JPH09267456A - Laminated body and method for manufacturing the same - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: To produce a leather-like laminate having a high-grade silver surface layer, which is excellent in chemical resistance, abrasion resistance, peeling strength between layers, and the like, and to produce the laminate at high speed. Providing a way that can be done. SOLUTION: The surface of the fibrous base layer (A) has a JIS-A hardness of
Non-porous layer consisting of 70-98 polyester elastomer
A laminate having (B) and having an uneven pattern or a silver surface pattern on its surface; a fibrous base layer (A) and a non-porous layer (B)
A laminate having a porous layer (C) containing a bubble and containing a thermoplastic elastomer between the two; and a method for producing the laminate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fibrous base layer (A).
And a laminate composed of two layers of a non-porous layer (B) made of a polyester elastomer having a JIS-A hardness of 70 to 98; a fibrous base layer (A), a porous layer (C) made of a thermoplastic elastomer. And JIS-A hardness of 70-9
Non-porous layer (B) consisting of polyester elastomer of No. 8
And a method for producing these laminated bodies. According to the present invention, a leather-like laminate with a silver surface layer, which is excellent in chemical resistance, abrasion resistance, peeling strength between layers, etc. and has a high-grade feeling, is provided.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a leather-like laminate having a silver surface layer, a polyurethane solution is applied onto release paper,
A so-called dry method is generally used in which a film is dried to form a film, and then the film is attached to the surface of a substrate made of a woven or non-woven fabric with an adhesive and the release paper is peeled off. Further, a polyurethane solution is applied to the surface of the substrate, a porous polyurethane layer is formed by a wet coagulation method or a dry coagulation method, and a resin solution containing a colorant is applied and dried on the porous polyurethane layer to form a colored layer. After that, a method of forming an uneven pattern with an embossing roll is also commonly used.

In Japanese Patent Laid-Open No. 53-62803, a synthetic resin extruded in a film form is laminated on the surface of a synthetic resin layer provided on a substrate, and a skin layer surface is formed by using a release material. A method for forming a skin layer of synthetic leather, which comprises embossing JP-A-62-2
282078 discloses a method for producing a sheet in which a polyurethane melt extruded from a T-die is laminated on a metal vapor deposition layer. In addition, JP-A-2-307986
In the gazette, a silane coupling agent is applied to the surface of a synthetic fiber cloth in advance, and then a thermoplastic resin is melt-extruded on the surface and pressure-bonded to the cloth, and the adhesive strength between the cloth and the thermoplastic resin layer is increased. The method of improving is described.

[0004]

However, in these known methods, an organic solvent that deteriorates the working environment is used, or an uneven pattern that gives a cheesy impression to the surface when pulled or bent appears, Since the base layer and the surface layer are easily peeled off or the surface layer requires a long time to solidify, the production rate cannot be increased, resulting in a high production cost. I have a problem. Furthermore, the laminate using the thermoplastic polyurethane layer as the surface layer is inferior in chemical resistance and cannot be used in applications where it may come into contact with chemicals.

The object of the present invention is excellent in chemical resistance, abrasion resistance, peeling strength between layers, etc., and does not show a cheesy uneven pattern on the surface when pulled or bent, a high-grade silver surface To provide a layered leather-like laminate. Further, another object of the present invention is to provide a method capable of producing a laminate having the above characteristics at a high speed in a good working environment without using an organic solvent.

[0006]

The present invention has a non-porous layer (B) made of a polyester elastomer having a JIS-A hardness of 70 to 98 on the surface of a fibrous substrate layer (A), and The present invention relates to a laminate having an uneven pattern or a mirror surface pattern on the surface of the non-porous layer (B) [hereinafter, may be referred to as a laminate (I)].

The present invention provides the surface of the fibrous base layer (A) with
It has a porous layer (C) made of a thermoplastic elastomer and containing cells, and has a non-porous layer (B) made of a polyester elastomer having a JIS-A hardness of 70 to 98 thereon, and the non-porous layer The present invention relates to a laminate having an uneven pattern or a mirror-like pattern on the surface of the texture layer (B) [hereinafter, may be referred to as a laminate (II)].

In the present invention, (i) a polyester elastomer having a JIS-A hardness of 70 to 98 melt-extruded in a film shape is pressed against the surface of the fibrous base layer (A) while having fluidity. And adhere to form a non-porous layer (B) on the surface of the fibrous base layer (A),
(Ii) A method for producing a laminate in which the surface of the non-porous layer (B) is embossed to form an uneven pattern or a mirror pattern while the polyester elastomer has fluidity.

