JPH0959883A - Nubuck-tone sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nubuck-tone sheet having unique hue and surface design by forming a colored middle skin layer on a surface of a raised foundation cloth and forming a surface skin layer having fine unevenness and different color on the middle skin layer. SOLUTION: A compounded polyurethane resin liquid containing transparent or translucent coloring agent is applied to a releasing paper having fine unevenness on the surface and the liquid is dried by heating to obtain a surface skin layer 3. Another compounded polyurethane resin liquid containing an opaque coloring agent having a hue different from the hue of the former coloring agent is applied to the surface skin layer 3 and dried by heating to obtain a middle skin layer 4. The raised face of a raised polyester fiber foundation cloth is pressed against the middle skin layer 4 interposing an adhesive 5 composed of a polyurethane resin containing a crosslinking agent, dried with heat and aged to cure the adhesive 5. The releasing paper is peeled off to obtain the objective nubuck-tone sheet 1 having fine unevenness 3a on the surface.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bag, bag, belt,
Regarding sheet-like materials useful as materials for shoes, sandals, etc.,
Specifically, the present invention relates to a nubuck-like sheet material having a hue and surface design which have not been hitherto available.

[0002]

2. Description of the Related Art Conventionally, as one of the materials for bags, bags, belts, shoes, sandals, etc., a fiber base material is coated or impregnated with a polymer solution containing polyurethane resin as a main component, and a non-solvent for the polyurethane resin is used. Wet coagulate with, and grind the microporous layer surface of the polyurethane resin formed on the fiber base material,
A sheet-like product obtained by exposing the inner surface of the pores, or a sheet obtained by grinding a microporous layer of a polyurethane resin formed on the raised portion of a fiber base material to expose a part of the raised portion of the fiber base material A sheet-like material having a nubuck-like or suede-like appearance, such as a sheet-like material, is used.

[0003]

On the other hand, bags, bags, belts, shoes, sandals and the like are required to have higher designability, and even for the materials of the above products, natural leather, There is a demand for new sensations that cannot be found in materials such as synthetic leather and textiles. However, the nubuck-like or suede-like sheet material obtained as described above tends to have a monotonous and white hue, and it is difficult to obtain a novel feeling that has never been obtained. In particular, in order to prevent the blurring of the hue, it is necessary to use a large amount of a colorant or separately dye it, which results in an increase in the cost of the product such as an extra material cost or a complicated manufacturing process. there were.

The present invention has been made in order to solve the above-mentioned demands of the prior art, and can be colored in an arbitrary hue, and has a nubuck-like sheet shape having a unique hue and surface design that has never existed before. The purpose is to provide things.

[0005]

The nubuck-like sheet material of the present invention for solving the above-mentioned problems is a polyurethane resin intermediate layer containing an opaque colorant on the surface of a substrate, and a hue of the polyurethane resin intermediate layer. And a transparent or semi-transparent coloring agent different from the above, and a polyurethane resin skin layer having fine irregularities formed on the surface is sequentially laminated.

The present invention will be described below with reference to the drawings. FIG. 1 is a partially enlarged cross-sectional view showing an embodiment of the nubuck-like sheet material of the present invention. In the figure, reference numeral 1 is the nubuck-like sheet material of the present invention, reference numeral 2 is a base material, and reference numeral 3 is A polyurethane resin skin layer, reference numeral 4 indicates a polyurethane resin middle skin layer, and reference numeral 5 indicates an adhesive agent made of a polyurethane resin used as necessary.

As the base material 2 used in the present invention, any base material conventionally used for materials such as bags, bags, belts, shoes and sandals can be used. Generally, a knitted fabric, a woven fabric, a non-woven fabric, or the like, which is raised or napped as necessary, is used. Further, the knitted fabric, woven fabric, non-woven fabric and the like may be provided with an elastic polymer such as polyurethane resin or synthetic rubber in advance.

As the fibers constituting the substrate 2, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, polyvinyl alcohol, etc., natural fibers such as cotton and hemp, regenerated fibers such as rayon, suf, acetate, etc., or these It is possible to use the mixed-spun fiber, or the multi-component fiber modified into an ultrafine fiber by dissolving and removing at least one component or dividing the two-component fiber.

