JPS59228088A - Leather-like sheet similar to shoe upper and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a leather-like sheet material suitable for use as a shoe cover. More specifically, when producing artificial leather shoes by integrally molding an outsole onto a cover made of a leather-like sheet material by an injection molding method, it is possible to obtain an artificial leather shoe with excellent adhesion strength to the outsole. Regarding sheet products.

Conventionally, a base layer is a sheet material made of a fiber aggregate such as a nonwoven fabric, a woven fabric, or a knitted fabric impregnated with an elastic polymer such as a polyurethane elastomer, and a porous covering layer made of a polymer mainly composed of a polyurethane elastomer is used as a base layer. If necessary, a non-porous surface coating layer is provided on top of the leather, as its texture, appearance, etc. are similar to natural leather.
It is widely used as a substitute for natural leather.

One field of application of natural leather is shoe coverings, and the above-mentioned leather-like sheet products are also used in these fields.

Conventionally, as a method of manufacturing artificial leather shoes, a method has generally been used in which a shoe cover made from a leather-like sheet material and a pre-formed outsole are bonded together with an adhesive. However, this method requires personnel to apply the adhesive and requires a large number of steps, and furthermore, this method has disadvantages that cannot be overlooked unless the adhesive force between the shoe cover and the outsole is sufficient.

Instead of this method, recently, an adhesive such as acrylonitrile butadiene adhesive, methyl methacrylate, or type polyurethane is applied to the bottom of a cover made from a leather-like sheet material. The outsole is injection molded by injecting a molding material such as polyvinyl chloride into the molding space formed by the male and female molds. Compared to the above-mentioned method, this method has the advantages of being able to streamline the process and save labor because the outsole can be integrally molded, and the adhesive force between the outsole and the cover is strong. However, it still requires a process and personnel to apply the adhesive, and there are cases where shoes do not have sufficient adhesion due to unevenness of the adhesive. 1] is not constant, so the adhesive protrudes from the side of the shoe after molding, resulting in a disadvantage in that the appearance is greatly impaired.

If an integrally molded shoe in which the hem and the outsole are immediately and firmly bonded can be obtained by injection molding without applying adhesive to the bottom of the hem in advance, the conventional method has This will eliminate all shortcomings. However, even with a leather-like sheet material that enables such a simple shoe-making method, its texture, folding wrinkles, and bending resistance are affected by various surface finishes added before molding. Such leather-like sheets, if severely damaged by the process,
It is not satisfactory as a material for clothing.

The object of the present invention is to provide a leather-like sheet material that can firmly adhere to the underwater bottom by injection molding without applying an adhesive to its surface, and which has a texture and folding wrinkles similar to natural leather. It is an object of the present invention to provide a leather-like sheet material which also has excellent bending resistance.

This purpose consists of a fibrous base layer (1) and a porous coating layer (1) made of a polymer mainly composed of polyurethane
II), a non-porous coating layer (II) consisting of a polymer mainly composed of polyurethane efstomer having a softening temperature of 160°C or higher, and a polymeric diol and an aliphatic or fatty material. A leather-like sheet material in which a non-porous surface layer (g) consisting of a polymer mainly composed of a polyurethane elastomer synthesized from a cyclic diisocyanate and an organic diamine is sequentially laminated, the coating layer (1) An uneven pattern is given to the surface of 9.
, and the thickness of the surface layer (5) is either thick in the four parts and thin in the convex parts, or thin in the four parts and thick in the convex parts, according to the uneven pattern of the coating layer (1). This is achieved by producing a leather-like sheet material with the following characteristics.

In addition, such a leather-like sheet material has a fibrous base layer (1
) and a porous coating layer (II) mainly made of a polymer mainly composed of polyurethane elastomer. A porous coating m□□□) is applied, and then an uneven pattern is applied to the surface by embossing treatment, and then a polyurethane efstomer synthesized mainly from an older polymer diol, an aliphatic or alicyclic diisocyanate, and an organic diamine. A solution or dispersion of a polymer mainly composed of
It is obtained by applying the coating to a thickness such that the four parts are thick and the convex parts are thin, or the four parts are thin and the convex parts are thick, according to the uneven pattern of [), and drying.

