JPS5912788B2 - Suguretaritsutaikannoerareruhikakuyoshi - Tobutsu no Seizouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a leather-like sheet product that provides an excellent three-dimensional effect.

As fashion has become more and more popular in all fields and luxury has been strongly discouraged, the quality of the surface finish of leather-like sheets, especially the quality of the surface color, has become an extremely important element that influences the value of the product.

Conventionally, the surface color of the leather-like sheet material has been relatively uniform and flat, but recently three-dimensional colors have become more preferred because they have a deeper and more luxurious appearance.

The three-dimensional coloring of leather-like sheets has been done so far: 1. Applying color shading by spraying; 2. Applying color shading using a roll engraved with a non-uniform pattern; and 2. Adjusting to any color. A method is used in which a nitrocellulose solution whose color has been adjusted with a pigment is applied again to the base, and then a part of the outermost layer is removed.

However, the spray method (■) requires a high level of skill and has drawbacks such as poor workability, and the method (■) using an engraved roll produces uniform colors and patterns that cannot be tailored to individual tastes. None of these methods were satisfactory, as they had drawbacks such as the lack of a desired color or pattern on the final product, such as shoes, bags, interior decorations, etc.

On the other hand, the method (2) in which two types of colored layers are provided and a portion of the outermost layer is removed does not have any of the drawbacks of the above two methods.

In other words, with this method, it is possible to obtain a leather-like sheet material that is easy to work with and has a unique three-dimensional effect without requiring a high degree of skill.

However, this method also has one major drawback.

This means that in order to obtain one product, the color of the base layer must be adjusted and then the color of the outermost layer must be adjusted, which means that one brand must be colored twice.

This type of coloring work is one of the most important jobs in the finishing process, and this work involves finishing even just one coloring process, that is, coloring, embossing, enamel processing, and polishing. This accounts for most of the costs required for adjustments.

Especially in today's world, when there is a strong demand for multiple brands of products, coloring a single brand twice will complicate the process and waste time, resulting in a significant drop in productivity. This leads to an increase in the cost of large-scale products.

Therefore, it has been a major challenge for those concerned to obtain a leather-like sheet product that is free from the above-mentioned drawbacks in terms of production and work, and has a unique and excellent three-dimensional effect.

The inventors of the present invention have conducted extensive research in order to address the above-mentioned problems. As a result, we first applied a polymer mainly composed of polyurethane elastomer to the surface of the substrate, and then added a solvent for the polymer into the surface layer. Applying a resin solution consisting mainly of cellulose nitrate containing a dye soluble in an organic solvent while the dye is present to a certain extent.Thus, the color of the surface transfers appropriately to the base layer, and the base layer becomes stronger than the outermost layer. Since the material is almost colored, the inventors have discovered that by removing a portion of the outermost layer at the end, a leather-like sheet material with excellent three-dimensional effect can be obtained very easily, and the present invention has been achieved.

In other words, the present invention provides all at once a leather-like sheet product that can provide an excellent three-dimensional effect with one coloring process. It has become possible to obtain leather-like sheets with excellent commercial value.

In addition, since the present invention uses dye instead of the conventionally used pigment as a coloring agent, it is possible to obtain vivid colors on the irises that were previously unavailable, which has the advantage of further increasing the sense of luxury. have

□ First, the base of the leather-like sheet material of the present invention is composed of a fiber aggregate and a polymer mainly composed of polyurethane elastomer.

As the fiber assembly method, woven or nonwoven fabrics of single spun fibers such as staple fiber, rayon, nylon, polyester, polypropylene, etc. or mixed spun fibers of nylon, polyester, polypropylene, etc., and polyethylene, polystyrene, etc. are used.

In addition, as a polyurethane elastomer, the molecular weight is 500~
Soft segments such as 4000 polyethylene glycol, polytetramethylene glycol, polyethylene adipate glycol, polyhexylmethylene adipate glycol, polycaprolactone glycol, ethylene glycol, butanediol, hexamethylene glycol,
Chain extenders such as nolamine, hydrazine, 4,4/-methylabis(2chloroaniline) and Schifthenylmethane-4,4'-diisocyanate, tolylene diisocyanate
It consists of diisocyanates such as anate and hexamethylene diisocyanate.

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 formal, and polymethyl acrylate. , a copolymer of vinylidene chloride and acrylonitrile, a copolymer of vinyl chloride and vinyl acetate, etc. can be mixed as necessary.

The base of the leather-like sheet material is a fiber obtained by combining the above-mentioned fiber aggregate or a fiber layer filled with a polymer mainly composed of polyurethane elastomer and a coating layer of a polymer mainly composed of polyurethane elastomer. It is desirable that at least one of the layers or the polymer of the coating layer has a porous structure in view of texture, creases, physical properties, etc.

