JP3506570B2 - Leather-like sheet and method for producing the same - Google Patents

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 silver surface, which is excellent in smoothness and is excellent in creasing when folded, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting a silver surface to the surface of a fabric composed of a fiber entangled body and a polymer elastic body, a colored polymer elastic body is applied onto a release paper, which is called a dry method, and dried. After that, a method of applying a polymer elastic body liquid for adhesion and then laminating with a cloth, also called a wet method, after applying a polymer elastic body to the surface of the cloth, a non-solvent or a poor solvent of the applied polymer elastic body A method of dipping a cloth coated with the polymer elastic material therein to solidify and solidify the applied polymer elastic material, and further a method of laminating a film made of a thermoplastic polymer elastic material on the surface of the cloth, Alternatively, a method is known in which a polymer elastic body solution is directly applied onto a cloth and dried.

However, in the method called the dry method,
The residual solvent of the adhesive layer penetrates into the fabric, and as a result, the creases on the surface of the fabric deteriorate, and it is difficult to obtain fine fine leather-like creases. When the permeability of the resin liquid applied to the surface to the cloth is high, the elastic polymer penetrates into the cloth and a layer of the elastic polymer is formed at the interface,
The texture becomes hard and the creases become large wrinkles and deteriorate.
If it is not permeable, the cloth and the applied polymer elastic material have no adhesiveness, the silver surface layer is peeled off from the cloth, and there is a problem in practical use, and the desired leather-like sheet cannot be obtained. Further, in a method called a wet method, in the step of coagulating the applied polymer elastic body, the foreign matter and air that have entered the polymer elastic body solution to be applied, and the inclusion of air in the cloth to be applied or a coagulation bath Due to changes in the solidification state of the applied polymer elastic material due to unevenness of liquid permeability, unevenness in the thickness of the surface coat layer due to foaming and unevenness of solidification is likely to occur, and silver with good creasing and smoothness It is not preferable as a method for obtaining the surface layer.

Further, in the case of a method of laminating a film on the surface of a fabric, the film needs to have a thickness of several tens of μm or more in order to ensure processability. When it is placed on a cloth, the surface hardness becomes hard, and due to the balance with the substrate layer, it becomes a wrinkle like a corrugated board, which is not preferable.

In addition, the method of directly applying the elastic polymer on the surface of the cloth has the advantages of the simplicity of the apparatus and the process treatment, but like the dry method, the elastic polymer solution is used. A leather-like sheet having a good texture and creases has not been obtained due to the effect of the permeation into the fabric. When the coated elastic polymer is dried, especially when the cloth to be coated is impregnated with a poor solvent for the elastic polymer, the vapor during evaporation penetrates into the coated surface of the elastic polymer liquid. Therefore, a leather-like sheet having good smoothness cannot be obtained.

Further, Japanese Patent Application Laid-Open No. 60-71777 discloses that
The average distance between the fiber entanglement points of the cloth applied to the surface is 200μ
It is described that an artificial leather with a silver surface having smoothness can be obtained by setting the thickness to m or less, but it is difficult to obtain a smooth surface when the average distance between fiber entanglement points of the cloth is not 200 μm or less, and Since the non-porous polymer elastic material layer is applied after the porous polymer elastic material liquid is applied on the cloth, the porous polymer elastic material layer is in the middle, so that the cloth and the porous polymer The adhesive force at the interface between the elastic body layer, the porous polymer elastic body layer and the non-porous polymer elastic body layer becomes weak, which is not preferable. Further, Japanese Patent Publication No. 46-9154 discloses a method in which a polyurethane elastic body liquid is applied to the surface of a fabric by adding water to the surface of the fabric before laminating the polyurethane elastic layer serving as a surface layer. However, since water is present on the entire surface of the cloth, the adhesive force between the polymeric elastic body of the surface layer and the cloth becomes too weak.

[0007]

As described above, in the method of providing the silver surface layer on the surface of the fiber cloth which has been conventionally proposed,
It was not possible to obtain a leather-like sheet with a silver surface, which has natural leather-like small creases, has a good texture, and has a smooth surface. The present invention provides a leather-like sheet with a silver surface, which solves the above problems at the same time, has small folds of natural leather that have not been obtained so far, has a good texture, and has a smooth surface. The purpose is to do.

