JPH09250063A - Standed sheet and method for manufacturing the same - Google Patents

Abstract

(57) [Abstract] PROBLEM TO BE SOLVED: To provide a napped sheet which is excellent in abrasion strength and is excellent in texture and dye color evaluation. SOLUTION: A napped fiber sheet composed of ultrafine fibers and an elastic polymer has a Brinell hardness of 8 or more and an average particle size of 10
Fine powder having a particle size of μm or less is used as a dispersion liquid and impregnated directly or with a dispersion liquid in which a binder is dispersed, and then dried to obtain a content of the fine powder in a sheet of 0.2 to 15% by weight.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent wear resistance,
The present invention relates to a napped sheet which has a good texture, is flexible, and has an appropriate degree of stretchability, and a method for producing the napped sheet.

[0002]

2. Description of the Related Art Conventionally, as a method for increasing the wear resistance of a leather-like sheet, a method of providing a resin layer having a high modulus as a surface layer has been widely used as a method for increasing the wear resistance of a silver surface layer. However, when the leather-like sheet is a napped sheet, applying a resin with a high modulus on the surface impairs the feeling of fluff, and gives a nubuck tone or half-silver tone, and as a suede, looks, texture, touch,
This method is not suitable for a napped sheet, because it is inferior in fluffiness. When the napped sheet has low wear resistance, problems such as perforation and tearing occur due to friction between elastic bodies or between fibers and elastic bodies. As a method for improving the abrasion resistance of the napped sheet, for example, in Japanese Patent Publication No. Sho 64-6304, 0.5-
A method for producing a sheet having excellent surface abrasion resistance by melting and fixing the monofilaments on the surface of a web made of a thermoplastic monofilament having a denier of 10 has been proposed. In addition, special fair 3
No. 60945 discloses that a three-layered sheet consisting of a strongly twisted knitted fabric sheet, an ultrafine elastic fiber entangled sheet, and an ultrafine inelastic fiber entangled sheet is entangled and then only the ultrafine fibers are melt-treated. A method for producing a sheet having excellent wear resistance is described. In addition to these methods, as a method of increasing the wear resistance of the napped sheet, a method of increasing the fiber density by increasing the thickness of the ultrafine fibers constituting the sheet, or increasing the modulus of the elastic body to be impregnated, or increasing the resin concentration There are possible ways to raise it.

[0003]

However, in the case of the technique disclosed in the above Japanese Patent Publication No. 64-6304, the naps on the surface are collected and the suede-like appearance cannot be obtained. Further, in the case of the technique described in Japanese Patent Publication No. 3-60945, when a thin suede-like sheet is to be obtained, the stitches of the strongly twisted knitted fabric sheet are transparent to the surface and a high-quality suede-like sheet is obtained. I can't get it. In addition, the single fibers are melted and fixed, resulting in a hard texture. Further, in the case of a method of increasing the fiber density by increasing the thickness of the ultrafine fibers, it is not possible to obtain a suede tone with a soft touch and a high-quality feeling. Further, in the case of the method of increasing the resin modulus of the impregnated elastic body or increasing the resin concentration, there are problems in the texture and the stretchability. The present invention solves the above problems, and provides a napped sheet that is flexible, has excellent stretchability and texture, and has high abrasion resistance, and a method for producing the napped sheet.

[0004]

Means for Solving the Problems The present inventors have focused their attention on the structure of a napped sheet, and as a result of diligent studies, as a result, the inner surface of the void in the elastic body, or the surface inside or outside the ultrafine fiber bundle is specified. It has been found that the inclusion of particles makes it possible to improve the abrasion resistance without impairing the fluffy feeling and the like, the texture, and the flexibility, and has completed the present invention.

That is, the present invention provides a napped fiber sheet comprising a base layer composed of an ultrafine fiber bundle and an elastic polymer and a napped layer existing on the surface thereof, and having a hardness of 8 or more in Brinell hardness and an average particle diameter of 10 μm or less. A napped sheet, characterized in that fine powder is applied to the surface. And
As a manufacturing method thereof, a napped fiber sheet made of a base layer made of ultrafine fibers and an elastic polymer and a napped layer existing on the surface of the base layer has a Brinell hardness of 8 or more and an average particle size of 1
By impregnating a fine powder of 0 μm or less as a dispersion liquid and drying it, the content ratio of the fine powder to the sheet is 0.2.
The method is to use 15 to 15% by weight.