The surface of the substrate is coated with a solution of a polymer mainly composed of polyurethane elastomer having a nitrogen content of 3% to 7% by weight based on diisocyanate as a solid content of 0.2g/m to 7% by weight.
Apply 10g/m.

The same polyurethane elastomers as in the case of the above-mentioned substrate can be used for the polymer layer, but among them, polyurethane elastomers containing polyethylene glycol in the soft segment are the best from the viewpoints of necrochromia, color clarity, and light resistance. be.

If the amount of nitrogen based on diisocyanate in the polyurethane elastomer is less than 3% by weight, heat resistance, solvent resistance, resistance, etc. will be poor, and conversely, if it is more than 8% by weight, bending fatigue strength, folding wrinkles, etc. will be poor. Deteriorate.

Further, the polyurethane elastomer may also contain additives or polymers similar to those used for the above-mentioned substrate.

The coating amount of the polymer is determined from 0.2 g/m to 109/m in terms of solid content based on color development, bending fatigue strength, creases, texture, etc.
m is appropriate.

Next, a solvent for the polymer is added to the surface layer, that is, the substrate surface layer and the polymer layer at a rate of 2 g/tri' to Ioog/m'.
A colored layer is applied in a state where it is present.

The amount of solvent present in the surface layer is 2'9/rt? In the following cases, there is little color transfer from the colored layer to the base (polymer layer), making it difficult to obtain the desired color;
0. When it exceeds p/m, severe tack often occurs, which impedes the application of the next colored layer.

Methods for making the solvent exist in the surface layer include leaving a necessary amount of the solvent in the polymer solution applied as described above, or applying the necessary amount of solvent again after the polymer i has been applied. .

Examples of the solvent include dimethylformamide, diethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, cyclohexanone, toluene, and mixtures of these with non-solvents such as methanol, ethyl acetate, and water.

Next, a colored layer is applied.

The colored layer contains a dye soluble in an organic solvent in an amount of 5% to 300% by weight based on the resin and a plasticizer in an amount of 20% to 250% by weight based on the resin, and has a degree of nitrification (N) of 9.5. weight%
It is formed by applying a resin solution mainly composed of ~13.0% by weight of cellulose nitrate with a solid content of 0.2 g'/m ~109/rn and drying.

If the amount of dye used is less than 5% by weight, it will be difficult to obtain the desired color, and if it exceeds 300% by weight, not only will the adhesion with the polymer layer deteriorate, but the migration resistance, flexural fatigue strength, etc. will deteriorate. Deteriorate.

Any dye that is soluble in an organic solvent can be used, but metal complex dyes are the best in terms of light resistance, migration resistance, color development, etc.

Plasticizers include commonly commercially available tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, dibutyl glycolate, polymethyl ether, ethyl abietate, triacetin, etc., as well as olive oil, castor oil, and coconut oil. Oil, palm oil, linseed oil, cottonseed oil, pepper oil, cow leg oil, etc., or sulfated or epoxidized products thereof are used.

If the amount of the plasticizer used is less than 20% by weight, cracking will occur over time and the bending fatigue strength and abrasiveness will be poor.

On the other hand, if it exceeds 250% by weight, it becomes sticky and the surface strength decreases.

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

Solvents used to prepare the resin solution include acetone, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl butyl ketone, methanol, phthanol, benzene, toluene, xylene, dimethylformamide, dimethylacetamide, and the like.

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

If the coating amount of the resin liquid is less than 0.2 g/rr/' in terms of solid content, the coloring will be insufficient, whereas if it is more than 10 g/d, the flexural fatigue strength and abrasiveness will deteriorate.

The resin solution contains polyurethane elastomer, polyvinyl chloride, polyacrylic acid resin, which is compatible with cellulose nitrate,
Polyvinyl acetate, a copolymer of vinyl acetate and vinylidene chloride, etc. can be mixed to the extent that the polishing properties are not bad.

・The degree of discoloration of the polymer layer, that is, the base, as mentioned above, of course varies depending on the type and amount of solvent present in the surface layer when applying the resin solution, but It is also affected by the atmosphere, the temperature of the substrate and the resin liquid.

Therefore, when carrying out the present invention, it is necessary to fully consider the type and amount of the solvent present in the surface layer as well as the temperature thereof.

Finally, before or after making into any final product, such as shoes, bags, clothing, etc., a portion of the outermost layer at the desired location is appropriately removed with an abrasive material to create the desired pattern or color.

The leather-like sheet material thus obtained has a colored base partially visible, an antique look, an extremely clear color, and a very luxurious feel.

Hereinafter, the present invention will be specifically described with reference to Examples.

In addition, all percentages in the examples are based on weight.

