 to 1 part by weight based on 1 part by weight of the thermal decomposition type foaming agent (III). .

Further, the foamable polyurethane composition of the present invention may further contain other additives, for example, a cell regulator (for example, an inorganic fine powder) for forming uniform and fine cells, a filler, a reinforcing material, a pigment, One or more additives such as an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a hydrolysis inhibitor, and a flame retardant may be contained as necessary.

In producing the foamable polyurethane composition of the present invention, the production method is not particularly limited. However, when the thermoplastic polyurethane absorbs moisture, the foaming state and mechanical properties are affected. Any method may be employed as long as it avoids the absorption of moisture as much as possible during the production of, and when a foaming aid is used, it is a method that does not lose the function of the foaming aid.
In the production of the foamable polyurethane composition of the present invention, without limitation, for example, thermoplastic polyurethane (I), thermoplastic polyurethane (II), pyrolytic foaming agent (III), and if necessary, After pre-mixing the block copolymer (IV), the foaming aid and other components at a predetermined ratio using a vertical or horizontal mixer as commonly used for mixing resin materials, It can be manufactured by melt-kneading under heating in a batch system or a continuous system using a single-screw or twin-screw extruder, mixing roll, Banbury mixer, or the like.

The foamable polyurethane composition of the present invention is thermoplastic, and the type and composition of the thermoplastic polyurethane (I), the thermoplastic polyurethane (II) to be used, and the block copolymer (IV) to be blended if necessary. Although it depends on the ratio, it is generally melted by heating to a temperature of about 150 to 250 ° C. Therefore, when melt foaming is performed using the foamable polyurethane composition of the present invention, fine bubbles having a uniform size are distributed without unevenness throughout, and furthermore, mechanical properties, physical properties, appearance, etc. An excellent foam can be produced smoothly. At that time, if the melt extrusion foam molding method is adopted, foamed films, foamed sheets, foamed boards, laminates, and other foamed extruded materials having the above-mentioned excellent characteristics can be converted into environmental pollutants such as organic solvents and CFCs. It is preferable because it can be produced with good workability and high productivity without using a.

When foaming is carried out simultaneously with molding and processing using the foamable polyurethane composition of the present invention, a temperature not lower than the decomposition temperature of the pyrolytic foaming agent (III) is employed at least at a certain stage of molding and processing. Then, molding and processing may be performed. The temperature varies depending on the type of the thermal decomposition type foaming agent and the type of the foaming auxiliary used together, but since the thermal decomposition type foaming agent as described above generally decomposes within a temperature range of about 100 to 250 ° C, In order to decompose the pyrolytic foaming agent to produce a foam, it is preferable to heat and foam within a temperature range of 100 to 250 ° C. depending on the type of the pyrolytic foaming agent and the foaming auxiliary used.

In producing the foam of the present invention, the thermoplastic polyurethane (I), the thermoplastic polyurethane (II), and the pyrolytic foaming agent (III) are prepared without preparing the foamable polyurethane composition in advance. And, if necessary, a block copolymer (IV) and other components,
For example, a foam can be manufactured by directly supplying a melt extrusion foaming apparatus or another melt foaming molding apparatus.

The foam thus obtained may be used as it is, or a layer of this foam [foam layer (B)] may be formed on the fibrous base material layer (A). It may be used as a laminate in which a nonporous layer (C) made of a thermoplastic elastomer is formed on the foam layer (B). This laminate has the toughness of the fibrous base material layer (A) and the foam layer (B).
The properties of three layers, such as the flexibility and moderate elasticity of the non-porous layer (C), and the supple feel and touch, are exhibited in a complex manner.
Since it has a good feeling, appearance, touch, and the like very similar to natural leather, it is useful as synthetic leather or artificial leather.

The laminate of the present invention (hereinafter referred to as "3
).

As the fibrous base material used as the fibrous base material layer (A), any sheet-like fibrous base material having an appropriate thickness and a sense of fulfillment and having a soft feeling can be used. Various types of fibrous base materials conventionally used in the production of leather-like laminates can be used. Although not limited, as the fibrous base material, for example, ultrafine fibers or bundled fibers thereof, special porous fibers, ordinary synthetic fibers,
Fibrous sheets such as entangled nonwoven sheets or knitted woven sheets formed using semi-synthetic fibers, natural fibers, inorganic fibers, etc .;
Use of a fibrous sheet in which a polymer material such as polyurethane is contained in the above fibrous sheet; a fibrous sheet in which a porous coating layer of a polymer material is further formed on the surface of any of the above fibrous sheets Can be.

Among the above, as the fibrous base material,
A fibrous sheet formed using ultrafine fibers or ultrafine fiber bundles is preferably used. In such a case, the fineness of the single fibers of the ultrafine fibers is set at 0. It is preferably 5 deniers or less,
More preferably, it is 0.1 denier or less. Further, when the fibrous base material is formed from the ultrafine fiber bundle, the total denier of the ultrafine fiber bundle is in the range of 0.5 to 10 deniers. Is preferred. Further, the ultrafine fibers constituting the fibrous base material are preferably formed from polyester fibers and / or nylon fibers in view of the strength, feel, cost, and the like of the obtained three-layer structure laminate.

In particular, when a fibrous sheet formed of a non-woven fabric of the above-described ultrafine fiber bundle and containing a polymer material in the non-woven fabric is used as the fibrous base material, a good quality closer to natural leather can be obtained. This is preferable because a three-layer structure laminate having a feeling, a touch, and the like can be obtained. In that case, as the polymer material to be contained in the nonwoven fabric, urethane-based polymers, amide-based polymers, vinyl chloride-based polymers, vinyl butyral-based polymers, acrylic polymers, silicon-based polymers, and the like. These polymers can be used alone or in combination of two or more. Among the above, when the fibrous sheet containing the polyurethane polymer is used as the fibrous base material, the foam layer (B) laminated on the fibrous base material layer (A) (that is, the above-described present invention This is particularly preferred because it has a high affinity for the foam layer formed from the foamable polyurethane composition) and the adhesion between the fibrous base material layer (A) and the foam layer (B) becomes strong. When a fibrous base material made of a fibrous sheet impregnated with a polymer material is used, the content of the polymer material in the fibrous base material depends on the weight of the fibrous sheet before impregnation with the polymer material. Is preferably in the range of 10 to 70% by weight based on

Further, in order to improve the adhesiveness between the fibrous base material layer (A) and the foam layer (B), the surface of the fibrous base material layer (A) has an affinity with the foam layer (B). A coating layer of a surface treating agent containing a polymer having a high property may be formed, and in that 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 three-layer structure laminate having a feeling of flexibility and a sense of unity.