Hereinafter, the present invention will be described in detail. The base layer of the napped sheet of the present invention is a napped sheet containing a polymer mainly composed of an elastic polymer in a fiber assembly. The napped sheet of the present invention is obtained, for example, by combining the following steps. That is, (1) a step of producing ultrafine fiber-generating fibers, (2) a step of producing an entangled nonwoven fabric made of the fibers, (3) a step of temporarily fixing the nonwoven fabric as necessary,
(4) a step of impregnating the entangled nonwoven fabric with an elastic resin liquid to form a dense foam, (5) a step of modifying the fibers into an ultrafine fiber bundle, (6) a step of forming naps on the substrate surface, (7)
The napped sheet of the present invention can be obtained by the step of dyeing the obtained napped sheet, and / or the step of impregnating or applying a softening agent on the surface and (8) the step of impregnating fine particles.

The ultrafine fiber bundle of the base layer used in the present invention is made of ultrafine fiber-generating fibers composed of at least two kinds of polymers, for example, sea-island structure fibers or split type fibers. Then, the sea component is dissolved or decomposed by a solvent or a decomposing agent such as sodium hydroxide so that the island component remains as ultrafine fibers, or it is divided into ultrafine fibers composed of each polymer mechanically or by a treating agent. Examples of the split type fibers include:

As the polymer constituting the ultrafine fibers, 6
-Nylon, 66-nylon, 610-Nylon and other melt-spinnable polyamides, polyethylene terephthalate, polybutylene terephthalate, cation dyeable modified polyethylene terephthalate and other melt-spinnable polyesters, and polypropylene. At least one polymer selected from polyolefins. In addition, the component extracted or decomposed and removed by the extractable fiber is a polymer having a difference in solubility or decomposability with respect to a solvent or a decomposer from the ultrafine fiber component and having low compatibility with the ultrafine fiber component, and a spinning condition. A polymer having a lower melt viscosity or a lower surface tension than the ultrafine fiber component below, for example, at least one polymer selected from polymers such as polyethylene, polystyrene, polyethylene propylene copolymer, and modified polyester. The volume ratio of the sea component and the island component of this ultrafine fiber is in the range of 80:20 to 20:80, and as a suitable denier after extracting the sea component,
A range of 0.1 to 0.001 denier is preferred.

The ultrafine fiber-generating fiber is defibrated with a card,
A web is formed through a webber, and the obtained fiber web is laminated to a desired weight and thickness, and then a known method, for example, a entanglement treatment by a needle punch or high-pressure water flow to form a nonwoven fabric, or The staple is entangled with a knitted fabric using a high-pressure water stream or the like to form a fibrous sheet. In addition, in order to prevent the fibrous sheet from receiving a tension in the following steps to cause structural destruction, a method of impregnating the fibrous sheet with an aqueous solution of polyvinyl alcohol, drying it, or melting the fiber surface to fix the fibers is used. You may use.

Next, the fiber-entangled non-woven fabric is impregnated with an elastic resin liquid and gelled by heating and drying, or by immersing in a liquid containing a non-solvent of the elastic resin and wet coagulation to form a dense foam sponge. Form. The elastic resin impregnated here is, for example, at least one type of polymer diol selected from polyester diols having an average molecular weight of 500 to 3000, polyether diols, polycarbonate diols, or composite diols such as polyester polyether diols and 4, 4 ′. -At least one diisocyanate selected from aromatic, alicyclic, and aliphatic diisocyanates such as diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, and at least one kind having at least two active hydrogen atoms It may be polyurethane obtained by reacting a low molecular weight compound at a predetermined molar ratio and its modified product, or other elastic resin such as polyester elastomer and acrylic resin. Further, a polymer composition in which these are mixed may be used. However, the above polyurethane is preferably used because of its flexibility, elastic recovery property, sponge forming property and the like. The polymer concentration of the elastic body is 10-
The range of 50% by weight and Young's modulus is preferably 1 to 15 kg / mm ² .

A resin liquid obtained by dissolving or dispersing the above elastic resin in a solvent or a dispersant is impregnated into a fiber entangled body and treated with a non-solvent of the resin to wet-coagulate to form a sponge, or it is heated as it is. A fibrous substrate is obtained by a method of drying, gelling and forming a sponge. Additives such as a colorant, a coagulation regulator, an antioxidant, and a dispersant are added to this resin liquid as needed. The ratio of the elastic resin in the fibrous substrate is 10% or more, preferably 30% by weight as a solid content in order to give the substrate a soft texture and elastic recovery property.
It is preferable that the content be within the range of 50%. Elastic body ratio is 1
If it is less than 0%, a dense elastic sponge cannot be formed, and the ultrafine fibers cannot be sufficiently fixed when raising the surface of the substrate. Further, since the elastic sponge itself is dense and not smooth, nap before applying the resin The surface does not become a sufficiently smooth surface. Therefore, the surface of the product which is buffed by applying the resin cannot have a sufficiently fine smooth surface enough to be called a high-quality suede tone.