[0008]

[Means for Solving the Problems] That is, the present invention provides a cloth comprising a fiber entangled body and a polymer elastic body (A),
A silver-faced leather-like sheet having a layer of the same or different polymer elastic body (B) as (A), characterized in that the surface of the cloth and the layer are bonded discontinuously. It is a leather-like sheet with a silver surface. Further, the present invention provides a cloth comprising a fiber entangled body and a polymer elastic body (A),
In a silver-faced leather-like sheet in which a layer made of a polymer elastic body (B) which is the same as or different from (A) is present, a portion where the interface between the fabric surface and the layer is unclear and a portion where it is clear are mixed. And a gap between the unclear portion and the adjacent unclear portion is 10 to 200 μm. Furthermore, the present invention is directed to forming a silver surface layer by applying a liquid of a polymer elastic body (B) which is the same as or different from (A) onto a cloth composed of a fiber entangled body and a polymer elastic body (A). A method for producing a leather surface-like sheet with a silver surface, wherein the surface of the cloth and the silver surface layer are bonded in a discontinuous manner. Furthermore, in the present invention, a solution of the polymer elastic body (B) is applied onto a cloth composed of the fiber entangled body and the polymer elastic body (A) and dried to form a silver surface layer composed of the polymer elastic body (B). Before that, the polymer elastic body (A)
And a substance that inhibits the adhesion of the polymer elastic body (B) are applied in a non-continuous manner.

The present invention will be described in detail below. The fiber entangled body constituting the cloth used in the present invention is at least 1
By removing the components, 30 to 100% by weight of multi-component fibers that can be transformed into ultrafine fiber bundle fibers or porous fibers that have a large number of fine hollow parts, and ultrafine fibers such as polyester and polyamide. Fibers or fibers of ordinary thickness, for example, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, polyvinyl alcohol, etc., chemical fibers such as recycled cellulose, natural fibers etc. are mixed by 0 to 70% by weight, or A typical example is a laminate of a multi-component fiber layer and a fiber layer other than that, from which at least one component described above is removed.

For applications characterized by flexibility and drapability, it is preferable to use ultrafine fiber bundle fibers such as polyester and polyamide. In order to further increase fiber strength, the ultrafine fiber bundle fibers are 40 It is preferable to combine 30 to 60% by weight of a fiber having a normal thickness, for example, 30 to 60% by weight of a synthetic fiber such as polyester, polyamide, polyacrylonitrile, polyolefin and polyvinyl alcohol. When the amount of the ultrafine fiber bundle-shaped fibers is 30% or less, the texture of the fiber entangled body and the wrinkles are impaired. In addition, the average fine denier is preferably 0.1 denier or less, and the normal thickness fiber is preferably 0.5 to 3 denier. These fibers are made into a web or a sheet by a wet papermaking method, and then entangled by needle punching or high-speed fluid flow to give a nonwoven fabric. If necessary, these non-woven fabrics may be laminated with a knitted fabric.

The entangled body of fibers 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 polyurethane polymer, acrylonitrile-butadiene copolymer, and styrene-butadiene copolymer. A polymer elastic body is used as a main component. Polyurethane is particularly preferable in terms of feeling and durability. 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 dio-
At least one kind of polymer diol selected from among diol, polyvalerolactone diol, polycarbonate diol and organic diisocyanate, for example, aromatic diisocyanate such as 4,4′-diphenylmethane diisocyanate and phenylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate. Of 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, etc. 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 the above range, flexibility is lacking and a natural leather-like texture cannot be obtained, which is not preferable. On the other hand, when the number average molecular weight of the polymer diol exceeds 5,000, the concentration of urethane groups decreases, and it is difficult to obtain a sheet having a good balance of flexibility, durability, heat resistance, and hydrolysis resistance. The composition and mixing ratio of these polymer elastic materials are selected from those satisfying various physical properties such as feeling, deterioration resistance, surface abrasion resistance, and yellowing resistance according to the intended field of application of the leather-like sheet. It can be selected appropriately. Also, if necessary, a pigment,
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 elastic polymer (A) is the elastic polymer (A).
In a non-solvent, solidify by coagulation, dewashing or drying. Further, the multi-component fibers are modified into ultrafine fiber bundle fibers and the like, and dried to obtain a cloth. The proportion of the polymeric elastomer in the cloth is preferably 20 to 80% by weight.

