JPH10102383A - Leather-like sheet and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a grained leather-like sheet having small broken wrinkles similar to those of a natural leather and having a good touch by discontinuously adhering a fabric comprising an interlaced fiber product and a polymer elastomer to a polymer elastomer layer. SOLUTION: This grained leather-like sheet is obtained by impregnating an interlaced non-woven fabric consisting mainly of conjugate fibers comprising 6-nylon and polyethylene with the dimethylformamide solution of a polyethylene adipate/ polyethylene glycol polyurethane A, subjecting the impregnated fabric to a coagulation treatment, eluting the polyethylene, coating the surface of the obtained porous fabric with an adhesion-inhibiting substance such as water in a mesh-like pattern, and immediately again coating the coated surface of the porous fabric with the same polyurethane A solution or a different polyether polyurethane B solution by the use of a comma coater. The obtained grained leather-like sheet has a distribution comprising uncertainly adhered parts and certainly adhered parts at an average distance of 10-200μm on the interface between the surface of the fabric and the coated layer. The porous fabric comprises the interlaced fiber product consisting mainly of nylon ultrafine fibers and the polyurethane A existing on the interlaced fiber product in a porous state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a leather-like sheet with a grain surface, which is excellent in smoothness and excellent in creasing when folded, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for giving a silver surface to the surface of a fabric comprising a fiber entangled body and a polymer elastic body, a colored polymer elastic body is applied on release paper called a dry method and dried. After that, a method of applying a polymer elastic body liquid for bonding and then bonding it to a fabric, or a method called a wet method, in which a polymer elastic body is applied to the surface of a fabric and then applied to a non-solvent or poor solvent of the applied polymer elastic body Inside, a method of solidifying and solidifying the applied polymer elastic body by dipping the cloth coated with the polymer elastic body, and a method of bonding a film made of a thermoplastic polymer elastic body to the surface of the fabric, Alternatively, a method of applying a polymer elastic solution directly onto a fabric and drying the solution is known.

However, in the above-mentioned method called dry method,
The solvent remaining in the adhesive layer penetrates into the fabric, and as a result, the crease is deteriorated, and it is difficult to obtain a fine, fine leather-like crease. When the permeability of the resin liquid applied to the surface to the fabric is high, the polymer elastic body penetrates into the fabric, and a layer of the polymer elastic body is generated at the interface,
The texture becomes hard, and the folds become large wrinkles and become worse.
In addition, if there is no permeability, there is no adhesion between the cloth and the applied polymer elastic body, and the silver surface layer is peeled off from the cloth, which poses a practical problem, and a desired leather-like sheet cannot be obtained. Further, in a method called a wet method, in a step of coagulating the applied polymer elastic body, foreign matter and air entering into the applied polymer elastic body solution and air in the applied fabric are entrapped and coagulated. The solidified state of the applied polymer elastic body changes due to the unevenness of liquid permeability, etc., and the thickness unevenness of the surface coat layer due to foaming and uneven solidification is apt to occur, and silver having good crease and smoothness It is not preferable as a method for obtaining a surface layer.

In the case of a method of attaching a film to the surface of a cloth, the film needs to have a thickness of several tens of μm or more in order to ensure processability. When placed on a cloth, the surface hardness becomes hard, and it becomes undesired to be folded wrinkles like corrugated cardboard due to the balance with the base material layer.

The method of directly applying a polymer elastic material to the surface of a cloth has the advantages of simplicity of equipment and simplicity of process treatment. No leather-like sheet having a good texture and folds has been obtained due to the effect of permeation into the fabric. Also, when the applied polymer elastic body is dried, particularly when the cloth to be applied is impregnated with a poor solvent for the polymer elastic body, the vapors at the time of evaporation penetrate the polymer elastic body liquid to the application surface side. A leather-like sheet having better smoothness cannot be obtained.