Next, when the above-mentioned ultrafine fiber-generating fiber, for example, the sea component is polyethylene and the island component is nylon, the sea component is extracted with toluene, and the sea component is an easily decomposable alkali-modified polyester. When the island component is an alkali-resistant polymer, the sea component is decomposed and removed by treating with an aqueous solution of caustic soda, and the fibers are made into ultrafine fiber bundles.

Subsequently, the surface of this substrate is raised to form a smooth raised surface having raised fibers mainly composed of ultrafine fibers.
As a raising method, a raising method using a cloth raising machine may be used, but a buffing method using sandpaper or the like is preferable since a delicate and uniform raised layer can be obtained. The napped fiber has a fineness of less than 0.5 denier, particularly 0.1.
Ultra fine fibers of ˜0.001 denier can form delicate suede-like naps. When it exceeds 0.5 denier, the napped hair is slightly delicate. If it is less than 0.001 denier, the color developability is not sufficient. The length of nap is 2 mm
The following is particularly preferable that it is 0.5 mm or less. With naps exceeding 2 mm, delicate naps cannot be obtained and a smooth surface cannot be obtained.

This napped sheet-like material is dyed with a metal-containing complex salt dye, an acid dye, a sulfur dye, etc. by a conventional method, and if necessary, a softening treatment is carried out as described above.

The particles to be imparted to the so-called surface such as the void surface in the elastic body, the inner surface or the outer surface of the ultrafine fiber bundle in the present invention may be either inorganic particles or organic particles, but it is the object of the present invention to be flexible. In order to obtain a napped sheet which is excellent in elasticity and texture and has high abrasion resistance, the hardness is 8 or more in Brinell hardness and the average particle size (when it is not a true sphere, the arithmetic average of the minor axis and the diameter is used). It is necessary to satisfy the condition of 10 μm or less. If the particles have a Brinell hardness of less than 8, the particles themselves wear due to friction and a sufficient wear resistance effect cannot be obtained. Since the Brinell hardness of the fine particles cannot be directly measured, it is expressed by the Brinell hardness of the non-porous material forming the fine particles. The average particle size is 10
If it is larger than μm, it adheres to the outer surface, but it is difficult for it to penetrate into the elastic body, so that a sufficient effect cannot be obtained. The particle size is 0.
If it is less than 1 μm, slippage becomes poor and wear strength becomes insufficient. Therefore, it is preferable that the average particle diameter is 0.1 to 5 μm.

The material of such fine particles is not particularly limited, but examples of the inorganic substance include aluminum powder, silica powder and titanium oxide powder, and examples of the organic substance include melamine resin, benzguanamine resin, urea resin and the like. Examples of the natural product include powders of silk, wool and the like. When the affinity between these fine particles and the resin of the elastic polymer is low, it is preferable to perform surface treatment with a suitable binder in advance. The mixing ratio with the binder resin is 0.2 to 15 times the resin weight. However, if the fine particles are colored, a high proportion of the fine particles causes discoloration, and the proportion of the fine particles is low. For example, it may cause deterioration of wear resistance. More preferably, it is in the range of 0.4 to 6 with respect to the resin weight. The type of binder is not particularly limited as long as it is a binder for fine particles such as a thermoplastic resin and a polymer, but an aqueous urethane resin is preferable. The concentration is preferably in the range of 0.5 to 10% by weight, particularly preferably 1 to 5% by weight, based on the solvent such as water or alcohol mixed solution. The impregnation method is a dip-nip method, and the pickup rate is 60 to 90% by weight on the base layer.
It is preferable to apply and dry it. The napped sheet obtained by the present invention has high abrasion resistance, good texture, and excellent flexibility.

[0017]

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

Example 1 A sea-island type composite fiber consisting of 60 parts of 6-nylon (island component) and high-fluidity low-density polyethylene (sea component) with an average number of islands of 300 to 400 and ultrafine fibers of the island component of 0.001 to 0. ．
A sea-island type mixed-spun fiber having a denier of 01 was obtained by melt-spinning, drawn, mechanically crimped and cut into staples, and a web having a basis weight of 500 g / m ² was formed by a cross lap method, and then needle punched. , A entangled nonwoven fabric with a smooth surface was made. The basis weight of this entangled nonwoven fabric is 5
It was 40 g / m ² and the apparent specific gravity was 0.3 g / cm ³ . This entangled nonwoven fabric is impregnated with a dimethylformamide (abbreviated as DMF) solution of polyurethane mainly composed of polytetramethylene ether type polyurethane, dipped in a DMF / water mixed solution and wet-coagulated, and then the composite fiber in hot toluene. The sea component inside was eluted and removed to express ultrafine fibers to obtain a fibrous sheet substrate. The obtained fibrous substrate was divided into two in the thickness direction, the divided surface was buffed to a thickness of 0.5 mm, and the opposite surface was raised with sandpaper to give a napped sheet.