Example 1 A nylon nonwoven fabric was impregnated with a solution consisting of 20% polyurethane elastomer synthesized from polyethylene adipate glycol, diphenylmethane-4,4'-diisocyanate and ethylene glycol, 5% titanium oxide and 75% dimethylformamide, and the above-mentioned The same solution was applied to a solid content of 80 g/m'', then immersed in an aqueous solution containing 50% dimethylformamide at 50°C for 30 minutes to solidify, followed by solvent removal and drying to form a porous material. A substrate was manufactured.

After stamping the kid pattern, a solution of the same polyurethane elastomer as above, 6% dimethylformamide, 56% methyl ethyl ketone, and 28% cyclohexanone, was applied to give a solid content of 3 g/m'. 38g/r of solvent for the polyurethane elastomer
Air dry until d' remains, and then dry in an atmosphere at 25°C with a stone cutting degree (N) of 12%, 4% cellulose nitrate, 0.5% vinyl acetate-vinyl chloride copolymer, 5% dioctyl phthalate, and a brown color. A solution consisting of 7.5% metal complex dye, 40% toluene and 43% ethyl acetate, kept at 25° C., was applied by gravure printing to a solid content of 297 m′ and dried.

The obtained leather-like sheet material had a clear surface color.

When women's shoes were made from the leather-like sheet material and a part of the outermost layer was arbitrarily polished, the suitably colored base was partially visible, giving the shoes a very deep color and a beautiful antique-like appearance. Was.

Furthermore, the manufacturing cost of the leather-like sheet material is much lower than that of conventional products that require two coloring steps.

On the other hand, the same polyurethane elastomer solution as above was applied to the same substrate as above, and after the solvent was completely blown off, the same colored layer as above was applied in exactly the same manner as above.

Shoes were made using the obtained leather-like sheet material in the same manner as described above, and a part of the outermost layer was polished.This material was significantly different from the previous material, as there was almost no color transfer to the base material.
The product value was low because the desired color could not be obtained.

Example 2 Polycaprolactone glycol, diphenylmethane-4
, 4'-diisocyanate, ■, A solution consisting of 12% polyurethane elastomer synthesized from 4-butanediol, 2% polyvinyl chloride, 0.3% carbon black, and 85.7% dimethylacetamide was mixed into polyethylene with a rough texture pattern. 659/ as solid content on the sheet
After applying the coating in an amount of m', it was treated with a 30% aqueous solution containing 30% dimethylacetamide for 30 minutes.

The obtained porous film was peeled from the polyethylene sheet, solvent removed and dried, and then laminated onto a nylon woven fabric with the polyethylene sheet side as the adhesive surface to produce a porous substrate.

Next, poly, ethylene glycol/polyhexamethylene adipate glycol 3/2, diphenylmethane 4,4'
- Polyurethane elastomer with a nitrogen content of 5.5% synthesized from diisocyanate and ethylene glycol 6%, polyvinyl chloride 1%, dimethylformamide 17
%, a solution consisting of 5α% tetrahydrofuran and 26% cyclohexanone as solid content 2 j! /rr
It was applied in an amount of 100 ml and completely dried.

Furthermore, a solvent consisting of 10% dimethylacetamide, 40% acetone, and 50% methanol was added to the surface at a rate of 9 g/
Immediately after applying 3.5% cellulose nitrate with a degree of nitrification ('N) of 10.5%, 2% dibutyl phthalate, 1.5% bimash oil, and a dark green oil-soluble dye in an atmosphere of 25°C after applying m'. 6%, methyl ethyl ketone 40% and toluene 47%
%, the solid content of the solution kept at 25°C is 3.
It was coated and dried so that it became fi/m.

The resulting leather-like sheet material had a clear color, and when a portion of the outermost layer was polished, a medium-colored base was partially visible, and the three-dimensional effect was excellent.

The leather-like sheet material was ideal for women's shoes, bags, interior materials, etc., and had extremely high commercial value.

Furthermore, the manufacturing cost of the leather-like sheet material is also much lower than that of conventional products that require two coloring steps.

Claims (1)

[Claims] 1. A solution of a polymer mainly composed of a polyurethane elastomer having a nitrogen content of 3% to 7% by weight based on diisocyanate is applied to the surface of a substrate made of a fiber aggregate and a polymer mainly composed of a polyurethane elastomer in terms of solid content. 2
g/m" to 10 g/m, and then, in a state where the solvent for the polymer is present in the surface layer at 297 m: to 100 g/m, an organic solvent can be added in an amount of 5% to 300% by weight based on the resin. Nitrification degree (N) 9.5% by weight, containing 20% to 250% by weight of plasticizer based on soluble dye and resin
~13.0% by weight of a resin solution mainly composed of cellulose nitrate with a solid content of 0.29/m~10,! A method for producing a leather-like sheet material that provides an excellent three-dimensional effect by removing a part of the outermost surface layer with an abrasive material.