The thickness of the fibrous base material layer (A) in the three-layer structure laminate can be determined according to the intended use of the obtained laminate, etc. The thickness is preferably in the range of 0.3 mm to 3 mm, and more preferably in the range of 0.5 mm to 2 mm, from the viewpoint of balance with the thickness of the foam layer (B) and the nonporous layer (C). More preferred.

From the viewpoint of obtaining a three-layered laminated body having a soft feel, moderate resilience and a feeling of stiffness, the apparent specific gravity of the fibrous base material is 0.25 to 0.5 g. / Cm ³ , preferably from 0.3 to 0.35 g / cm 3
More preferably, it is within the range of 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 close to natural leather It becomes difficult to obtain a feeling.

The foam layer (B) laminated on the fibrous base material layer (A) is formed by foaming the foamable polyurethane composition of the present invention. The thickness of the foam layer (B) in the three-layer structure laminate can be selected according to the application and the like, but is generally 100 to 1000.
μm, preferably 200-600 μm
Is more preferably within the range. The expansion ratio [(apparent specific gravity of foam) / (specific gravity of foamable polyurethane composition before foaming)] of foam layer (B) is about 1.5.
It is preferably in the range of -4. When the expansion ratio of the foam layer (B) is within the above range, the layer has flexibility and moderate elasticity, and has a low-grade wrinkle or unevenness on the surface when the laminate is pulled or bent. Does not occur,
It becomes a high-quality leather-like laminate, and the bonding strength between the fibrous base material layer (A) and the foam layer (B) increases.
No delamination occurs.

The non-porous layer (C) on the foam layer (B)
The thermoplastic elastomer which forms is a thermoplastic elastomer having excellent flexibility, elasticity, abrasion resistance, mechanical strength, weather resistance, hydrolysis resistance, etc. and having an affinity for the foam layer (B). Any can be used. Examples of the thermoplastic elastomer forming the nonporous layer (C) include thermoplastic polyurethane; crystalline aromatic polyesters such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate as hard segments; aliphatic polyethers; Polyester elastomer having an aliphatic polyester, aliphatic polycarbonate, aliphatic polyester polycarbonate or the like as a soft segment; 6-nylon, 6,6-nylon,
Polyamide elastomer having a polyamide such as 12-nylon as a hard segment and an aliphatic polyether, aliphatic polyester, aliphatic polyester ether or the like as a soft segment; a styrene-based polymer as a hard segment, polyisoprene, polybutadiene, hydrogenated poly Styrene-based elastomer having soft segments such as isoprene and hydrogenated polybutadiene; silicone-based elastomer; chlorinated polymer-based elastomer; polyolefin-based elastomer having polypropylene as a hard segment and soft segments such as ethylene propylene rubber or partially cross-linked ethylene propylene rubber; A fluorine-based polymer elastomer having a fluorine-based resin as a hard segment and a fluorine-based rubber as a soft segment;
1,2-butadiene polymer elastomer; urethane /
Vinyl chloride-based elastomers; and ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid-sodium acrylate terpolymer, and the like. The non-porous layer (C) can be formed by using one kind or two or more kinds.

In the three-layer structure laminate of the present invention, the non-porous layer (C) is formed of a thermoplastic polyurethane or a mixture of a thermoplastic polyurethane and another thermoplastic elastomer among the thermoplastic elastomers described above. It is preferred to form In that case, the material of the polymer forming the nonporous layer (C) and the material of the foam layer (B) formed from the foamable polyurethane composition described above are similar to each other, and the foam layer ( The adhesive strength between B) and the non-porous layer (C) is increased, so that peeling between the two layers does not occur, and a three-layer laminate having extremely excellent physical properties can be obtained. In forming the non-porous layer (C) from a thermoplastic polyurethane or a mixture of a thermoplastic polyurethane and another thermoplastic elastomer, the thermoplastic polyurethane for forming the non-porous layer (C) is used as the foamable material of the present invention. Various thermoplastic polyurethanes described above that can be used in the polyurethane composition can be used. In that case, the foam layer (B) of the three-layer structure laminate
Is the same as the thermoplastic polyurethane constituting the non-porous layer (C),
Or it may be different. In general, when a thermoplastic polyurethane having a somewhat higher hardness than the thermoplastic polyurethane used for forming the foam layer (B) is used as the thermoplastic polyurethane constituting the nonporous layer (C), a three-layer laminated structure is used. The wear resistance of the body can be further improved.

The thickness of the non-porous layer (C) can be adjusted depending on the kind of the thermoplastic elastomer forming the non-porous layer (C), the use of the three-layer laminate, and the like. It is preferably in the range of 10 to 200 μm from the viewpoint that the feeling can be imparted to the three-layer structure laminate and the surface strength, the adhesive strength to the foam layer (B), the durability against bending, and the like can be imparted. More preferably, it is in the range of 30 to 100 μm. If the nonporous layer (C) is too thin, the abrasion resistance of the surface of the resulting three-layer structure laminate tends to decrease. On the other hand, if the nonporous layer (C) is too thick, the flexibility of the three-layer structure laminate is reduced, resulting in a rubber-like inferior hand, and a natural leather-like hand tends to be lost. Further, it is necessary that the non-porous layer (C) does not contain bubbles. If there are bubbles, 3
The wear resistance, strength, and smoothness of the surface of the layered laminate decrease,
Color spots and the like easily occur.

In the three-layer structure laminate of the present invention, the surface of the non-porous layer (C) is subjected to an embossed pattern, a textured pattern or the like and / or a mirror-finished processing. When the surface of the non-porous layer (C) is subjected to unevenness, an embossed pattern or a grain pattern 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 (C) is mirror-finished, a glossy surface having an enamel tone is imparted to the three-layer structure laminate. Further, in the three-layer structure laminate of the present invention, the surface of the non-porous layer (C) may be subjected to both uneven processing and mirror finishing, in which case the glossy enamel surface is further provided with an uneven pattern. Is applied.