Further, examples of the elastic polymer (B) applied to the surface of the cloth include known polyurethanes, acrylic elastic polymers, polystyrene elastic polymers, etc., which can impart strength and surface feeling like natural leather. However, due to its natural leather-like texture, folding wrinkles when folded, and smoothness in the subsequent process, it is easy to produce a polymer elastic body (B) for the surface.
Of these, polyurethane is the most preferable. The polymer elastic bodies (A) and (B) may be the same polymer, the same type of polymer, or different types of polymers, but from the viewpoint of adhesive strength, they are preferable. It is the same or the same kind of polymer, and particularly preferably both are polyurethane type polymers.

As the step of applying the elastic polymer (B) to the cloth, a known method may be adopted as long as the elastic polymer (B) is directly and uniformly applied to the cloth. Examples thereof include a blade coater, a roll coater, a reverse roll coater, a comma coater, and an air doctor blade coater. The comma coater is preferred from the standpoints of uniform application and simplicity of the device itself.

Particularly important in the present invention is, as described above, that the cloth and the silver surface layer are bonded to each other in a non-continuous manner, and that the interface between the cloth surface and the layer is unclear and clear. There are mixed parts, and in the unclear part,
The polymer elastic body (A) and the polymer elastic body (B) are mixed and the polymer elastic body (B) permeates the fabric layer, and further, the unclear portion and the adjacent unclear portion Interval is 10
It is 200 μm, and for this reason, a very special method is used in the method of the present invention. That is, as a method of applying a substance that inhibits the adhesion between the polymeric elastic body (B) to be applied on the cloth and the cloth, the adhesion is inhibited on the surface of the cloth before applying the polymeric elastic body (b). The substance to be applied is partially applied in a thin layer. As a specific coating method for that purpose, although it depends on a substance that inhibits adhesion, if it is a liquid, a method of applying it in a mesh form with a gravure roll coater is preferable, and if it is a solid, it is partially unevenly distributed and heat-pressed. Examples of the method include a method of unevenly distributing a substance that inhibits adhesion on the surface of the cloth, such as a method of adhering to the surface of the cloth. In addition, a penetrating agent or the like may be added to the coating liquid of the substance that inhibits adhesion, because the substance that inhibits adhesion easily adheres to the cloth. When a large amount of a substance that inhibits adhesion is partially applied, the surface smoothness of the obtained leather-like sheet is impaired, which is not preferable.

It is important that the substance that inhibits adhesion is applied in a non-continuous manner. Discontinuous means 2 on the surface of the fabric.
The polymer elastic body (B) is not dimensionally continuous, and when the polymer elastic body (B) is coated, the polymer elastic body (A) on the surface of the fabric is partially dissolved and the polymer elastic body (B) is dispersed in the fabric. ) Is a mixture of parts that have penetrated and parts that have not. Further, the permeated state is a state in which the polymeric elastic body (A) on the surface of the cloth is dissolved and the polymeric elastic body (B) permeates and exists in the ultrafine fiber bundle constituting the cloth. Refers to. Since the state of adhesion between the cloth and the elastic polymer (B) applied to the surface and the state of the elastic polymer (A) formed on the surface of the cloth are partially dissolved, the repulsive force against the stress changes. This is a place to absorb the stress when the leather-like sheet is bent, and small wrinkles will occur.

The adhesion-inhibiting substance may be adhered in a stripe shape or a cloud shape, but the wrinkling when bent is uneven in the vertical and horizontal directions.
It is preferable that the entire surface is coated in a mesh form. In particular, it is preferable to use a gravure roll coater having a mesh-shaped depression. If the amount of the substance that inhibits the adhesion is 100 g / m ² or more on the surface, the effect of the substance that inhibits the adhesion is increased and the applied polymer elastic body (B) is partially peeled off, 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 .

Further, the distance between the substances which adhere to the surface of the fibrous sheet and inhibit the adhesion, that is, the distance between the adjacent inhibitor-coated portions is preferably 10 to 200 μm. If the distance between the substances that inhibit adhesion is less than 10 μm, the penetration of the polymeric elastic body (B) applied to the surface into the cloth is inhibited,
It is not preferable because the adhesive force between the polymeric elastic body (B) and the cloth becomes low. On the other hand, when it exceeds 200 μm, there are few places where the polymeric elastic body (B) applied to the surface does not penetrate into the cloth, and it is not preferable because small wrinkles when the intended bending is not obtained. The distance between the substances that inhibit adhesion is preferably 10 to 200 μm, more preferably 50 to 100 μm. The distance between the adjacent inhibitor-coated portions in the present invention means a microscopic photograph of a cross section of the sheet in a direction such that the value of the distance is the shortest, and from the photograph, the interface between the fabric surface and the silver surface layer is determined. It is obtained by dividing into an unclear portion and a clear portion, and obtaining the average value of the distance between the central portion of the portion where the interface is unclear and the central portion of the similar portion adjacent to the interface.