The polyurethane resin forming the polyurethane resin skin layer 3, the polyurethane resin skin layer 4 or the adhesive 5 is a polymer diol having an average molecular weight of 500 to 4000, for example, polyester diol, polyether diol, polyester ether diol, polycaprolactone diol. , At least one diol selected from polymethylvalerolactone diol, polycarbonate diol, and the like, and a group of organic polyisocyanates such as aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates having a cyclic group. At least one organic polyisocyanate selected and a low molecular weight compound having at least two active hydrogen atoms are chain extenders such as aliphatic diols, alicyclic diols, and fats. Diamines, alicyclic diamines, at least one-and one chain extender obtained by reacting or two-part polyurethane resin selected from the group of such hydrazine derivatives. These polyurethane resins may be modified polyurethane resins obtained by reacting amino acids, silicone, fluorine and the like.

The composition of the above polyurethane resin is selected from those satisfying various performances such as texture, hydrolysis resistance, light deterioration resistance and discoloration resistance depending on the intended use and purpose of the nubuck-like sheet material. It can be selected appropriately.

The above-mentioned polyurethane resin, particularly the polyurethane resin used for the polyurethane resin skin layer 3 and the polyurethane resin skin layer 4, has a 100% modulus of 20.
It is preferably about 200 kg / cm ² . If the 100% modulus is too low, the mechanical strength will decrease, and conversely, if the 100% modulus is too high, the texture will be hard.

Pigments, dyes and the like can be used as the colorant added to the above-mentioned polyurethane resin. Examples of the pigment include carbon black, inorganic pigments such as titanium oxide, azo pigments, phthalocyanine pigments, organic pigments such as anthraquinone pigments, metallic pigments, pearl pigments, mica pigments, daylight fluorescent pigments, and special organic pigments such as phosphorescent pigments. They can be used alone or in combination. Further, as the dye, a metal-containing complex salt type acid dye having good solubility in a solvent can be used alone or in combination.

The amount of the above-mentioned colorant used is at least 5 parts by weight, preferably 10 parts by weight or more based on 100 parts by weight of the polyurethane resin in order to obtain a sufficient coloring effect and color effect.

In the nubuck-like sheet material of the present invention,
The polyurethane resin inner skin layer 4 is formed of a polyurethane resin containing an opaque colorant having a hiding power, and the polyurethane resin outer skin layer 3 contains a transparent or translucent colorant different from the hue of the inner skin layer 4. Is formed by. The thickness of the polyurethane resin skin layer 3 and the polyurethane resin skin layer 4 is preferably 3 to 50 μm.

Further, on the surface of the polyurethane resin skin layer 3 of the nubuck-like sheet material 1 of the present invention, fine irregularities 3a are formed.
Are formed. Due to these fine irregularities 3a, the color tone of the surface changes subtly according to the viewing angle, and the convex portions of the fine irregularities 3a appear as if they were floating like a Ubu hair, and a nubuck-like design is exhibited. Further, the fine concave and convex concave portions formed on the skin layer 3 are affected by the hue of the intermediate skin layer 4 to develop a color different from the hue of the fine convex and concave convex portions formed on the skin layer 3, resulting in an unprecedented color tone. A nubuck-like sheet having a contrast of is obtained.

A specific example of the method for producing the nubuck-like sheet material of the present invention having the polyurethane resin skin layer 3 having fine irregularities is, for example, a paper casting method using a release paper having fine irregularities on the surface. Can be mentioned. That is, first, on a release paper having fine irregularities on the surface,
A polyurethane resin solution for forming the polyurethane resin skin layer 3 is applied by means such as a knife coater and dried to gel the polyurethane resin, and then a polyurethane resin solution for forming a polyurethane resin skin layer on the polyurethane resin skin layer 3 is applied. The polyurethane resin is gelled by coating and drying by means such as a knife coater. Then, an adhesive consisting of a two-component polyurethane resin solution is applied on the polyurethane resin inner skin layer 4 by means of a knife coater or the like, and then the base material 2 is placed and pressure-bonded, dried and wound for several days. The temperature is kept warm for the reaction aging to complete the reaction of the polyurethane resin adhesive, and the adhesion between the base material 2 and the adhesive layer 5 and between the adhesive layer 5 and the inner skin layer 4 is perfected. After that, by peeling off the release paper, the fine irregularities on the surface of the release paper are transferred to the polyurethane resin skin layer 3, and the sheet-like article 1 having a nubuck-like appearance is obtained.