The three-layer laminate is formed by melt-extrusion foaming the foamable polyurethane composition of the present invention into a film to form a foam layer (B), and the foam layer (B) has fluidity. During this process, the foam layer (B) was laminated on the surface of the fibrous base material layer (A) by pressing and bonding the foam layer (B) to the surface of the fibrous base material layer (A). Thereafter, the thermoplastic elastomer is melt-extruded into a film, and while the thermoplastic elastomer has fluidity, the film-like thermoplastic elastomer is pressed against and adhered to the surface of the foam layer (B), A nonporous layer (C) made of a thermoplastic elastomer is laminated on the surface of the foam layer (B), and the nonporous layer (C) is formed while the nonporous layer (C) has fluidity. ) Is manufactured by a method of embossing and / or mirror finishing the surface by embossing. Door can be.

That is, (1) the foamable polyurethane composition of the present invention is melt-extruded and foamed, and the foam is extruded from a T-die into a film in a melt-foamed state, and the foam has fluidity. A laminate comprising the fibrous substrate layer (A) and the foam layer (B) is formed by a method of laminating the foam layer (B) on the surface of the fibrous substrate layer (A). Manufacturing step; and (2) after manufacturing the above-mentioned laminate, melt-extruding a thermoplastic elastomer on the foam layer (B), extruding it in a molten state from a T-die into a film, A method of laminating while the plastic elastomer has fluidity, that is, a so-called melt film forming method, comprising a fibrous base material layer (A) / a foam layer (B) / a nonporous layer (C) 3
The method of manufacturing a layered laminate has a process of producing a high-quality three-layered laminate that is free of delamination and that makes full use of the characteristics of each layer. , And can be manufactured smoothly with good productivity.

In the step (1) for producing the three-layer structure laminate, the molding conditions such as the foaming temperature during melt extrusion foaming are the same as those described above for the production of the foam. Can be adopted.

In the step (2) of laminating the thermoplastic elastomer, for example, (a) a foam layer of a laminate comprising a fibrous base material layer (A) and a foam layer (B) may be used. (B) A method in which a thermoplastic elastomer is directly melt-extruded and laminated thereon, and the laminate is pressed between a roll and a back roll facing the same; (A) After the thermoplastic elastomer is melt-extruded onto a roll A laminate comprising a fibrous base material layer (A) and a foam layer (B) is supplied between the roll and a back roll facing the roll, and the laminate is formed on the foam layer (B) of the laminate. (C) a method in which a roll is arranged on the foam layer side of a laminate comprising the fibrous base material layer (A) and the foam layer (B); Foam layer (B)
The thermoplastic elastomer is directly melt-extruded into the gap between the base material and the roll, and a back roll is disposed on the back side (fibrous base material side) of the laminate comprising the fibrous base material layer (A) and the foam layer (B). And stacking while pressing. Then, as long as the above-described laminating step is performed while the thermoplastic elastomer has fluidity, any of the above methods (A) to (C) is adopted,
The desired three-layer structure laminate can be obtained smoothly.

On the surface of the nonporous layer (C) of the three-layer structure laminate,
There is no particular limitation on the method of performing the concavo-convex processing and / or the mirror-finish processing. The surface of the above-mentioned roll disposed on the foam layer (B) side of the laminate comprising the foam layer (A) and the foam layer (B) is subjected to a concavo-convex process and / or a mirror-finish process, so that a laminate made of a thermoplastic elastomer is obtained. A method of pressing and laminating a certain non-porous layer (C) on the foam layer (B) and, at the same time, subjecting the surface of the non-porous layer (C) to roughening and / or graining; (2) From a thermoplastic elastomer After forming the non-porous layer (C) on the foam layer (B), while the non-porous layer (C) still has fluidity, the above-mentioned non-porous layer (C) for unevenness processing and / or mirror finishing is formed. The surface of the non-porous layer (C) is roughened using a roll. Beauty / or method of applying a mirror finish; can be carried out by. Among them, the method (1) is preferable because the number of steps is small and the productivity is high. When the method (1) is adopted, the pressing force exerted by the roll and the back roll is set to a gauge pressure in the range of 5 to 15 kg / cm ² , and the non-porous layer is formed. (C) Unevenness processing and / or mirror processing on the surface can be performed smoothly.

The surface of the non-porous layer (C) is processed to have irregularities and / or
Alternatively, when performing mirror finishing, for example, a roll that has been subjected to uneven processing and / or mirror finishing is directly brought into contact with the surface of the non-porous layer (C) to form an uneven pattern and / or on the surface of the non-porous layer (C). Alternatively, a method of forming a mirror-like pattern; a mold-releasable processed sheet having been subjected to unevenness processing and / or mirror-finished processing is brought into contact with the surface of the nonporous layer (C) and pressed from the back of the processed sheet by a roll or the like. A method of forming a concavo-convex pattern and / or a specular pattern on the surface of the nonporous layer (C). Then, when the latter method using a mold release work sheet is adopted, an arbitrary concavo-convex pattern and / or a mirror-like pattern is formed on the surface of the nonporous layer (C) simply by replacing the work sheet. Can be convenient.

In any of the above-mentioned methods, a surface processing roll for forming a concavo-convex pattern and / or a mirror pattern on the surface of the non-porous layer (C) or a releasable processing sheet is used. It is preferable that the porous layer (C) is separated from the non-porous layer (C) after the porous layer (C) no longer flows. If the surface processing roll or the releasable processed sheet is peeled off from the surface of the non-porous layer (C) while the non-porous layer (C) is still fluid, the non-porous layer (C) There is a possibility that the uneven pattern and / or mirror pattern formed on the surface may be broken or lost due to the fluidity of the non-porous layer (C), so that a clear uneven pattern or a mirror pattern excellent in gloss may not be obtained. is there. The surface of the non-porous layer (C) has an uneven pattern and / or
Or as a pressing roll arranged on the back of a surface processing roll or a releasable processing sheet for forming a mirror pattern,
A type in which a cooling liquid is circulated inside is adopted, or cool air is forcibly sent to the vicinity of performing the unevenness processing and / or the mirror finishing, so that the surface processing rolls and the release sheet are not used. If a method of actively cooling the area near the peeling from the porous layer (C) is adopted, the non-porous layer (C) that has been subjected to the uneven processing and / or the mirror-finished processing is rapidly cooled, and It is preferable because the release-processed sheet can be separated at an early stage.