As the substance which inhibits the adhesion between the cloth and the polymeric elastic body (B), a substance which does not dissolve in the solvent of the polymeric elastic body (B) to be applied and the polymeric elastic bodies (A) and (B) are mainly used. The non-solvents of the polymeric elastomers (A) and (B) can be used as the non-solvent of the polymeric elastomers (A) and (B) because the smoothness of the surface after application, the folding wrinkles when bent, and the fact that they do not remain in the substrate layer in a later step. Preferably there is. As a method of distinguishing whether it is a non-solvent of the elastic polymer, if one drop of the elastic polymer solution to be applied is dropped in the solvent to be investigated and it solidifies within 5 seconds, It can be judged as a solvent.
Specific examples of the substance that inhibits adhesion include water, liquids such as methanol, resins such as silicon-based polymers and fluorine-based polymers, and the like, and water is most preferable because it has no working environment and does not remain in the product after evaporation.

When a substance which inhibits the adhesion between the cloth and the elastic polymer (B) is applied to the entire surface of the cloth, the coating film of the elastic polymer (B) on the surface does not adhere to the cloth and is peeled off for practical use. It will not be offered. Further, when a substance that inhibits the adhesion between the cloth and the polymeric elastic body (B) is uniformly applied to the entire surface without a gap, the cloth and the polymeric elastic body (B) are evenly adhered, so that the stress is absorbed when the material is bent. There is no place and it becomes a bent corner and it feels like it was broken and it is not preferable. Even when the substance that inhibits the adhesion between the cloth and the elastic polymer (B) is not applied at all, the cloth and the elastic polymer (B) are evenly adhered to each other and the adhesive force is strong, so that the cloth is bent. When there is no stress, there is no place to absorb the stress, resulting in a bent corner, which is unfavorable because it gives a feeling of a sharp break.

Further, in order to impart a feeling of unity, it is preferable to control the thickness of the layer of the polymeric elastic body (B) within an appropriate range. The thickness of the layer of the elastic polymer (B) is preferably 2 to 120 μm, more preferably 10 to 80 μm, and if it is less than 2 μm, the surface smoothness cannot be sufficiently obtained.
If it exceeds 120 μm, the wrinkles will be large and the wrinkles will not be as fine as natural leather, and the texture will also lack a sense of unity. As long as the total thickness of the layers of the elastic polymer (B) applied to the surface is within the above preferred range, the number of elastic polymer layers may be any. The obtained sheet coated with the elastic polymer is immediately dried by a drier to form a leather-like sheet. If necessary, embossing, coloring,
Be flexible. The state of adhesion between the cloth and the polymeric elastic body (B) was determined by cutting the sheet in a direction perpendicular to the sheet surface.
By observing with a microscope, it is possible to easily discriminate whether or not the interface between the fabric surface and the silver surface layer is unclear or clear, as to whether or not they are bonded in a discontinuous manner. The interface where the substance that inhibits the adhesion between the cloth and the elastic polymer (B) is applied is a clear interface, and the part where it is not applied is an unclear interface.

[0022]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. Parts and% in the examples relate to weight unless otherwise specified.

Example 1 Polyethylene adipate / polyethylene glycol copolymerization was carried out on an entangled non-woven fabric composed of 80 parts of multi-component fibers 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 fibers. Polyurethane (A)
(Softening point 160 ° C) 16% dimethylformamide (D
MF) solution was impregnated and coagulated in a 30% DMF aqueous solution, and then polyethylene was dissolved and removed to obtain a cloth. This fabric contains polyurethane (A) in a porous state in a non-woven fabric in which 66.7% of fibers in which ultrafine fibers having an average fineness of 0.005 denier are bundled are bundled, and the fibers and polyurethane (A) are contained.
Was 45/55. As a coating liquid, 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 cloth, as a substance that inhibits adhesion,
An aqueous solution prepared by adding a penetrant to water, which is a non-solvent of the coating solution, was applied to a mesh shape by a gravure roll coater system with a roll of 55 mesh at an adhesion amount of 35 g / m ² ,
Immediately 120 g of the above coating solution on the cloth 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 bent, it became a small wrinkle similar to natural leather.

