JP2953532B2 - Highly breathable synthetic leather - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to synthetic leather, and more particularly, to a surface having a natural tactile sensation and having functions such as moisture permeability, moisture absorption, and moisture release. Have breathability, in some cases,
The present invention also relates to a synthetic leather that is hard to stain on the surface.

[Conventional technology]

Synthetic leather has been proposed as a substitute for natural leather, and has been proposed for many improvements, and has now grown into a material that is indispensable for applications such as shoes, balls, and clothing. In these applications, humans are often used in direct contact with the skin, have a comfortable surface feel when in contact with the skin, have no stickiness due to sweat, and have high moisture permeability, high moisture absorption, Synthetic leather having high moisture release properties has been desired.

Nothing currently meets these requirements,
As a recent measure, there has been proposed a synthetic leather in which a polyurethane into which a hydrophilic group is introduced, a polyurethane in which leather powder is dispersed, a silicone-modified polyurethane, or a polyamino acid urethane is formed as a surface film.

However, these methods have not been practically satisfactory. For example, synthetic leather in which a hydrophilic group-introduced polyurethane or silicone-modified polyurethane is formed as a surface film has increased moisture permeability, but has a sticky feeling peculiar to polyurethane, particularly a sticky feeling when contacted with sweaty skin. Is not preferable because it is large. In order to improve this, synthetic leather having a surface film in which leather powder is dispersed in polyurethane has been proposed.However, in the case of a white paint, the coloring is large and unsuitable because the leather powder contains a metal. If the content of the leather powder is too large, the functionality such as surface feel and moisture permeability is satisfied, but there are disadvantages such as the leather powder falling off the surface film when rubbing with a small film strength, and it is satisfied. It is not something. In addition, breathable synthetic leather has been proposed in which a through hole is mechanically formed on the surface, or the surface film is made continuous, but dirt adheres to the surface pores, making it difficult to remove and easily dirt. Has disadvantages.

As described above, there is no satisfactory material at present, and the demand for synthetic leather as a new material having these functions is increasing from various application fields.

[Problems to be Solved by the Invention] 4 The present invention has a surface feel that is not uncomfortable with human skin that is not satisfied by the conventional method, and has functions such as moisture permeability, moisture absorption, and moisture release. Another object of the present invention is to provide a synthetic leather which has air permeability in some cases and is hardly stained on the surface.

[Means for solving the problem]

The present invention is a synthetic leather in which a coating of a high molecular polymer containing fine particles made of silk fibers and / or wool is formed on the surface of a synthetic leather substrate made of fibrous material or fibrous material and synthetic resin, A highly moisture-permeable synthetic leather characterized in that the synthetic resin is a synthetic resin mainly composed of a polyurethane resin containing fine particles composed of silk fibers and / or wool.

The present invention is also a synthetic leather comprising a synthetic leather substrate comprising a fibrous material or a fibrous material and a synthetic resin, on which a polymer polymer film containing fine particles comprising silk fibers and / or wool is formed. And the synthetic resin is a synthetic resin mainly composed of a polyamino acid urethane resin, and is a highly moisture-permeable synthetic leather.

Furthermore, the present invention relates to a synthetic leather in which a high-molecular polymer film containing fine particles made of silk fibers and / or wool is formed on the surface of a synthetic leather base made of fibrous material or fibrous material and synthetic resin. And the synthetic resin is a synthetic resin mainly composed of a polyamino acid urethane resin containing fine particles made of silk fiber and / or wool, and is a highly moisture-permeable synthetic leather.

The fibers constituting the synthetic leather substrate of the present invention include conventionally known synthetic fibers, regenerated fibers, nonwoven fabrics made of natural fibers, uneven cloths, woven fabrics, and the like, and the characteristics thereof are determined according to the use of the synthetic leather. Selection is made from the face.

As the synthetic resin constituting the synthetic leather substrate in combination with these fibers, conventionally known polymers can be used, for example, polyurethane resin, polyamino acid urethane resin, vinyl chloride, vinyl chloride-polyurethane copolymer, SBR resin, NBR
Resins. Among them, polyurethane and polyamino acid urethane can be suitably used from the viewpoint of durability such as abrasion resistance of the obtained synthetic leather.

Among them, a conventionally known polyurethane resin can be used as the polyurethane resin. For example, a polyurethane obtained by reacting an organic diisocyanate with a long-chain diol and a chain extender is typical.As the organic diisocyanate, an alicyclic organic diisocyanate, an aliphatic organic diisocyanate, an aromatic organic diisocyanate, and the like can be used. As the long-chain diol, polyester diols, polyether diols, polyamide ester diols, porcarbonate diols, and the like can be used.
As the chain extender, a compound containing two active hydrogens such as a low-molecular glycol, a low-molecular diamine, and a low-molecular amino alcohol can be used, and a polyurethane composed of a mixture thereof may be used. These raw materials should be selected according to the application.For example, in applications where hydrolysis resistance is required and discoloration resistance is required, an alicyclic organic diisocyanate or an aliphatic organic diisocyanate is used as the organic diisocyanate. As the chain diol, a polycarbonate diol or a polyether diol may be used.