Further, in the present invention, (i) a thermoplastic elastomer containing bubbles or bubble-generating substances melt-extruded in the form of a film is provided on the surface of the fibrous base layer (A) while having fluidity. A porous layer (C) is formed on the surface of the fibrous substrate layer (A) by pressing and adhering, and (i)
i) Next, a polyester elastomer having a JIS-A hardness of 70 to 98 melt-extruded in a film shape is pressed and adhered to the surface of the porous layer (C) while having fluidity, The non-porous layer (B) is formed on the surface of the porous layer (C), and (iii) the non-porous layer (B) while the polyester elastomer has fluidity.
The present invention relates to a method for manufacturing a laminate, in which the surface of a sheet is embossed to form an uneven pattern or a mirror pattern.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The fibrous base material used in the present invention may be a sheet-like one having a proper thickness and a feeling of fullness and having a soft texture, and has been conventionally used as a leather-like laminate. Various fibrous substrates used in manufacturing can be used. For example, ultrafine fibers or bundle fibers thereof,
Entangled non-woven sheet made of special porous fiber, ordinary fiber, natural fiber, etc., woven / knitted sheet, and porous or non-porous polymer elastic material such as polyurethane as a binder between fibers of these sheets Fibrous sheet,
Examples of the fibrous sheet include a fibrous sheet having a porous coating layer of a polymeric elastic material on the surface of these fibrous sheets. The fineness of the fibers forming the ultrafine fiber bundle is preferably 0.5 denier or less, more preferably 0.1 denier or less, and the total denier of the ultrafine fiber bundle is in the range of 0.5 to 10 denier. Is preferred. Examples of the type of fiber include nylon fibers and polyester fibers.

Among these, it is preferable to use a fibrous sheet containing a polymer elastic material in a nonwoven fabric composed of an ultrafine fiber bundle because a laminate having a texture close to that of natural leather can be obtained. As the polymer elastic body, a resin which has been conventionally used for producing a leather-like laminate can be used. Examples thereof include polyurethane resins, polyamide resins, polyvinyl chloride resins, polyvinyl butyral resins, polyacrylic acid resins, polyamino acid resins, silicone resins, and mixtures and copolymers of these resins. it can. Among these, the same resin as the resin layer [that is, the non-porous layer (B) made of a polyester elastomer or the porous layer (C) made of a thermoplastic elastomer] laminated on the surface of the fibrous base layer (A). The use of is preferable because it improves the adhesiveness between the fibrous base layer (A) and the resin layer laminated on the surface thereof. In particular, it is preferable to use a polyurethane-based resin because the peel strength between layers is excellent and a laminate having a texture of natural leather is easily obtained. The weight ratio of the fibers constituting the fibrous substrate to the polymeric elastic body is 40/60 to 90/10.
It is preferred that Further, in order to improve the adhesiveness between the fibrous base layer (A) and the resin layer laminated on the surface thereof,
A surface treatment agent containing a resin having a high affinity for the resin to be laminated can be applied to the surface of the fibrous base layer (A). In this case, the thickness of the coating layer is about 5 μm as a guide. When the thickness of the coating layer is increased, the resulting laminate has a tendency to impair the soft and unity feel.

The thickness of the fibrous substrate layer (A) can be arbitrarily selected according to the application of the resulting laminate and is not particularly limited, but the nonporous layer (B) or the porous layer laminated on the surface. From the viewpoint of the balance with the thickness of the quality layer (C), 0.
It is preferably 3 to 3.0 mm, and 0.5 to 2.0.
mm is more preferable.

The apparent density of the fibrous substrate layer (A) is 0.25 to 0.5 g / cm ^{3 in} order to obtain a soft texture.
Is preferable, and 0.3 to 0.35 g / cm ³ is more preferable. When the apparent density becomes large, the obtained laminate tends to lose its rigidity and has a rubber-like texture. On the other hand, when the apparent density decreases,
It has a resilience and a firm texture, and the leather-like texture tends to be impaired.

The layered product of the present invention comprises a porous layer (C) which is composed of a thermoplastic elastomer and contains cells between the fibrous substrate layer (A) and the non-porous layer (B), if necessary. May be formed. By forming the porous layer (C) between the fibrous substrate layer (A) and the non-porous layer (B), a cheesy uneven pattern does not appear on the surface, especially when pulled or bent. It is preferable since a leather-like laminate with a silver surface layer having a higher quality, which cannot be obtained by the conventional method, can be obtained.

Examples of the thermoplastic elastomer used in the porous layer (C) include, for example, polyester elastomers described below as a constituent component of the non-porous layer (B); polyester polyol, polyether polyol, polyester ether polyol, polycarbonate polyol, At least one selected from high-molecular polyols such as polyester polycarbonate polyols, organic diisocyanates such as 4,4′-diphenylmethane diisocyanate and 4,4′-dicyclohexylmethane diisocyanate, ethylene glycol, propylene glycol, 1,4-butanediol , A hydrazine, ethylenediamine or other low molecular weight compound having a molecular weight of 300 or less (chain extender) having two active hydrogen atoms capable of reacting with an isocyanate group Thermoplastic polyurethanes to be;
Polyamide elastomer having 6-nylon, 6,6-nylon, 12-nylon, etc. as a hard segment and polyether, polyester, polyester polyether, etc. as a soft segment; polystyrene, etc. as a hard segment, polyisoprene, polybutadiene, hydrogenation Styrene elastomers containing polyisoprene, hydrogenated polybutadiene, etc. as soft segments; silicone elastomers; vinyl chloride elastomers; olefin elastomers; fluorine elastomers; 1,2-polybutadiene elastomers; urethane / vinyl chloride elastomers; ethylene-acetic acid Ethylene-based copolymers such as vinyl copolymers, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid-sodium acrylate terpolymers; chlorine Polyethylene, etc. can be mentioned, may be used alone or two or more of them. Among these, it is preferable to use a polyester elastomer because it has excellent adhesiveness to the non-porous layer (B).