As a roll for forming the non-porous layer (C) on the foam layer (B) and / or a roll for performing unevenness processing and / or mirror finishing on the surface of the non-porous layer (C). In the case of a roll used in direct contact with the nonporous layer (C), a metal roll is generally preferably used. As the back roll used without directly contacting the non-porous layer (C) and the roll used on the back of the releasable surface-treated sheet, any of a metal roll and an elastic roll can be used. It is possible, and it is desirable to use an elastic roll because pressing can be stably performed.

Although there is no particular limitation, in the case of producing a three-layer structure laminate in which the surface of the nonporous layer (C) is provided with a concavo-convex pattern and / or a mirror-like pattern, for example, as shown in FIG. By a suitable process, a three-layer structure laminate can be manufactured. 1, 1 is a fibrous base material, 2 is a mirror-finished metal roll, 3 is an elastic back roll, 4 is an extruder, 5 is a foam layer, and 6 is a fibrous base material layer. A laminated body composed of a foam layer, 7 is a metal embossing roll provided with an uneven pattern, 8 is an elastic back roll, 9 is an extruder, 10 is a non-porous layer, and 11 is a three-layer laminated body. Show.

The foam of the present invention, such as a three-layer laminate having a fibrous base material layer (A) / foam layer (B) / nonporous layer (C), has excellent flexibility and elasticity. Utilizing wear resistance, mechanical properties, cushioning, cushioning, feel, etc., artificial leather, building materials such as wall materials and flooring materials, furniture such as chairs, seats for vehicles, interior materials such as vehicles, Footwear, bags, bags,
It can be effectively used for a wide range of uses as clothing, clothing accessories, gloves, cushioning materials, heat insulating materials, cushioning materials, lightweight belts, and the like. In particular, the above-described three-layer laminate comprising a fibrous base material layer (A) / a foam layer (B) / a non-porous layer (C) may be used as a substitute for natural leather, for example, in the form of a coat,
It can be effectively used for clothing such as blazer and skirt, footwear such as shoes and boots, bags and bags such as camera cases and wallets, clothing-related articles such as belts, and sports equipment such as basketball and volleyball.

[0073]

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

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

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

[Hardness of Thermoplastic Polyurethane] Thermoplastic polyurethane is injection-molded (cylinder temperature 180 to 20).
(0 ° C, mold temperature 30 ° C), diameter 120mm, thickness 2m
A m-shaped disc-shaped test piece was formed, and two of the test pieces were superimposed, and the Shore hardness A was measured in accordance with JIS K6301.

[Apparent Specific Gravity of Foam Layer] JIS K67
According to 67, the apparent specific gravity of the foamed film was measured.

[Tensile strength of foamed film] JIS K
The tensile strength in the length direction (extrusion direction) of the foamed film was measured according to 7311.

[Appearance of the foamed film] The surface condition of the foamed film was visually observed, and the surface of the foamed film was free of irregularities and roughness due to breakage of bubbles and unevenness of the bubble diameter. If the surface of the foamed film is covered with a thin skin layer and is smooth (good), the surface of the foamed film is broken (bubble) or irregularities due to unevenness of the bubble diameter, etc. evaluated.

[Abrasion resistance of the surface of the three-layer structure laminate] Paper-type rotary abrasion device (with dust suction unit)
(Rotary ablation tester manufactured by Toyo Seiki Co., Ltd.) using JIS L 1096 6.17.3.
The amount of wear reduction on the surface of the non-porous layer constituting the three-layer laminate was measured in accordance with.

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

The contents of the abbreviations used in Tables 2 and 3 are shown in Table 1 below.

[0083]

[Table 1]

Reference Example 1 A high-molecular-weight polyol having a number-average molecular weight of 3,500 (abbreviation: PMPA-2) in which the number of hydroxyl groups per molecule is 2.02, 1,4-butanediol (BD) and 50 ° C. 4,4'-diphenylmethane diisocyanate (MDI) melted by heating with PMPA:
The molar ratio of BD: MDI is 1: 2: 2.91 so that the molar ratio is 1: 2: 2.91.
g / min and continuously fed to a twin-screw extruder (30 mmφ, L / D = 36, cylinder temperature: 75-260 ° C.) coaxially rotated by a metering pump to perform continuous melt polymerization. To produce a thermoplastic polyurethane. The resulting thermoplastic polyurethane melt is continuously 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 20 hours, as shown in Table 2 below. A thermoplastic polyurethane having logarithmic viscosity and hardness was produced.

Reference Examples 2 to 9 The polymer polyol, organic diisocyanate and chain extender shown in Table 2 below were used.
Pellets of thermoplastic polyurethane were produced in the same manner as in Reference Example 1, except that thermoplastic polyurethane was produced using the proportions shown in Table 2. The results obtained are shown in Table 2 below.

Example 1 (1) As the thermoplastic polyurethane (I), 40 parts by weight of the thermoplastic polyurethane obtained in Reference Example 1, and as the thermoplastic polyurethane (II), the thermoplastic polyurethane obtained in Reference Example 2 Styrene-isoprene-styrene block copolymer [styrene content: 15% by weight,
Hardness: 37A, manufactured by Japan Synthetic Rubber “JSR-5000”
P "] and 1 part by weight of an azodicarbonamide-based blowing agent (" Vinihome AC # 3 "manufactured by Eiwa Chemical Co., Ltd.) to prepare a foamable polyurethane composition. (2) The foamable polyurethane composition produced in the above (1) was charged into a single screw extruder (25 mmφ), and the temperature of the melting zone was 170 to 220 ° C, the temperature of the die part was 180 ° C, and the T-die (lip interval was 0.2 mm) And a die width of 350 mm) to form a film by melt extrusion foaming.
A 0 mm foam film was produced. The apparent specific gravity, tensile strength, and appearance of the obtained film were measured or evaluated by the methods described above, and the results were as shown in Table 3 below.

