JPH0314949B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a flexible synthetic leather for vehicles, which has excellent drapability and excellent flexibility, has a texture and feel very similar to natural leather, and is resistant to hydrolysis. The purpose of the present invention is to provide a flexible synthetic leather for a vehicle that has not only high heat resistance and light resistance but also heat resistance that can withstand high temperatures of 100 to 120°C for a long period of time.

The present inventors have discovered that the leather has a texture and feel very similar to natural leather, has hydrolysis resistance, light resistance, and
We have developed a heat-resistant synthetic leather for vehicles that can withstand high temperatures of 100-120℃ for long periods of time.

However, the above-mentioned synthetic leather for vehicles has a drawback that it has excellent drapability but lacks flexibility. For this reason, conventional synthetic leather has been produced using (1) a dry method in which a skin layer is laminated on a raised cloth via an adhesive layer, or (2) an impregnated cloth in which a fiber web is wet-treated with a polyester-based polyurethane solvent solution. Methods for manufacturing synthetic leather include a wet method in which a polyester-based polyurethane solvent solution is wet-coagulated, and (3) an emulsion method in which a base material is impregnated with an aqueous dispersion of a polymer or is applied and dried. In all of the above methods, not only the adhesive or impregnating agent causes solidification, but also the synthetic resin layer is a single layer, so it is impossible to obtain excellent flexibility with drapability similar to that of natural leather. I can't.

Furthermore, it is difficult to make synthetic leather using polyester-based polyurethane that can withstand long-term use due to the poor hydrolysis resistance of polyester-based polyurethane.

Recently, it has been proposed that a polyurethane foam layer is laminated on a raised fabric with an adhesive, but polyurethane foam has strong rebound resilience, so it has cushioning properties but does not have drape properties, and it does not have drape properties. Due to the difference in material from polyurethane foam, the laminate does not have integrity, and even if it is given wrinkling properties through post-treatment, it cannot be given enough flexibility to drape. I can't.

By having the structure described in the claims, the present invention can provide cushioning properties and excellent flexibility with rich drapability, and also have hydrolysis resistance, light resistance, and temperature resistance of 100 to 120°C. We were able to obtain flexible synthetic leather for vehicles that can withstand high temperatures for long periods of time.

That is, the present invention provides a microporous material in which the surface of a fibrous base material is brushed, this is impregnated with a polycarbonate-based polyurethane solvent solution, and the polycarbonate-based polyurethane forms a microporous body by wet coagulation treatment. On the porous composite fiber base material,
100% modulus 10~50Kg/ ^cm2 , thickness 10~80μ polycarbonate polyurethane adhesive layer, 100
%modulus 40~100Kg/ ^cm2 , thickness 10~50μ-(
CH ₂ -) polyester-based polyurethane middle skin layer made of glycol dicarboxylic acid having a number of 4 or more, and a polycarbonate-based polyurethane skin layer with a 100 modulus of 80 to 200 Kg/cm ² and a thickness of 10 to 50μ, which are sequentially laminated. This is a flexible synthetic leather for vehicles.

The fibrous base materials mentioned above include natural fibers such as cotton, wool, silk, and hemp; regenerated fibers such as rayon, viscose sulfur, and acetate; and synthetic fibers such as polyester, polyacrylonitrile, polyvinyl chloride, polyamino acids, and polyvinylidene chloride. alone or in various blended fibers or glass fibers,
Woven and non-woven fabrics made of inorganic fibers such as asbestos fibers.

In addition to the above, the microporous composite fiber base material according to the present invention is produced by raising the surface of the fibrous base material, applying a polycarbonate-based polyurethane solvent solution to the raised surface so as to cover the raised layer, and then applying a wet coagulation treatment. Alternatively, the polycarbonate polyurethane may be laminated onto a microporous body.

The polycarbonate polyurethane used in the present invention is a polymer of a polycarbonate polyol, a diisocyanate compound (hereinafter abbreviated as diisocyanate), and a chain extender,
The polycarbonate polyol has the following general formula: (However, R=-( _CH2- ) _p , and p≧2.
Further, it is a polyalkylene polycarbonate polyol represented by n=5 to 200), and specifically, 1,6-hexane polycarbonate polyol is preferable.

Further, a mixture in which a part of the polyalkylene polycarbonate polyol is replaced with polyoxyalkylene modified polycarbonate can also be used.

In addition, diisocyanates include aliphatic or alicyclic diisocyanates as non-yellowing diisocyanates, such as tetramethylene diisocyanate; 1,6-hexane diisocyanate; 2,2,4-trimethyl-
1,6-hexane diisocyanate; 1-methylcyclohexane-2,4-diisocyanate;
3,3'-dimethyl-4,4'-diisocyanate dicyclohexylmethane; 4,4'-dicyclohexylmethane diisocyanate can be used.