The porous layer (C) may be formed, for example, by adding the above-mentioned thermoplastic elastomer to a bubble-generating substance and, if necessary, a colorant, an antioxidant, a stabilizer, a plasticizer, a lubricant and a filler. After blending an additive such as an antistatic agent with an extruder, the mixture is melted and kneaded under heating and pressurization, and then extruded in a molten state into a film from a T-die to have fluidity. A method of forming a porous layer (C) on the surface of the fibrous base layer (A) by pressing and adhering it to the surface of the fibrous base layer (A), a so-called melt film-forming method can be used.

As the bubble-generating substance, various known foaming agents can be used and are not particularly limited. For example, azodicarbonamide, 4,4-oxybis (benzenesulfonylhydrazine), p-toluene. Sulfonylhydrazine, sodium bicarbonate, dinitrosopentamethylenetetramine and the like,
One or more of these may be used. The amount of the foaming agent used is preferably 0.3 to 1.5% by weight with respect to the thermoplastic elastomer, and is 0.1.
It is more preferably 6 to 1.0% by weight.

The thickness of the porous layer (C) may be appropriately selected depending on the intended use, but generally it is preferably 10 to 300 μm, more preferably 20 to 150 μm. As the degree of foaming of the porous layer (C), 20 to 80% by volume of the porous layer (C) is preferably bubbles, and more preferably 30 to 70% by volume.
When the content ratio of air bubbles in the porous layer (C) is within the above range, the peeling strength between the layers of the laminate is not lowered,
It is preferable because a leather-like laminate with a high-grade silver surface layer, which does not cause a chewy uneven pattern on the surface when pulled, can be obtained.

The bubbles contained in the porous layer (C) are preferably generated by the above-mentioned gas generating substance generating gas. In the conventional method of producing a leather-like laminate by coagulating polyurethane in a porous manner by a wet coagulation method, a polyurethane solution is applied to a substrate and then placed in a coagulation bath to replace the polyurethane solvent with the coagulation liquid. Must be allowed to coagulate to a porosity and then the solvent must be removed from the porous layer of polyurethane. If the solvent is not removed sufficiently, the bubbles will collapse, so it will take a lot of time and utility to completely remove the solvent.
Therefore, the speed of the manufacturing line cannot be increased and the manufacturing cost must be increased. On the other hand, in the melt film-forming method of the present invention, the porous layer can be obtained by simply cooling the foamed resin layer, so that the line speed can be markedly increased and the manufacturing cost can be reduced.

As the polyester elastomer constituting the non-porous layer (B), for example, a hard segment made of crystalline aromatic polyester, an aliphatic polyether, an aliphatic polyester, an aliphatic polycarbonate,
Examples thereof include block copolymers composed of at least one soft segment selected from aliphatic polyester polycarbonate and the like.

The crystalline aromatic polyester segment constituting the polyester elastomer is, for example,
Segments of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and the like can be mentioned, and of these, the segment of polybutylene terephthalate is preferable.

Examples of the aliphatic polyether segment constituting the polyester elastomer include segments such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, segments of polypropylene glycol and polytetramethylene glycol are included. Is preferred.

The aliphatic polyester segment constituting the polyester elastomer is, for example, a segment derived from a lactone such as ε-caprolactone, β-methyl-δ-valerolactone; glutaric acid, adipic acid, pimelic acid, suberic acid, Dicarboxylic acid components such as azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, orthophthalic acid and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1 , 5-
Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,
8-octanediol, 1,9-nonanediol, 1,
10-decanediol, cyclohexanedimethanol,
Mention may be made of segments derived from diol components such as cyclohexanediol. Among these, it is preferable to use adipic acid, azelaic acid, and sebacic acid as the dicarboxylic acid component, and 1,6-hexanediol and 3-methyl-1,5-as the diol component.
Pentanediol, 2-methyl-1,8-octanediol and 1,9-nonanediol are preferably used.
Further, if necessary, a tribasic or more polybasic acid such as trimellitic acid or pyromellitic acid, trimethylolethane, trimethylolpropane, glycerin, 1,2,6
A small amount of polyhydric alcohol such as hexanetriol and pentaerythritol may be used together.