Next, the leather-like sheet material of the present invention and its manufacturing method will be explained in detail.

First, the fibrous base layer (1) constituting the leather-like sheet material of the present invention is composed of a fiber aggregate, or a fiber aggregate and an elastic polymer impregnated therein.

A fiber aggregate is a fiber formed into a nonwoven fabric, woven fabric, knitted fabric, or the like. In particular, nonwoven fabrics obtained by entangling multi-fiber webs by needle punching, high-pressure water jets, etc. are preferred because they provide a natural leather-like feel. The fibers used in this fiber assembly include ordinary fibers, such as natural fibers such as cotton, hemp, and wool, recycled or semi-synthetic fibers such as rayon and acetate, and fibers such as nylon, polyester, polyacrylonitrile, vinylon, and polyolefin. Examples include synthetic fibers. In the case of synthetic fibers, not only single spun fibers but also mixed spun fibers (including composite spun fibers) may be used. When mixed spun fibers are used, at least one polymer from among the plurality of polymers constituting the fibers is extracted and removed at any stage of producing the leather-like sheet material, or It is preferable to convert the fibers into a bundle of ultrafine fibers or a porous array fiber having a large number of hollow parts inside by employing a method of dividing the fibers into each component. By extraction and removal or division treatment, the fibrous base layer (1) becomes supple, and the leather-like sheet material having such a base layer also has a supple and luxurious feel. Specifically, for example, a method in which polystyrene is extracted and removed with toluene from a spun fiber mixture obtained from nylon and polystyrene or polypropylene and polystyrene, a spun fiber mixture obtained from polyethylene terephthalate and polyethylene, or nylon and polyethylene. A method of extracting and removing polyethylene with toluene to obtain polyethylene terephthalate and nylon.

Benzyl alcohol/I/
Alternatively, there is a method of extracting and removing calcium chloride-containing methanol/L/methane. The thickness of the fibers constituting the fibrous base layer (1) is suitably from 0.0005 to 10 deniers, particularly preferably from o, ooi to 2.0 deniers.

Furthermore, the fibers do not all have to have a uniform thickness, and fibers of different thicknesses or fibers of different cross-sectional shapes may be mixed.

The inside of the fiber aggregate may be impregnated with an elastic polymer, but any elastic polymer used in general synthetic leather or artificial leather can be used as the elastic polymer to be impregnated inside. , such as natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer,
Examples include methyl methacrylate-butadiene copolymer, polyvinyl chloride, polyurethane, synthetic rubbers thereof, and mixtures thereof. When these elastic polymers are impregnated into fiber aggregates, they may be in the form of an emulsion or a solution. In addition, in order to appropriately reduce the rebound elasticity of the leather-like sheet material and give it a texture similar to natural leather, the elastic polymer contained in the fiber aggregate must be in a porous state. is preferable. As a method for making an elastic polymer porous, for example, a fiber aggregate is impregnated with a solution of the elastic polymer, and then the polymer is wet-coagulated, that is, it has an affinity with the solvent, but the polymer A typical example is a method in which the aggregate is immersed in a liquid that has no affinity with the polymer to solidify the polymer.

The amount of impregnated elastomeric polymer is usually 250 weight or less, particularly preferably within the range of 30 to 200 weight, based on the fiber aggregate. The thickness of the base layer is 0.3 to 5 ml.
The density is preferably within the range of 0.2 to 0.8 Q/c.
A range of d is preferred.

In the present invention, a porous coating layer (1) made of a polymer mainly composed of polyurethane elastomer is formed on one side of the fibrous base layer. This coating layer (1) corresponds to the silver surface of natural leather.