Among the above polyurethanes, polyurethane containing a polyethylene ether segment in the molecular structure, polyurethane containing a silicone segment in the molecular structure, and the like are preferable from the object of the present invention in pursuit of properties such as moisture permeability.

Unlike the above polyurethane resin, the synthetic resin constituting the synthetic leather substrate of the present invention needs to be a polyamino acid urethane resin. Here, the polyamino acid urethane resin is a copolymer of polyurethane and polyamino acid, and a conventionally known polyamino acid urethane resin can be used. As a general method for producing a polyamino acid urethane resin, there is a method in which N-carboxy-α-amino acid anhydride is addition-polymerized to polyurethane. As the polyurethane used here, all conventionally known polyurethanes can be used.

Depending on the use of the synthetic leather, water absorption from the back side or hygroscopicity may be required. Therefore, the fine powder composed of the highly hygroscopic silk fiber and / or wool used for the surface coating of the present invention is used as the above. It is necessary to use in combination with the synthetic resin. That is, the base material is a polyurethane resin or a polyamino acid urethane resin containing fine powder of silk fibers.

A synthetic leather substrate is formed from these fibrous materials and a synthetic resin. Examples of the synthetic leather substrate include a type obtained by impregnating a synthetic resin into a fiber and a type obtained by further forming a synthetic resin on the surface of the impregnated substrate. A type in which a synthetic resin is formed on a fibrous surface can be used in the present invention. further,
Fiber alone can also be used as a synthetic leather substrate.

These synthetic resins are compounded with a fiber by a conventionally known molding method. That is, a conventionally known wet method of impregnating a solution such as N, N-dimethylformamide or the like or coating and immersing in water for coagulation, water was dispersed in a solution or dispersion of an organic solvent such as methyl ethyl ketone.
The W / O emulsion is impregnated or coated and dried by a conventionally known dry method, a water-based emulsion is conventionally compounded as a porous material by a wet method, a dry method, or the like. Naturally, nonporous composite can also be adopted.

The fine particles made of silk fibers contained in the high molecular polymer formed as a coating on the surface of the synthetic leather substrate are obtained by pulverizing silk fibers into fine particles.

Silk fibers are presumed to be fibroin, which is a polyamino acid in which β-structure portions composed of amino acids such as glycine, alanine, serine, and sericin and amorphous portions alternately exist.

Fine particles made of wool, which are contained in a high-molecular polymer in the same manner as silk fibers, are obtained by pulverizing wool into fine particles. Wool is made up of a type of protein called keratin.

As a method for producing fine particles of silk fiber or wool, for example, there is a method of cutting molecules of the fibroin or keratin by enzymatic treatment or the like, followed by pulverization and fine particle formation.

Silk fibers and wool have high water absorbency, but they have a characteristic that even if they contain 30% by weight of silk fiber and 20% by weight of wool, they do not feel wet and appear dry. I have.

This property is presumed to be expressed from the polyamino acid structure described above. According to the present invention, a great effect can be obtained by imparting such characteristics of silk fibers and / or wool to the surface of synthetic leather.
It is preferably 30 μm or less, more preferably 15 μm or less. Fine particles composed of silk fibers and / or wool having such characteristics are added to the polymer to improve the properties of the polymer, and the resulting coating has no discomfort with human skin and is transparent. It is a feature of the present invention to impart properties such as moisture, moisture absorption, and moisture release.

As the polymer for forming a film of the present invention to which the fine particles composed of the silk fibers are added, all conventionally known polymers for forming a film can be used, and examples thereof include a polyurethane resin, a vinyl chloride resin, and a vinyl chloride resin. Polyurethane copolymer, SB
Examples include R resin, NBR resin, polyamino acid resin, polyamino acid urethane resin, vinyl acetate resin, acryl-styrene copolymer, vinyl acetate-acryl copolymer, and the like.

Among them, the object of the present invention has a surface feel that is not uncomfortable with human skin, moisture permeability, moisture absorption, in order to further satisfy the functionality such as moisture release, polyurethane resin,
Polyamino acid urethane resins are preferred.

As the polyurethane resin as a polymer for forming a film, the same polyurethane resin as described in the section of the synthetic leather substrate can be used.