Further, JP-A-60-71777 discloses that
200μ average distance between fiber entanglement points of the fabric to be coated on the surface
m or less to obtain an artificial leather with a silver surface having smoothness, but it is difficult to obtain a smooth surface if the average distance between fiber interlacing points of the fabric is not 200 μm or less, and Since the non-porous polymer elastic body layer is applied after the porous polymer elastic body liquid is applied on the fabric, the porous polymer elastic body layer is located in the middle, so that the cloth and the porous polymer elastic body are applied. The adhesive strength at the interface between the elastic layer, the porous polymer elastic layer and the non-porous polymer elastic layer is weakened, which is not preferable. In addition, Japanese Patent Publication No. 46-9154 discloses that prior to laminating a polyurethane elastic layer serving as a surface layer, the surface of the fabric is impregnated with water so that a polyurethane elastic liquid applied to the surface is applied to the fabric layer. A method has been proposed to prevent the permeation of water, but in this method, since water is present on the entire surface of the cloth, the adhesive force between the polymer elastic body of the surface layer and the cloth is too weak, which is not preferable.

[0007]

As described above, in the method of providing a grain surface layer on the surface of a fiber fabric which has been conventionally proposed,
A leather-like sheet with a grained surface having small wrinkles like natural leather, good texture, and a smooth surface could not be obtained. The present invention provides a leather-like sheet with a silver surface having a natural leather-like small wrinkle, a good texture, and a smooth surface which has not been obtained until now by simultaneously solving the above problems. The purpose is to do.

[0008]

That is, the present invention provides a method for fabricating a fabric comprising a fiber entangled body and a polymer elastic body (A).
In a leather-like sheet with a grain side, in which a layer made of a polymer elastic body (B) which is the same or different from (A) is present, the cloth surface and the layer are discontinuously adhered. It is a leather-like sheet with a grain surface. Further, the present invention provides a method for fabricating a fiber entangled body and a polymer elastic body (A),
In a leather-like sheet with a grained surface in which a layer made of a polymer elastic body (B) which is the same or different from (A) is present, a portion where the interface between the fabric surface and the layer is unclear and a portion where the interface is clear are mixed. And a gap between the unclear portion and the adjacent unclear portion is 10 to 200 μm. Further, the present invention relates to a method for applying a liquid of the same or different polymer elastic body (B) to the cloth comprising the fiber entangled body and the polymer elastic body (A) to form a silver surface layer. A method for producing a leather-like sheet with a grain surface, wherein the surface of the fabric and the grain surface layer are adhered in a discontinuous manner. Further, in the present invention, a solution of the polymer elastic body (B) is applied and dried on a fabric comprising the fiber entangled body and the polymer elastic body (A) to form a silver surface layer made of the polymer elastic body (B). Before doing this, elastic polymer (A)
A method for producing a leather-like sheet with a grained surface, comprising applying a substance that inhibits the adhesion between the elastic body (B) and the polymer elastic body (B) in a discontinuous manner.

Hereinafter, the present invention will be described in detail. The fiber entangled body constituting the fabric used in the present invention is at least 1
By removing the components, 30 to 100% by weight of a multicomponent fiber which can be transformed into an ultrafine fiber bundle fiber or a porous fiber having a large number of fine hollow portions, and an ultrafine fiber such as polyester or polyamide. By mixing 0 to 70% by weight of fibers or fibers having a normal thickness, for example, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, and polyvinyl alcohol, chemical fibers such as regenerated cellulose, natural fibers, and the like, or A typical example is obtained by removing at least one component from a laminate of a multi-component fiber layer and another fiber layer.

[0010] In the case of applications that are characterized by flexibility and drapability, it is preferable to use bundles of ultrafine fibers such as polyester and polyamide. It is preferable to combine a fiber having a thickness of about 70% by weight with a normal thickness, for example, a synthetic fiber such as polyester, polyamide, polyacrylonitrile, polyolefin, or polyvinyl alcohol in an amount of 30 to 60% by weight. When the amount of the ultrafine fiber bundle fibers is 30% or less, the feeling of the fiber entangled body and the folding wrinkles are impaired. The average diameter of the ultrafine fibers is preferably 0.1 denier or less, and the average thickness of the fibers is preferably 0.5 to 3 denier. These fibers are formed into a web or a sheet by a wet papermaking method, and then entangled by needle punching or high-speed fluid flow to form a nonwoven fabric. If necessary, the nonwoven fabric and the woven fabric may be laminated.

