JPH0450276A - Paint-blending solution - Google Patents

Abstract

PURPOSE:To obtain a paint-blending solution useful for surface finishing of vinyl chloride leather or hides giving touch of enriched feeling of natural skin and giving a coated film having excellent strength by dispersing particles of natural collagen in an organic solvent solution of polyamino acid urethane resin, etc. CONSTITUTION:The aimed blending solution is composed of a dispersion dispersing particles comprising natural collagen (preferably particles purified from skin, etc., of animals and chemically crosslinked by heating) in an organic solvent solution of synthetic resin principally composed of polyamino acid urethane (preferably polyamino acid segment containing poly-gamma-methyl-L-glutamate as a principal component) resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating solution used for finishing the surface of leather such as PVC leather, synthetic leather, artificial leather, and natural leather, or for finishing the surface of molded resin, metal, woodwork, etc. In particular, paint formulations that provide a texture rich in natural skin feel, have functionality such as moisture permeability, and provide coatings with excellent mechanical strength. It is related to.

[Prior art] Many paints have been used as finishing paints for leather, synthetic resin molded products, metal molded products, woodwork products, etc., but synthetic resin paints have been selected based on their functionality depending on the purpose. has been used.

However, in the field where people use it in direct contact with the skin, it has a surface that feels natural when it comes in contact with the skin, does not feel sticky due to sweat, and has high moisture permeability, high moisture absorption, and high moisture absorption. A paint coating that has moisture wicking properties is desired. As examples of paints that fall under this category, paints in which leather powder is dispersed in synthetic resin paints such as polyurethane or vinyl chloride have been proposed, or white paints are unsuitable because they contain metals and are highly colored. However, if the content of leather powder is too high, the surface texture may be good, but the strength will be reduced.
It has drawbacks such as the leather powder falling off from the coating when rubbed, and is not satisfactory.

The present inventor has completed the present invention as a result of intensive research into a paint that can provide a coating film that does not feel strange to human skin, which was unsatisfactory with these conventional methods.

[Structure and Effects of the Invention] That is, the present invention is a coating composition comprising a dispersion in which particles of natural collagen are dispersed in an organic solvent solution of a synthetic resin mainly composed of polyamino acid urethane resin.

In the present invention, polyamino acid urethane is a copolymer of polyurethane and polyamino acid, and conventionally known polyamino acid urethanes can be used. A general method for producing polyamino acid urethane is a method of addition polymerizing N-carboxy-α-amino acid anhydride to polyurethane. The polyurethane used here is
All conventionally known polyurethanes can be used. For example, polyurethane obtained by reacting an organic diisocyanate with a long-chain diol and a chain extender is typical.As the organic diisocyanate, alicyclic organic diisocyanates, aliphatic organic diisocyanates, aromatic organic diisocyanates, etc. can be used. As long-chain diols, polyester diols, polyether diols, polyamide ester diols, polycarbonate diols, etc. can be used, and as chain extenders, active agents such as low-molecular glycols, low-molecular diamines, and low-molecular amino alcohols can be used. Compounds containing two hydrogen atoms can be used, and polyurethane composed of a mixture of these can be used. These raw materials should be selected depending on the application. For example, if hydrolysis resistance is required and In applications requiring color fastness, an alicyclic diisocyanate or an aliphatic diisocyanate may be used as the organic diisocyanate, and a polycarbonate diol or a polyether diol may be used as the long chain diol.

N-carboxy- added to the above polyurethane
Examples of the α-amino acid anhydride include the anhydride of γ-methyl-L-glutamate, the anhydride of ethyl, propyl, butyl ester of carboxylic acid at the γ-position, and the anhydride of leucine. The polyamino acid segment ratio in the polyamino acid urethane obtained by these reactions is 3% to 85% by weight, preferably 10% to 60% by weight. If the polyamino acid segment ratio is less than 3% by weight, disadvantages such as the synthetic polyamino acid particles falling off from the coating film or unsatisfactory functional properties such as moisture permeability may occur, and the present invention may not be possible. I don't like it because I can't be satisfied with it.

Furthermore, if the polyamino acid segment ratio exceeds 85% by weight, the elongation of the obtained coating film will be low and the mechanical strength against bending, rubbing, etc. will be reduced, which is not preferable. The polyamino acid urethane thus obtained is used as an organic solvent solution. Organic solvents for dissolving polyamino acid urethane include chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane, but they are difficult to dissolve when the polyamino acid segment ratio in polyamino acid urethane is high. In addition, from the viewpoint of hygiene and handling, preferred organic solvents that should be avoided as much as possible include dioxane, N, and N.
-dimethylformamide, N,N-dimethylacetamide 1N-methylpyrrolidone, methyl ethyl ketone, TeI
- There are polar organic solvents such as lahydrofuran. When the organic solvent used is such a polar organic solvent, the ratio of amino acid segments in the polyamino acid urethane is 40%.
% or more, the amino acid segment ratio tends to become a translucent gel without being radially dissolved. Therefore, the amino acid segment ratio should be designed taking into account the type of organic solvent used, the concentration used, etc. In the present invention, other synthetic resins or natural resins are mixed and dissolved in the organic solvent solution of the polyamino acid urethane thus obtained in order to modify the properties of the resulting coating film. can be used. In this case, naturally, the polyamino acid segment ratio in the mixed resin is 3.
It is preferable that it is 85% by weight.