As the polyamino acid urethane resin, the same polyamino acid urethane resin as described in the section of the synthetic leather substrate can be used. In the process for producing a polyamino acid urethane resin, N-carboxy-α which is added to polyurethane is reacted.
-As the amino acid anhydride, N-carboxy-γ-methyl-L-glutamate anhydride, N-carboxy anhydride such as ethyl, propyl, butyl ester of carboxylic acid at γ-position, or N-carboxy anhydride of leucine There are things. Since these polyamino acid urethane resins have a polypeptide bond, they have a high affinity for fine particles made of a silk fiber and / or wool having a polypeptide bond used in the present invention, and the silk fiber and / or Alternatively, fine particles made of wool hardly fall off from the coating film. Therefore, when a polyamino acid urethane resin is used, it is possible to increase the amount of fine particles composed of silk fibers and / or wool, and further enhance the functional properties of the present invention such as moisture permeability, moisture absorption, and moisture release. It can be improved and is preferable. Furthermore, since the polyamino acid urethane resin has a polypeptide bond as described above, there is little discomfort with human skin, and in the case of a polyamino acid urethane resin using a hydrophilic polyamino acid, moisture permeability, Since the material itself has functional properties such as hygroscopicity and moisture release, the effects of the present invention can be enhanced, which is preferable.

The polyamino acid segment ratio in the polyamino acid urethane resin is preferably 3% by weight to 85% by weight, and more preferably 10% by weight to 60% by weight. When the polyamino acid segment ratio is less than 3% by weight, the properties of general polyurethane resin become strong and do not have the properties of a polyamino acid urethane resin, and can satisfy functional properties such as moisture permeability, moisture absorption, and moisture release. It is not preferable because it cannot be performed. On the other hand, if the polyamino acid segment ratio exceeds 85% by weight, the resulting coating film has low elongation, and the mechanical strength against bending, kneading, elongation and the like is undesirably reduced.

Further, when the coating formed on the surface of the synthetic leather of the present invention is porous, mixing the fluorine-modified polyurethane with the high-molecular polymer, particularly the polyamino acid urethane, can prevent contamination and improve water resistance. Is preferred.

The fluorine-modified polyurethane resin is obtained by substituting a part of hydrogen atoms in a polyurethane molecular structure with fluorine atoms. In the present invention, conventionally known resins can be used as the fluorine-modified polyurethane resin.

These fluorine-modified polyurethane resins have the effect of preventing the feeling of stickiness due to sweat, and have the antifouling effect, water resistance, etc., which are disadvantageous when the coating is made of a porous film, and are liable to stain, water penetration, etc. Serves to give an effect. Further, in the present invention, the surface coating imparts functions such as moisture permeability, moisture absorption and moisture release by the effect of a polyamino acid urethane resin described later or fine particles composed of silk fibers and / or wool, while a fluorine-modified polyurethane is used. By giving water repellency to the outermost surface by the effect of the resin, when the skin is touched, it is characterized by giving a refreshing surface feel without wet feeling.

Therefore, since the effect can be enhanced by allowing a large amount of the fluorine-containing segment to be present on the surface of the coating film, the fluorine-containing segment should be present in the side chain rather than in the main chain of the polyurethane resin, to prevent stickiness and stain resistance. Effect is easily obtained.

This is because the fluorine-containing segment tends to be oriented on the surface when the solvent is dried at the time of forming the coating film.

The above-mentioned polymer for forming a film is used as an organic solvent solution. The organic solvent that dissolves the polymer is
It is selected according to the type of the high molecular polymer. For example, as an organic solvent for dissolving the polyamino acid urethane resin,
There are chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, but they are difficult to dissolve when the polyurethane segment ratio in the polyamino acid urethane is high, and the polyamino acid urethane resin and the fluorine-modified polyurethane resin In the case of mixing and using, it is better to avoid as much as possible because the fluorine-modified polyurethane resin is difficult to dissolve. Polar organic solvents such as dioxane, N, N-dimethylformalamide, N, N-dimethylacetamide, N-methylpyrrolidone, methylethylketone, and tetrahydrofuran are also preferable because they are common solvents when mixed with polyurethane resins.

Fine particles consisting of silk fibers and / or wool are added and uniformly dispersed in the above organic solvent solution of the high molecular polymer to obtain a coating material for forming a surface film of synthetic leather.

The addition amount of fine particles composed of silk fibers and / or wool increases the effect of the present invention, but should be determined according to the type of the high molecular polymer used. For example,
When used in combination with a polyamino acid urethane resin, the amount of fine particles composed of silk fibers and / or wool is preferably 1 part by weight to 120 parts by weight based on 100 parts by weight of the polyamino acid urethane resin. If the amount is less than 1 part by weight, a coating having an excellent surface texture according to the present invention cannot be obtained, which is not preferable. On the other hand, when the added amount of fine particles composed of silk fibers and / or wool exceeds 120 parts by weight, fine particles composed of silk fibers and / or wool may fall off from the coating when rubbing or following synthetic leather. Not preferred.

When used in combination with another polymer having no polypeptide structure, the amount of fine particles composed of silk fibers and / or wool is preferably 1% by weight to 80% by weight for the same reason as described above. .