Examples 2 to 6 (1) Thermoplastic polyurethane (I), thermoplastic polyurethane (II), styrene-isoprene-styrene block copolymer [styrene content: 15% by weight, hardness: 37
A, Nippon Synthetic Rubber “JSR-5000P”], an azodicarbonamide-based blowing agent (Einawa Kasei's “Vinihome AC”
# 3 ") was used in the same manner as in Example 1 (1), except that the ratio shown in Table 3 below was used, to produce a foamable polyurethane composition. (2) Using the foamable polyurethane composition produced in (2) above, melt extrusion foaming was performed in the form of a film in the same manner as in (2) of Example 1, and the thickness shown in Table 3 below was obtained. Was produced. The apparent specific gravity, tensile strength, and appearance of the obtained film were measured or evaluated by the methods described above, and the results were as shown in Table 3 below.

<< Comparative Examples 1-4 >> Thermoplastic polyurethane (I), thermoplastic polyurethane (II), styrene-isoprene-styrene block copolymer [styrene content: 1
5% by weight, hardness: 37A, Japan Synthetic Rubber "JSR-5"
000P "], and an azodicarbonamide-based blowing agent (" Vinihome AC # 3 "manufactured by Eiwa Chemical Co., Ltd.) at a ratio shown in Table 3 below, in the same manner as (1) of Example 1, except that A foamed film having a thickness shown in Table 3 below was prepared by subjecting the foamed polyurethane composition to melt extrusion foaming molding using the foamable polyurethane composition in the same manner as in Example 1, (2). Was manufactured. The apparent specific gravity, tensile strength, and appearance of the obtained film were measured or evaluated by the methods described above, and the results were as shown in Table 3 below.

[0089]

[Table 2]

[0090]

[Table 3]

As is clear from the results in Table 3 above, when the foamable polyurethane compositions of Examples 1 to 6 were used, a foamed film having excellent tensile strength and a smooth appearance was obtained. On the other hand, Comparative Examples 1 and 2 using thermoplastic polyurethane (I) or thermoplastic polyurethane (II) alone, and hydroxyl groups after blending thermoplastic polyurethane (I) and thermoplastic polyurethane (II) The molar ratio of isocyanate groups to (b / a +
In the case of Comparative Example 3 in which c) was out of the range of 0.99 to 1.02, the melt viscosity was too low to be suitable for foaming,
The foamed film obtained by melt extrusion molding is defective because the surface has an irregular pattern or roughness due to breakage of bubbles, unevenness in bubble diameter, and the like. Moreover, the tensile strength is low,
Poor mechanical properties. Further, the foamable polyurethane composition of Comparative Example 4 in which the thermoplastic polyurethane obtained in Reference Example 9 using a polymer polyol having a functional group of 2.10 per molecule was used as the thermoplastic polyurethane (II) was melted. The resulting foamed sheet is inferior in surface shape because the viscosity is too high and there are many unmelted substances and the dispersibility is poor.

Example 7 (1) An entangled nonwoven fabric (having a basis weight of 360 g / m ² ) manufactured using polyester fibers having a single fiber fineness of 2.5 denier was used to form a polyurethane elastic material (“Kuramilon U219” manufactured by Kuraray Co., Ltd.).
5 ", logarithmic viscosity 1.05 dl / g, Shore A hardness 9
5) impregnating with the N, N-dimethylformamide solution of
After drying, a fibrous base material having a thickness of 1.3 mm and a basis weight of 455 g / m ² was prepared (weight ratio of polyester entangled nonwoven fabric to polyurethane elastic body in the fibrous base material = 8: 2). (2) 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 roll 3 and supplied. Between the metal roll 2 and the fibrous base material 1, the foamable polyurethane composition obtained in the above Example 3 was charged into a single screw extruder (65 mmφ) 4, and the melting zone temperature was 180 to 220.
C. and a die temperature of 180.degree.
(2 mm, die width: 350 mm), melt-extruded and foamed into a film form and supplied in a fluidized state, and a gauge pressure of 8 kg / cm ^2.
Cold pressing with a thickness of 5 on the surface of the fibrous base material layer 1
The laminated body 6 on which the foam layer 5 of 10 μm was formed was manufactured. The expansion ratio of the foam layer 5 in the laminate 6 is 1.
It was 9 times.

(3) Apart from the above (2), a polyester diol (a) comprising a 3-methyl-1,5-pentanediol unit having a number average molecular weight of 1,500 and an adipic acid unit, 1,4-butane The diol (c) and 4,4'-diphenylmethane diisocyanate (b) melted by heating at 50 ° C. are mixed in a molar ratio of (a) :( c) :( b) of 1:
A thermoplastic polyurethane having a logarithmic viscosity of 1.02 dl / g and a Shore hardness A of 90 was produced using a ratio of 2.6: 3.6. (4) The thermoplastic polyurethane 1 obtained in the above (3)
Of the black pigment pellet (pigment concentration 20
5% by weight of a polyethylene pellet (% by weight) were mixed to prepare a thermoplastic polyurethane pellet blend for the non-porous layer. (5) A metal embossing roll 7 and an elastic backing roll 8 in which a laminate 6 comprising the fibrous base material layer 1 and the foam layer 5 obtained in the above (2) have been subjected to pore-like unevenness processing.
And between the metal embossing roll 7 and the surface of the foam layer 5 of the laminate 6, the heat adjusted for the non-porous layer obtained in (4) above. The pellet blend of the thermoplastic polyurethane is mixed with a single screw extruder (65 m
mφ) 9, a melting zone temperature of 180 to 230 ° C, a die temperature of 220 ° C, and a T-die (lip interval 0.5 mm,
A melt-extruded film from a die width of 350 mm) is supplied in a fluid state, and is cold-pressed at a gauge pressure of 8 kg / cm ² to have a non-porous layer 10 having a thickness of 35 μm on the surface of the foam layer 5. A three-layer laminate 11 consisting of a fibrous base material layer / a foam layer / a nonporous layer was produced. The three-layered structure 11 could be manufactured stably at a line speed of 10 m / min. (6) The three-layer structure laminate 11 obtained in the above (5) is
Its surface strength is great, it is excellent in flexibility, and it has a good pore-like grain pattern that is very close to the pore grain product of natural leather, and when it is pulled or bent, it has low-grade uneven wrinkles on the surface It did not occur, was extremely excellent in appearance, feeling, touch, and the like, and was a high-quality leather-like laminate. Further, the peel strength of the three-layer structure laminate 11 was measured by the above-mentioned method, and was a high value of 15 kg / 25 mm.