Examples of the aliphatic polycarbonate segment constituting the polyester elastomer include the diol component described as the constituent unit of the above aliphatic polyester segment, a dialkyl carbonate such as dimethyl carbonate and diethyl carbonate, an alkylene carbonate such as ethylene carbonate, and the like. Mention may be made of segments derived from carbonate compounds such as diaryl carbonates such as diphenyl carbonate.

As the aliphatic polyester polycarbonate segment constituting the polyester elastomer,
For example, a segment obtained by simultaneously reacting the above diol component, dicarboxylic acid component and carbonate compound; obtained by reacting the aliphatic polyester and aliphatic polycarbonate previously produced by the above method with the above carbonate compound A segment obtained by reacting the aliphatic polyester and the aliphatic polycarbonate previously produced by the above method with the above-mentioned diol component and dicarboxylic acid component.

The polyester elastomer constituting the non-porous layer (B) has a JIS-A hardness of 70 to 98, 7
It is preferably 5 to 90. When a polyester elastomer having a JIS-A hardness of less than 70 is used, surface properties such as abrasion resistance of the obtained laminate are deteriorated. Further, since the releasability from the shaping roll is poor, the surface of the non-porous layer (B) cannot be embossed at a high speed, and after the embossing, a so-called grain flow in which the corners of the convex portions flow easily occurs. . On the other hand, when a polyester elastomer having a JIS-A hardness of more than 98 is used, the non-porous layer (B) becomes stiff, and the soft feel of the resulting laminate is impaired.

The intrinsic viscosity of the polyester elastomer is
When dissolved in phenol / tetrachloroethane and measured at 30 ° C., it is preferably 1.0 dl / g or more, more preferably 1.2 dl / g or more.
It is more preferably 4 dl / g or more. By using a polyester elastomer having an intrinsic viscosity of 1.0 dl / g or more, a laminate having more excellent surface properties such as abrasion resistance can be obtained.

The non-porous layer (B) can be formed by, for example, adding the above-mentioned polyester elastomer to a colorant, antioxidant, stabilizer, plasticizer, lubricant, filler, antistatic agent, if necessary. , An additive such as a pigment, and melt-kneaded under heating and pressurization with an extruder, and then extruded in a molten state into a film form from a T-die to have a fibrous base layer while having fluidity. A method of forming the non-porous layer (B) on the surface of (A) [or the surface of the porous layer (C)], that is, a so-called melt film forming method can be used. Although the thickness of the non-porous layer (B) varies depending on the type and performance of the polyester elastomer, it generally has a leather-like texture and has a surface strength,
5 because of excellent physical properties such as adhesion strength and flexibility
The thickness is preferably 400 μm, more preferably 10 to 200 μm. If the thickness of the non-porous layer (B) is too thin, surface properties such as abrasion resistance of the resulting laminate tend to be deteriorated. Further, if the thickness of the non-porous layer (B) is too thick, the flexibility of the obtained laminate may be deteriorated or the rubber-like texture may be obtained, and the leather-like texture may be impaired. It is necessary that the non-porous layer (B) does not contain bubbles. In the case of containing bubbles, the abrasion resistance, strength, smoothness, color spots and the like of the surface are inferior and the object of the present invention cannot be obtained.

As a method for pressing and adhering the polyester elastomer melt-extruded in the form of a film onto the surface of the fibrous substrate layer (A) [or the surface of the porous layer (C)], for example, a polyester elastomer is previously prepared. Surface of fibrous base layer (A) [or porous layer (C)
Surface), after being melted and extruded, a method of pressing through between a roll and a back roll facing the roll,
After melt-extruding the polyester elastomer onto a roll, a fibrous substrate [or a laminate composed of the fibrous substrate layer (A) and the porous layer (C)] is supplied between the roll and the back roll facing the roll. And pressing, between the fibrous substrate layer (A) [or the porous layer (C)] and the roll,
A method of directly melt-extruding the polyester elastomer and pressing it with an opposing back roll can be mentioned. However, if the polyester elastomer has fluidity at the time of pressing, there is a particularly large difference in any method. Absent.

As a method for forming a concavo-convex pattern or a mirror pattern on the surface of the non-porous layer (B), for example, a polyester elastomer melt-extruded in the form of a film can be made into a fibrous material while it has fluidity. By pressing the surface of the base layer (A) [or the surface of the porous layer (C)] with a shaping roll, the surface of the fibrous base layer (A) [or the porous layer (C)]
The surface of the non-porous layer (B) is adhered to the surface of the non-porous layer (B) at the same time as the uneven surface pattern or the mirror surface pattern is formed. In addition to having the fibrous base layer (A)
Of the non-porous layer (B) on the surface of the fibrous substrate layer (A) [or the surface of the porous layer (C)] by pressing the surface [or the surface of the porous layer (C)] with a pressing roll. And the like, after the polyester elastomer has fluidity, a method of forming a concavo-convex pattern or a mirror-like pattern on the surface of the non-porous layer (B) with a shaping roll can be mentioned. However, it is not particularly limited. From the viewpoint of increasing the production rate, a method of simultaneously performing adhesion and shaping using a shaping roll is preferable.