An impregnated polyurethane (A) constituting a cloth by taking an electron micrograph of a cross-sectional layer of the obtained sheet
When the interface between the coated polyurethane (B) forming the silver surface and the silver surface is confirmed, the polyurethane (A) existing on the surface of the fabric is in a film shape, and the place where the interface is clearly visible and the polyurethane (A) is dissolved. The polyurethane (B) layer applied to the inside of the ultrafine fiber bundle had penetrated, and there were areas where the interface was unclear. Further, the distance between the portion where the interface was not clear and the adjacent portion where it was adjacent was measured, and the average was 200 μm. This is a phenomenon in which the polyurethane (B) partially penetrates into the inside of the cloth, and the cloth and the polyurethane (B) partially adhere to each other. In this state, small wrinkles like leather are generated. Is a necessary condition for. After applying white gravure ink on the surface of the sheet and embossing and softening the hair grain, it was finished,
A leather-like sheet having small folds and wrinkles similar to natural leather and having a smooth surface feel and a high-grade drape texture was obtained.

Example 2 Polyethylene adipate / polyethylene glycol copolymer polyurethane (A) (softening point 160) was added to an entangled nonwoven fabric consisting of 100 parts of multi-component fibers containing 50 parts of polyester as a dispersion component and 50 parts of polyethylene as a dispersion medium component. ℃) 1
Impregnate with 6% dimethylformamide (DMF) solution and
After coagulation in a 0% DMF aqueous solution, polyethylene was dissolved and removed to obtain a cloth. This cloth is made of polyurethane (A) on a non-woven fabric of ultrafine fiber bundle fibers (average fineness 0.005 denier).
Was a porous sheet, and the ratio of fiber to polyurethane (A) was 50/50. As a coating liquid, 100 parts of a 30% solution of polyether polyurethane (B) (softening point 140 ° C.), 30 parts of a black pigment solution, DMF30
Parts and 30 parts of MEK were mixed and sufficiently stirred. An aqueous solution prepared by adding a penetrant to water, which is a non-solvent of the coating solution, is applied to the surface of the fabric by a gravure roll coater method using a 140 mesh roll to deposit 20 g of the solution.
/ M ^{2 in a} mesh form, then immediately apply 120 g / m ^{2 of the} above coating solution on a cloth with a comma coater and dry at 130 ° C. for 4 minutes to give a smooth silver surface and a natural leather-like texture. A leather-like sheet was obtained. Also, when this sheet was folded, it became a small wrinkle similar to natural leather.

An impregnated polyurethane (A) constituting a cloth by taking an electron micrograph of the cross-sectional layer of the obtained sheet
When the interface between the coated polyurethane (B) that constitutes the silver surface and the silver surface is confirmed, the polyurethane (A) existing on the surface of the fabric is in the form of a film, and the place where the interface is clearly visible and the polyurethane (A) is dissolved. Then, the layer of polyurethane (B) applied to the inside of the ultrafine fiber bundle was permeated, and there were areas where the interface was unclear. Further, the distance between similar portions adjacent to the portion where the interface was not clear was measured and found to be 100 μm on average. Further, when the distance between the places in which the polyurethane (B) was infiltrated at the interface and in the same state as the place was measured, it was 100 μm on average. Further, black gravure ink was applied to the surface of the sheet, and embossing and softening treatment of hair grain were performed to finish, resulting in a leather-like sheet having a natural leather-like texture and creases.

Example 3 Polyethylene adipate / polyethylene glycol copolymerization was carried out on an entangled nonwoven fabric composed of 80 parts of multi-component fibers 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 fibers. Polyurethane (A)
(Softening point 160 ° C) 16% dimethylformamide (D
MF) solution was impregnated and coagulated in a 30% DMF aqueous solution, and then polyethylene was dissolved and removed to obtain a cloth. This fabric has an ultrafine fiber (average fineness of 0.004 denier) 66.
A sheet containing polyurethane (A) in a porous state in 7% non-woven fabric, and the ratio of fiber to polyurethane (A) is 4
It was 5/55. As a coating liquid, a 30% solution of polyether polyurethane (B) (softening point 140 ° C.) 100
Parts, 30 parts of white pigment solution, 30 parts of DMF, and 30 parts of MEK were mixed and sufficiently stirred. An aqueous solution prepared by adding a penetrant to water, which is a non-solvent for the coating liquid, was applied to the surface of the cloth as a substance that inhibits adhesion by a gravure roll coater method.
After applying in a stripe shape at an adhesion amount of 80 g / m ² with a roll stamped on the stripe at 4 mm intervals, 120 g / m ^{2 of the} coating liquid is applied onto the cloth with a comma coater,
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. Further, when this sheet was bent, a large wrinkle was formed in the linear direction of the stripe transferred to the surface of the fabric, but a small wrinkle similar to natural leather was formed in the normal direction of the stripe.