Example 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 were converged. Polyurethane elastic (Kuraray “Kuramilon U919”
8 ", logarithmic viscosity 1.05 dl / g, Shore A hardness 9
8) impregnating with the N, N-dimethylformamide solution of
After drying, a fibrous base material having a thickness of 1.3 mm and 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) 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 roll 3 and supplied. Between the metal roll 2 and the fibrous base material 1, the foamable polyurethane composition obtained in the above Example 4 was charged into a single-screw extruder (65 mmφ) 4, and the melt zone temperature was 180 to 220.
C. and a die temperature of 180.degree.
(2 mm, die width: 350 mm), melt-extruded and foamed into a film form and supplied in a fluidized state, and a gauge pressure of 8 kg / cm ^2.
Cold pressing with a thickness of 5 on the surface of the fibrous base material layer 1
The laminate 6 on which the foam layer 5 of 30 μm was formed was manufactured. The expansion ratio of the foam layer 5 in the laminate 6 is 2.
It was 0 times. (3) Apart from the above (2), the number average molecular weight is 1,000
Polytetramethylene ether glycol (a), 1,
4-butanediol (c) and 4,4'-diphenylmethane diisocyanate (b) heated and melted at 50 ° C
With a molar ratio of (a) :( c) :( b) of 1: 1.7:
The logarithmic viscosity is 1.03d when used at a ratio of 2.7.
A thermoplastic polyurethane having a l / g and a Shore hardness A of 90 was produced. (4) The thermoplastic polyurethane 1 obtained in the above (3)
Of the black pigment pellet (pigment concentration 20
5% by weight of a polyethylene pellet (% by weight) were mixed to prepare a thermoplastic polyurethane pellet blend for the non-porous layer.

(5) The laminated body 6 composed of the fibrous base material layer 1 and the foam layer 5 obtained in the above (2) is combined with a metal embossing roll 7 which has been subjected to a pore embossing process and an elastic material. The non-porous layer obtained in (4) above is supplied between the metal embossing roll 7 and the surface of the foam layer 5 of the laminate 6 while being supplied between the body back roll 8 and the metal embossing roll 7. The thermoplastic polyurethane pellet blend adjusted to the above was charged into a single screw extruder (65 mmφ) 9 and the melt zone temperature was set to 180 to
At 230 ° C. and a die temperature of 220 ° C., a melt-extruded film from a T-die (lip interval: 0.5 mm, die width: 350 mm) is supplied in a flowing state, and a gauge pressure of 10 kg / c is supplied.
and cold pressing m ^{2, and} the thickness of 3 on the surface of the foam layer 5
A three-layer laminate 11 composed of a fibrous base material layer / foam layer / nonporous layer having a 5 μm nonporous layer 10 was produced. The three-layered structure 11 could be manufactured stably at a line speed of 10 m / min. (6) The three-layer structure laminate 11 obtained in the above (5) is
Its surface strength is great, it has excellent flexibility, and it has a good pore-like grain pattern that is very close in appearance to natural leather pore grain products. No appearance was observed, the appearance, feeling, touch feeling, and the like were extremely excellent, and the leather-like laminate had a luxurious feeling. When the peel strength of the three-layered structure 11 was measured by the method described above, it was a high value of 15 kg / 25 mm. On the other hand, the amount of reduction in abrasion was as small as 8 mg, and the abrasion resistance was excellent.

<< Comparative Example 5 >> In Example 2 (2),
Except that the foamable polyurethane composition obtained in Comparative Example 1 was used instead of the foamable polyurethane composition obtained in Example 3, the same procedure as in Example 7 was repeated. A three-layer laminate comprising a foam layer / a nonporous layer was produced at a line speed of 10 m / min. As a result, when manufacturing a laminate consisting of a fibrous base material layer and a foam layer,
Due to the low melt viscosity of the foamable polyurethane composition, the foam was enlarged, crushed, and broken immediately after the extrusion, and 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 rough surface shape of the foam layer below 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 flow. Moreover,
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 method described above, the peel strength was as low as 6 kg / 25 mm, while the abrasion loss was as large as 18 mg, and the wear resistance was poor.

<< Comparative Example 6 >> In Example 8 (2),
Except that the foamable polyurethane composition obtained in Comparative Example 3 was used in place of the foamable polyurethane composition obtained in Example 4, a fibrous base material layer / foamed A three-layer laminate comprising a body layer and a nonporous layer was produced at a line speed of 10 m / min. As a result, when producing a laminate consisting of a fibrous base material layer and a foam layer, the melt viscosity of the foamable polyurethane composition is low, the foam sheet is partially torn, or the bubbles are enlarged immediately after extrusion. In this case, the foam layer was crushed or broken, and 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 rough surface shape of the foam layer below 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 method described above, it was 4 kg / 25 m.
m, on the other hand, the wear reduction was as large as 22 mg, and the wear resistance was poor.

[0098]

According to the present invention, fine bubbles having a uniform size are uniformly distributed inside the foam without irregularities, and the surface is rough or uneven due to breakage of the bubbles or unevenness of the bubble diameter. -Free thermoplastic polyurethane foam having good surface condition and excellent flexibility, mechanical properties, abrasion resistance and the like, and a foamable polyurethane composition for providing a laminate having the polyurethane foam layer Is provided. The three-layer laminate of the present invention comprising the fibrous base material layer (A) / foam layer (B) / nonporous layer (C) has flexibility, elasticity, abrasion resistance, and mechanical strength. It has excellent characteristics such as no delamination, no low-grade wrinkles or irregularities on the surface when pulled or bent, and has a high-quality appearance, texture, touch, etc. similar to natural leather Have.
Further, using the foamable polyurethane composition of the present invention,
When a polyurethane foam or a three-layer structure laminate is manufactured by the method of the present invention, the above-described high foaming method can be used without using a fluorocarbon gas or an organic solvent which is a major problem in terms of environment and safety. Quality products can be manufactured smoothly and with high productivity.