The means for forming fine irregularities on the surface of the polyurethane resin skin layer 3 is not limited to the above-mentioned method. For example, first, a nubuck-like sheet having a polyurethane resin skin layer without fine irregularities on the surface is used. It is also possible to manufacture the product and form fine irregularities by using an embossing roll or the like in a later step.

Further, the nubuck-like sheet material 1 of the present invention
1 is not limited to the one shown in FIG. 1, and may be one in which a foam layer 6 is provided between the base material 2 and the polyurethane resin lining layer 4 as shown in FIG. 2, for example. The foam layer 6 is a wet porous layer, a dry porous layer, or a dry foam layer of a polymer solution containing a polyurethane resin as a main component as described above. These foamed layers are formed by a known method such as a method of directly forming a foamed layer on a fiber base material, or a method of laminating a separately manufactured foamed layer on a fiber base material via an adhesive agent.

[0019]

EXAMPLES The present invention will be described in more detail with reference to specific examples below, but the present invention is not limited to the following examples. In the following description, “parts” or “%” is based on weight unless otherwise specified.

[Example 1] 100 parts of polyester-based polyurethane resin (Krisbon KS- was used) on a release paper (Ultra Suede, manufactured by Asahi Roll Co., Ltd.) having fine irregularities on the surface.
06, manufactured by Dainippon Ink and Co., Ltd.), 20 parts of a transparent colorant consisting of a daylight fluorescent pigment toned in yellow (Shin Loihi Color, manufactured by Dainippon Ink and Chemicals), and 20 parts of dimethylformamide and 20 of methyl ethyl ketone as a diluting solvent. Was mixed with a knife coater in an amount of 50 g / m ² · Wet and heated and dried at 90 ° C. for 2 minutes to form a polyurethane resin skin layer.

Next, on the surface of the polyurethane resin skin layer,
100 parts of polyester-based polyurethane resin (Resamine M
E44, manufactured by Dainichiseika Co., Ltd.), 20 parts of an opaque colorant toned in red (Dailac TV-color, manufactured by Dainippon Ink and Chemicals), and dimethylformamide 20 as a diluting solvent.
Part and 20 parts of methyl ethyl ketone were mixed to obtain a polyurethane resin-containing liquid with a knife coater at 120 g / m ²
-Coating with the amount of Wet, it heat-dried at 110 degreeC for 2 minutes, and formed the polyurethane-resin inner skin layer.

Further, 100 parts of a two-pack type polyester polyurethane resin (Crisbon 4010, manufactured by Dainippon Ink and Chemicals), and a cross-linking agent 1 are formed on the surface of the polyurethane resin intermediate layer.
2 parts accelerator 3 parts, and dimethylformamide 10 parts of 120 g / m ² of the polyurethane resin formulations liquid obtained by blending 20 parts of toluene with a knife coater as dilution solvent
・ Apply it in an amount of Wet, and place a raised surface with a raised surface on one side of a twill woven fabric made of a mixed yarn of polyester and rayon as a base material on this surface, press-bond and heat-dry at 120 ° C. for 3 minutes. Then, the adhesive was cured by aging it at 50 ° C. for 48 hours, and then the release paper was peeled off to obtain a sheet.