The particles made of natural collagen dispersed in the organic solvent solution of the synthetic resin mainly composed of polyamino acid urethane are particles made from animal skin, hair, etc. through various treatments6. Currently, the products that are industrially produced include leather powder made by grinding leather at low temperatures that has been treated with chrome staining, or so-called leather that has not been treated with chrome staining. There is particulate collagen that is purified by removing extra components other than collagen such as fat through an enzymatic decomposition reaction of hair.

In the present invention, any of the above can be used, but from the viewpoint of particle coloring and discoloration, leather without chrome finish,
Preferably, the latter particles purified from hair or the like are used. In other words, particles crushed from leather that has been subjected to the former chrome stain treatment are colored in chrome, so they cannot be used for light colors such as white, and if used. Because of impurities such as fat, they tend to discolor when exposed to light. On the other hand, collagen particles purified through biochemical reaction treatment without chromium depletion are colorless (white) particles, so they can be used for white purposes, and they do not contain impurities such as fat. , there is almost no discoloration due to light, etc., which is preferable. However, collagen purified through biochemical reaction treatment in this way,
Particles made of natural collagen as described above are preferably those that have been molecularly cross-linked through chemical reactions because of their high swelling ability in water and their ease of decomposition by proteolytic enzymes such as amylase. In some cases, processing such as pulverization is performed to make the particles even finer. The smaller the particle size, the larger the particle surface area per unit weight, which makes it easier to obtain functional properties such as moisture permeability, moisture absorption, and moisture release properties of the resulting coating film, and furthermore, the surface texture of the coating film becomes smoother. preferable. The average particle size of the particles is preferably 20 μm or less, more preferably 10 μm.
m or less. The particles made of natural collagen thus obtained are added and dispersed in the above-described organic solvent solution of polyamino acid urethane to obtain a dispersion coating composition, which is the object of the present invention.

[Operation of the invention] The coating film made from the paint mixture obtained from the resin mainly composed of polyamino acid urethane and particles made of natural collagen thus obtained cannot be subjected to mechanical force such as bending or rolling. However, because the polyamino acid segment of amino acid urethane, which has high elongation and excellent mechanical strength, and natural collagen particles have an affinity due to the same protein molecular structure, whitening may occur and particles made of natural collagen may fall off. Therefore, the amount of particles made of natural collagen added to polyamino acid urethane (solid) is
You can choose from a wide range. The amount of polyamino acid segments in particles made of polyamino acid urethane and natural collagen, which is a polyamino acid, in the total solid content greatly affects the surface touch and functional properties of the resulting coating film. By increasing the amount of particles added, a coating film rich in functional properties with a high amount of polyamino acid segments will be obtained. That is, when particles made of natural collagen are dispersed in an organic solvent solution of another polymer such as polyurethane without using polyamino acid urethane, there is a limit to the amount of particles added in order to prevent the particles from falling off. However, since the amount of polyamino acid segments in the coating film is relatively small compared to the present invention, it is difficult to obtain a coating film rich in the functional properties targeted by the present invention. In addition, a coating film obtained only from an organic solvent solution of polyamino acid urethane can provide a highly functional coating film, which is the objective of the present invention, when the polyamino acid segment ratio is high, but it has low elongation. Since it becomes a coating film, mechanical durability such as bending is poor, and the object of the present invention cannot be achieved. As described above, the present invention provides a coating composition comprising a dispersion liquid for obtaining a highly functional coating film having a high ratio of polyamino acid segments consisting of molecular polyamino acid segments and particulate polyamino acid segments. The coating film obtained from the liquid mixture also has excellent mechanical strength. It is preferable that the total weight of the polyamino acid segment in the polyamino acid urethane constituting the liquid mixture of the present invention and the particles made of natural collagen, which is a polyamino acid, is 20% by weight or more based on the total weight of the polyamino acid segment. , more preferably 40% by weight or more. However, these values are not intended to limit the invention.

The cosmetic properties of the resulting coating film can be improved by adding a coloring agent such as a pigment or dye to the coating composition thus obtained, as the case may be. Further, antioxidants, #N Ox gas discoloration inhibitors, various deterioration inhibitors, etc. can also be added in order to obtain a good coating film.

