JPH111878A - Transparent leather like sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a leather like sheet usable for shoes, bags, clothes, etc., excellent in transparency. SOLUTION: This leather like sheet comprises a substrate layer constituted of a fiber assembly immersed with a polymer consisting mainly of polyurethane elastomer, a concealing layer coated on the surface of the substrate, having thickness of 0.5-100 μm made from a resin solution containing 1-100 wt.% based on the solid resin, of a coloring agent having below 30 of CIE 1976 series chromatically (L*) and a coloring layer having thickness of 0.1-50 μm made from a resin solution containing 1-50 wt.% based on the solid resin, of a coloring agent having above 30 of chromaticity (L*).

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 having transparency. More specifically, the present invention relates to a leather-like sheet material having an unprecedented transparency and usable for shoes, bags, clothing, and the like.

[0002]

2. Description of the Related Art Heretofore, there have been several proposals regarding artificial leather having a vivid color. For example, JP-A-51-41
778 and JP-A-51-2785 disclose a porous sheet material having an excellent pearly feeling by applying a colored layer containing a pearl pigment and a colored layer containing a dye or a pigment on a base layer. Is described. However, these sheets were not satisfactory because transparency was sometimes reduced by the coloring agent used.

Japanese Patent Application Laid-Open Nos. 51-41778 and 51-2785 describe that a clear layer having no coloring agent is applied. Although the transparency increases, if the coating amount is large, the surface glare increases, resulting in a lack of luxury. Further, when the amount of application is small, there is a problem that the transparency is lowered and the transparency is affected by the transparency of the lower layer, so that a satisfactory product cannot be obtained.

Further, Japanese Patent Publication No. 60-15753 discloses that a colored layer using a dye and a pigment is coated on a base layer to produce a clear and dark colored artificial leather. However, according to measurements by the present inventors, the C of the uppermost layer of the artificial leather described in the examples of the publication was
The IE1976L * chromaticity was less than 30, and the resulting artificial leather had insufficient transparency.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to eliminate the occurrence of color spots on the surface of a substrate, to improve the uniformity of the color of a product, to obtain a desired color, and at the same time, to obtain artificial leather having a sharp hue. Is to get

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a concealing layer B containing a coloring agent having a high concealing power was formed on the surface of a base layer of artificial leather.
In addition, the present inventors have found that the formation of a colored layer C containing a coloring agent having a low hiding power but a high lightness expresses unprecedented transparency, thereby completing the present invention.

That is, according to the present invention, in a leather-like sheet material, a CIE1976L * -based chromaticity of 30 is formed on the surface of a base layer A made of a fiber aggregate impregnated with a polymer mainly composed of a polyurethane elastomer (I). A concealing layer B having a thickness of 0.5 μm to 100 μm, comprising a resin solution containing a colorant of less than 1% by weight to 100% by weight with respect to the resin solid weight, and a surface of the concealing layer B And C
The coloring layer C having a thickness of 0.1 μm to 50 μm is formed by a resin solution containing a colorant having an IE1976L * chromaticity of 30 or more based on the solid weight of the resin and having a thickness of 0.1 μm to 50 μm. And a leather-like sheet having transparency. The leather-like sheet material of the present invention can provide clear artificial leather.

Hereinafter, the present invention will be described in detail. The base material layer A of the present invention is made of a fiber aggregate impregnated with a polymer mainly composed of the polyurethane elastomer (I). As the fiber aggregate, a woven fabric, a nonwoven fabric, or the like made of a synthetic fiber such as polyamide, polyester, polypropylene, and polyacrylonitrile, and one or a combination of two or more of them is used.

As the polymer mainly composed of the polyurethane elastomer (I), one or more polymer diols such as polyester diol, polyether diol, polyester ether diol, polycaprolactone diol and the like are used as an organic diisocyanate and a chain extender. A polyurethane elastomer obtained by reacting a diol or a diamine having two hydride atoms with an impregnation regulator, a coagulation regulator, an anti-adhesion agent between fibers in a fiber tissue, a flame retardant, an antistatic agent, a fungicide, It is constituted by adding a fatliquor, a coloring agent and the like as required.

The surface of the base material layer A is preferably further covered with a porous silver surface layer of a polymer mainly composed of polyurethane elastomer (II). Here, as the polyurethane elastomer (II), the same polymer as the polymer mainly composed of the polyurethane elastomer (I) can be used, but the polyurethane elastomer concentration of the polyurethane elastomer (II) is the same as that of the polyurethane elastomer (I). It is preferable to use one having a higher concentration than the elastomer concentration.