In some cases, the cosmetic properties of the coating film obtained by adding a coloring agent such as a pigment or a dye to the organic solvent solution of the high polymer containing the fine particles composed of the silk fibers and / or wool are added. Can be enhanced. Also,
Antioxidants, anti-NO _x gas anti-tarnish agents, various antidegradants,
Various functional agents and the like can be added to obtain a good surface film.

The organic solvent solution of the high polymer containing fine particles composed of silk fibers and / or wool obtained as described above is applied to the surface of the synthetic leather substrate and dried to form a coating film. As the surface forming method, conventionally known methods such as spray coating, gravure coating, knife coating, roll coating, and lamination using release paper can be employed.

The concentration of the mixed solution may be adjusted so as to have an optimum viscosity according to these application methods. If the thickness of the coating film after one application is insufficient, the application and drying may be repeated to adjust the thickness of the coating film to a target value.

The synthetic leather thus obtained has a surface feel that is comfortable when a person comes into direct contact with the skin, has no stickiness due to sweat, and has moisture permeability, moisture absorption, and high moisture release.

Further, by making the coating film porous, the above-mentioned functional characteristics can be greatly enhanced, and the air permeability can be further enhanced.

As a method for obtaining a porous coating film, a polymer organic solvent solution containing fine particles composed of silk fibers and / or wool is applied to the surface of a synthetic leather substrate, and then immersed (water immersed) in water. A conventionally known method such as a wet method for extracting a solvent by means of a solvent can be employed, or a particularly effective method is a phase separation coagulation method. In this method, the solubility of the organic solvent in the polymer organic solvent solution is limited,
In this method, a compound having high crystallinity and evaporating the organic solvent and precipitating in the form of fine particles is added and dissolved as a phase separation coagulation nucleating agent. For example, using N, N-dimethylformamide as an organic solvent, an organic solvent solution of the mixed resin using urea as a phase separation coagulation nucleating agent is applied to the surface of a synthetic leather substrate and dried to form a porous coating film. can get. In some cases, the urea is extracted with water or the like to make it more porous. Synthetic leather having on its surface a porous coating of a polymer containing fine particles of silk fibers and / or wool thus obtained is characterized in that the synthetic resin serving as the base of the synthetic leather is made of fine particles of silk fibers and / or wool. A synthetic resin mainly composed of a polyurethane resin, or a synthetic resin mainly composed of a polyamino acid urethane resin, or a polyamino acid urethane resin mainly containing fine particles composed of silk fibers and / or wool. Since it is a synthetic resin that is breathable and has breathability, it has a surface feel comparable to human skin compared to synthetic leather having a non-porous coating film of the high molecular polymer on the surface Of course, functional properties such as moisture permeability, moisture absorption, and moisture release are several steps better. However, on the other hand, since the surface is generally porous, problems such as easiness of contamination during use and water resistance are problematic. To cope with this, a fluorine-modified polyurethane resin may be used as the polymer as described above. Even when used in combination with another polymer, the effects of antifouling property and water resistance can be sufficiently obtained.

Such a synthetic leather having a porous surface coating can be given a special function by various post-treatments. For example, various pharmaceuticals, dyes, deodorants, water repellents, perfumes,
By treating and drying a solution such as an antifungal agent by applying, spraying, impregnating, etc., these agents are retained in the surface pores, and the effect can be exhibited.

In the present invention, these functional characteristics and effects can be further enhanced by optimizing the material constituting the present invention according to the use of the synthetic leather. For example, when designing as an upper material for shoes, a silk fabric which is preferable for forming the surface coating of the present invention as a synthetic resin using a base cloth such as rayon or cotton having high hygroscopicity as a fiber constituting a synthetic leather substrate. And / or using a polyamino acid urethane resin containing fine particles composed of wool, and the outer membrane is made of polyamino acid urethane acid and a fluorine-modified polyurethane resin as porous material and about 45:45:10 of fine particles composed of silk fiber and / or wool. (Weight ratio) mixed resin may be used.

In other words, by absorbing sweat escaping from the feet from the back surface with a large hygroscopic property and escaping from the surface porous membrane excellent in moisture permeability, moisture release properties, and antifouling properties, shoes with less stuffiness of feet can be obtained. I can do it.

As described above, the present invention brings about an even greater effect by appropriately selecting the materials constituting the present invention according to the intended use.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “part” or “%” means
All are based on weight, and the evaluation and characteristic values are obtained by the following methods.

(A) Stickiness on sweat skin Hands were put in a polyethylene bag of 25 cm x 25 cm and hermetically closed, and the stickiness was evaluated with the palm that sweated 10 minutes later based on the following.

 A: Very good without stickiness.

 ：: Good without stickiness.

 Δ: Slightly sticky and not good.

 ×: Bad feeling due to stickiness.

(B) Moisture permeability Expressed in terms of moisture permeability (mg / cm ² · hr) according to the method of JIS K6549.