The polymer mainly composed of polyurethane efstomer constituting the coating layer (II) refers to the polyurethane efstomer itself or a mixture of this and a curved polymer.

Preferred representative examples of the polyurethane elastomer used here include one or more polymeric diols such as polyester diol, polyether diol, polyester/ether di-ρ, and organic polyisocyanate, preferably aromatic or So-called hard segment blocks and soft segment blocks that are mainly polymerized from one or more alicyclic organic diisocyanates and a chain extender having two active hydrogen atoms such as low-molecular diols, low-molecular diamines, and hydrazine. Polyurethane consisting of: Among them, the weight percentage of nitrogen atoms constituting the isocyanate groups in the organic polyisocyanate used to synthesize the polyurethane efstomer, based on the total weight of the polyurethane efstomer (
A polyurethane efstomer having a content of 3 to 7% (hereinafter referred to as N%) or a polymer mixture mainly composed of this polyurethane efstomer is preferred. If N% is less than 3%, the resulting coating layer (1) will not have the desired porous structure, resulting in poor appearance, texture, folding wrinkles, etc., and if N% is less than 7%. If it exceeds 100%, the resulting coating layer (1) will not be hard and will also have poor texture, folding wrinkles, bending resistance, etc.

Polymers that can be used in combination with these polyurethane elastomers include polyvinyl chloride, natural or synthetic rubber, polyvinyl acetate, cellulose derivatives, poly7-crylonitrile, and the like. Further, the coating layer (1) K may contain fillers, softeners, stabilizers, colorants, antistatic agents, etc., as necessary. The special base layer (1) has irregularities and embossments (@ solid spots) due to the density unevenness of the fibers.
In order to hide these spots, it is preferable that a coloring agent such as a pigment or dye be mixed in the coating layer (1).

In the present invention, the thickness of the coating layer (I) is 10 to 1000
It is preferably within the range of μ. If the thickness of the coating layer (II) exceeds the above range, the resulting leather-like sheet material will not have a rubber-like texture; If the unevenness and embossment of the substrate layer (1) are not sufficiently hidden, the resulting leather-like sheet product will give the impression of being a cheap imitation.

The coating layer (1) can be formed by applying a solution of a polymer mainly composed of polyurethane elastomer directly onto the base layer and wet-coagulating it, or by coating a sheet of another polymer material, a metal bell) or It is obtained by applying a solution of a polymer mainly composed of polyurethane elastomer to the surface of a glass plate, wet-coagulating it to produce a film, and pasting this onto the substrate W(1).

Such a fibrous base layer (1) and a porous covering layer (I
The above-mentioned special non-porous coating layer (i) and non-porous surface layer (g) are sequentially laminated on the surface of the leather-like sheet material consisting of t). (I
If necessary, a non-porous layer may be inserted between t) and the coating layer. For example, a non-porous layer consisting of a polymer mainly composed of polyurethane extomer and a colorant is used as a coating layer (to form the gap of the cotton coating layer (1), and the coating layer (i) is mainly composed of polyurethane extomer. If a transparent layer made of a polymer containing substantially no colorant and having a softening temperature of 160°C or higher or a matte layer containing a matting agent such as silicon oxide or polyethylene wax is used, a leather-like sheet can be obtained. The adhesive strength between the object and the outsole is further increased.

In addition, a non-porous layer consisting of a pigment and a polymer mainly composed of polyurethane efstomer is provided between the coating layer (1) and the coating M (1), and a coating layer ai> is formed on the non-porous layer of a polyurethane efstomer. By providing a non-porous layer mainly composed of a polymer and a dye and having a softening point of 160°C or higher, a leather-like sheet material having a deep and vivid color can be obtained.

A fibrous base layer (1), a porous coating layer (It) consisting of a polymer mainly composed of polyurethane efstomer, and a non-porous coating layer provided thereon as necessary on the surface of a leather-like sheet product. A non-porous coating layer made of a polymer mainly composed of polyurethane efstomer having a softening temperature of 160° C. or higher is laminated thereon. Moreover, the non-porous coating layer (1
) must be given a rough pattern by embossing.

