JPS5917226B2 - Manufacturing method for leather-like sheet material with rich color changes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a leather-like sheet material with a rich color change and a luxurious appearance.

Leather-like sheet products are used as substitutes for natural leather for shoes, balls, etc.
Widely used for bags, clothing, interior materials, etc.

In the past, the color of the surface of the leather-like sheet material was relatively uniform and flat, but recently, the color of the surface of the leather-like sheet material has been relatively uniform and flat, but recently, the color of the surface of the leather-like sheet material has been changed to three-dimensional colors that are deep and look more luxurious. ing.

One method for manufacturing such leather-like sheet materials has been proposed in which a composition comprising nitrocellulose and a pigment is applied as a finishing agent, and then the finishing layer is unevenly polished.

The leather-like sheet material obtained by this method has an extremely three-dimensional and vivid color, giving it a very luxurious feel compared to leather-like sheet materials obtained by other conventional methods.

However, with this method, the polishing work is quite difficult, and it is difficult to achieve the desired uneven polishing, especially in the case of mass production, where polishing work must be performed before the final product is manufactured. A pattern was obtained, but there was a dark defect.

Furthermore, the leather-like sheet material obtained by this method also had the drawback of poor bending resistance.

As a result of extensive research into finishing agents and finishing methods, the present inventors were able to apply a polymer that has good affinity with the coating layer to the surface of a substrate consisting of a fibrous material and a coating layer. Then, a resin solution consisting of a colorant, a plasticizer, and cellulose nitrate with a degree of nitrification (N) of 9.5 to 13.0 by weight is applied, and then a resin solution that has an affinity with the resin but is more abrasion resistant than this is applied. It has been found that by non-uniformly applying a polymer having high properties and then polishing, it is possible to obtain a leather-like sheet material which has no defects as described above, has a very rich color change, and has a luxurious feel.

That is, an object of the present invention is to provide a method for producing a leather-like sheet material having a desired color and pattern and good bending resistance with high productivity.

With the present invention, for the first time, it has become possible to mass-produce leather-like sheet materials with rich color changes, a luxurious feel, and good physical properties.

The fibrous material in the present invention is a sheet-like material mainly composed of fibers such as nonwoven fabrics, woven fabrics, and knitted fabrics, and is optionally impregnated with and coagulated with a polymer as a binder.

The fibers that can be used include ordinary fibers such as cotton, hemp, wool, rayon, acetate, nylon, polyester, polyacrylonitrile, bisilon, and polyethylene, as well as their mixtures or Examples such as composite prevention fibers can also be used.

As the binder optionally added to the above-mentioned fibrous material, any binder commonly used in synthetic leather or the like can be used, such as natural rubber, styrene, etc.
Butadiene copolymers, acrylonitrile-butadiene copolymers, nylon, polyacrylic acid resins, polyvinyl chloride, polyurethane elastomers, 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, a spray method, etc., and the amount of the binder deposited is usually in the range of 150% by weight or less per fiber.

A coating layer is formed on one side of the fibrous material thus obtained.

The coating layer corresponds to the silver surface of natural leather, and preferably has a porous structure from the viewpoint of texture, creases, physical properties, etc.

For the coating layer, polyurethane elastomer, polyvinyl chloride, nylon, polyamino acid resin, etc. are used.

Among these, polyurethane elastomers are particularly preferred because they can easily form a porous structure and have good scratch resistance, bending resistance, and texture.

Polyurethane elastomer has a molecular weight of 500 to 4000
Ethylene glycol with soft segments such as polyethylene glycol, polytetramethylene glycol, polyethylene adipate glycol, polyhexamethylene adipate glycol, polycaprolactone glycol, etc.
butanediol hexanediol, ethanolamine,
It consists of a chain extender such as hydrazine or 4,4'-methylenebis(2-chloroaniline) and an incyanate such as diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate.

The polyurethane elastomer is desired to have appropriate hardness from the viewpoint of heat resistance, surface strength, bending resistance, tactile feel, etc., and it is usually preferred that the nitrogen content based on diisocyanate is 3 to 7 parts by weight.

The polyurethane elastomer contains fillers, pigments, softeners, stabilizers, antistatic agents, gloss modifiers, etc., as well as polymers with good compatibility in a solution state, such as polyvinyl chloride, polyvinyl acetate, polyvinyl formal, etc. polyacrylic acid resin,
A copolymer of vinylidene chloride and acrylonitrile, a copolymer of vinyl chloride and vinyl acetate, etc. can be mixed as necessary.

Method C' of applying the polymer solution to the fibrous material: The coating method is preferred, but it is also possible to prepare a separate coating layer and bond it together.