(C) Moisture absorption Moisture absorption (g / m ² ) when left for 1 hour in an atmosphere at a temperature of 23 ° C and a relative temperature of 30%, and then left for 30 minutes in an atmosphere of a temperature of 23 ° C and a relative temperature of 80%. Expressed by

(Iv) Humidity release Moisture release after leaving for 1 hour in an atmosphere at a temperature of 23 ° C and a relative temperature of 80%, and then leaving for 30 minutes in an atmosphere of a temperature of 23 ° C and a relative temperature of 30% (g / m ₂ ) Expressed by

(E) Air permeability A value measured using a Gurley densometer according to the method of JIS P8117, and is expressed as the time (seconds) required for 50 cc of air to pass.

(F) Oxidation-resistant nitrogen gas discoloration resistance Expressed by a gray scale judgment in accordance with the strong test method of JIS L0855.

(G) Dirt resistance Tobacco ash (mild seven) is ground in a mortar, rubbed with a mortar and sized at 36 mm in diameter with the middle finger clockwise 25 times and counterclockwise 25 times, then wiped with absorbent cotton, grade 5 Is expressed in 1 to 5 levels as no stain.

Reference Example 1 (Preparation of Synthetic Leather Substrate) A non-woven fabric made of polyester fiber weighing 280 g / m ² and having a thickness of 1.0 mm was impregnated with a 13% polyester-polyurethane-dimethylformamide solution. 18% concentration of Porieteru polyurethane - dimethylformamide solution After coated with basis weight of 600 g / m ^2, water immersion coagulation, washed with water to create a synthetic leather substrate -1 drying it.

(Preparation of Paint-1) Paint-1 was prepared with the following composition.

 Crisbon NY320 100 parts (Dainippon Ink and Chemicals Co., Ltd.) Howlack A1004 White 80 parts (Dainippon Ink and Chemicals Co., Ltd.) Howlack A1008 Mat 30 parts (Dainippon Ink and Chemicals Ltd.) Isopropyl alcohol 50 Part Methyl ethyl ketone 40 parts N, N-dimethylformamide 10 parts (Preparation of paint-2) Paint-2 was prepared with the following composition.

Haurac A3454 (20%) 100 parts (Dainippon Ink and Chemicals, Inc.) Fine particles made of silk fiber 5 parts (Tosco Corporation, average particle size 15 μm) Haurac A1008 Mat 30 parts (Dainippon Ink and Chemicals Co., Ltd.) Isopropyl alcohol 50 parts Methyl ethyl ketone 50 parts (Coating on the surface of synthetic leather substrate) Paint-1 on the surface of synthetic leather substrate-1 created on the left
Is applied and dried three times with a gravure coater (using a 110 mesh roll), and then the pattern is formed with a heated embossing roll. Then, the paint-2 is applied with a gravure coater (using a 110 mesh roll). Drying was repeated three times to obtain a synthetic leather having a white surface.

When the surface of the obtained synthetic leather touches the skin, it does not make you feel cold, feels warm, and has excellent feeling without stickiness even on sweaty skin, for volleyball, handball It was excellent. In addition,
The moisture permeability was greater than that of conventional synthetic leather, and it was also excellent as an upper material for sports shoes.

 Table 1 shows the obtained characteristic values.

Reference Example 2 (Preparation of paint-3) Polyamino acid urethane (use of non-yellowing type urethane:
Fine particles composed of silk fibers (Tosco Corporation, average particle size) in 100 parts of an N, N-dimethylformamide solution (solid content: 12%) of LUCKSKIN-UA-3295A; polyamino acid segment (35%) manufactured by Seiko Chemical Co., Ltd. 9 parts of 15 μm) and 15 parts of a matting agent (manufactured by Dainippon Ink and Chemicals, Incorporated; Haulac B1356) were added and mixed to obtain a dispersion solution paint.

(Application to Synthetic Leather Substrate Surface) Synthetic leather was obtained in the same manner as in Reference Example 1, except that Paint-3 was used instead of Paint-2.

The surface of the obtained synthetic leather had the same tactile sensation as the surface of the synthetic leather obtained in Reference Example 1, and was excellent for volleyball and handball. In addition, the moisture permeability was larger than that of the conventional synthetic leather, and was excellent as an upper material for sports shoes.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 3 (Preparation of paint-4) Polyamino acid urethane (use of non-yellowing type urethane:
70 parts of N, N-dimethylformamide solution (solid content: 12%) of LUCKSKIN-UA-3295A (polyamino acid segment: 35%) manufactured by Seiko Chemical Co., Ltd. and fluorine-modified polyurethane (non-yellowing type urethane used: Dainichi Seika) Resinoid LU-4110 manufactured by Kogyo Co., Ltd., 30 parts of a mixed solution (1: 1: 1) of N, N-dimethylformamide: isopropyl alcohol: toluene (solid content: 12%) was mixed to prepare a mixed resin solution. . 8 parts of fine particles made of silk fiber (manufactured by Tosco Corporation, average particle size 15 μm) and 15 parts of a matting agent manufactured by Dainippon Ink and Chemicals, Inc .; Paint was obtained.