The polyurethane elastomer used for the coating layer (II) must have a softening temperature of 160°C or higher. Polyurethane fstomers having such a softening temperature are made of polymeric diols such as Id, rk: sx-ter diol, polyester diol, polyether p-ester diol, organic diisocyanate, and two active hydrogen atoms. A low molecular weight compound having the above-mentioned N%
It is synthesized by reacting the raw materials at a fixed molar ratio so that the
There is also a method of using an aromatic type material as a raw material for the polyurethane efstomer described in lfh.

In addition, the softening temperature referred to in the present invention refers to the softening temperature when the target polymer is sandwiched between a sulfide glass and a cover glass and the temperature is raised using Micro Melting Point Measurement M (manufactured by Yanagimoto Seisakusho), and when the top of the cover glass is pressed. It means the temperature at which the liquid becomes fluid and spreads. Softening temperature is 160°C
If it is less than 1, the coating layer (ill) may have adhered to the embossing roll during embossing, or the coating layer (if) may have peeled off from the leather-like sheet material, resulting in a desired uneven pattern. The drawback is that the appearance, such as smoothness and gloss, is significantly impaired. In the present invention, aromatic diisocyanates, diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate, and xylylene diisocyanate are used as organic diisocyanates, and fullylene glycols such as ethylene glycol, propylene glycol, and butylene glycol are used as chain extenders. When a polyurethane efstomer synthesized using polyurethane having a softening temperature of 160° C. or higher is used for the coating layer 1), embossing can be carried out smoothly and the appearance is good.

In the taE layer □□□), polymers that can be used in combination with polyurethane efstomer include polyvinyl chloride, natural or synthetic rubber, polyvinyl acetate, cellulose derivatives, polyacrylonitrile, etc., but in particular polymers with a softening temperature of 160 ° C Resins having the above properties are preferred. In addition, the coating layer (
Fillers, colorants, stabilizers, antistatic agents, matting agents, etc. may be added to 1) as necessary. The thickness of the non-porous coating layer (Ill) is usually preferably in the range of 1 to 20 .mu.m from the viewpoint of texture and folding wrinkles. Non-porous coating layer (l
It) can be obtained by applying a polymer solution or dispersion by gravure coating, spray coating, etc. and then drying it. Dimethylformamide, isoglopanol, etc. are used as the solvent.

In the present invention, the surface of the non-porous coating layer (1) has been given an uneven pattern by embossing.
The uneven pattern imparted to the surface of the non-porous coating layer (If) has a difference in crystallinity between the four parts and the convex parts of 10 to 1000 μ, and there are approximately 10 to 1000 convex parts. Preferably something that looks like this. Of course, it is preferable that the uneven pattern has a natural leather-like pattern as a whole, such as a kid pattern, a kinpi pattern, a diamond skin pattern, a beracari pattern, or the like.

A commonly used embossing method can be employed as a specific method for imparting an embossed pattern to the surface of the non-porous coating layer (1). Examples include a method in which the coating layer portion of the leather-like sheet material is heated in advance and pressed against an embossing roll, or a method in which the leather-like sheet material is pressed against a heated embossing roll. At this time, the non-porous f&coating layer (II) contains a solvent, and the embossing heating may be performed to form the embossed pattern and remove the solvent by evaporation at the same time.

A non-porous coating layer is applied to the surface of the leather-like sheet material provided with such an embossed pattern. Moreover,
The thickness of the surface layer (lv) must be either thick in the concave parts and thin in the convex parts, or thin in the four parts and thick in the convex parts, according to the uneven pattern on the surface of the covering layer (lll).