The fiber entangled body is impregnated with the elastic polymer (A). As the polymer elastic body (A) to be impregnated, at least one kind of polymer elastic body selected from the group of polymer elastic bodies such as a polyurethane polymer, an acrylonitrile-butadiene copolymer, and a styrene-butadiene copolymer is used. A polymer elastic body mainly used is used. Particularly, polyurethane is preferable from the viewpoint of feeling, durability and the like. As the polyurethane, a polymer diol having an average molecular weight of 500 to 3000, for example,
Polyethylene glycol, polypropylene glycol,
Polytetramethylene glycol, polyethylene propylene adipate glycol, polycaprolactone di-
, Polyvalerolactone diol, at least one polymer diol selected from polycarbonate diol and the like, and an organic diisocyanate, for example, 4,4′-diphenylmethane diisocyanate, aromatic diisocyanate such as phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. At least one diisocyanate compound selected from aliphatic or alicyclic diisocyanates, and a low molecular weight compound having at least two active hydrogen atoms as a chain extender, for example, ethylene glycol, propylene glycol, butanediol, Diols such as 1,4-cyclohexanediol, ethylenediamine, propylenediamine, isophoronediamine, piperazine, phenylenediamine and the like Amines, hydrazines, a mixture of at least polyurethane and one obtained by reacting in the desired proportions or these polyurethanes, selected from among such hydrazines or hydrazides such as adipic dihydrazide.

The number average molecular weight of the polymer diol is 500
If it is less than 10%, it is not preferable because it lacks flexibility and a natural leather-like texture cannot be obtained. On the other hand, when the number average molecular weight of the polymer diol exceeds 5,000, the urethane group concentration is reduced, so that it is difficult to obtain a sheet having well-balanced flexibility, durability, heat resistance and hydrolysis resistance. The composition and mixing ratio of these polymer elastic bodies are selected from among those satisfying various physical properties such as feeling, deterioration resistance, surface wear resistance, yellowing resistance, etc., depending on the intended application field of the leather-like sheet. It can be selected as appropriate. Also, if necessary, pigments,
Dyes, coagulation regulators, stabilizers and the like may be added, and two or more polymers may be used in combination. The composition liquid of the impregnated polymer elastic body (A) is the polymer elastic body (A)
Solidified by coagulation, dewashing or drying in a non-solvent. Further, the multicomponent fiber is subjected to a denaturation treatment to ultrafine fiber bundle-shaped fibers and the like, and dried to obtain a fabric. The proportion of the elastic polymer in the fabric is preferably from 20 to 80% by weight.

Further, examples of the polymer elastic body (B) applied to the surface of the fabric include known polyurethanes, acrylic elastic polymers, and polystyrene elastic polymers which can impart the natural leather-like strength and appearance. However, due to the natural leather-like texture, wrinkles when folded, and the smoothness of the subsequent process, the polymer elastic body (B) used on the surface
Is most preferably polyurethane. The polymer elastic bodies (A) and (B) may be the same polymer, the same kind of polymer, or different kinds of polymers, but are preferably used from the viewpoint of adhesive strength. The same or the same kind of polymer is used, and particularly preferably both are polyurethane-based polymers.

The step of applying the polymer elastic body (B) to the cloth may be performed by a known method as long as the polymer elastic body (B) is directly and uniformly applied to the entire surface of the cloth. Examples of the method include a blade coater, a roll coater, a reverse roll coater, a comma coater, and an air doctor blade coater. A comma coater is preferred from the viewpoints of uniform application and simplicity of the apparatus itself.

Particularly important in the present invention, as described above, is that the fabric and the silver surface layer are discontinuously adhered to each other, and that the interface between the fabric surface and the layer is unclear. Parts are mixed, and in the unclear part,
The polymer elastic body (A) and the polymer elastic body (B) are mixed, and the polymer elastic body (B) has penetrated into the fabric layer. The interval is 10
It is 200 μm, and therefore, in the method of the present invention, a very special method is used. That is, as a method of applying a substance that inhibits the adhesion between the polymer elastic body (B) and the cloth to be applied on the cloth, the adhesion to the surface of the cloth is inhibited before the application of the polymer elastic body (b). A method is used in which a substance to be applied is partially applied in a thin layer. As a specific application method therefor, although it depends on a substance that inhibits adhesion, a method of applying a mesh using a gravure roll coater is preferable for a liquid, and a hot press is performed by partially distributing the material if it is a solid. Examples of the method include a method in which a substance that inhibits adhesion is unevenly distributed on the surface of the fabric by a method of causing the substance to adhere to the surface of the fabric. Further, a penetrant or the like may be added to a coating solution of the substance that inhibits adhesion so that the substance that inhibits adhesion easily adheres to the cloth. It is not preferable to apply a large amount of a substance that inhibits adhesion, because the surface smoothness of the obtained leather-like sheet is impaired.

