JP3078208B2 - Nubuck-like sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to bags, bags, belts,
Shoes, sandals and other useful sheet materials,
More specifically, the present invention relates to a nubuck-like sheet having a hue and a surface design which have not existed conventionally.

[0002]

2. Description of the Related Art Conventionally, as one of materials such as bags, bags, belts, shoes, sandals, etc., a polymer solution mainly composed of a polyurethane resin is applied or impregnated on a fiber base material, and a non-solvent of the polyurethane resin is used. By wet solidification, grinding the microporous layer surface of the polyurethane resin formed on the fiber substrate,
A sheet-like material obtained by exposing the inner surface of the hole, or a sheet-like material obtained by grinding a microporous layer of polyurethane resin formed on the raised portion of the fiber base material and exposing a part of the fiber base raised portion. A sheet-like material having a nubuck or suede-like appearance, such as a material, is used.

[0003]

On the other hand, bags, bags, belts, shoes, sandals, and the like are required to have higher design properties, and natural leather, There is a demand for new sensations not found in materials such as synthetic leather and textiles. However, the nubuck or suede-like sheet material obtained as described above tends to have a monotonous and blurred hue, and it has been difficult to obtain an unprecedented new feeling. In particular, in order to prevent hue blurring, it is necessary to use a large amount of colorant or separately dye, which leads to problems such as an increase in material cost and an increase in product cost due to 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 an unprecedented unique hue and surface design. The purpose is to provide things.

[0005]

The nubuck sheet according to the present invention for solving the above-mentioned problems comprises a polyurethane resin intermediate layer containing an opaque colorant and a hue of the polyurethane resin intermediate layer on the surface of a substrate. and contain different transparent or translucent coloring agents, Ri Na polyurethane resin skin layer in which fine irregularities are formed are sequentially laminated on the surface, the polyurethane
The skin layer of polyurethane resin and the skin layer of polyurethane resin
Each polyurethane resin solution has a fine concave on the surface
Formed by being applied on release paper with convexity
It is characterized in that it is .

Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is a partially enlarged cross-sectional view showing one embodiment of a nubuck tone sheet-like material of the present invention, wherein reference numeral 1 denotes a nubuck tone sheet-like material of the present invention, reference numeral 2 denotes a substrate, and reference numeral 3 denotes a substrate. Reference numeral 4 denotes a polyurethane resin skin layer, and reference numeral 5 denotes an adhesive made of a polyurethane resin used as needed.

As the base material 2 used in the present invention, any base material conventionally used for materials such as bags, bags, belts, shoes, sandals and the like can be used. Generally, a knitted fabric, woven fabric, nonwoven fabric, or the like, which has been raised or raised as necessary, is used. The knitted fabric, woven fabric, non-woven fabric, etc. may be those to which an elastic polymer such as a polyurethane resin or a synthetic rubber has been added in advance.

The fibers constituting the base material 2 include synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, and polyvinyl alcohol; natural fibers such as cotton and hemp; and recycled fibers such as rayon, swoof, and acetate alone or in combination. Or a multicomponent fiber modified into ultrafine fibers by dissolving and removing at least one component or splitting a bicomponent fiber.

The polyurethane resin forming the polyurethane resin skin layer 3, the polyurethane resin intermediate 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 organic polyisocyanates, for example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, and aliphatic diisocyanate 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 fatty acids. 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.

[0010] The composition of the 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 sheet. It can be selected as appropriate.

The above-mentioned polyurethane resin, particularly the polyurethane resin used for the polyurethane resin skin layer 3 and the polyurethane resin middle coat layer 4, has a 100% modulus of 20%.
~ 200 kg / cm ² is preferred. If the 100% modulus is too low, the mechanical strength decreases, and if the 100% modulus is too high, the hand becomes hard.

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

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

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

The surface of the polyurethane resin skin layer 3 of the nubuck sheet-like material 1 of the present invention has fine irregularities 3a.
Are formed. Due to the fine irregularities 3a, the color tone of the surface changes delicately according to the viewing angle, and the convex portions of the fine irregularities 3a appear to be raised in the shape of a nap hair, thereby exhibiting a nubuck-like design. In addition, the concave portions of the fine irregularities 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 convex portions of the fine irregularities formed on the skin layer 3, and have a color tone that has not existed before. A nubuck-like sheet having the following contrast is obtained.

As a specific example of the method for producing the nubuck-like sheet of the present invention having fine irregularities in the polyurethane resin skin layer 3, a paper casting method using release paper having fine irregularities on the surface is exemplified. No. That is, first, on a release paper having fine irregularities on the surface,
The polyurethane resin solution for forming the polyurethane resin skin layer 3 is applied by means of a knife coater or the like and dried to gel the polyurethane resin, and then the polyurethane resin solution for forming the polyurethane resin skin layer on the polyurethane resin skin layer 3 is prepared. The polyurethane resin is gelled by applying and drying by means such as a knife coater. Next, an adhesive composed of a two-component polyurethane resin solution is applied onto the polyurethane resin intermediate layer 4 by means such as a knife coater, and then the substrate 2 is placed and pressed, dried and wound up, and then for several days. The temperature is maintained for reaction aging to complete the reaction of the polyurethane resin adhesive, and complete adhesion between the base material 2 and the adhesive layer 5, and between the adhesive layer 5 and the mesothelium layer 4. Thereafter, by releasing the release paper, fine irregularities on the surface of the release paper are transferred to the polyurethane resin skin layer 3, and the sheet-like material 1 having a nubuck appearance is obtained.