[Brief description of the drawings]

FIG. 1 shows an example of a production process preferably employed in the production of a three-layer structure laminate of the present invention comprising a fibrous base material layer (A) / a foam layer (B) / a nonporous layer (C). FIG.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 fibrous base material 2 mirror-finished metal roll 3 elastic back roll 4 extruder 5 foam layer 6 laminate composed of fibrous base layer and foam layer 7 metal emboss roll with uneven pattern Reference Signs List 8 elastic back roll 9 extruder 10 non-porous layer 11 three-layer laminate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 18/00 C08G 18/00 M 18/08 18/08 C08J 9/10 CFF C08J 9/10 CFF C08L 53 / 02 C08L 53/02 // (C08G 18/08 101: 00) B29K 21:00 75:00 F term (reference) 4F074 AA08B AA13B AA80 AA81 AG20 BA03 BA04 BA12 BA13 BA14 BA15 BA16 BA17 BA18 BA19 CA22 CC22X CC28X CC32X CC32Y CE02 DA08 DA12 DA32. JB16C JK01 JK06 JK07 JK09 JK13 JK15C JL04 YY00A YY00H 4F207 AA31A AA31K AA45 AA47F AA47K AB02 AD16 AF01 AF14 AG01 AG03 AG05 A G20 AH26 AH48 AH51 AH59 AH67 AH71 KA01 KA11 KA17 KB13 KB26 KK88 KW42 4J002 BP01Y CK02W CK02X EQ016 ER016 ET006 FD326 GF00 GG00 4J034 BA08 CA02 CA04 CA13 CA15 CB03 CC26 CC03 CC02 CC03 CC02 CC03 CC02 CC03 CC02 DF22 DG03 DG04 DG06 DG14 HA01 HA07 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC64 HC67 HC71 HC73 MA22 NA01 QA01 QA05 QC03 QD04 RA03 RA05

Claims (7)