To explain this state with the attached drawings, in the drawing, 1 is a fibrous base layer (1), 2 is a porous covering layer (1), 3 is a non-porous layer *#l]ll), and 4 is a non-porous layer. The surface layer (g) is
Reference numeral 5 indicates a concave portion with an embossed pattern provided on the non-porous coating layer (III), and 6 indicates a convex portion.

Figure 1 shows the case where the non-porous surface layer is applied so that the concave parts are thicker and the convex parts are thinner according to the uneven pattern of the non-porous coating layer. This is a case where the convex portion is thin and the convex portion is thick. In the present invention, the surface layer (g) may be either the one shown in FIG. 1 or the one shown in FIG. 2, and the object of the invention can be achieved in either case.

When obtaining a leather-like sheet material, it is a common practice to emboss the surface of the material to give it an uneven pattern similar to natural leather. It is not common practice to apply a resin to the surface of a similar sheet. This is because, if a resin is applied to an embossed surface, the embossed pattern that has been applied will be hidden by the resin, or the surface color and luster will disappear, reducing the effectiveness of the embossing process by half. The present invention has surprisingly improved the texture and texture of leather-like sheet materials by employing a method that has not been generally used in the past, that is, a method of applying a resin layer to the surface after embossing. We have discovered that it is possible to obtain a leather-like sheet material that can firmly adhere to the underwater bottom without wrinkles or loss of flexibility, without applying an adhesive when injection molding the underwater bottom. be. Folding wrinkles refer to surface wrinkles that occur when a leather-like sheet material is folded with the surface layer inside. Items with numerous fine, shallow wrinkles are high-quality natural leather. Leather-like sheet materials are good because they are similar to , but on the other hand, leather-like sheets with large, deep wrinkles have bad folding wrinkles.

The thickness of the surface layer (G) differs between the concave and convex portions as described above, and the thickness is 1 to 20 μm at the thicker portions.
The thickness of the thinner portion is preferably 90% or less of the thickness of the thicker portion, particularly preferably in the range of 10 to 70%. If the surface V (IV) has no thickness difference between the convex part and the four parts, or even if it has a thickness difference, the thickness difference does not follow the uneven pattern of the coating N pieces). If the thickness is uneven, the texture and folding wrinkles of the leather-like sheet material will be impaired, and the bending resistance and adhesive strength with the outsole will also deteriorate.

As a method for forming the surface layer (IV) having such a special morphology, for example, a polymer solution is applied to the surface of a leather-like sheet material having an uneven pattern, or to the surface of a gravure roll having a regular mesh. One method is to thoroughly drain the liquid with a doctor knife and then apply gravure coating with light printing pressure. When this method is used, a surface layer is formed which is thin in four parts and thick in convex parts. When gravure is applied without draining the surface of a gravure roll or when it is applied by a spray method, a surface layer (■) is formed that is thick in the four parts and thin in the convex parts. It happens.

Further, the resin constituting the surface layer GV) must be a polymer mainly composed of a polyurethane efstomer synthesized from a polymeric diol, an aliphatic or alicyclic diisocyanate, and an organic diamine. Examples of polymeric diols include commonly used polyester glycols, polyether glycols, polyether/ester glycols, etc. Among them, alkanediols having 4 or more carbon atoms and aliphatic dicarboxylic acids are commonly used. Polyester glycol or polycaprolactone glycol is preferred. Examples of alkanediols having 4 or more carbon atoms include glycols in which the alkylene group has 4 or more carbon atoms, such as 1,4-butanediol, hexamethylene glycol, and octamethylene glycol; and examples of aliphatic dicarboxylic acids include adipine Examples include acids and sebacic acid. Examples of aliphatic diisocyanates include ethylene diisocyanate, tetofumethylene diisocyanate, hexamethylene diisocyanate, and examples of alicyclic diisocyanates include cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4+4'-diisocyanate,
Examples include dicyclohexyldimethylmen-4T4'-diisocyanate. As organic cyamine, p
-Phenylenediamine, metaphenylenediamine, tolylenediamine, 4.4'-diaminodiphenylmethane, ethylenediamine, propylenediamine, isophoronediamine, cyclohexylenediamine, 4.4'-diaminodicyclohexylmethane, 4.4'-diamino-3
+6'-dimethyldicyclohexylmethane and the like.