This napped sheet was dyed brown under the following conditions. Dyeing conditions Gold-containing dye Raney Brown GR (Sumitomo Chemical Co., Ltd.) 4% owf Leveling agent Levelan NK-D (Maruhishi Yuka Co., Ltd.) 1g / l Dyeing temperature 90 ° C After drying and rubbing, it is uniform and delicate. A suede-like sheet having naps was obtained. This sheet material was subjected to a dip-nip treatment under the following conditions and then a dry hair conditioning treatment. Impregnation conditions Water-based Pu resin H-6010 (manufactured by Dainippon Ink) 1% / water Surfactant DX-110 (manufactured by Dainippon Ink) 7% / Emulsion titanium oxide (Brinell hardness 100 or more, average particle size 1μ ) 1.2% / water The amount of titanium oxide fine particles deposited is 0.8 on the sheet.
%, It was confirmed that the adhered state of the fine particles was intensively adhered to the void surface in the elastic body or to the inside or outside surface of the ultrafine fiber bundle. Then, a suede-like napped sheet having extremely excellent abrasion resistance and good flexibility and texture was obtained. When a glove was manufactured so that the napped sheet could be used as a palm, the life until the perforation was about 2.5 times that of the conventional napped sheet.

Example 2 The suede-like sheet of Example 1 was subjected to a dip-nip treatment under the following conditions and then a dry hair styling treatment. Impregnation condition Benzguanamine formaldehyde condensation product (Eposter MS: Nippon Shokubai Co., Ltd.) (Brinell hardness 50 average particle size 2 μm) 3% / water After the drying treatment, the amount of fine particles adhered to the sheet was 2%, and the adhered state of the fine particles. When confirmed with an electron microscope, it was confirmed that the adhered state was intensively adhered to the void surface in the elastic body or to the inside or outside surface of the ultrafine fiber bundle. The suede-like napped sheet was excellent in abrasion resistance and had good flexibility and texture.

Comparative Example 1 The suede-like sheet of Example 1 was compared with Examples 1 and 2
The hair styling treatment was performed without the impregnation treatment as described above. Comparative Example 2 With respect to the suede-like sheet of Example 1 described above, this sheet was subjected to a dip-nip treatment under the following conditions and then a dry hair styling treatment. Impregnation conditions As a polyamide resin, 6-nylon 3% / water Brinell hardness 5 Average particle size 10μ After drying treatment, the amount of fine particles adhered to the sheet was 1.7%. It was confirmed that the adhered state was intensively adhered to the void surface in the elastic body or to the inside or outside surface of the ultrafine fiber bundle. And this sheet was a suede-like napped sheet having good flexibility and texture.

Comparative Example 3 With respect to the suede-like sheet of Example 1 described above, this sheet was subjected to a dip-nip treatment under the following conditions and then a dry hair conditioning treatment. Impregnation condition Benzguanamine formaldehyde condensation product (Eposter LS: manufactured by Nippon Shokubai Co., Ltd.) Brinell hardness 50 Average particle size 15 μm 3% / water After the drying treatment, the amount of fine particles adhered was 1.4% with respect to the sheet, and the adhered state of the fine particles. When observed with an electron microscope, it was confirmed that the adhered state was concentrated on the surface of the napped sheet rather than in the elastic body. Then, a napped sheet having good flexibility and texture was obtained.

Table 1 shows the performance of the napped sheets obtained by the above examples and leather examples. As is clear from the results in Table 1, the napped sheet containing the fine particles according to the present invention was a material having excellent abrasion resistance, and having good texture and dyed color evaluation.

[0024]

[Table 1]

[0025]

EFFECTS OF THE INVENTION According to the present invention, a suede napped sheet which is excellent in abrasion resistance, has a good texture, is flexible, and has an appropriate stretchability can be obtained. The suede napped sheet of the present invention is suitable for applications that are easily broken by abrasion, such as gloves and sofa upholstery.

Claims (2)

[Claims] 1. A napped fiber sheet comprising a base layer composed of an ultrafine fiber bundle and an elastic polymer and a napped layer present on the surface of the base layer, wherein fine powder having a Brinell hardness of 8 or more and an average particle size of 10 μm or less is obtained. A napped sheet characterized by being provided on the surface. 2. A napped fiber sheet consisting of a base layer made of ultrafine fibers and an elastic polymer and a napped layer existing on the surface of the base layer has a Brinell hardness of 8 or more and an average particle size of 10 μm.
By impregnating the following fine powder as a dispersion liquid and drying, the content ratio of the fine powder to the sheet is 0.2 to 15:
A method for producing a napped sheet, characterized in that the content is in% by weight.