The thickness and apparent density of the base material layer A vary depending on the purpose of use, but are usually 0.3 mm to 5 mm in thickness and apparent density.
It is about 0.25 g / cm3 to 0.50 g / cm3.

The leather-like sheet material of the present invention comprises the base material layer A
And a concealing layer B and a colored layer C are laminated on the surface of the substrate.

The resin constituting the concealing layer B and the colored layer C used in the present invention includes polyurethane, polyamide, a mixture of polyurethane and an amino acid resin, polyvinyl chloride, acrylate resin, and the like. Preferably, polyurethane is used. In particular, it is preferable to use a more transparent resin for the colored layer C.

The coloring component contained in the hiding layer B is CIE
It must be a colorant having a 1976L * -based chromaticity of less than 30. Here, “CIE1976L * chromaticity (hereinafter, referred to as
The term “L *”) is defined in JIS 2068, and in the present invention, a value obtained by measuring the chromaticity of a film containing 10% by weight of a colorant based on the solid weight of a polyurethane elastomer resin. It is. The present inventors have determined that a colorant having a value of L * of 30 or more is a transparent colorant, and a colorant having a value of less than 30 is a colorant having poor transparency but a hiding power. It was found.

The colorants used in the present invention are pigments and dyes other than pearl pigments.
There is no particular limitation as long as it satisfies the * value, but the L * of the coloring agent used in the preferred concealing layer B is 0 or more and less than 25, and the L * of the coloring agent used in the preferred coloring layer C is preferably
Is 35 or more and less than 90. Specifically, L * is 30
Examples of the colorant that is less than the above include a carbon black black pigment (L * 0), an azo red pigment (L * 5.9), and a disazo yellow pigment (L * 23.8).

As the colorant having an L * of 30 or more, a disazo yellow pigment (L * 73.3) and an azo red pigment (L * 36) in which a pigment component is finely dispersed by a solvent for a pigment vehicle are used. .2), a brown metal complex dye (L * 76.
6) and the like.

The concealing layer B contains the colorant in an amount of 1% by weight to 100% by weight, preferably 2% by weight to 50% by weight based on the solid weight of the resin.
Weight% of the resin solution is coated on the surface of the base layer A to a thickness of 0.5 μm to 100 μm, preferably 0.8 μm to 60 μm.
Apply.

The coloring layer C is a resin solution containing a coloring agent in an amount of 1% by weight to 50% by weight, preferably 1% by weight to 30% by weight based on the resin solid weight, and has a thickness of 0% on the surface of the base layer A. 1 .mu.m to 50 .mu.m, preferably 0.5 .mu.m to 30 .mu.m.

Further, other coloring agents may be added to the coloring layer C to adjust the color tone. However, the coloring agent should have a L * of less than 30 as long as the transparency is not lost. Can be. In this case, the amount of the coloring agent used is the coloring layer C
Should be less than 40% by weight, preferably less than 20% by weight, based on the colorant used in the above.

The concealing layer B and the colored layer C are laminated on the surfaces of the base layer A and the concealing layer B, respectively, and a conventionally known laminating method is used. For example,
Gravure roll, knife coater, reverse coater,
A coating method using an inverse coater, a spray or the like can be used, and a coating method using a gravure roll is preferable.

Further, the L of the colored layer C is formed on release paper having a pattern.
* A resin solution containing a colorant of 30 or more is applied, and a resin solution containing a colorant less than L * 30 of the concealment layer B is applied thereon. It is also possible to take off the pattern paper.

If necessary, a concealing layer similar to the concealing layer B may be further formed between the base layer A and the concealing layer B according to the intended use of the obtained leather-like sea-like material. It is possible to provide a thin layer of a polyurethane elastomer layer containing no colorant on top of the above, as long as the effects of the present invention are not impaired.

[0023]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition,
The method for measuring L * is as follows.

(1) Preparation of Film 10 parts by weight of a colorant is added to 100 parts by weight of the solid content of the polyurethane elastomer. Further, the polyurethane elastomer is diluted with an organic solvent so that the solid content becomes 10% by weight. Next, the solution is coated on a polyester film using a roll bar having an appropriate clearance, and then dried with a hot air drier to form a film. Note that the thickness of the film is 30 μm ± 10 μm.