(Application to Synthetic Leather Substrate Surface) Synthetic leather was obtained in the same manner as in Example 1, except that Paint-4 was used instead of Paint-2.

The surface of the obtained synthetic leather had an excellent tactile sensation similarly to the surface of the synthetic leather obtained in Reference Example 1, and was suitable for similar uses.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 4 (Preparation of Paint-5) Paint-5 was prepared with the following composition.

LUCKSKIN-UA3295A (Seiko Chemical Co., Ltd.) (18
%) 80 parts Resroid LU-4110 (manufactured by Dainichi Seika Kogyo Co., Ltd.) (18
%) 20 parts Fine particles made of silk fiber (Tosco Corporation, average particle size 15
μm) 10 parts Dirac SL-3440 red (Dai Nippon Ink Chemical Industry Co., Ltd.) 5 parts N, N-dimethylformamide 40 parts Methyl ethyl ketone 40 parts (application to synthetic leather substrate surface) Paint-5 was used in Reference Example 1. A gravure coating machine (using a 110 mesh roll) is applied to the surface of the synthetic leather substrate-1 thus prepared.
The coating and drying were repeated three times, and the pattern was formed with a heated embossing roll to obtain a synthetic leather having a red coating film on the surface.

When the surface of the obtained synthetic leather touches the skin, it does not make you feel cold, feels warm, and has excellent tackiness without sweatiness even on sweaty skin, basketball, rugby ball It was chosen for business.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 5 (Preparation and application of paint-6) Polyamino acid urethane (use of non-yellowing type urethane:
Manufactured by Mitsubishi Kasei Corporation, PAU-300: Polyamino acid segment 3
5%) N, N-dimethylformamide solution (solid content 15%)
60 parts and fluorine-modified polyurethane resin (Rezroid LU-41
10. N, N-dimethylformamide: isopropyl alcohol: toluene mixture (1: 1:
1) Into a mixed resin solution obtained by mixing 40 parts of a solution (solid content: 15%), 5 parts of fine particles made of silk fiber (manufactured by Tosco Corporation, average particle size: 15 μm) are added and uniformly dispersed and mixed. A liquid was obtained. In this, 7 parts of urea are dissolved while heating,
Further, as a coloring agent, 8 parts of a black pigment (manufactured by Dainippon Ink and Chemicals, Inc .; Dailac SL-3430) and 3 parts of a black dye (manufactured by Nippon Kayaku Co., Ltd., Kayaset BLACK-KR) are added and uniformly mixed. A black paint was obtained. This black paint was applied on a release paper with a pattern so as to have a basis weight of 70 g / m ² and dried at 110 ° C., and then an adhesive was applied so as to have a basis weight of 50 g / m ^2. It was stuck to the surface of the synthetic leather substrate-1 to be formed and was sufficiently adhered.

The synthetic leather separated from the release paper was washed with warm water of 60 ° C. to obtain a black synthetic leather having a porous surface. The resulting synthetic leather, when touched on the skin, does not feel cold, feels warm, has excellent tackiness without sweatiness even on sweaty skin, grip material of tennis racket,
It was suitable for gloves.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Example 1 (Preparation of Synthetic Leather Substrate-2) Polycarbonate polyurethane (manufactured by Dainichi Seika Kogyo Co., Ltd .; Rezamin CU 9450NL) and polyamino acid were added to a nonwoven fabric made of polyester fiber having a weight of 280 g / m ² and a thickness of 1.0 mm. A urethane (PAU-300) mixture (mixing ratio 60:40) impregnated with an N, N-dimethylformamide solution (concentration 10%) was impregnated with a polycarbonate-based urethane (resamine
N of CU9450NL) and polyamino acid urethane (PAU-300) a mixture of (mixing ratio 60:40), after coated N- dimethylformamide solution (18% concentration) with basis weight of 600 g / m ^2, water immersion coagulation, washing with water And dried to prepare a synthetic leather substrate-2.

(Preparation of Paint-7) Polyamino acid urethane (use of non-yellowing type urethane:
60 parts of N, N-dimethylformamide solution (solid content: 10%) of Seiko Chemical Co., Ltd .; LUCKSKIN-UA3295A) and N, N of fluorine-modified polyurethane resin (Rezaloid LU-4110: manufactured by Dainichi Seika Kogyo Co., Ltd.) N-dimethylformamide: isopropyl alcohol: toluene mixture (1: 1: 1) solution (solid content 1
(0%) To 40 parts of the mixed resin solution, 5 parts of fine particles made of silk fibers (manufactured by Tosco Corporation, average particle size: 15 μm) were added to obtain a mixed dispersion. 5 parts of urea was dissolved therein while heating, and 2 parts of a white pigment, Dailac SL-3410 (manufactured by Dainippon Ink and Chemicals, Incorporated Co., Ltd.) was added and uniformly mixed as a colorant to obtain a white paint. .