[Claims] 1. The method according to claim 1, wherein the number of hydroxyl groups per molecule is from 2.00 to
2.08 polymer polyol (a ₁ ) having a number average molecular weight of 800 to 8,000, organic diisocyanate (b ₁ )
And is composed of a chain extender (c _1), polymer polyol (a _1), organic diisocyanate (b ₁₎ and formula ratio is below the chain extender _{(c 1) (1):} 0.92 ≦ b 1 / (A ₁ + c ₁ ) ≦ 0.97 (1) (where a ₁ is the number of moles of the polymer polyol (a ₁ ), b ₁
Represents the number of moles of the organic diisocyanate (b ₁ ), and c ₁ represents the number of moles of the chain extender (c ₁ ). Thermoplastic polyurethane (I) satisfying the above condition), the number of hydroxyl groups per molecule is 2.00.
～2.08 or a number-average molecular weight 800～8,000 of polymer polyol is (a _2), is composed of an organic diisocyanate (b ₂₎ and a chain extender (c _2), polymer polyol (a _2), the organic diisocyanate (b ₂₎ and a chain extender formula proportion of the following _{(c 2) (2):} 1.03 ≦ b 2 / (a 2 + c 2) ≦ 1.08 (2) ( wherein, a ₂ Is the number of moles of the polymer polyol (a ₂ ), b ₂
Represents the number of moles of the organic diisocyanate (b ₂ ), and c ₂ represents the number of moles of the chain extender (c ₂ ). A foamable polyurethane composition comprising a thermoplastic polyurethane (II) satisfying the above-mentioned (1) and a pyrolytic foaming agent (III); The ratio of the organic diisocyanate and the chain extender is represented by the following formula (3): 0.99 ≦ b / (a + c) ≦ 1.02 (3) (where a is a polymer polyol (a ₁ ) and a polymer The total number of moles of the polyol (a ₂ ), b is the total number of moles of the organic diisocyanate (b ₁ ) and the organic diisocyanate (b ₂ ), c is the total number of moles of the chain extender (c ₁ ) and the chain extender (c ₂ ) The ratio of the total weight of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) to the weight of the pyrolytic foaming agent (III) is 100: 0.0.
5 to 100: 10; a foamable polyurethane composition, 2. The number of hydroxyl groups per molecule is 2.00 to 2.
2.08 polymer polyol (a ₁ ) having a number average molecular weight of 800 to 8,000, organic diisocyanate (b ₁ )
And is composed of a chain extender (c _1), polymer polyol (a _1), organic diisocyanate (b ₁₎ and formula ratio is below the chain extender _{(c 1) (1):} 0.92 ≦ b 1 / (A ₁ + c ₁ ) ≦ 0.97 (1) (where a ₁ is the number of moles of the polymer polyol (a ₁ ), b ₁
Represents the number of moles of the organic diisocyanate (b ₁ ), and c ₁ represents the number of moles of the chain extender (c ₁ ). Thermoplastic polyurethane (I) satisfying the above condition), the number of hydroxyl groups per molecule is 2.00.
～2.08 or a number-average molecular weight 800～8,000 of polymer polyol is (a _2), is composed of an organic diisocyanate (b ₂₎ and a chain extender (c _2), polymer polyol (a _2), the organic diisocyanate (b ₂₎ and a chain extender formula proportion of the following _{(c 2) (2):} 1.03 ≦ b 2 / (a 2 + c 2) ≦ 1.08 (2) ( wherein, a ₂ Is the number of moles of the polymer polyol (a ₂ ), b ₂
Represents the number of moles of the organic diisocyanate (b ₂ ), and c ₂ represents the number of moles of the chain extender (c ₂ ). From the group consisting of thermoplastic polyurethane (II), pyrolytic foaming agent (III), and a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene polymer block, and a hydrogenated product thereof. A foamable polyurethane composition comprising at least one selected block copolymer (IV); a thermoplastic polyurethane (I) and a polymer polyol constituting the thermoplastic polyurethane (II), an organic diisocyanate, and a chain extender. Is the following formula (3): 0.99 ≦ b / (a + c) ≦ 1.02 (3) (where a is the total of the polymer polyol (a ₁ ) and the polymer polyol (a ₂ )) The number of moles, b is the total number of moles of the organic diisocyanate (b ₁ ) and the organic diisocyanate (b ₂ ), and c is the total of the chain extender (c ₁ ) and the chain extender (c ₂ ). And the ratio of the total weight of the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) to the weight of the block copolymer (IV) is 60: 40-9.
5: 5; the ratio of the total weight of the thermoplastic polyurethane (I), the thermoplastic polyurethane (II) and the block copolymer (IV) to the weight of the pyrolytic foaming agent (III) is 10
0: 0.05 to 100: 10; a foamable polyurethane composition, 3. The number of hydroxyl groups per molecule is 2.00 to 3.
2.08 polymer polyol (a ₁ ) having a number average molecular weight of 800 to 8,000, organic diisocyanate (b ₁ )
And is composed of a chain extender (c _1), polymer polyol (a _1), organic diisocyanate (b ₁₎ and formula ratio is below the chain extender _{(c 1) (1):} 0.92 ≦ b 1 / (A ₁ + c ₁ ) ≦ 0.97 (1) (where a ₁ is the number of moles of the polymer polyol (a ₁ ), b ₁
Represents the number of moles of the organic diisocyanate (b ₁ ), and c ₁ represents the number of moles of the chain extender (c ₁ ). A) a thermoplastic polyurethane (I) that satisfies)), and a number average molecular weight of 800 to 8, in which the number of hydroxyl groups per molecule is 2.00 to 2.08.
000, a polymer polyol (a ₂ ), an organic diisocyanate (b ₂ ) and a chain extender (c ₂ ). The polymer polyol (a ₂ ), the organic diisocyanate (b ₂ ) and the chain extender (c ₂ ) Is the following formula (2): 1.03 ≦ b ₂ / (a ₂ + c ₂ ) ≦ 1.08 (2) (where a ₂ is the number of moles of the polymer polyol (a ₂ ) and b ₂
Represents the number of moles of the organic diisocyanate (b ₂ ), and c ₂ represents the number of moles of the chain extender (c ₂ ). A) a foam comprising a thermoplastic polyurethane (II) that satisfies the following; Formula (3): 0.99 ≦ b / (a + c) ≦ 1.02 (3) (where a is the total number of moles of the polymer polyol (a ₁ ) and the polymer polyol (a ₂ ), and b is an organic The total number of moles of the diisocyanate (b ₁ ) and the organic diisocyanate (b ₂ ), and c represents the total number of moles of the chain extender (c ₁ ) and the chain extender (c ₂ ). Foam. 4. The number of hydroxyl groups per molecule is 2.00 to 4.
2.08 polymer polyol (a ₁ ) having a number average molecular weight of 800 to 8,000, organic diisocyanate (b ₁ )
And is composed of a chain extender (c _1), polymer polyol (a _1), organic diisocyanate (b ₁₎ and formula ratio is below the chain extender _{(c 1) (1):} 0.92 ≦ b 1 / (A ₁ + c ₁ ) ≦ 0.97 (1) (where a ₁ is the number of moles of the polymer polyol (a ₁ ), b ₁
Represents the number of moles of the organic diisocyanate (b ₁ ), and c ₁ represents the number of moles of the chain extender (c ₁ ). Thermoplastic polyurethane (I) satisfying the above condition), the number of hydroxyl groups per molecule is 2.00.
～2.08 or a number-average molecular weight 800～8,000 of polymer polyol is (a _2), is composed of an organic diisocyanate (b ₂₎ and a chain extender (c _2), polymer polyol (a _2), the organic diisocyanate (b ₂₎ and a chain extender formula proportion of the following _{(c 2) (2):} 1.03 ≦ b 2 / (a 2 + c 2) ≦ 1.08 (2) ( wherein, a ₂ Is the number of moles of the polymer polyol (a ₂ ), b ₂
Represents the number of moles of the organic diisocyanate (b ₂ ), and c ₂ represents the number of moles of the chain extender (c ₂ ). And at least one block copolymer selected from the group consisting of a block copolymer consisting of an aromatic vinyl compound polymer block and a conjugated diene polymer block and a hydrogenated product thereof. A foamed product composed of the united product (IV); the ratio of the polymer polyol, the organic diisocyanate and the chain extender constituting the thermoplastic polyurethane (I) and the thermoplastic polyurethane (II) is expressed by the following formula (3): 0 .99 ≦ b / (a + c) ≦ 1.02 (3) (where a is the total number of moles of the polymer polyol (a ₁ ) and the polymer polyol (a ₂ ), b is the organic diisocyanate (b ₁ ) The total number of moles of the organic diisocyanate (b ₂ ), and c represents the total number of moles of the chain extender (c ₁ ) and the chain extender (c ₂ ). The ratio of the total weight of the urethane (I) and the thermoplastic polyurethane (II) to the weight of the block copolymer (IV) is 60:40 to 9
5: 5; foam. 5. A method for producing a foam, comprising subjecting the foamable polyurethane composition according to claim 1 to melt extrusion foam molding. 6. A fibrous base material layer (A) having a foam layer (B) comprising the foam according to claim 3 on the surface thereof,
Non-porous layer made of thermoplastic elastomer (C)
And the surface of the non-porous layer (C) has irregularities and / or
Or a mirror-finished laminate. 7. A foam layer (B) is formed by subjecting the foamable polyurethane composition according to claim 1 to melt extrusion foaming into a film, and the foam layer (B) has fluidity. After the foam layer (B) is laminated on the surface of the fibrous base material layer (A) by pressing and bonding the foam layer (B) to the surface of the fibrous base material layer (A) The thermoplastic elastomer is melt-extruded into a film, and while the thermoplastic elastomer has fluidity, the film-like thermoplastic elastomer is pressed and adhered to the surface of the foam layer (B) to form a foam. A nonporous layer (C) made of a thermoplastic elastomer is laminated on the surface of the body layer (B), and the nonporous layer (C) is formed while the nonporous layer (C) has fluidity. A laminate characterized by embossing and / or mirror-finish processing the surface of the laminate Manufacturing method.