The polyurethane fstomer forming the surface layer (5) is synthesized from the above-mentioned compounds, but the diisocyanate base material and chain extender used in this polyurethane fstomer are all aliphatic. Alternatively, it is not necessary to use alicyclic diisocyanate and organic diamine, and other diisocyanate compounds and chain extenders can be used in small amounts. In addition, the softening temperature of the polyurethane efstomer constituting the surface layer Ov) is 80~
Preferably, the temperature is within the range of 160°C. The softening temperature of the polyurethane efstomer can be freely changed, for example, by changing the N% of the polyurethane efstomer. That is, if the N% is increased, a polyurethane FST marker with a high softening temperature can be obtained. If the softening temperature of the polyurethane efstomer constituting the surface layer is 160°C or higher, the adhesive strength with the outsole may be insufficient.
On the other hand, if the temperature is below 80°C, it will cause problems during shoe making or wearing.

In addition, the first surface layer (IV) K is made of polyurethane elastomer, if necessary, polyurethane FSTMER other than the above-mentioned polyurethane FSTMER, polyvinyl chloride, polyvinyl acetate, polyvinyl formal, methacrylic acid resin, etc. May contain a small amount. Furthermore, it may contain additives, various stabilizers, colorants, etc. that do not significantly impair the adhesive strength between the outsole and the leather-like sheet material.

The leather-like sheet material of the present invention has the structure as detailed above, and such a leather-like sheet material is cut into the shape of a cover and sewn so that the surface layer (T) is on the outside. In particular, you will receive υ胛cover. Such a cover can be directly subjected to the injection molding process of the outsole without applying an adhesive. Injection molding is carried out by putting this cover on a male mold and combining it with a female mold to fill the void for molding the outsole with a molten resin, preferably polyurethane, butadiene fuvar, polyvinyl chloride, or vinyl chloride. ) The process is completed by injecting any of the copolymers mainly composed of v and cooling.

Through this molding process, a shoe in which the cover and the outsole are integrated is obtained. The artificial leather shoes thus obtained have a beautiful appearance because no adhesive is used, and the bond between the shoe cover and the outsole is extremely strong. Furthermore, the texture, folding wrinkles, bending fatigue resistance, etc. of the leather-like sheet material are not impaired in any way, and the obtained artificial leather shoes have an extremely high-class feel.

Hereinafter, the present invention will be specifically explained with reference to Examples.

All percentages in the examples are based on weight.

Example 1 Polyethylene adipate glycol, ethylene glycol and diphenylmethane-4,4'-
15% polyurethane elastomer with N% 4.2% consisting of diisocyanate, 0.4% titanium oxide, 10.5% stearyl alcohol/L and 8% dimethylformamide
A water-dimethylformamide mixture containing 40% dimethylformamide at 45°C is impregnated with a polymer solution consisting of 4.3% and coated on top of the polymer solution at a solid content of 10 o y/rrl. After being immersed for 60 minutes in a coagulation bath consisting of the following, solvent removal and drying were performed to produce a leather-like substrate layer having a porous coating layer on the surface. The base layer of the resulting leather-like sheet material had a binding content of 60% to the fibers.