The paint composition of the present invention obtained as described above is applied as a finishing paint to the surfaces of leather, synthetic resin molded products, metal molded products, woodwork, etc. As the coating method, conventionally known methods such as spray coating, gravure coating, knife coating, roll coating, and lamination using release paper can be employed. Depending on these application methods, the concentration may be adjusted to achieve the optimum viscosity. With one application. If the coating film thickness is insufficient, repeat coating and drying to adjust the target coating thickness.

The coating film obtained in this way has a surface that does not feel uncomfortable when it comes into direct contact with a person's skin, does not feel sticky due to sweat, and has high moisture permeability, high moisture absorption, and high moisture release properties.
It has great strength so that the powder does not fall off even when rubbed.

[Examples] Hereinafter, the present invention will be specifically explained in detail with reference to Examples. In the Examples, "parts" and "%" are all based on weight, and the measured characteristic values were obtained by the following method.

(a) Moisture permeability It is expressed as water vapor permeability (g/rr+'-day) according to JIS L1099 A-1 method.

(0) Moisture absorption expressed as the amount of moisture absorbed (g7rr?) when left in an atmosphere with a temperature of 23°C and relative humidity of 30% for 1 hour, and then left in an atmosphere with a temperature of 23°C and relative humidity of 80% for 30 minutes. .

(7→ Moisture release amount (g/rd) after being left in an atmosphere with a humidity temperature of 23°C and a relative humidity of 80% for 1 hour, and after being left in an atmosphere with a temperature of 23°C and a relative humidity of 30% for 30 minutes (g/rd) Expressed as

(Uniform bending resistance is expressed in grades 1 to 5 according to the JIS K6545 method.

Example 1 (Creation of artificial leather base) A non-woven fabric with a weight of 280 tons/I and a thickness of 1.0 mm was impregnated with a 13% polyurethane-dimethylformamide solution. A dimethylformamide solution was coated with a basis weight of 600 g/rrl', followed by water immersion coagulation, water washing, and drying to prepare an artificial leather base.

(Preparation and application of paint mixture-1) Polyamino acid urethane (uses non-yellowing type urethane: Seiko Kasei ■ LUCKSKIN-UA-3295A
.

Particles made of natural collagen (manufactured by Showa Denko ■; CX260;
A stable dispersion liquid was prepared by adding, mixing, and dispersing 5 parts (average particle size: 7 μm). To this, 3 parts of a red pigment (manufactured by Dainippon Ink & Chemicals, Ltd.; Dailac 5L-3440) was added as a coloring agent and mixed uniformly to obtain a red paint mixture. The coating and drying process was repeated three times using gravure coating I! (using a roll of 110 mesh) on the surface of the leather base, and a pattern was added using a heated embossing roll to obtain artificial leather having a red coating film on the surface. The surface of the obtained artificial leather does not make you feel cold when it comes in contact with your skin, it gives you a feeling of warmth, and it does not feel sticky even on sweaty skin and has an excellent texture.It is suitable for volleyball, handball, It was excellent for use with bass target balls.The obtained characteristic values are shown in Table 1.

(Creation of paint mixture-2) Paint formulation-2 was prepared with the following composition.

Crisbon NY320 100 parts (manufactured by Dainippon Ink and Chemicals) Hauluck A1003 White (manufactured by Dainippon Ink and Chemicals) 80 parts Howlac A1008 Matte (manufactured by Dainippon Ink and Chemicals) 30 parts Isopropyl alcohol 50 parts Methyl ethyl ketone 40 parts NN- Dimethylformamide 10 parts (Preparation of paint formulation-3) Paint formulation-3 was prepared with the following composition.

LUCKSKIN-U A 3295A
100 parts (manufactured by Seiko Kasei ■) (18%) Natural collagen particles CX-26010 parts (Showa Denko @
Ii Ri Haulak 81356 Matte (manufactured by Dainippon Ink & Chemicals) 20 parts N,N-dimethylformamide 40 parts Methyl ethyl ketone 40 parts (application on the surface of artificial leather) Paint mixture liquid-2 was applied with a gravure roll (110 mesh). Coating on the surface of the artificial leather base prepared in Example 1 - After drying 30 times, a pattern was added with a heated embossing roll, and then coating liquid mixture - 3 was applied on the surface with a gravure roll (110 mesh) - Drying was repeated three times to obtain artificial leather with a white surface. When the surface of the resulting artificial leather comes in contact with the skin, it does not feel cold but feels warm, and has an excellent feel without stickiness even on sweaty skin, and has a moisture permeability that is lower than that of conventional leather. It was superior to artificial leather, and was suitable as a material for shoe uppers. The obtained characteristic values are also shown in Table 1.