The optimum pressure at which to press the membrane in melt-extruded polyester elastomer, generally, a guide range gauge pressure of 5~15kg / cm ^2, the shaping of the layers of surface adhesion strong All you have to do is satisfy.

When imprinting on the surface of the non-porous layer (B),
It is preferable to peel the laminate from the shaping roll after the temperature of the non-porous layer (B) is substantially lowered and the fluidity is lost. When the laminate is peeled from the shaping roll while the non-porous layer (B) is still fluid, the uneven pattern or the mirror-like pattern collapses and a so-called grain flow occurs, resulting in a sharp uneven pattern or an extremely smooth pattern. It is difficult to obtain a mirror pattern.
For this reason, it is desirable to cool the vicinity of the peeling point of the shaping roll by circulating a cooling liquid inside the shaping roll or forcibly blowing cold air.

The above-mentioned imprinting roll is an embossing roll having a mirror surface or an embossing pattern of concavo-convex pattern on the roll surface, and may be a combination of a releasable embossing sheet and a normal roll. When using an embossing roll, it is preferable in that a desired deep unevenness can be easily imparted, and when using an embossing sheet, it is preferable in that an arbitrary embossing pattern can be easily selected only by replacing the embossing sheet. . When a mirror-shaped imprinting roll is used, an enamel-like synthetic leather is obtained, but in some cases, an embossed embossing may be applied to the enamel-like surface.

In the case of an embossing roll, a metal roll is usually used as the roll material. The back roll may be either a metal roll or an elastic roll, but it is preferable to use the elastic roll from the viewpoint of stability of pressing.

The laminate of the present invention may have a surface finishing agent or a coloring agent, if necessary, in order to further improve the abrasion resistance and stain resistance of the surface of the laminate, or to impart a deeper color tone. An agent or the like may be applied to the surface of the non-porous layer (B).

According to the present invention, since the surface layer [non-porous layer (B)] is made of a polyester elastomer having a specific hardness, the surface layer has a deep texture similar to the pore-like texture of natural leather and is chemically resistant. It is possible to produce a laminate having excellent properties at high speed, and it is possible to produce a leather-like laminate having a significantly lower production cost than the conventional production method. Furthermore, since the laminate (II) of the present invention has the porous layer (C) between the fibrous base layer (A) and the non-porous layer (B), the laminate (II) can be particularly stretched or pulled. In addition, when bent or bent, a cheesy uneven pattern does not occur on the surface, and it has a high-class feeling that cannot be obtained by the conventional method.

The laminate of the present invention may be used, for example, in shoes, boots,
It can be usefully used as a substitute material for natural leather products such as belts, coats, blazers, skirts, bags, camera cases and wallets. In particular, since it has excellent chemical resistance, it is extremely useful as a material for applications in which it may come into contact with chemicals and the like, for example, shoes worn at medical sites, chemical manufacturing sites, and the like.

[0038]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, wear resistance, peel strength and chemical resistance were evaluated by the following methods.

[Abrasion resistance] JIS L1096 6. Using a Taber type rotary dresser (with dust suction unit) device.
According to 17.3, the amount of wear reduction on the surface of the non-porous layer (B) was measured.

[Peeling Strength] The non-porous layer (B) of the laminate was adhered to a support, allowed to stand in a standard state for 24 hours, and then peeled by 180 degrees.

[Chemical resistance] N, N-dimethylformamide or acetone was applied to the surface of the non-porous layer (B) of the laminate using absorbent cotton, and the embossed pattern on the surface was observed after 30 minutes.

Reference Example 1 [Polyester elastomer (T
Production of PEE (1)] Dimethyl terephthalate, 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of 2000, and tetrabutyl titanate as a catalyst are charged in a reactor, and transesterification reaction and then polycondensation reaction are carried out. As a result, JIS-A hardness of 88, intrinsic viscosity of 1.02 dl / g
A polyester elastomer (hereinafter referred to as TPEE (1)) was obtained.

Reference Example 2 [Polyester elastomer (T
Production of PEE (2)]] Dimethyl terephthalate, 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of 2000 and tetrabutyl titanate as a catalyst are charged in a reactor, and transesterification reaction is carried out, followed by polycondensation reaction. As a result, JIS-A hardness of 88, intrinsic viscosity of 1.65 dl / g
A polyester elastomer (hereinafter referred to as TPEE (2)) was obtained.

Reference Example 3 [Polyester elastomer (T
Production of PEE (3)]] Dimethyl terephthalate, 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of 2000, and tetrabutyl titanate as a catalyst are charged in a reactor, and transesterification reaction and then polycondensation reaction are carried out. As a result, JIS-A hardness of 67 and intrinsic viscosity of 1.20 dl / g
A polyester elastomer (hereinafter referred to as TPEE (3)) was obtained.

