JPS5919010B2 - Manufacturing method for sheets with excellent three-dimensional appearance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a sheet with excellent three-dimensional effect.

More specifically, the present invention relates to a method for producing a sheet with excellent three-dimensional effect by treating the surface of a substrate having irregularities with a specific roll. Sheets made of a fibrous base material and a polymer layer, or sheets made only of a polymer, are often used for interior materials, shoes, bags, J-cases, balls, belts, etc. The appearance of the sheet, especially the color and gloss of the surface, together with the properties of the substrate, are important factors that influence the commercial value. In the past, the color and gloss of the surface of the sheet were often uniform, but recently, the color and gloss of the sheet surface are non-uniform. Also, due to the synergistic effect with gloss, it looks more three-dimensional and has a luxurious feel, so it has become popular. A method for obtaining a sheet having such an appearance is as follows: a method of spraying or gravure a polymer solution of an arbitrary composition onto the surface of a substrate having an uneven pattern so as to create a color difference or gloss difference along the uneven pattern; A commonly used method is to apply an arbitrary polymer composition having poor abrasion resistance to a substrate and then polish the polymer layer with a special stone or cloth.

Among these methods, the spray method is a method often used for natural leather, and is effective even if the depth of the uneven pattern on the sheet surface is relatively small. However, it is difficult to work with and has poor productivity when mass production. It is unsuitable for

On the other hand, the conventional gravure method is effective when the depth of the uneven pattern on the sheet surface is large, that is, when the depth is about 200 μm or more, but it is not possible to obtain the desired appearance when the depth is less than that. Furthermore, as mentioned above, the method of using abrasives is mostly done manually after making final products such as shoes and bags, which is not only difficult to apply to mass production, but also requires time to polish and is prone to staining. Alternatively, a shallow grain with a small difference in unevenness has the disadvantage that it is difficult to obtain the desired appearance, that is, it is difficult to obtain a color or grain difference that faithfully follows the unevenness of the substrate surface. Therefore, even if there are no such operational or production defects and the depth of the uneven pattern on the substrate surface is small, it is difficult to obtain a product with a bright color or gloss difference between the concave and convex areas. This was a major challenge for everyone involved. As a result of extensive research into finishing agents and finishing methods, the inventors of the present invention have found that a roll with unevenness, a so-called friction roll, is a roll with an unevenness, in which a solvent for the substrate is adhered to the surface of a substrate whose uneven pattern, color, and line are arbitrarily adjusted. It has been found that by bringing the sheets into surface contact and operating them in a frictional manner, it is extremely easy to obtain a sheet in which the concave portions and convex portions have different colors or glosses even when the depth of the concavo-convex pattern is shallow.

In other words, the present invention uses a specific roll under specific conditions when partially dissolving and removing only the convex portions on the surface of a substrate having irregularities to create a three-dimensional and deep-colored appearance. With the present invention, for the first time, it has become possible to obtain a product with a very luxurious feel and high commercial value with good workability and productivity, regardless of the uneven pattern.

First, the substrate in the present invention consists of a fibrous base material and a polymer layer or only a polymer.

The fibrous base material is a sheet-like material mainly composed of fibers such as nonwoven fabric, woven fabric, or knitted fabric, which is optionally impregnated and coagulated with a polymer as a binder.

Common fibers can be used here, including cotton, linen, wool, rayon, acetate, nylon, polyester, polyacrylonitrile, pinylon,
Not only single spun fibers such as polyolefin, but also mixtures thereof, composite spun fibers, etc. can be used. As the binder optionally added to the above-mentioned fibrous base material, any binder that is generally used for synthetic leather etc. can be used, such as natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer. Combine,
Polyvinyl chloride, polyurethane, other synthetic rubbers, or mixtures thereof are used.

These binders are applied in a solution, emulsion, or other form as required by an impregnation method, a coating method, or the like.

The amount of adhesion is usually within 150% of the fiber. Form a polymer coating layer on one side of the fibrous base material.

The coating layer corresponds to the silver surface of ordinary leather, and has a texture, texture,
Porous is preferable from the viewpoint of creases, physical properties, etc. As the polymer, polyurethane, acrylonitrile-butadiene copolymer, polypinyl chloride, polyamide, etc. can be used, and among them, polyurethane elastomer is preferred. The polymer may contain fillers, softeners, stabilizers, antistatic agents,
In addition to pigments, dyes, blowing agents, coagulation regulators, etc., polymers with good compatibility in solution state, such as polyvinyl chloride, polyvinyl acetate, polyvinyl formal, polyacrylic acid resin, pinylidene chloride-acrylonitrile copolymer , pinychloride-vinyl chloride copolymer, etc. can be mixed.