(Preparation and application of paint formulation-4) N,N-dimethylformamide solution of polyamino acid urethane (PAU-300 made by Mitsubishi Kasei using yellowing type urethane, polyamino acid segment 35%) (solid content 15 %), particles made of natural collagen (CX-260 manufactured by Showa Denko Kagi, average particle size 7 μm>8
A stable dispersion liquid was prepared by adding, mixing and dispersing 1 part. In this, black pigment (manufactured by Dainippon Ink and Chemicals) is used as a coloring agent;
8 parts of Dylac 5L-3430) and 3 parts of black dye (Nippon Gunpowder Kayaset BLACK-R) were added and mixed uniformly to obtain a black paint. This black paint was applied onto a patterned release paper to a basis weight of 80 f/d and dried.
Next, after applying an adhesive, the surfaces of the artificial leather base prepared in Example PA-1 were bonded together to ensure sufficient adhesion. The surface of the artificial leather separated from the N-pattern paper does not feel cold when it comes in contact with the skin, but gives a sense of warmth, and has an excellent feel without stickiness even on sweaty skin. It was suitable for racket grips and glove linings. The obtained characteristic values are shown in Table 1.

Comparative example-1 (Creation of paint mixture-5) A paint formulation-5 was prepared with the following composition.

Howlac A 3454 (20%) 100 parts (manufactured by Dainippon Ink & Chemicals) Natural collagen particles CX-26010 parts (Showa Denko)
Manufactured by Hauluck A1008 Mat 30 copies (
(manufactured by Dainippon Ink & Chemicals) 50 parts of isopropyl alcohol 50 parts of methyl ethyl ketone (application to the surface of artificial leather) Apply paint mixture 2 to the surface of the artificial leather base prepared in Example 1 using a gravure roll (110 mesh). After repeating coating and drying three times, patterning and marking is done with a heated embossing roll, and then apply paint mixture 5 on the surface with a gravure roll (110 mesh) and repeat drying three times to create a white surface. An artificial leather having the following properties was obtained. The transparency of the obtained artificial leather was unsatisfactory, and when subjected to a bending test,
Powder that appeared to be particles CX-260 made of natural collagen fell off.

The obtained characteristic values are also shown in Table 1.

Comparative example-2 (Creation of paint mixture-6) Paint formulation 6 was prepared with the following composition.

LUCKSKIN-U A 3295A
100 parts (manufactured by Seiko Kasei ■) (18%) Hauluck B 1356 Matte 20 parts (manufactured by Dainippon Ink & Chemicals ■) N,N-dimethylformamide 40 parts Methyl ethyl ketone 40 parts (application on the surface of artificial leather) Paint mixture - 2 in gravure roll (110 meters)
After repeating coating and drying three times on the surface of the artificial leather base prepared in Example 1, a pattern was applied using a heated embossing roll, and then paint mixture 6 was applied to the surface using a gravure roll (110 mesh). ) The coating and drying process was repeated three times to obtain artificial leather with a white surface. The resulting artificial leather had unsatisfactory transparency and the surface had a slightly sticky feel to the touch. The obtained characteristic values are also shown in Table 1.

Comparative example-3 (Creation of paint mixture-7) Paint formulation-7 was prepared with the following composition.

Howlac A 3454 (20%) 100 parts (manufactured by Dainippon Ink & Chemicals) Hauluck A 1008 Matte 30 parts (manufactured by Dainippon Ink & Chemicals) Isopropyl alcohol 50 parts Methyl ethyl ketone 50 parts (application to artificial leather surface) Paint formulation Liquid-2 was applied to the surface of the artificial leather base prepared in Example-1 using a gravure roll (110 mesh).After drying was repeated three times, a pattern was applied using a heated embossing roll, and then paint was applied to the surface. Apply and dry the blended liquid-7 using a gravure roll (110 mesh) three times,
An artificial leather with a white surface was obtained. The resulting artificial leather had unsatisfactory transparency, and the surface texture was sticky, which is typical of polyurethane in conventional artificial leather, and it felt particularly sticky when touched with sweaty skin. there were. The obtained characteristic values are also shown in Table 1.

Claims (3)

[Claims] (1) A paint formulation liquid characterized by comprising a dispersion liquid in which particles of natural collagen are dispersed in an organic solvent solution of a synthetic resin mainly composed of polyamino acid urethane resin. (2) Polyamino acid urethane is poly-γ-methyl-L
- The paint formulation liquid according to claim 1, wherein the content thereof is 3% to 85% by weight based on the weight of the polyamino acid urethane resin. (3) The paint formulation according to claim 1 or 2, wherein the particles made of natural collagen are particles purified by biochemical treatment from animal skin or the like and heat-chemically crosslinked.