(Application to Synthetic Leather Substrate Surface) On the surface of the synthetic leather substrate-2, the paint-1 prepared in Reference Example 1 was gravure-coated (using a 110-mesh roll).
The coating and drying were repeated three times, and then the pattern was formed with a heated embossing roll.
Coating-drying was repeated three times. Next, it was immersed in warm water of 80 ° C. for 5 minutes and dried.

The surface of the obtained synthetic leather has not only excellent surface texture as in the case of the synthetic leather obtained in Example 1, but also more excellent moisture permeability, moisture absorption, and moisture release. As an upper material, it was an excellent material without stuffiness when worn.

This was because the surface was porous and had high air permeability. The reason why the air permeability is obtained is that the organic solvent of the paint 7 dissolves and destroys the film obtained from the non-porous paint 1 when applying and drying the paint 7, and forms a porous film by itself. Therefore, it is considered that the whole becomes a communicating pore.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Example 2 (Preparation of Synthetic Leather Substrate-3) Polycarbonate-based polyurethane (Dainichi Seika Kogyo Co., Ltd.) was applied to a nonwoven fabric composed of polyester fiber and rayon fiber (mixing ratio 30:70) weighing 280 g / m ² and 1.0 mm thick. Fine particles composed of silk fibers (Tosco Corporation) in a N, N-dimethylformamide solution (concentration: 10%) of a mixture (mixing ratio: 60:40) of resamine CU9450NL) and polyamino acid urethane (PAU-300). ), Average particle size of 15 μm) A non-yellowing polycarbonate urethane (manufactured by Dainichi Seika Kogyo Co., Ltd .; Rezamin CNU5) is impregnated with a mixed dispersion in which 8 parts of a mixed dispersion liquid is dispersed.
In a N, N-dimethylformamide solution (concentration: 18%) of a mixture (mixing ratio: 60:40) of a mixture of 30) and a polyamino acid urethane (use of non-yellowing lip urethane: manufactured by Seiko Chemical Co., Ltd .; LUCKSKIN-UA3295A). , A mixed dispersion of 10 parts of fine particles made of silk fiber (manufactured by Tosco Corporation, average particle size: 15 μm) is coated with a basis weight of 600 g / m ² , then immersion-coagulated, washed with water, and dried to produce synthetic leather. Substrate-3 was produced.

(Application to Synthetic Leather Substrate Surface) The surface of the synthetic leather substrate-3 was patterned with a heated embossing roll, and then the paint-7 prepared in Example 1 was applied by a gravure coating machine (using a 110 mesh roll). After the drying was repeated three times, it was immersed in warm water at 80 ° C. for 5 minutes and dried to obtain white synthetic leather.

The surface of the obtained synthetic leather is excellent in surface feel, of course, it is excellent in moisture permeability, moisture absorption, moisture release, breathability, as upper material of sports shoes,
It was excellent without stuffiness when worn.

In general, those with a porous membrane and breathable are easily discolored by nitrogen oxide gas, but this type uses non-yellowing polyurethane from the surface of the synthetic leather base to the porous coating. Therefore, there was no discoloration due to nitrogen oxide gas.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 6 (Coating on Synthetic Leather Base Surface) Paint-7 prepared in Example 1 on the surface of nylon taffeta
Is applied so as to have a basis weight of 70 g / m ² and dried, and then at 80 ° C.
In warm water for 5 minutes to dry.

The obtained product had high moisture permeability, good touch, and was optimal for sports clothing.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 7 In place of 5 parts of fine particles made of silk fiber, 5 parts of trace particles made of wool (manufactured by Tosco Corporation, average particle size 15 μm) were used to prepare paint-2 ′ instead of paint-2. Otherwise in the same manner as in Reference Example 1, a synthetic leather was obtained.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 8 Instead of using 9 parts of fine particles made of silk fiber, 9 parts of fine particles made of wool (manufactured by Tosco Corporation, average particle size 15 μm) were used, and instead of paint 3, paint-3 ′ was prepared. Reference example 2
Synthetic leather was obtained in the same manner as described above. Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 39 In addition to preparing paint-4 'instead of paint-4, using 8 parts of fine particles made of wool (manufactured by Tosco Corporation, average particle size 15 μm) instead of 8 parts of fine particles made of silk fiber In the same manner as in Reference Example 3, synthetic leather was obtained.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 10 In addition to preparing paint-5 'instead of paint-5, using 10 parts of fine particles made of wool (manufactured by Tosco Corporation, average particle size 15 μm) instead of 10 parts of fine particles made of silk fiber. In the same manner as in Reference Example 4, synthetic leather was obtained.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Reference Example 11 Instead of 5 parts of fine particles made of silk fiber, 5 parts of fine particles made of wool (manufactured by Tosco Corporation, average particle size 15 μm) were used to prepare paint 6 ′ instead of paint 6. In the same manner as in Reference Example 5, a synthetic leather was obtained.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Example 3 In addition to preparing paint-7 'instead of paint-7, using 5 parts of fine particles made of wool (manufactured by Tosco Corporation, average particle size 15 μm) instead of 5 parts of fine particles made of silk fiber In the same manner as in Example 1, a synthetic leather was obtained.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Example 4 In Example 2, 8 parts of fine particles composed of silk fiber used for producing a synthetic leather substrate, and 10 parts of fine particles composed of silk fiber, were replaced with fine particles composed of wool (manufactured by Tosco Corporation,
Synthetic leather was obtained in the same manner as in Example 2 except that 8 parts and 10 parts of an average particle size were used.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Example 16 Synthetic leather was obtained in the same manner as in Reference Example 6, except that Paint-7 'prepared in Example 3 was used instead of Paint-7.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Comparative Example 1 (Preparation of Paint-8) Paint-8 was prepared with the following composition.

