JPS5917227B2 - Manufacturing method for seats with a luxurious feel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a sheet having an excellent three-dimensional effect and a luxurious feel, particularly a leather-like sheet.

As fashion is becoming more and more popular in all fields and luxury is being strongly discouraged, the quality of the surface color of leather-like sheets, among other surface finishes, has become an extremely important factor that influences the product value.

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

Conventional methods for three-dimensional coloring of leather-like sheets include: - Applying color shading by spraying; - Applying color shading using a roll engraved with a non-uniform pattern; and - Adjusting to any color. A method is used in which a nitrocellulose solution color-adjusted with a pigment is applied again to the base to color it, and a part of the outermost surface layer is removed.

However, the spraying method (■) requires a high level of skill or has poor workability, and the method (■) using an engraved roll results in uniform colors and patterns that cannot be adjusted to suit individual tastes. None of these methods were satisfactory, as it was difficult to create the desired color or pattern on any part of the final product, such as shoes, bags, interior decorations, etc.

On the other hand, method (3) in which two types of colored layers are provided and a part of the surface layer is removed does not have any of the drawbacks of the above two methods.

In other words, with this method, a leather-like sheet with good workability, individuality, and excellent three-dimensional effect can be obtained without requiring a high level of skill.

However, this method also has one major drawback.

In order to obtain one product, it is necessary to adjust the color of the base layer and then the color of the outermost layer, which means that one brand has to be colored twice.

This type of coloring work is one of the most important jobs in the finishing process, and this work includes finishing even just one coloring process, that is, coloring, embossing, fir processing, and enamel processing. ,
This accounts for most of the costs required for things like gloss adjustment.

Especially at a time when there is a strong demand for multiple brands of products like today, applying color twice for each brand will complicate the process and waste a huge amount of time, resulting in a significant drop in productivity. This results in a significant increase in the cost of products.

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

In response to such problems, the present inventor conducted extensive research and found that a layer (1) containing a dye and a polymer having good affinity with the surface of the substrate is first applied to the surface of the substrate. granted,
Next, a layer (I) containing a plasticizer and cellulose nitrate with a degree of nitrification (Nl of 9.5 to 13.0 wt) is applied, and a part of the dye to be contained in the layer (I) is applied by heat treatment. Layer C1
By removing a part of layer (II) with an abrasive after transferring to step 1), a sheet with a unique three-dimensional effect and a high-class feel, which is free from the above-mentioned defects and has a very rich color change, can be obtained. The present invention was achieved by discovering that it can be obtained.

In other words, the purpose of the present invention is to provide a high-quality sheet with an excellent three-dimensional effect by one coloring process. It has become possible to obtain a sheet with high commercial value, which has an excellent three-dimensional effect.

In addition, since the present invention uses dyes instead of conventionally used pigments as coloring agents, it is now possible to easily obtain vivid colors that were previously unavailable, and the advantage is that the sense of luxury has further increased. have

Furthermore, the present invention has the advantage that a wide variety of colors can be easily obtained by appropriately changing the heat treatment conditions and polishing conditions.

First, as the substrate used in the present invention, any substrate for producing a sheet structure can be used, but it is preferable to use a substrate commonly used as a substrate for artificial leather or synthetic leather.

That is, when the artificial leather or synthetic leather is manufactured as a shoe, bag, or other interior material, it is required to impart a desired color shading to a desired location, and in such a case, the method of the present invention can be applied. This is because it is most advantageous to adopt.

Although it is possible to use a substrate for synthetic leather or artificial leather consisting of a porous polymer layer alone, it usually consists of a fiber aggregate and a polymer coating layer.

The fiber aggregate in this case is a sheet-like material mainly composed of fibers such as nonwoven fabric, woven fabric, knitted fabric, etc., and is impregnated and coagulated with a polymer as a binder, if desired.

Ordinary fibers can be used as the fibers,
Not only single spun fibers such as cotton, hemp, wool, rayon, acetate, nylon, polyester, polyacrylonitrile, bisilon, polyethylene, etc., but also mixtures thereof, composite spun fibers, etc. can be used.

As the binder optionally added to the above-mentioned fiber aggregate, any binder that is generally used for synthetic leather etc. can be used, such as natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer. , nylon, polyacrylic acid resin, polyvinyl chloride,
Polyurethane elastomers, other synthetic rubbers, or mixtures thereof are used.

These binders are applied as needed in solutions, emulsions, etc., and the amount of adhesion is usually in the range of 150 weight molecules per fiber.

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

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

Among these, polyurethane elastomer is preferred because it can easily provide a porous structure and has good scratch resistance, bending resistance, and texture.

The polyurethane elastomer has a molecular weight of 500 to 4,00.
0 polyethylene glycol, polytetramethylene glycol, polyethylene adipate glycol, polyhexamethylene adipate glycol, polycaprolactone glycol, etc. and ethylene glycol, butanediol, hexanediol, ethanolamine, hydrazine, 4,4'-methylene bis( chain extenders such as 2-chloroaniline) and diphenylmethane-4,4'
- Polyurethane elastomers made of diisocyanates such as diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate are preferably used.