To this leather-like sheet material, 7% of the same polyurethane efstomer (softening temperature g 196°C), 7% of titanium oxide,
A pigment ink consisting of an anti-yellowing agent o, s%, dimethylformamide 26%, acetone 34% and cyclohexanone 25.5% was applied at a solid content of 497nf and dried to form a non-porous coating layer with a thickness of 4μ, On top of that, apply a rough cloth pattern (
The difference in height between the four parts and the convex part is 80μ, the number of convexities per CD is about 400), and four leather-like sheet products (A) are produced. 8% of the same polyurethane elastomer as above, 2% of silicon oxide, 0.5% of anti-yellowing agent, 28% of dimethylformamide, 55% of acetone and 26% of cyclohexanone.
Applying strong printing pressure to an ink consisting of 5% solids, the solid content is 59%. /rd gravure coating and drying to obtain a leather-like sheet material CB). The surface layer of this leather-like sheet material (Bl) is coated with a thickness of approximately -VC5μ on all four parts including the embossed convex portions, and the texture, folding wrinkles and bending resistance are improved. ) It was really bad.

In addition, polybutylene hexamethylene adipate glycol, dicyclohexylmethane-
Polyurethane fstomer made of 4,4'-diisocyanate and isophoronediamine (softening temperature 142°
C1-N% 5.4%) 8%, silicon oxide 2%, dimethylformamide 36%, toluene 18% and methanol 5
Apply an ink containing 5% with a gravure roll, make an e-cut with a doctor knife, apply a relatively light printing pressure, apply 5Q/yd with a solid content, and dry to create a leather-like sheet [C]
I got it.

The surface layer of this leather-like sheet was thick in the convex portions (reaching a maximum of 7 μm or more) and gradually became thinner toward the concave portions (at a minimum of 1 μm or less) according to the horizontal pattern of the embossed irregularities. This product had good texture, folding wrinkles, and bending resistance.

Further, the remaining leather-like sheet material (A) K Leather-like sheet material [CD ink used for the leather-like sheet material (B) was coated with a solid content of 57β, and dried to form the leather-like sheet material (D ) was obtained. This leather-like sheet material has a surface layer with an almost uniform thickness of 5 μm on all four parts and convex parts, regardless of the embossed uneven pattern, and has excellent wrinkles, texture, folding wrinkles, and bending resistance. Leather-like sheet [was worse than the CD.

The above four types of leather-like sheet materials (A) to (D) are cut and sewn to make a cover for sports shoes, and then worn on a male shoe, and when combined with a female shoe, the space created is filled with polyvinyl chloride. was injected and cooled to produce sports acid. The leather-like sheet material (A), (B, the sports acid made in l) had poor adhesion between the shoe cover and the outsole, and peeled off in several places even immediately after shoe making9.
It was of little practical use. Also, leather-like sheets (0
) and CD) did not show any peeling, so when I wore it, I found that the leather-like sheet material CD) developed flex cracks in the covered area after a while.
The sports acid using the leather-like sheet material [CD showed no abnormality at all after 6 months, and had a high corrosion quality and high value.

Example 2 Polyurethane F Stomer 1 made of polycaprolactone glycol, diphenylmethane-4,4'-diisocyanate and ethylene glycol was added to a needle-punched nonwoven fabric made of 2.5 denier polyester fibers.
8%, PVC/11/2 bullet.

A polymer solution consisting of 0.5% carbon black and 79.5% dimethylformamide was impregnated, and 120q~ of the same polymer solution was coated on top of this in solid content, and then 30% dimethylformamide was added at 50°C. After being immersed in a coagulation bath consisting of a water-dimethylformamide mixture for 30 minutes, the solvent was removed and dried to produce a gimp-like base layer having a porous coating layer on its surface. The obtained base layer contained 110 layers of resin per fiber, had a thickness of 1.8 mm, and a density of 0.539/d. Further, the porous coating layer had a thickness of 380μ. This leather-like sheet
8% of the same polyurethane elastomer (softening temperature 182'C) and 1.5% of carbon black on the surface of the object.
, an ink consisting of 52% dimethylformamide, 66% acetone, and 22.5% cyclohexanone was coated with a solid content of 29/rrl by gravure method, and dried to a coating layer thickness of 2μ), height of the convex part and the four parts. The difference is 250μ%1d
A leather-like sheet material (■) was obtained by stamping a numerically 100 Yampi patterns on the convex portions of the sheet. This leather-like sheet material was then treated with 6% polyurethane elastomer (softening temperature 118°C, N% 3.0%) of polyethylene hexamethylene adipate glycol, isophorone diisocyanate and isophorone diamine, 1% carpump hook, and oxidation. Silicon 0.5%, detofhydrofuran 33%
, isopropano-/v41% and methano-714.
A leather-like sheet material CF) was prepared by applying an ink containing 5% solid content by a 7 f/rr/spray method and drying. The thickness of the surface layer formed in one strip on this ink was 10 μm or more in the four parts and 3 μm or less in the convex parts, according to the embossed uneven pattern.