Haurac A3454 (20%) (Dainippon Ink & Chemicals, Inc.) 100 parts Haurac A1008 Mat (Dainippon Ink & Chemicals, Inc.) 30 parts Insopropyl alcohol 50 parts Methylethylketone 50 parts (manufacture of synthetic leather surface) The paint-1 was applied and dried three times on the surface of the synthetic leather substrate-1 prepared in Example 1 with a geravia roll (110 mesh), and then patterned with a heated embossing roll. -8 to gravure roll (110
The coating and drying were repeated three times with a mesh) to obtain a synthetic leather having a white surface.

The resulting synthetic leather was unsatisfactory in moisture permeability, hygroscopicity, moisture release and the like, and had a tactile feel on the surface of conventional polyurethane synthetic leather.

 Table 1 shows the characteristic values of the obtained synthetic leather.

Comparative Example 2 (Preparation of Paint-9) Paint-9 was prepared with the following composition.

LUCKSKIN-UA3295A (Seiko Chemical Co., Ltd.) (18
%) 100 parts Haurak B1356 mat (manufactured by Dainippon Ink and Chemicals, Inc.) 20 parts N, N-dimethylformamide 40 parts methyl ethyl ketone 40 parts (manufacture of synthetic leather surface) Use paint-9 instead of paint-8 Otherwise, in the same manner as in Comparative Example 1, a synthetic leather having a white surface was obtained.

The resulting synthetic leather had a slightly sticky surface feel and was easily soiled.

 Table 1 shows the characteristic values of the obtained synthetic leather.

(Effects of the Invention) According to the present invention, it has a surface feel that is not uncomfortable with human skin, and has functions such as moisture permeability, moisture absorption, and moisture release, and in some cases also has air permeability, It is possible to provide a synthetic leather whose surface is not easily stained.

────────────────────────────────────────────────── (5) References JP-A-4-41783 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06N 3/00-3/18 D06M 15 / 564 D06M 15/15

Claims (8)

(57) [Claims] A synthetic leather comprising a synthetic leather substrate comprising a fibrous material or a fibrous material and a synthetic resin, wherein a surface of a high molecular polymer containing fine particles comprising silk fibers and / or wool is formed on the surface of the synthetic leather substrate. A highly moisture-permeable synthetic leather, wherein the synthetic resin is a synthetic resin mainly composed of a polyurethane resin containing fine particles made of silk fibers and / or wool. 2. A synthetic leather comprising a fibrous material or a synthetic leather substrate comprising a fibrous material and a synthetic resin, on which a high-molecular polymer film containing fine particles comprising silk fibers and / or wool is formed. A highly moisture-permeable synthetic leather, wherein the synthetic resin is a synthetic resin mainly composed of a polyamino acid urethane resin. 3. Synthetic leather in which a coating of a high molecular polymer containing fine particles made of silk fibers and / or wool is formed on the surface of a synthetic leather substrate made of fibrous material or fibrous material and synthetic resin. A highly moisture-permeable synthetic leather, wherein the synthetic resin is a synthetic resin mainly composed of a polyamino acid urethane resin containing fine particles composed of silk fibers and / or wool. 4. The high molecular weight polymer is a polyurethane resin.
The highly moisture-permeable synthetic leather according to claim 1. 5. The highly moisture-permeable synthetic leather according to claim 1, wherein the high molecular weight polymer is a polyamino acid urethane resin. 6. The highly moisture-permeable synthetic leather according to claim 1, wherein the high molecular weight polymer is a mixture of a polyamino acid urethane resin and a fluorine-modified polyurethane resin. 7. The method according to claim 7, wherein the polyamino acid urethane resin is poly-γ-polyurethane.
6. A polyamino acid segment containing methyl-L-glutamate as a main component, the content of which is 3% by weight to 85% by weight based on the weight of the polyamino acid urethane resin.
Or a highly moisture-permeable synthetic leather according to 6. 8. The highly moisture-permeable synthetic leather according to claim 1, wherein the high-molecular polymer film is continuous porous.