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, polymethyl acrylate, etc. 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 binder optionally added thereto, and a coating layer of a polymer preferably 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.

Next, a layer (I) containing a dye and a polymer having good affinity with the surface of the substrate is applied to the surface of the substrate.

Although any polymer can be used as long as it has good affinity, it is preferable to use a polyurethane elastomer in view of its combination with the layer (II) to be applied next.

The coating amount of the polymer is 0.29/rrl to 1 (M
? /m” is appropriate.

As the polyurethane elastomer for the polymer layer (I), the same polyurethane elastomer as that applied to the surface of the substrate can be used, but among them, polyether glycol with a large number of carbon atoms such as polytetramethylene glycol, Polyurethanes made of polyester glycols such as polybutylene adipate glycol and polyhexamethylene adipate glycol are preferred.

As the dye used, any dye can be used as long as it migrates to the layer (II) when heated, and the preferable proportion of the dye used is 5 to 300% by weight based on the resin, and the amount of weight dye used is If it is less than 5% by weight, it is difficult to transfer and obtain the desired color, which is undesirable. On the other hand, if it increases by 300% by weight, the adhesion between the base layer and layer (1) becomes poor, and it is difficult to use it as a leather-like sheet. In this case, the bending fatigue strength decreases, which is not preferable.

Nitrification degree (N) 9.5% to 13.0% by weight, containing plasticizer in an amount of 20% to 250% by weight based on the resin, after optional stamping or fir processing as necessary. 0.2 g/solid content of resin solution mainly composed of cellulose nitrate
rrt~109/rrt coating layer (forming IQ).

As plasticizers, in addition to commercially available tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, dibutyl phthalate, butylphthalyl butyl glycolate, polyvinyl methyl ether, ethyl abietate, triacetin, etc. Olive oil, castor oil, coconut 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 200% by weight, cracks are likely to occur over time, and the bending fatigue strength and abrasiveness are poor.

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

Further, as mentioned above, the degree of nitrification of cellulose nitrate is preferably in the range of 95% by weight to 13.0% by weight because 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, butanol, 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 0.29/rrt in terms of solid content, the coloring will be insufficient, and if it is more than 10.9/771'', the flexural fatigue strength and abrasiveness will be poor.

The resin solution contains other fillers, pigments, softeners, stabilizers, antistatic agents, gloss modifiers, etc. Polyurethane elastomers, polyvinyl chloride, polyacrylic acid resins, polyacetic acid resins that are compatible with nitrate cellulose, etc. Vinyl, a copolymer of vinyl acetate and vinylidene chloride, etc. can be mixed in to the extent that the abrasiveness is not bad, and it is especially good to add resins and additives to make it easier for the dye to migrate to layer (II). .

Then, the surface of the resin layer is heat-treated at a temperature of 70°C to 250°C.

When the heat treatment temperature is 70°C or lower, there is little migration of the dye, and on the other hand, when it exceeds 250°C, the cellulose nitrate and polyurethane elastomer decompose, the porous structure of the base layer is destroyed, and wind In some cases, the bending fatigue strength, etc. may deteriorate.

The heat treatment time is determined by the treatment temperature and the desired color of the base, but it is usually 2 seconds to 2 seconds from the viewpoint of productivity and reproducibility.
Approximately 30 minutes is desirable.

In addition, the heat treatment can be performed either under pressure or under pressure. When heat treatment is performed under pressure, the desired shape can be achieved by using an embossing roll or embossing plate with an arbitrary pattern. Pressing is also possible at the same time.

The present invention has a major feature in that it is possible to change the amount of dye transfer very easily by changing the heat treatment conditions, and therefore products of various colors can be manufactured in small quantities and in many brands.

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

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

In the present invention, other dyes with different migration properties or organic or inorganic pigments with almost no migration properties are added to layer (1), and/or dyes (with migration properties) are added to layer (II). By adding pigments, pigments, etc., you can easily obtain more complex colors, and by heat-treating the parts, only the transition areas will have a different color, making it easy to change the color. can be obtained.

Furthermore, in the present invention, other intermediate layers and surface layers can be added within a range that does not impair the effects of the present invention.

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 A nonwoven fabric of nylon fibers was impregnated with a solution consisting of 20% polyurethane elastomer synthesized from polyethylene adipate glycol, diphenylmethane-4,4'-diisocyanate, and ethylene glycol, 5% brown pigment, and 75% dimethylformamide. The same solution as above was applied to a solid content of 80'//rrt, and then immersed in an aqueous solution containing 50% dimethylformamide at 50°C for 30 minutes to solidify, followed by solvent removal and drying. A porous substrate was produced.