It is important that the substance that inhibits adhesion is applied discontinuously. Non-continuous means that 2
When the polymer elastic body (B) is coated, the polymer elastic body (A) on the fabric surface is partially dissolved and the polymer elastic body (B ) Appears in a mixture of a portion where the permeation has occurred and a portion where the penetration has not occurred. The state of permeation refers to a state in which the polymer elastic body (A) on the surface of the fabric is dissolved and the polymer elastic body (B) permeates and exists in the ultrafine fiber bundle constituting the fabric. Point to. Since the state of adhesion between the fabric and the polymer elastic body (B) applied to the surface and the state of the polymer elastic body (A) formed on the fabric surface are partially dissolved, the repulsive force against stress changes. Thus, it becomes a place for absorbing the stress when the leather-like sheet is bent, and a small wrinkle is generated.

The substance that inhibits adhesion may be attached in a stripe or cloud shape, but the way of wrinkling when folded varies in the vertical and horizontal directions.
Preferably, it is applied to the entire surface in a mesh form. In particular, it is preferable to use a gravure roll coater with a mesh-shaped depression. When the amount of the substance that inhibits adhesion is applied to the surface at 100 g / m ² or more, the effect of the substance that inhibits adhesion is increased, and the applied polymer elastic body (B) is partially peeled, which is not preferable. Preferably, the adhesion amount is in the range of 0.1 to 50 g / m ² ,
More preferably, it is in the range of 10 to 35 g / m ² .

It is preferable that the distance between the substances that inhibit adhesion adhered to the surface of the fibrous sheet, that is, the distance between adjacent inhibitor-applied portions is 10 to 200 μm. When the distance between the substances that inhibit adhesion is less than 10 μm, the penetration of the polymer elastic body (B) applied to the surface into the cloth is inhibited,
It is not preferable because the adhesive strength between the polymer elastic body (B) and the fabric becomes low. On the other hand, if it exceeds 200 μm, the portion where the polymer elastic body (B) applied to the surface has not penetrated into the fabric is reduced, and the desired small wrinkles at the time of bending cannot be obtained, which is not preferable. The preferred distance between the substances that inhibit adhesion is from 10 to 200 μm, more preferably from 50 to 100 μm. The distance between adjacent inhibitor-applied portions referred to in the present invention means that a micrograph of a cross section of the sheet is taken in a direction in which the value of the distance is the shortest, and from the photograph, the interface between the cloth surface and the silver layer is determined. It is obtained by dividing an unclear portion and a clear portion, and calculating the average value of the interval between the center portion of the portion where the interface is unclear and the center portion of a similar portion adjacent thereto.

The substance which inhibits the adhesion between the cloth and the polymer elastic body (B) is mainly a substance which does not dissolve in the solvent of the polymer elastic body (B) to be applied and the polymer elastic bodies (A) and (B) Non-solvents of the polymer elastic bodies (A) and (B) may be used because of the smoothness of the surface after application, wrinkles when folded, and the fact that they do not remain in the base layer in a later step. Preferably, there is. As a method of determining whether or not the polymer elastic body is a non-solvent, a drop of the polymer elastic body solution to be applied is dropped into the solvent to be examined, and if the solution solidifies within 5 seconds, It can be determined as a solvent.
Specific examples of the substance that inhibits adhesion include water, a liquid such as methanol, and a resin such as a silicon-based polymer and a fluorine-based polymer. Water is most preferable because it has a work environment and does not remain in the product after evaporation.