Reference Example 4 [Polyester elastomer (T
Production of PEE (4)]] Dimethyl terephthalate, 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of 2000, and tetrabutyl titanate as a catalyst are charged in a reactor, and transesterification reaction is carried out, followed by polycondensation reaction. By this, JIS-A hardness 99, intrinsic viscosity 0.90 dl / g
A polyester elastomer (hereinafter referred to as TPEE (4)) was obtained.

Reference Example 5 [Polyester polyol (TP
Production of EE (5)]] Aliphatic polyester having an intrinsic viscosity of 0.8 dl / g composed of 1,6-hexanediol unit and adipic acid unit and intrinsic viscosity of 0 composed of dimethyl terephthalate unit and 1,4-butanediol unit A crystalline aromatic polyester of 0.85 dl / g is melt-stirred at 250 ° C. under a reduced pressure of 1 mmHg or less to obtain a polyester elastomer having a JIS-A hardness of 87 and an intrinsic viscosity of 1.42 dl / g (hereinafter, TPEE ( 5) is obtained.

Reference Example 6 [Thermoplastic polyurethane (TPU
Production of (1))] Polyester diol having a number average molecular weight of 1497 and having hydroxyl groups at both ends, obtained by reacting 3-methyl-1,5-pentanediol and adipic acid, 4,4′-diphenylmethane diisocyanate and 1 , 4-butanediol was continuously supplied to a twin-screw extruder to carry out melt polymerization to obtain a thermoplastic polyurethane having a JIS-A hardness of 88 (hereinafter referred to as TPU (1)).

Example 1 An entangled nonwoven fabric made of polyester fiber having a fineness of 2.5 denier was impregnated with polyurethane as a binder. The thickness was 1.3 mm, the basis weight was 455 g / m ² , and the weight ratio of fiber to polyurethane was 1. An 8: 2 fibrous substrate was prepared. TP
Using a composition of 100 parts by weight of EE (1) and 5 parts by weight of black pigment pellets, a 25 mmφ extruder and a T-die (lip width 0.5 mm, die width 300 mm) were used.
The film was melt extruded into a film under the conditions of a melting zone temperature of 190 to 220 ° C and a die temperature of 200 ° C. The above fibrous substrate is passed between a metallic embossing roll having an uneven pattern of pores and grain on its surface and an elastic back roll, and the melt extruding material having fluidity between the fibrous substrate and the embossing roll. By supplying the product and cold-pressing with a gauge pressure of 10 kg / cm ² , a leather-like laminate having pores on the surface could be stably produced at a line speed of 30 m / min. The thickness of the non-porous layer of this laminate is 100 μm
Met. The peel strength was as high as 15 kg / 25 mm, and the amount of wear reduction was 14 mg. Regarding chemical resistance, neither N, N-dimethylformamide nor acetone was observed in the embossed pattern.

Example 2 Polyurethane as a binder was impregnated with an entangled non-woven fabric made of polyester fiber having a fineness of 2.5 denier, the thickness was 1.3 mm, the basis weight was 455 g / m ² , and the weight ratio of the fiber to the polyurethane was 1. An 8: 2 fibrous substrate was prepared. TP
Using a 25 mmφ extruder and a T-die (lip width 0.5 mm, die width 300 mm), a composition prepared by mixing 5 parts by weight of black pigment pellets with 100 parts by weight of EE (2) was used.
The film was melt extruded into a film under the conditions of a melting zone temperature of 190 to 220 ° C and a die temperature of 200 ° C. The above fibrous substrate is passed between a metallic embossing roll having an uneven pattern of pores and grain on its surface and an elastic back roll, and the melt extruding material having fluidity between the fibrous substrate and the embossing roll. By supplying the product and cold-pressing with a gauge pressure of 10 kg / cm ² , a leather-like laminate having pores on the surface could be stably produced at a line speed of 30 m / min. The thickness of the non-porous layer of this laminate is 100 μm
Met. The peel strength was as high as 17 kg / 25 mm, and the amount of wear reduction was 4 mg. Regarding chemical resistance, neither N, N-dimethylformamide nor acetone was observed in the embossed pattern.