The cross-section layer of the obtained leather-like sheet was photographed by an electron microscope to confirm the interface between the impregnated polyurethane (A) constituting the cloth and the coated 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 layer of polyurethane (B) applied to the inside of the ultrafine fiber bundle penetrates, The location where the interface was unclear was mixed, and the distance between the location where the polyurethane (B) had permeated at the interface and the adjacent location was measured and found to be 100 μm on average. White gravure ink was applied to the surface of the obtained sheet, and embossing and softening of hair wrinkles were performed and finished.Slight creases were observed in one direction. A leather-like sheet having a unique surface feeling was obtained.

Comparative Example 1 The cloth of Example 1 was Diped 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 onto this cloth using a comma coater 12
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 bent, small wrinkles like natural leather did not crease, but large wrinkles like folded corrugated cardboard, which made it impossible to obtain a high-class feeling. An electron micrograph of the cross-sectional layer of the obtained sheet was taken to confirm the interface of the impregnated polyurethane (A) constituting the cloth and the coated polyurethane (B) constituting the silver surface, and a clear interface was present. However, there was no place where the applied polyurethane penetrated inside the ultrafine fiber bundle. When white gravure ink is applied to the surface of the sheet and embossing and softening of hair grain are applied to finish, large wrinkles are generated, and a leather-like sheet with a natural leather-like texture and wrinkles is obtained. There wasn't.

Comparative Example 2 The coating solution of Example 1 was applied onto the fabric of Example 1 on the base layer sheet with a comma coater at 120 g / m ² and 130 ° C.
And dried for 4 minutes to obtain a leather-like sheet having a smooth silver surface. When this sheet was bent, small wrinkles like natural leather did not crease, but large wrinkles like folded corrugated cardboard, which made it impossible to obtain a high-class feeling. An electron micrograph of the cross-sectional layer of the obtained sheet was taken to confirm the interface between the impregnated polyurethane constituting the cloth and the applied polyurethane constituting the silver surface, and the surface side of the ultrafine fiber bundle which is considered to be the surface of the cloth There was no place where the interface existed, and only the place where the layer of polyurethane applied penetrated inside the ultrafine fiber bundle. When white gravure ink is applied to the surface of the sheet, and embossing and softening treatments are applied to hair grain, the creases have large wrinkles, and a natural leather-like texture and crease-like leather sheets cannot be obtained. It was

[0031]

EFFECTS OF THE INVENTION According to the present invention, there can be obtained a leather-like sheet with a silver surface which has natural leather-like small folds and wrinkles, has a good texture, and has a smooth surface. It can be used for bags, bags, school bags, clothing and the like.

Claims (4)

(57) [Claims] 1. A leather-like sheet with a silver surface in which 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 leather-like sheet with a silver surface, the surface of the fabric and the layer are bonded discontinuously. 2. A leather-like sheet with a silver surface, in which 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 is mixed with an unclear part and a clear part, and the average interval between the unclear part and the adjacent unclear part is 10 to 200 μm. Characteristic leather sheet with a silver surface. 3. When a silver surface layer is formed by applying a liquid of a polymer elastic body (B), which is the same as or different from (A), onto a cloth composed of a fiber entangled body and a polymer elastic body (A). A method for producing a leather-like sheet with a silver surface, characterized in that the surface of the fabric and the silver surface layer are bonded in a discontinuous manner. 4. A silver elastic layer composed of the elastic polymer (B) is formed by applying a solution of the elastic polymer (B) onto a cloth composed of the fiber entangled body and the elastic polymer (A). First, a method for producing a leather surface sheet with a silver surface, characterized in that a substance that inhibits adhesion between the polymeric elastic body (A) and the polymeric elastic body (B) is applied discontinuously.