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

[0018]

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] Release paper (ultra suede,
Asahi Roll Co., Ltd.), 100 parts of a polyester-based polyurethane resin (Chrisbon KS-06, manufactured by Dainippon Ink) and 20 parts of a transparent colorant composed of a yellow-colored daylight fluorescent pigment (Shinroicolor, 50 g / m ² · W of a polyurethane resin compounded liquid obtained by mixing 20 parts of dimethylformamide and 20 parts of methyl ethyl ketone as a diluting solvent with a knife coater.
The resultant was applied in the amount of et and dried by heating 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 (Rezzamine M
E44, manufactured by Dainichi Seika Co., Ltd.), 20 parts of a red-based opaque colorant (Dailac TV-Color, manufactured by Dainippon Ink), and dimethylformamide 20 as a diluting solvent
Of a polyurethane resin obtained by mixing 20 parts of methyl ethyl ketone with 20 parts of methyl ethyl ketone by a knife coater at 120 g / m ^2.
-Wet-coated and dried by heating at 110 ° C for 2 minutes to form a polyurethane resin midcoat layer.

Further, 100 parts of a two-pack type polyester-based polyurethane resin (Chrisbon 4010, manufactured by Dainippon Ink) and a crosslinking agent 1
A polyurethane resin blended liquid obtained by blending 2 parts, 3 parts of an accelerator, and 10 parts of dimethylformamide and 20 parts of toluene as a diluting solvent was mixed at 120 g / m ² with a knife coater.
・ Wet-coating is applied, and a brushed surface of one side of a twill woven fabric made of a blend of polyester and rayon as a base material is placed on the surface, pressed and pressed, and heated and dried at 120 ° C. for 3 minutes. After aging at 50 ° C. for 48 hours to cure the adhesive, 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 an unprecedented color feeling due to the matching between the different hues of each layer and the fine irregularities. It has a surface design, and the color tone of the surface changes delicately according to the viewing angle, and when viewed from an oblique direction, the fine irregularities have a unique hue, and the raised portions are raised and appear to be conspicuous and have a nap-like appearance. Was.

Example 2 100 parts of a polyester-based polyurethane resin (Rezamin CU43) was formed on one side of a twill woven fabric made of a blended yarn of polyester and rayon, and brushed on one side (water content: 70%).
10, Dainichi Seika Co., Ltd.), 3 parts of surfactant, colorant 10
Parts, a filler of 5 parts, and a polyurethane resin compounded liquid obtained by mixing 50 parts of dimethylformamide as a diluting solvent with a knife coater in an amount of 780 g / m ² · Wet,
Then, after immersion in water at 20 ° C. to coagulate the polyurethane resin, the solvent was removed in warm water at 60 ° C. for 50 minutes, followed by washing with water,
After dehydration, the substrate was dried under hot air at 120 ° C. for 10 minutes to form a wet porous layer on the substrate surface.

On the other hand, 100 parts of a silicone-modified polyester-based polyurethane resin (Rezamine SP3190, Dainichi Seika Co., Ltd.) was placed on a release paper (AR-120, US-60, manufactured by Asahi Roll Co., Ltd.) having fine irregularities on the surface. Polyurethane resin obtained by blending 20 parts of a transparent colorant (Dailac TV-Color, manufactured by Dainippon Ink Co., Ltd.), and 25 parts of dimethylformamide and 25 parts of methyl ethyl ketone as diluting solvents. The blended solution was applied with a knife coater in an amount of 100 g / m ² · Wet, and dried by heating 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 a polyester-based polyurethane resin (Chris Bon 348, manufactured by Dainippon Ink), 20 parts of an opaque colorant toned in blue (Dailac TV-Color, manufactured by Dainippon Ink), and 20 parts of dimethylformamide as a diluting solvent 120 g of a polyurethane resin compounded liquid obtained by compounding and 20 parts of methyl ethyl ketone with a knife coater
/ M ² · Wet, 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 obtained above was formed was thermocompression bonded while heating 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 had a nubuck-like appearance in which a skin pattern was formed on the surface and fine irregularities were formed on the skin pattern pattern surface. In addition, this nubuck-like sheet-like material has a surface design having an unprecedented color feeling by matching different hues of each layer with fine unevenness and squeezed pattern, and a hue contrast due to non-uniform thickness of each layer. Was further emphasized. Further, the color tone of the surface was subtly changed according to the viewing angle, and when viewed from an oblique direction, the fine irregularities exhibited a unique hue, and the protruding portions were raised and conspicuous and looked like Ubu hairs.

[0028]

The nubuck sheet according to the present invention has a unique hue and an unprecedented surface due to the fine irregularities on the surface of the polyurethane resin skin layer and the polyurethane resin skin layer having different hues, and the surface of the polyurethane resin skin layer. Has a design, for example, bags, bags, high design is required,
It is useful as a material for belts, shoes, sandals and the like.

[Brief description of the drawings]

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

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

[Explanation of symbols]

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

Claims (1)

(57) [Claims] 1. A polyurethane resin intermediate layer containing an opaque colorant, a transparent or translucent colorant different from the hue of the polyurethane resin intermediate layer on the surface of the base material, and fine irregularities are formed on the surface. A nubuck-like sheet material in which a polyurethane resin skin layer is sequentially laminated , wherein the polyurethane resin skin layer and the polyurethane resin middle skin
The layers are displayed in this order with the respective polyurethane resin solutions.
Being applied on release paper with fine irregularities on the surface
Nubuck characterized by being formed by
Toned sheet .