Example 3 An entangled nonwoven fabric made of polyester fiber having a fineness of 2.5 denier was impregnated with polyurethane as a binder. The thickness was 1.3 mm, the basis weight was 455 g / m ² , and the weight ratio of the fiber to the polyurethane was 1. An 8: 2 fibrous substrate was prepared. TP
A composition in which 5 parts by weight of black pigment pellets and 1 part by weight of an azodicarbonamide-based foaming agent (“Viniihole AC- # 3” manufactured by Eiwa Chemical Industry Co., Ltd.) were mixed with 100 parts by weight of EE (1) were extruded at 25 mmφ. We put in machine and melt zone temperature 180-
195 ° C, die temperature 200 ° C, lip width 0.5 mm,
The film was melt-extruded into a film under the condition that the die width was 300 mm. The fibrous base material is passed between a metal roll and an elastic back roll, and the melted extrudate having fluidity is supplied between the fibrous base material and the metal roll to press the fibrous base material. A laminated body was obtained in which a foamed porous layer having a thickness of 100 μm was formed on the surface of the porous substrate layer. The content of bubbles in the porous layer was 64% by volume. Next, TPEE (2) 10
0 parts by weight of black pigment pellets was mixed with 5 parts by weight of the composition, and the same extruder and T-die (lip width 0.
5 mm, die width 300 mm) and melt zone temperature 19
The film was melt extruded into a film under the conditions of 0 to 220 ° C. and a die temperature of 200 ° C. A laminate comprising a fibrous base layer and a porous layer obtained by the above method is passed between a metallic embossing roll having an uneven pattern of pores and grain on the surface and an elastic back roll to form a laminate. The melted extrudate having fluidity is supplied between the embossing roll and the gauge pressure 10
By cold pressing at kg / cm ² , a porous layer having a thickness of 100 μm is provided on the surface of the fibrous substrate layer, and a non-porous layer having a thickness of 100 μm is further provided on the surface of the porous layer 3.
A laminate consisting of layers was obtained. This laminate could be stably manufactured at a line speed of 30 m / min. The resulting laminate has a deep texture similar to the pore-like texture of natural leather, and when pulled or bent, does not cause a cheesy concavo-convex pattern on the surface and has extremely good sensitivity.
It had a sense of quality. In particular, since it had a porous layer, it was excellent in embossable moldability and flexibility. The peel strength of the obtained laminate was as high as 10 kg / 25 mm, and the friction reduction amount was 4 mg. For chemical resistance, N,
No deformation or the like was observed in the embossed pattern for both N-dimethylformamide and acetone.

Example 4 A entangled nonwoven fabric made of polyester fiber having a fineness of 2.5 denier was impregnated with polyurethane as a binder. The thickness was 1.3 mm, the basis weight was 455 g / m ² , and the weight ratio of fiber to polyurethane was 5. An 8: 2 fibrous substrate was prepared. TP
A composition in which 5 parts by weight of black pigment pellets and 1 part by weight of an azodicarbonamide-based foaming agent (“Viniihole AC- # 3” manufactured by Eiwa Chemical Industry Co., Ltd.) were mixed with 100 parts by weight of EE (1) were extruded at 25 mmφ. We put in machine and melt zone temperature 180-
195 ° C, die temperature 200 ° C, lip width 0.5 mm,
The film was melt-extruded into a film under the condition that the die width was 300 mm. The fibrous base material is passed between a metal roll and an elastic back roll, and the melted extrudate having fluidity is supplied between the fibrous base material and the metal roll to press the fibrous base material. A laminated body was obtained in which a foamed porous layer having a thickness of 100 μm was formed on the surface of the porous substrate layer. The content of bubbles in the porous layer was 64% by volume. Next, TPEE (5) 10
0 parts by weight of black pigment pellets was mixed with 5 parts by weight of the composition, and the same extruder and T-die (lip width 0.
5 mm, die width 300 mm) and melt zone temperature 19
The film was melt extruded into a film under the conditions of 0 to 220 ° C. and a die temperature of 200 ° C. A laminate comprising a fibrous base layer and a porous layer obtained by the above method is passed between a metallic embossing roll having an uneven pattern of pores and grain on the surface and an elastic back roll to form a laminate. The melted extrudate having fluidity is supplied between the embossing roll and the gauge pressure 10
By cold pressing at kg / cm ² , a porous layer having a thickness of 100 μm is provided on the surface of the fibrous substrate layer, and a non-porous layer having a thickness of 100 μm is further provided on the surface of the porous layer 3.
A laminate consisting of layers was obtained. This laminate could be stably manufactured at a line speed of 30 m / min. The obtained laminate has a deep texture similar to the pore-like texture of natural leather, and when pulled or bent, does not cause a cheesy uneven pattern on the surface and has an extremely good sensitivity.
It had a sense of quality. In particular, since it had a porous layer, it was excellent in embossable moldability and flexibility. The peel strength of the obtained laminate was as high as 14 kg / 25 mm, and the friction reduction amount was 6 mg. For chemical resistance, N,
No deformation or the like was observed in the embossed pattern for both N-dimethylformamide and acetone.

Comparative Example 1 TPU was used instead of TPEE (1) which constitutes the non-porous layer.
A laminate was produced at a line speed of 30 m / min in the same manner as in Example 1 except that (1) was used. The thickness of the non-porous layer of the obtained laminate was 100 μm. The production rate was too high, the uneven pattern was not sufficiently imprinted on the surface of the non-porous layer, and a wrinkled flow occurred at the corners of the convex portion. In addition, the unity feeling of the laminated body was poor and it became a hard texture. The peel strength of the obtained laminate was 1 kg / 25 mm, and the wear reduction amount was 49.
mg. Regarding chemical resistance, in the case of N, N-dimethylformamide, disappearance of the embossed pattern accompanied by remarkable deformation was observed, and also in the case of acetone, the embossed pattern collapsed.