A polymer layer is applied onto the coating layer of the substrate thus obtained.

Any polymer can be used as long as it has good affinity with the coating layer, but polyurethane elastomer is particularly preferred.

The coating amount of the polymer is 0.2g/rrj to 10g in terms of solid content.
β is appropriate.

Various additives such as a coloring agent may be mixed into the polymer layer according to preference.

Next, a colorant, a plasticizer, and a degree of nitrification (N) of 9.5% by weight or more
A resin bath solution containing 13.0 weight molecules of cellulose nitrate is applied.

As the colorant, either dye or pigment can be used.

When dyes are used as coloring agents, brighter colors can be obtained than when using only pigments, and the advantage is that many different colors can be easily obtained by heat treatment after the resin layer is applied, and many brands can be produced. has.

The appropriate amount of the coloring agent to be used is 5 to 300 parts by weight based on the resin, depending on the color feel, adhesion to the coating layer, bending resistance, etc.

Common plasticizers include commercially available tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, dibutyl phthalate, dioctyl phthalate, butyl phthalyl butyl glycolate, polyvinyl methyl ether, ethyl abietate, and triacetin. In addition to olive oil, castor oil, coconut oil, palm oil, linseed oil, cottonseed oil, pepper oil, cow leg oil, etc.
Sulfated and epoxidized products of these are used.

The amount of plasticizer used depends on bending resistance, texture, migration properties, abrasiveness,
20 weight φ ~ 250 for 1 resin due to surface strength etc.
The weight section is appropriate.

Further, as mentioned above, the degree of nitrification (N) of cellulose nitrate is preferably in the range of 9.5% by weight to 13.0% by weight because common paint solvents can be used and abrasive properties are good.

The bath agents used to prepare the resin solution include acetone, ethyl acetate, butyl acetate, methyl ethyl ketone,
Examples include methylbutylketone, methanol, phthanol, benzene, toluene, xylene, dimethylformamide, and dimethylacetamide.

It is more advantageous in terms of productivity to apply the resin solution by gravure printing than by spraying.

The coating amount of the resin solution is 0.2 g/co~10 ji/rrr in terms of solid content from the viewpoint of productivity, color feel, bending resistance, abrasiveness, etc.
is desirable.

Furthermore, this surface has an affinity for cellulose nitrate, which is the resin mentioned above, and has an abrasion resistance of 10 or more, preferably 5.
0% or more larger polymer is applied non-uniformly.

Here, abrasion resistance refers to the thickness of approximately 2 μm on a colored support.
A non-porous film of polymer (resin) was applied, and AST
In place of the wear ring according to MD-1175, BrushWAX-Quinn A with the same shape and size as this one.
4602 under a load of 500 g and checking the number of times the support was exposed.

As the polymer, the same types as those for the above-mentioned coating layer can be used, but among them, polyurethane elastomer or a mixture of this and cellulose nitrate is easy to obtain appropriate wear resistance.
It is preferable because it has good bending resistance.

The polymer is applied by spraying or using a roll (patterned plate) engraved with a desired pattern, and the amount of application is 0-2 g in solid content from the viewpoint of folding, bending resistance, abrasion resistance, etc. /rrl
~10.9/m'' is desirable.

Finally, polishing is performed using an appropriate method before or after making final products such as shoes or bags.

The leather-like sheet material produced according to the present invention has been devised as described above so that the desired color and pattern can be obtained in advance, so that polishing work can be easily performed without special consideration even before making the final product. It has the advantage of being flexible, making mass production possible, which was difficult with conventional leather-like sheets.

Furthermore, the leather-like sheet material of the present invention has a more three-dimensional color than the leather-like sheet material obtained by other methods, that is, by simply applying a colored polymer bath liquid by spraying or using a roll engraved with a certain pattern. It has an excellent feel and a luxurious feel.

In addition, in the present invention, when a dye that is heat transferable is used in at least one of the surface layers, heat treatment at a temperature range of 70 to 250 ° C. before polishing facilitates coloring. This is preferable in terms of diversification.

The present invention will be explained below with reference to specific examples.

Note that all figures in the examples are based on weight EC.

Example 1 Polytetramethylene glycol, diphenylmethane-4
A nonwoven fabric of polyester fibers was impregnated with a solution consisting of 10% polyurethane elastomer synthesized from , 4'-diisocyanate and ethanolamine, 3 parts polyvinyl chloride, and 87 parts dimethylformamide, and the same bath solution as above was applied on top of this in a solid content. 70,! Apply 9/mE evenly and then apply 30% dimethylformamide containing 30%
After being immersed in a water bath solution at 30° C. for 30 minutes to solidify, the solvent was removed and dried to produce a porous substrate.