When a substance that inhibits the adhesion between the cloth and the polymer elastic body (B) is applied to the entire surface of the cloth, the coating film of the polymer elastic body (B) on the surface does not adhere to the cloth and is peeled off for practical use. It cannot be offered. Further, when a substance that inhibits the adhesion between the cloth and the polymer elastic body (B) is uniformly applied to the entire surface without any gap, the cloth and the polymer elastic body (B) have uniform adhesion, and therefore absorb the stress when bent. There is no place, the corners are broken, and the appearance is like a broken one, which is not desirable. Even when a substance that inhibits the adhesion between the fabric and the polymer elastic body (B) is not applied at all, the fabric and the polymer elastic body (B) are similarly folded because the adhesion is uniform and the adhesive strength is strong. When there is no place to absorb the stress, there is no corner where the corner is bent, which is unfavorable because it gives a feeling of breaking.

Further, in order to give a feeling of unity, it is preferable to control the thickness of the layer of the polymer elastic body (B) in an appropriate range. Preferably, the thickness of the layer of the polymer elastic body (B) is 2 to 120 μm, more preferably 10 to 80 μm, and if it is less than 2 μm, sufficient surface smoothness cannot be obtained,
When the thickness exceeds 120 μm, wrinkles are large and fine wrinkles, such as natural leather, are not obtained, and the feeling is lacking in unity. Any number of polymer elastic layers may be used as long as the total thickness of the layers of the polymer elastic body (B) applied to the surface is within the above preferred range. The sheet coated with the obtained polymer elastic body is immediately dried by a dryer to form a leather-like sheet. Further embossing, coloring,
Be flexible. The adhesion between the cloth and the elastic polymer (B) was determined by cutting the sheet in a direction perpendicular to the sheet surface.
By observing with a microscope, it is easy to determine whether or not the interface between the fabric surface and the silver surface layer is unclear and whether the adhesive is discontinuous or not. The portion where the substance that inhibits the adhesion between the fabric and the polymer elastic body (B) is applied is a portion where the interface is clear, and the portion where the material is not applied is a portion where the interface is not clear.

[0022]

Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. Parts and percentages in the examples relate to weight unless otherwise specified.

Example 1 A polyethylene adipate / polyethylene glycol copolymer was prepared on an entangled non-woven fabric comprising 80 parts of multicomponent fibers containing 20 parts of 6-nylon and 50 parts of polyethylene as a dispersion medium component and 20 parts of 6-nylon fibers. Polyurethane (A)
(Softening point 160 ° C) 16% dimethylformamide (D
MF) solution and coagulated in a 30% DMF aqueous solution to dissolve and remove polyethylene to obtain a cloth. This fabric has a nonwoven fabric in which 66.7% of fibers in which ultrafine fibers having an average fineness of 0.005 denier converge in a bundle contain polyurethane (A) in a porous state.
Was 45/55. As a coating solution, 100 parts of a 30% solution of polyether polyurethane (B) (softening point 140 ° C.), 30 parts of a white pigment solution, 30 parts of DMF, and 30 parts of methyl ethyl ketone (MEK) were mixed and sufficiently stirred. On the surface of the fabric, as a substance that inhibits adhesion,
An aqueous solution obtained by adding a penetrating agent to water, which is a non-solvent of the coating liquid, is applied in a gravure roll coater system with a 55-mesh roll at a deposition amount of 35 g / m ^{2 in a} mesh form.
Immediately 120 g of the above coating solution on the fabric with a comma coater
/ M ² and dried at 130 ° C. for 4 minutes to obtain a leather-like sheet having a smooth silver surface and a natural leather-like texture. When this sheet was folded, it became a small wrinkle-like wrinkle resembling natural leather.

The cross-sectional layer of the obtained sheet is photographed with an electron microscope to obtain an impregnated polyurethane (A) constituting a fabric.
When the interface between the coated polyurethane (B) and the silver surface was confirmed, the polyurethane (A) existing on the surface of the fabric was in the form of a film. As a result, the layer of the polyurethane (B) applied to the inside of the ultrafine fiber bundle penetrated, and there were places where the interface was unclear. When the distance between a portion where the interface was unclear and a similar portion adjacent thereto was measured, it was 200 μm on average. This is a phenomenon in which the polyurethane (B) partially penetrates into the inside of the fabric and the fabric and the polyurethane (B) are partially adhered to each other. In this state, small wrinkles like leather are generated. This is a necessary condition. After applying white gravure ink on the surface of the sheet and embossing and softening the hair grain,
A leather-like sheet having small wrinkles similar to natural leather and having a luxurious feeling with a smooth surface and drape property was obtained.