The sheet-like material obtained as described above has a nubuck-like appearance having fine irregularities on the surface, and has a color impression that has never been obtained by matching different hues of each layer with fine irregularities. It has a surface design, and the color tone of the surface changes subtly according to the viewing angle.When viewed from an oblique direction, the fine irregularities have a unique hue, and the convex parts are raised to make them look like a Ubu hair. It was

Example 2 100 parts of a polyester-based polyurethane resin (Resamine CU4310, Dainichiseika) was applied to a raised surface (moisture content 70%) obtained by raising one side of a twill woven fabric made of a mixed yarn of polyester and rayon. 780 g with a knife coater obtained by blending 3 parts of a surfactant, 10 parts of a colorant, 5 parts of a filler, and 50 parts of dimethylformamide as a diluent solvent with a knife coater.
/ M ² · Wet applied, then immersed in water at 20 ° C to solidify the polyurethane resin, then desolvated in warm water at 60 ° C for 50 minutes, washed with water, dehydrated, and hot air at 120 ° C And dried for 10 minutes to form a wet porous layer on the surface of the substrate.

On the other hand, 100 parts of silicone-modified polyester-based polyurethane resin (Resamine SP3190, Dainichi Seika Co., Ltd.) was placed on a release paper (AR-120, US-60, manufactured by Asahi Roll Co.) with a leather pattern having fine irregularities on the surface. Polyurethane resin obtained by blending 20 parts of violet-based transparent colorant (Dailac TV-color, manufactured by Dainippon Ink and Chemicals), and 25 parts of dimethylformamide and 25 parts of methyl ethyl ketone as a diluent solvent. The blended solution was applied with a knife coater in an amount of 100 g / m ² · Wet and heated and dried at 90 ° C. for 2 minutes to form a polyurethane resin skin layer.

Next, on the surface of the polyurethane resin skin layer,
100 parts of polyester-based polyurethane resin (Krisbon 348, manufactured by Dainippon Ink and Chemicals, Inc.), 20 parts of blue-colored opaque colorant (Dailac TV-color, manufactured by Dainippon Ink and Chemicals, Inc.), and 20 parts of dimethylformamide as a diluting solvent. 120 g of a polyurethane resin mixture obtained by mixing 20 parts of methyl ethyl ketone with a knife coater
/ M ² · Wet applied and dried by heating at 110 ° C. for 2 minutes to form a polyurethane resin intermediate layer.

Further, on the surface of the polyurethane resin intermediate layer,
The porous layer surface of the substrate on which the wet porous layer was formed was thermocompression bonded while being heated to 140 ° C., laminated and integrated, and then the release paper was peeled off to obtain a sheet-like material. .

The sheet-like material obtained as described above was a sheet-like material having a nubuck-like appearance in which a leather pattern was formed on the surface and fine irregularities were formed on the leather pattern surface. In addition, this nubuck-like sheet material has a surface design that has an unprecedented color feeling due to the matching of different hues of each layer with fine irregularities and leather patterns, and the contrast of the hue due to the unevenness of the thickness of each layer. Was further emphasized. Further, the color tone of the surface slightly changed depending on the viewing angle, and when viewed from an oblique direction, the fine irregularities had a unique hue, and the convex portions were raised to make them stand out and look like Ubu hairs.

[0029]

The nubuck-like sheet material of the present invention has a unique hue and an unprecedented surface due to the fine unevenness of the surface of the polyurethane resin skin layer and the polyurethane resin skin layer of different hues, and further the surface of the polyurethane resin skin layer. Has a design, for example, a bag, a bag, which requires a high design,
It is useful as a material for belts, shoes, sandals, etc.

[Brief description of drawings]

FIG. 1 is a partially enlarged cross-sectional view showing an embodiment of a sheet-like material of the present invention.

FIG. 2 is a partially enlarged sectional view showing another embodiment of the sheet material of the present invention.

[Explanation of symbols]

 1 ... Nubuck-like sheet-like material 2 ... Base material 3 ... Skin layer 4 ... Middle skin layer 5 ... Adhesive agent 6 ... Foam layer

Claims (1)

[Claims] 1. A polyurethane having a surface of a base material containing a polyurethane resin inner skin layer containing an opaque colorant and a transparent or translucent colorant having a hue different from that of the polyurethane inner skin layer, and having fine irregularities formed on the surface thereof. A nubuck-like sheet material in which resin skin layers are sequentially laminated.