(2) Measurement of L * The prepared film was peeled off from the polyester film, and L * was measured by transmitted light using SM-4-2 type manufactured by Suga Test Instruments Co., Ltd. L * is a value according to JIS2068.

Example 1 A polyurethane elastomer having the same composition was solidified on a composition formed by impregnating a polyurethane elastomer in a nonwoven fabric layer of a polyester fiber aggregated nonwoven fabric at a solid content of 55% by weight of the nonwoven fabric. The coating was performed at a rate of 250 g / m 2 per minute to form a porous silver surface layer, thereby forming a base layer. The coating material of Table 1 (concealing layer) was applied three times with a # 110 gravure roll on the obtained base layer and dried to form a 5 μm concealing layer. In this case, the pure solid content of the pigment component was 14% by weight based on the solid content of the polyurethane elastomer. Further, the coating material X shown in Table 2 (colored layer) was applied twice with the same gravure roll, and dried to form a 3 μm colored layer. In this case, the pure solid content of the pigment component was 4.5% by weight based on the solid content of the polyurethane elastomer. Then
Pore embossing was performed. Thus, the obtained sheet-like material was a transparent one.

Example 2 A composition formed by impregnating a non-woven fabric layer of a non-woven fabric made of a mixed spun fiber of nylon and polyethylene with a polyurethane elastomer at a solid content of 30% by weight of the non-woven fabric was prepared by using polyethylene in toluene. Except for the above, a substrate layer having a fine fiber was prepared. Next, the paint Y shown in Table 2 (colored layer) was coated on paper having a kangaroo pattern and dried to form a 5 μm finished layer. In this case, the pure solid content of the pigment component was 3.9% by weight of the polyurethane elastomer based on the solid content. Further, the coating material of Table 1 (concealing layer) was similarly coated thereon and dried to some extent to form a colored layer of 20 μm. In this case, the pure solid content of the pigment component was 3.3% by weight of the polyurethane elastomer based on the solid content. Next, the coated paper was bonded to the prepared base layer using a press roll, and placed in a heat storage at 70 ° C. for 24 hours to perform a crosslinking treatment. Thereafter, when the paper was peeled off, the obtained sheet-like material had a transparent feeling.

Comparative Example 1 The procedure of Example 1 was repeated, except that the paint X was used instead of the paint X used in the colored layer. The obtained sheet-like material had no transparency and lacked a sense of quality.

Comparative Example 2 The procedure of Example 1 was repeated, except that the paint X was used instead of the paint used for the hiding layer, and the paint X was used instead of the paint X used for the colored layer. Was. Although the obtained sheet-like material had hiding properties, the hue of the coating material X appeared on the surface, and lacked a high-grade feeling without a somewhat matte transparency.

Comparative Example 3 In Example 2, paints (L * 73.3 and L * 33.3) were used instead of the paint used for the hiding layer.
Example 2 except that * 36.2 pigment was used).
The same was done. In this case, the pure solid content of the pigment component of the coating material was 4.0% based on the solid content of the polyurethane elastomer.
% By weight. Although the obtained sheet-like material had a sense of transparency, color unevenness of the substrate layer appeared on the surface, and was not a high-grade feeling.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

The leather-like sheet obtained according to the present invention is excellent in transparency and has sharp hue.

Claims (2)

[Claims] 1. In a leather-like sheet material, CIE197 is formed on the surface of a base layer A made of a fiber aggregate impregnated with a polymer mainly composed of a polyurethane elastomer (I).
A resin solution containing 1% to 100% by weight of a colorant having 6L * -based chromaticity of less than 30 with respect to the resin solid weight;
A concealing layer B having a thickness of 0.5 μm to 100 μm is laminated, and a colorant having a CIE1976L * -based chromaticity of 30 or more is added to the surface of the concealing layer B in an amount of 1 to the solid resin weight.
A transparent leather-like sheet comprising a resin solution containing 50% by weight to 50% by weight, and a colored layer C having a thickness of 0.1 μm to 50 μm laminated thereon. 2. The surface of the base layer A according to claim 1 is coated with a porous silver surface layer of a polymer mainly composed of a polyurethane elastomer (II). 2. The leather-like sheet having transparency according to claim 1, wherein the colored layer C is laminated.