EXAMPLE 2 A polyethylene adipate / polyethylene glycol copolymer-based polyurethane (A) (softening point 160) was added to an entangled nonwoven fabric comprising 100 parts of a multicomponent fiber containing 50 parts of polyester as a dispersion component and 50 parts of polyethylene as a dispersion medium component. ℃) 1
Impregnated with 6% dimethylformamide (DMF) solution,
After coagulation in a 0% DMF aqueous solution, the polyethylene was dissolved and removed to obtain a cloth. This fabric is made of a non-woven fabric made of ultrafine fiber bundle fibers (average fineness: 0.005 denier) and polyurethane (A).
Was contained in a porous state, and the ratio of fiber to polyurethane (A) was 50/50. 100 parts of a 30% solution of a polyether-based polyurethane (B) (softening point 140 ° C.), 30 parts of a black pigment solution, DMF 30
Parts and 30 parts of MEK, and mixed well. An aqueous solution obtained by adding a penetrant to water, which is a non-solvent of the coating liquid, as a substance that inhibits adhesion to the surface of the fabric, is applied in an amount of 20 g with a 140 mesh roll using a gravure roll coater method.
/ M ² , immediately apply 120 g / m ^{2 of the} above coating solution to the cloth with a comma coater, and dry at 130 ° C. for 4 minutes to remove a smooth silver surface and a natural leather-like texture. A leather-like sheet was obtained. When this sheet was folded, the wrinkles became small wrinkles similar to natural leather.

The cross-sectional layer of the obtained sheet is photographed with an electron microscope to obtain an impregnated polyurethane (A) constituting a fabric.
When the interface between the polyurethane and the applied polyurethane (B) constituting the silver surface was confirmed, the polyurethane (A) existing on the surface of the fabric was in the form of a film. As a result, the layer of the applied polyurethane (B) penetrated to the inside of the ultrafine fiber bundle, and places where the interface was unclear were mixed. When the distance between a portion where the interface was unclear and a similar portion adjacent thereto was measured, it was 100 μm on average. The distance between the places where the polyurethane (B) had permeated at the interface and the place where the state was similar to that of the place where the polyurethane (B) had permeated was measured. Further, a black gravure ink was applied to the surface of the sheet, and embossing and softening of the hair grain were performed, and the sheet was finished to give a leather-like sheet having a natural leather-like texture and wrinkles.

Example 3 A polyethylene adipate / polyethylene glycol copolymer was prepared on an entangled non-woven fabric comprising 80 parts of a multicomponent fiber containing 50 parts of 6-nylon as a dispersion component and 50 parts of polyethylene as a dispersion medium component and 20 parts of 6-nylon fiber. Polyurethane (A)
(Softening point 160 ° C) 16% dimethylformamide (D
MF) solution and coagulated in a 30% DMF aqueous solution to dissolve and remove polyethylene to obtain a cloth. This fabric has 66. bundles of ultrafine fibers (average fineness: 0.004 denier) bundled fibers.
A sheet in which polyurethane (A) is contained in a porous state in a 7% nonwoven fabric, and the ratio of fiber to polyurethane (A) is 4
It was 5/55. 30% solution of polyether polyurethane (B) (softening point 140 ° C.) 100 as a coating liquid 100
Parts, 30 parts of a white pigment solution, 30 parts of DMF, and 30 parts of MEK, and sufficiently stirred. An aqueous solution obtained by adding a penetrant to water, which is a non-solvent of the coating solution, as a substance that inhibits adhesion to the surface of the cloth is used as a gravure roll coater method.
After applying in a stripe form at an adhesion amount of 80 g / m ² with a roll engraved on the stripe at an interval of 4 mm, the application liquid was applied on the cloth with a comma coater at 120 g / m ² ,
After drying at 130 ° C. for 4 minutes, a leather-like sheet having a smooth silver surface and a natural leather-like texture was obtained. When this sheet was folded, wrinkles were slightly large in the linear direction of the stripe transferred to the fabric surface, but were small wrinkles similar to natural leather in the normal direction of the stripe.