Next, part 5 of the same type of polyurethane elastomer as above, 2% polyvinyl chloride, part 3 of azo red pigment (manufactured by Inu Nissei Kagyo KK), and part 3 of azo yellow pigment (manufactured by Inu Nissei Kagyo KK).
A solution consisting of 1% dimethylformamide, 31% dimethylformamide, 36 parts methyl ethyl ketone, and 22 parts toluene has a solid content of 3 parts.
After coating to a ratio of g/m and embossing a rough pattern, add 5% cellulose nitrate with a degree of nitrification (N) ■ θ.
, 4% dioctyl phthalate, 2 parts castor oil, 1 part carbon black, 46% ethyl acetate, and 42% toluene.
A leather-like sheet material FA) was produced by applying a solution consisting of the resin component L5i/all over the area.

In addition, 1 piece of the leather-like sheet material (a part of N was taken, 5 pieces of polyurethane elastomer of the same type as above, and 2 pieces of polyvinyl chloride, whose abrasion resistance is higher than that of cellulose nitrate) were added.
tly, 0.6% silicon oxide, 27% dimethylformamide, 36% methyl ethyl ketone, and 29% toluene.
A leather-like sheet material (B) was produced by applying a solution containing 4% to a solid content of 2.5jj/m' using a gravure roll engraved with streak patterns.

Finally, the leather-like sheet material (N) and (B) were polished almost uniformly with cotton cloth, as shown in Table 1. In product (B), the desired pattern was clearly obtained, and the color was extremely three-dimensional and had a luxurious feel.

In addition, when shoes were made using this material, a leather-like sheet material (
B) O shoes are much more l than those of leather-like sheet material (A)
This product had a high value.

Example 2 On a polyethylene sheet embossed with a hair tie pattern (polyurethane elastomer 6 synthesized from polyethylene glycol, diphenylmethane-4゜4'-diisocyanate and ethylene glycol, cadmium-based red pigment (manufactured by Inu Nisseika Kogyo KK) ) A solution consisting of 28% dimethylacetamide, 48% dioxane, and 16% acetone was applied to give a solid content of 79/rri', and after drying, a non-porous film was prepared.

The non-porous film was then adhered to a woven fabric of nylon fibers raised with a solution of cross-linked polyurethane elastomer, then peeled off from the polyethylene sheet, and 8% of the same type of polyurethane elastomer as above, 28% of dimethylacetamide, 2.5g of solid content of bath liquid consisting of 39% tetrahydrofuran and 25% cyclohexanone
/m.

In addition, the degree of nitrification is 12.6%, 5% cellulose nitrate, Lany
A bath liquid consisting of 1% yellow G (manufactured by Sumitomo Chemical Industries KK), 1.6% of an ab-based brown pigment (manufactured by Inunichisei Kagyo KK), 0.4% carbon black, 56% methyl ethyl ketone, and 36% toluene was mixed with solid content. So 3.29/rrl
(After applying this, spray the polyurethane elastomer solution with the same composition as the one applied to the above substrate to obtain the desired pattern when polishing.
When the leather-like sheet material (C) produced in this way was coated with 9/rrr and then heat-treated at 150°C for 5 minutes and polished in the same manner as in Example 1, the color changed easily (rich, three-dimensional). A luxurious color was obtained.

Claims (1)

[Scope of Claims] 1. After applying a polymer having good affinity with the coating layer to the surface of a substrate consisting of a fibrous material and a coating layer, a nitrification degree (N) of 9 containing a colorant and a plasticizer is applied. A resin bath solution mainly composed of cellulose nitrate with a weight ratio of .5 to 13 wt. A method for producing a leather-like sheet material with a rich color change, which is characterized by applying a color to the material and then polishing it. 2. The method for producing a leather-like sheet material according to claim 1, characterized in that a dye or a pigment together with the dye is used as a coloring agent in the resin bath liquid.・3 After applying the resin solution and before polishing, the temperature is 70℃~
A method for producing a leather-like sheet material according to claims 1 and 2, characterized in that the heat treatment is carried out at -250°C. 4. A method for producing a leather-like sheet product according to claim 1, using a nonwoven fabric impregnated with an elastic polymer as the fibrous material. 5. A method for producing a leather-like sheet product according to claim 1 or 4, in which a porous elastic polymer is used in the coating layer. 6. An elastic polymer coating layer impregnated into a fibrous material, a polymer that has good affinity with the coating layer, and a polymer that has an affinity with cellulose nitrate, but has better abrasion resistance than this, such as a polyurethane elastomer. A method for producing a leather-like sheet material according to claim 1. 7. A method for producing a leather-like sheet product according to claim 1, wherein the coating layer is colored and/or stamped.