Comparative Example 2 TPEE (1) was used instead of TPEE (1) which constitutes the non-porous layer.
A laminate was produced at a line speed of 30 m / min in the same manner as in Example 1 except that (4) was used. The thickness of the non-porous layer of the obtained laminate was 100 μm. The production rate was too high, the uneven pattern was not sufficiently imprinted on the surface of the non-porous layer, and a wrinkled flow occurred at the corners of the convex portion. In addition, the unity feeling of the laminated body was poor and it became a hard texture. The peel strength of the obtained laminate was 4 kg / 25 mm, and the wear reduction amount was 14
mg. Regarding chemical resistance, neither N, N-dimethylformamide nor acetone was observed in the embossed pattern.

Comparative Example 3 TPEE (2) was used instead of TPEE (2) which constitutes the non-porous layer.
A laminate was produced at a line speed of 30 m / min in the same manner as in Example 3 except that (4) was used. The thickness of the porous layer of the obtained laminate was 100 μm, the bubble content was 62% by volume, and the thickness of the non-porous layer was 100 μm. The surface of the laminate became too hard, resulting in a dry touch and poor texture. The peel strength of the obtained laminate is 2 kg / 2.
The amount of abrasion was 5 mm and the amount of wear reduction was 17 mg. Regarding chemical resistance, neither N, N-dimethylformamide nor acetone was observed in the embossed pattern.

Comparative Example 4 TPEE (2) was used instead of TPEE (2) which constitutes the non-porous layer.
A laminate was produced at a line speed of 30 m / min in the same manner as in Example 1 except that (3) was used. The thickness of the non-porous layer of the obtained laminate was 100 μm. The production rate was too high, the uneven pattern was not sufficiently imprinted on the surface of the non-porous layer, and a wrinkled flow occurred at the corners of the convex portion. In addition, the unity feeling of the laminated body was poor and it became a hard texture. The peel strength of the obtained laminate was 2.9 kg / 25 mm, and the abrasion reduction amount was 50 mg. Regarding chemical resistance, the embossed pattern collapsed for both N, N-dimethylformamide and acetone.

[0056]

EFFECTS OF THE INVENTION The laminate of the present invention is excellent in chemical resistance, abrasion resistance, peeling strength between layers, etc., and when stretched or bent, a cheesy uneven pattern does not appear on the surface, It is a leather-like laminate with a silver surface layer. Further, according to the production method of the present invention, it is not necessary to use an organic solvent as in the prior art, and it is possible to produce a laminate having the above characteristics at high speed under a good working environment.

[Brief description of drawings]

FIG. 1 is a typical process diagram by which a laminate (II) of the present invention can be manufactured.

[Explanation of symbols]

 1 Fibrous Substrate Layer (A) 2 Molten Thermoplastic Elastomer for Porous Layer (C) 3 Porous Layer (C) 4 Molten Polyester Elastomer for Nonporous Layer (B) 5 Nonporous Layer (B) 6 Shaped roll 7 Back roll

Claims (4)

[Claims] 1. The surface of the fibrous base layer (A) is provided with JIS-
A laminate having a non-porous layer (B) made of a polyester elastomer having an A hardness of 70 to 98, and having an uneven pattern or a mirror pattern on the surface of the non-porous layer (B). 2. A fibrous substrate layer (A) having on its surface a porous layer (C) made of a thermoplastic elastomer and containing cells, and further having a JIS-A hardness of 70 to 98 polyester elastomer. Which has a non-porous layer (B), and in which the surface of the non-porous layer (B) has an uneven pattern or a mirror-like pattern. 3. (i) JIS extruded in a film form
-A polyester elastomer having a hardness of 70 to 98,
The non-porous layer (B) is formed on the surface of the fibrous base layer (A) by pressing and adhering it to the surface of the fibrous base layer (A) while having fluidity, and (ii) ) A method for producing a laminate in which the surface of the non-porous layer (B) is embossed to form an uneven pattern or a mirror pattern while the polyester elastomer has fluidity. 4. (i) A thermoplastic elastomer containing bubbles or bubble-generating substances melt-extruded in a film form,
A porous layer (C) is formed on the surface of the fibrous substrate layer (A) by pressing and adhering it to the surface of the fibrous substrate layer (A) while having fluidity. In the porous layer (C), a polyester elastomer having a JIS-A hardness of 70 to 98 melt-extruded in the form of a film is pressed against the surface of the porous layer (C) so that it has fluidity and is adhered to the porous layer. The non-porous layer (B) is formed on the surface of (C), and (iii) the surface of the non-porous layer (B) is embossed while the polyester elastomer has fluidity. A method for producing a laminate for forming a pattern or a mirror pattern.