Next, the same polyurethane elastomer 6 as above, brown dye (Lanyl Brown, manufactured by Sumitomo Chemical Co., Ltd., dimethyl formamide 10%, methyl ethyl ketone 51
Layer I) was coated with a solution consisting of 28% cyclohexanone and 28% cyclohexanone at a solid content of 3'l/rrt, and after drying, a kid pattern was embossed.

In addition, the degree of nitrification (~12% cellulose nitrate 4%, vinyl acetate-vinyl chloride copolymer 0.5%, dioctyl phthalate 5 parts, toluene 40% and methyl ethyl ketone 50 parts)
．． A 5% solution was coated using a gravure printing method (layer II) so that the solid content was 29/rrt, and then heat treatment was performed at 100° C. for 7 minutes.

The surface of the obtained leather-like sheet material was clearly discolored to brown.

When women's shoes were made from the leather-like sheet material and a part of the outermost layer was arbitrarily polished, the base layer (1) was partially visible and the color was very deep and had a beautiful antique 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.

Example 2 Polycaprolactone glycol, diphenylmethane-4
A solution consisting of 12% polyurethane elastomer synthesized from , 4'-diisocyanate, 1,4 butanediol, 2% polyvinyl chloride, 3% carbon black and 83% dimethylacetamide was placed on a polyethylene sheet as a solid content at 659/rrt. After coating the film in such a manner as to give the desired result, the film was treated with a 30°C aqueous solution containing 30% dimethylacetamide for 30 minutes.

Next, this was peeled from the polyethylene sheet, solvent removed and dried, and then laminated onto a nylon woven fabric to obtain a porous substrate.

Next, 6% polyurethane elastomer with a nitrogen content of 5.5% synthesized from polyhexamethylene adipate glycol, diphenylmethane-4,4' diisocyanate and ethylene glycol, 1% polyvinyl chloride, and a yellow dye (Lanyl Yellow Sumitomo Chemical company) 5chi,
Dimethylformamide 16 units, Tetrahydrofuran 45 units
A solution consisting of 27% and cyclohexanone was applied so that the solid content was 2 so/g, and then a satin pattern was embossed and a fir finish was applied to improve flexibility.

In addition, nitrate cellulose 3.5 with a nitrification degree of 10.5%,
A solution of 2% dibutyl phthalate, 1.5% castor oil, 6% blue pigment (phthalocyanine type), 40% ethyl acetate, and 47% toluene was applied to a solid content of 39/g and dried.

Further, this surface was stamped for 10 seconds at a temperature of 150° C. and a pressure of I Ky/m using an iron plate having a rough texture pattern.

The resulting leather-like sheet material had a clear color, and the surface was slightly discolored to green.

When a part of the outermost layer was polished, the 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.

In addition, by variously changing the heat treatment conditions, it was possible to arbitrarily change the amount of yellow dye transferred to the layer (I) depending on the heating conditions. Since it is possible to adjust the color to suit the desired color, it has a very high commercial value.

Example 3 A nonwoven fabric of nylon fibers was impregnated with a solution consisting of 20% polyurethane elastomer synthesized from polybutylene adipate glycol, diphenylmethane-4,4'-diisocyanate, and butanediol, 5% brown pigment, and 75% dimethylformamide. The same solution as above was applied on top so that the solid content was 809/rrt, and then immersed in an aqueous solution at 50°C containing 50% dimethylformamide for 30 minutes to solidify, followed by solvent removal and drying. A porous substrate was produced.

Next, polyethylene glycol, diphenylmethane-4,
Polyurethane elastomer 6 with a nitrogen content of 6 synthesized from 4'-diisocyanate and butanediol
%, red dye (Neozapon R, ed GE
A solution consisting of 4% (manufactured by BASF), 17% dimethylformamide, 46 parts of tetrahydrofuran, and 27 parts of cyclohexanone was applied so that the solid content was 29/vt, and after drying, a kid pattern was embossed.

Finally, 4.0% cellulose nitrate with a nitrification degree of 12, 0.5% vinyl acetate-vinyl chloride copolymer, 5.0% dioctyl phthalate, 7.5% brown metal complex dye, and 25% toluene. A solution of 38% ethyl acetate and 20% acetone was applied by gravure printing to a solid content of 2 fl/g, dried, and then heated at 120° C. for 3 minutes.

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 base layer (I) was partially visible.
It had a very deep color and a beautiful antique appearance.

Claims (1)

[Claims] 1. A layer (1) containing a dye and a polymer having good affinity with the surface of the substrate is provided on the surface of the substrate, and then a layer (1) containing a plasticizer and a nitrification degree (to) of 9.5 to 9.5 is applied. A layer (II) containing 13.0 wt cellulose nitrate is applied, and a part of the dye contained in the layer (I) is transferred to the layer (I) by heat treatment. A method for manufacturing a sheet with a high-class feel, characterized by removing a part of I with an abrasive material. 2. Claims in which a fiber aggregate with a porous elastic layer provided on the surface is used as a substrate. A method for producing a leather-like sheet according to item 1.