Although a coating method is preferred as the method for applying the polymer solution to the fibrous base material, it is also possible to separately prepare a polymer coating layer and bond it together. Further, as the substrate of the present invention, a porous or non-porous sheet consisting only of the same kind of polymer as the above-mentioned coating layer can also be used.

The substrate may be suitably colored or may further have a surface layer made of a polymer on its surface.

A polymer having a different solvent solubility from that of the underlying polymer layer is used as the surface layer, and additives such as colorants, erasers, metallic agents, burl agents, fluorescent agents, etc. are added to obtain the desired product. It is particularly preferable to use a composition in which additives for obtaining physical properties, such as anti-yellowing agents, antioxidants, plasticizers, etc., are mixed, since the dissolution friction removal operation in the subsequent step is considerably facilitated. Polymers used for the surface layer include cellulose nitrate, cellulose acetate, nylon, polyamino acid resin,
Examples include polyacrylic acid resin, synthetic rubber, etc., and in principle, any polymer can be used as long as it is different from the polymer layer described above and is soluble in a solvent.

If polyurethane elastomer is used in the polymer layer, the degree of nitrification is N9.5 to 13.0% by weight.
Cellulose nitrate is most suitable because it is easy to dissolve and remove friction.
The thickness of the surface layer is preferably 10 μm or less because if it is too thick, it will take a long time to remove the friction and the bending resistance of the product will decrease. Further, in the present invention, it is an essential condition that an uneven pattern exists on the surface of the substrate.

The uneven pattern is an arbitrary uneven pattern (embossed pattern) on the base surface.
It can be obtained by fabricating it on a certain support, or by stamping it with a metal plate or roll having an arbitrary uneven pattern. In the conventional method, the depth of the uneven pattern is a major factor that affects the three-dimensional appearance of the product, and it is
Although it was effective only for products with deep grains of the above degree, the present invention can be used not only for products with deep grains, but also for products with shallow grains of 50 μm or less without any problem. Next, the surface of the substrate is brought into surface contact with a friction roll having irregularities to which a solvent is adhered, and a portion of the surface of the convex portion of the substrate is dissolved and left by friction.

In principle, any solvent can be used as long as it dissolves the surface of the substrate, and it is necessary to have an appropriate drying rate in consideration of productivity. Specifically, toluene, cyclohexanone, dimethylformamide, dichloroethane, methanol, ethyl citrate, tetrahydrofuran, acetone, etc. or a mixture thereof can be used. The friction roll must have irregularities in order to allow these solvents to adhere uniformly and to more effectively remove the dissolving friction from the substrate surface.

The hardness of the friction roll may also be an important factor in achieving the present invention, where the unevenness is preferably obtained by engraving or foaming, has a depth of 5 μ or more, and has a shape that increases the coefficient of friction on the surface. Even when using a relatively soft material, it is better if the measured hardness is 10 degrees or more, preferably 20 degrees or more according to Japanese Industrial Standard JIS K63Ol (spring type hardness test), and generally metal, especially iron grapia rolls are used. is desirable.

When processing a substrate with small unevenness by using a foam or cloth with a hardness of 10 degrees or less as a friction roll, the surface layer is dissolved and frictionally removed up to the surface of the recesses of the sheet, resulting in the desired three-dimensional shape. You cannot get a sheet with a good feel. In order to selectively and efficiently dissolve and friction remove only the convex portions on the substrate surface, it is important to control the contact pressure, contact area, and friction speed between the substrate surface and the friction roll.

Of course, the higher the contact pressure, the better the dissolution friction removal effect, but if it is too high, the effect will extend to the recesses, and you may not be able to obtain the desired product. It needs to be adjusted appropriately. Therefore, especially in shallowly textured products, the contact pressure should be lower, and in this case the pressure is preferably adjusted by adjusting the tension of the base sheet. The friction speed is determined by the relative speed between the feed speed of the base fabric and the circumferential speed of the friction roll, and of course, the higher the speed, the better in terms of productivity.