An electron micrograph was taken of a cross-sectional layer of the obtained leather-like sheet to confirm the interface between the impregnated polyurethane (A) constituting the fabric and the applied polyurethane (B) constituting the silver surface. The polyurethane (A) present on the surface is in the form of a film and the interface is clearly visible, and the polyurethane (A) is dissolved and the polyurethane (B) layer applied to the inside of the ultrafine fiber bundle penetrates, There were places where the interface was unclear, and the distance between the place where the polyurethane (B) had permeated and the same place adjacent to the place where the polyurethane (B) had permeated was measured. The average was 100 μm. After applying white gravure ink to the surface of the obtained sheet and embossing the hair and performing softening, it is finished in a certain direction.It is a small wrinkle in a certain direction. Thus, a leather-like sheet having a unique appearance was obtained.

Comparative Example 1 The fabric of Example 1 was Dip in water containing a penetrant and pressed with a press roll to a liquid content of 95%. The coating liquid of Example 1 was applied on the cloth by a comma coater for 12 hours.
0 g / m ^{2 was} applied and dried at 130 ° C. for 4 minutes to obtain a leather-like sheet having a smooth silver surface. When this sheet was folded, the wrinkles did not become small wrinkles like natural leather, but became large wrinkles as if corrugated paper was folded, and a high-class feeling could not be obtained. An electron microscope photograph was taken of the cross-sectional layer of the obtained sheet to confirm the interface between the impregnated polyurethane (A) constituting the fabric and the applied polyurethane (B) constituting the silver surface. There was no place where the polyurethane applied inside the ultrafine fiber bundle penetrated. A white gravure ink was applied to the surface of the sheet, and embossing and embossing of the hair wrinkles were performed, followed by finishing the wrinkles. Did not.

Comparative Example 2 The coating solution of Example 1 was applied on the cloth of Example 1 at 120 g / m ² with a comma coater on a base layer sheet.
For 4 minutes to obtain a leather-like sheet having a smooth silver surface. When this sheet was folded, the wrinkles did not become small wrinkles like natural leather, but became large wrinkles as if corrugated paper was folded, and a high-class feeling could not be obtained. An electron micrograph of the cross-sectional layer of the obtained sheet was taken to confirm the interface between the impregnated polyurethane constituting the fabric and the applied polyurethane constituting the silver surface, and the surface side of the ultrafine fiber bundle considered to be the surface of the fabric was observed. There was no place where the interface existed, and only the place where the polyurethane layer applied inside the ultrafine fiber bundle permeated. After applying white gravure ink to the surface of the sheet and embossing and embossing the hair wrinkles, the wrinkles became large wrinkles, and a leather-like sheet with natural leather-like texture and wrinkles could not be obtained. Was.

[0031]

Industrial Applicability According to the present invention, a leather-like sheet with a grained surface having a natural leather-like small wrinkle, a good texture, and a smooth surface can be obtained. , Bags, school bags, clothing and the like.

Claims (4)

[Claims] 1. A grain-like leather-like sheet in which a layer comprising a polymer elastic body (B) which is the same as or different from (A) is present on a fabric comprising a fiber entangled body and a polymer elastic body (A). 2. The leather-like sheet with a grained surface according to claim 1, wherein the fabric surface and the layer are discontinuously adhered. 2. A leather-like sheet with a silver surface, wherein a layer made of a polymer elastic body (B) which is the same as or different from (A) is present on a fabric made of a fiber entangled body and a polymer elastic body (A). In the above, the interface between the fabric surface and the layer and the unclear part and the unclear part are mixed, and the average distance between the unclear part and the adjacent unclear part is 10 to 200 μm. A leather-like sheet with a silver surface. 3. A method of applying a liquid of a polymer elastic body (B), which is the same as or different from that of (A), onto a cloth comprising a fiber entangled body and a polymer elastic body (A) to form a silver surface layer A method for producing a leather-like sheet with a grain surface, wherein the surface of the fabric and the grain surface layer are adhered in a discontinuous manner. 4. A silver surface layer made of the polymer elastic body (B) is formed by applying a solution of the polymer elastic body (B) on a cloth made of the fiber entangled body and the polymer elastic body (A). A method for producing a leather-like sheet with a grained surface, characterized in that a substance that inhibits adhesion between the elastic polymer (A) and the elastic polymer (B) is applied discontinuously.