The above 2 m long leather-like sheets (E) and CF) were made into sports sheets in the same manner as in Example 1. However, when wearing the sportswear made from two-component polyurethane as the resin for the outsole, the sportswear made from the leather-like sheet material (E) lost its buttons within a day. While peeling occurred between the sole and the outsole, the technical leather-like sheet material CF)
The sportswear made from the same material showed no abnormalities even after being worn for 6 months, and was also extremely excellent in texture, folding wrinkles, and bending resistance.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are both cross-sectional views of the leather-like sheet product of the present invention. Patent applicant Rirashi Co., Ltd. Agent
Patent Attorney, Civil Engineering Ken Ta

Claims (1)

[Scope of Claims] 1. The surface of a leather-like sheet material mainly consisting of a fibrous base layer (1) and a porous coating layer (II) made of a polymer mainly composed of polyurethane efstomer has a softening temperature of 1.
A non-porous coating layer (i1M) consisting of a polymer mainly composed of polyurethane efstomer at a temperature of 60°C or higher, and a polyurethane efstomer mainly synthesized from a polymeric diol, an aliphatic or alicyclic diisocyanate, and an organic diamine. Non-porous surface layer (1) made of a polymer that
are sequentially laminated, the surface of the coating layer (II) is provided with an uneven pattern, and the thickness of the surface layer α) is equal to the uneven pattern of the atMtGll). Accordingly, a leather-like sheet material suitable for use as a shoelace is characterized in that it is either thick in four parts and thin in convex parts, or thin in four parts and thick in convex parts. 2. Claim 1, wherein the polymeric diol used in the synthesis of the surface layer (g) is polyester di-)V synthesized from aliphatic dicarboxylic acid having 4 or more carbon atoms or polycaprolactone glycol. Leather-like sheet material described in Section 1. 3. The thickness of the surface layer (ff) is 1 to 20μ at the thickest point.
A leather-like sheet material according to claim 1 or 2, which falls within the scope of claim 1 or 2. 4. The leather-like sheet material according to any one of claims 1 to 3, wherein the fibrous base layer is composed of a nonwoven fabric and a porous polyurethane efstomer contained therein. 5. The polyurethane efstomer forming the coating layer 01) is mainly synthesized from polymeric diol, aromatic diisocyanate and alkylene glyco-μ. A giskin-like sheet material according to any one of the above. 6. The leather-like sheet material according to claim 1, wherein the polyurethane elastomer constituting the front surface (ff) has a softening temperature of 80 to 160°C. 7. R fibrous base layer (1) and porous coating layer (1) consisting of a polymer mainly composed of polyurethane efstomer
A non-porous coating M (1) made of a polymer mainly composed of a polyurethane elastomer with a softening temperature of 160°C or higher is applied to the surface of a leather-like sheet material mainly consisting of . Gives an uneven pattern,
Thereafter, a solution or dispersion of a polymer mainly composed of a polyurethane elastomer synthesized with a polymeric di-ol, an aliphatic or alicyclic diisocyanate, and an organic diamine was added in four parts according to the uneven pattern of the coating layer. Production of a leather-like sheet material suitable for use as a shoe lace, characterized in that it is applied to a thickness such that it is either thick in the first part and thin in the convex parts, or thin in the fourth part and thick in the convex parts, and dried. Method.