The dissolving friction removal work can be carried out either when the feeding direction of the base fabric and the rotational direction of the friction roll are the same or reversed, but the circumferential speed of the friction roll is made larger than the feeding speed of the base fabric. It is necessary to do this efficiently. The larger the contact area between the substrate surface and the friction roll, the more efficient the surface layer can be removed by friction. Therefore, in order to carry out industrial production according to the present invention, guide rolls whose centers are on a line that is at least 5 degrees different from the line connecting the point where the base first contacts the friction roll and the center of the friction roll are moved up and down. Alternatively, a method and apparatus for adjusting the contact area between the friction roll and the substrate by moving the friction roll in the left-right direction is particularly effective. The sheet obtained in the manner described above had an excellent three-dimensional effect due to the synergistic effect of the uneven pattern and the color or gloss difference, and had a luxurious feel and high commercial value. The present invention will be specifically described below with reference to Examples. Note that all percentages in the examples are based on weight. Example 1 Polycaprolactone glycol,
Ethylene glycol and diphenylmethane-4,4'-
A nonwoven fabric made of nylon fibers is impregnated with a solution consisting of 10% polyurethane elastomer synthesized from diisocyanate, 2% polyvinyl chloride, 1 (!) titanium oxide, and 87% dimethylformamide, and the same solution is applied on top of this at a solid content of 7%.
07/d, and then treated with an aqueous solution containing 30% dimethylformamide at 40° C. for 30 minutes, followed by solvent removal and drying.

Next, on this surface, 6% polyurethane elastomer of the same type as above and 1% polyvinyl chloride LanylBrOwn were applied.
3R [manufactured by Sumitomo Chemical Co., Ltd.] 2%, dimethylformamide 26%, acetone 29% and cyclohexanone 36
% solid content of a solution consisting of 2f/n? The substrate 1 was obtained by applying the coating almost uniformly so that the coating was applied, and then embossing a fluid skin pattern with a depth of 86 μm using an embossing roll. Furthermore, the surface of a part of the substrate 1 has a nitrification degree of NlO. 8 (L cellulose nitrate 5%, dibutyl phthalate 3%, castor oil 2%) Ne
OzapOnBrOwnBE (manufactured by 2ゞDateshiyu Co., Ltd.) 1
．． A solution consisting of 6% NeOzapOnBlueFLE (manufactured by Badeish), 0.4% thinner and 88% thinner was applied almost uniformly at a solid content of 1.5 f/d and dried to produce a substrate. lastly. The above-mentioned substrate was lightly placed by 22 cm in the length direction on the surface of a graphia roll (friction roll) which rotated at a speed of 20 m/min and had 100 meshes of grooves with a depth of 20 μ in a grid pattern so that new solvent always adhered. in contact with the gravure roll at a speed of 7 in the opposite direction to the rotating direction of the roll.
It passed at m/min. However, in the case of substrate 1, a mixed solvent of 30% dimethylformamide and 70% acetone was used as the solvent, and in the case of substrate 1, thinner 1 was used.
Both Sheet A obtained from Substrate 1 and Sheet B obtained from Substrate 1 had a much more valley dyeing effect, that is, a three-dimensional effect, and had higher commercial value than Substrate 1 produced by the conventional method. Real TMflJ2 Polyurethane elastomer 6 synthesized from polytetramethylene glycol, ethanolamine, and tolylene diisocyanate on release paper soil with a rough texture pattern of 45 μ in depth! , Azo red pigment [manufactured by Dainichiseika Chemical Co., Ltd.] 1 (
L, dimethylacetamide 22% and dioxane 39%
and a solution consisting of 32% tetrahydrofuran with a solid content of 12f/Rr? Apply and dry.

Claims (1)

[Scope of Claims] 1. A roll having an uneven surface to which a solvent is attached when producing a sheet with a three-dimensional effect by treating the convex portions of a substrate having an uneven pattern on the surface with a solvent and dissolving and removing a portion thereof. (hereinafter referred to as a friction roll) and the surface of a substrate are brought into surface contact with each other, and an operation is performed so as to cause friction. 2. The sheet manufacturing method according to claim 1, wherein the peripheral speed of the friction roll is faster than the sheet feeding speed. 3. The sheet manufacturing method according to claim 1 or 2, wherein the feeding direction of the substrate and the rotating direction of the friction roll are reversed. 4. The sheet manufacturing method according to claim 1, 2, or 3, wherein the friction roll is a gravure roll. 5. The method of manufacturing a sheet according to claim 1, wherein the contact pressure between the base and the friction roll is adjusted by adjusting the tension of the base. 6. The method for producing a sheet according to claim 1, wherein the substrate is composed of a fibrous base material and a polymer layer. 7. Claim 1 in which the substrate has a polymer layer and a surface layer in which the polymer layer has a different solubility in a solvent.
Method of manufacturing the sheet described in Section 1. 8. The method for producing a sheet according to claim 1, wherein the surface layer solvent is used as the solvent for adhering to the friction roll. 9. The friction roll and the base are moved vertically or horizontally by moving a guide roll whose center is on a line that differs by at least 5 degrees from the line connecting the point where the base first contacts the friction roll and the center of the friction roll. A method for manufacturing a sheet according to claim 1, wherein the contact area of the sheet is adjusted.