Further, as the yellowing type diisocyanate in the present invention, aromatic compounds such as tolylene diisocyanate; diphenylmethane diisocyanate; xylylene diisocyanate and the like can be used.

In addition, the chain extender may be a primary or secondary aliphatic amine or a low molecular weight glycol, such as piperazine; hexamethylene diamine; ethylene diamine; propylene-1,2-diamine;
N-methyl-bis-(3-aminopropyl)amine; 1,4-diaminocyclohexane; 1-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane; 1,4-butanediol; ethylene glycol; 1,6-hexanediol;
Neopentyl glycol; P-xylene glycol, etc. can be used.

Furthermore, the polyester polyurethane used in the present invention is a polymer of a polyester polyol, a diisocyanate, and a chain extender, and the polyester polyol is a polyester made of a glycol dicarboxylic acid having -( _CH2- ) number of 4 or more. type polyurethane, and dicarboxylic acids such as adipic acid, sebazic acid, glutaric acid, succinic acid, azelaic acid, etc. can be used, and glycols include ethylene glycol; 1,4-butanediol; 1,6-hexanediol; Diethylene glycol; neopentyl glycol, etc. can be used. The diisocyanate and chain extender used in the polyester polyurethane can be the same as those used in the polycarbonate polyurethane described above.

The flexible synthetic leather for vehicles according to the present invention has a 100% modulus of 10 to 10% on the microporous composite fiber base material described above.
A polycarbonate-based polyurethane adhesive layer is formed by laminating 50 kg/cm ² of polycarbonate-based polyurethane to a thickness of 30 to 150 μm. In this case, the polycarbonate polyurethane used may be either a polycarbonate polyurethane or a copolymer of a polycarbonate polyurethane and a polyether polyurethane such as polytetramethylene ether glycol or polyoxypropylene glycol. 100% modulus is 10
If the peel strength is less than Kg/cm ² , the peel strength will be weak, and if it exceeds 50 Kg/cm ² , the adhesive layer will become too hard, impairing the texture, creasing, and feel that closely resemble natural leather.

Further, on the surface of the adhesive layer, a medium layer of polyester polyurethane made of glycol dicarboxylic acid having -(CH ₂ -) number 4 or more, which has a 100% modulus of 40 to 100 Kg/cm ² and has a thickness of 10 to 50 μm.
A polycarbonate polyurethane skin layer with a 100% modulus of 80 to 200 Kg/cm ² is laminated to a thickness of 10 to 50μ on the surface of the intermediate skin layer, resulting in a 4-layer structure including the fibrous base material. It is formed by laminating layers. in the mesothelial layer
If the 100 modulus is less than 40 Kg/cm ² , the adhesiveness will be weak and the physical properties will be poor. Also, 100% modulus is 100
If it exceeds Kg/cm ² , the texture of the intermediate layer will be impaired, and the surface wrinkles that closely resemble natural leather will not be obtained.

Furthermore, the 100% modulus in the epidermal layer is 80
If it is less than 200 kg/ ^cm2 , the physical properties of the epidermis layer will be poor.
If it exceeds Kg/cm ² , the skin layer becomes too hard and the texture, creasing, and feel that closely resembles natural leather are lost. The polycarbonate polyurethane used in the skin layer is a diisocyanate that reacts with the polycarbonate polyol, resulting in a yellowing type,
Any type of non-yellowing diisocyanate can be used, but it is preferable to use a non-yellowing type diisocyanate in consideration of the light resistance required for the skin layer. Titanium,
One or more pigments such as carbon black, flavance yellow, anthraquinone red, and copper phthalocyan blue can be added in an amount of 5 to 50% by weight based on the polycarbonate polyurethane.
In addition to these pigments, ultraviolet absorbers, ultraviolet shielding agents, crosslinking agents, and other fillers may be added as necessary, and the pigments, fillers, etc. It can be blended as appropriate.

That is, the present invention impregnates a fibrous base material with a raised surface as a base for synthetic leather with a polycarbonate-based polyurethane solvent solution, or coats a polycarbonate-based polyurethane solvent solution so as to cover the raised surface of the fibrous base material. By using a microporous composite fiber base material in which the polycarbonate-based polyurethane solvent solution is made microporous through a post-wet coagulation treatment, the microporous composite fiber base material
Polycarbonate-based polyurethane, polyester-based polyurethane, and polycarbonate-based polyurethane that can be manufactured in the same manner as the bag tissue in natural leather, and that form the adhesive layer, intermediate skin layer, and skin layer that are sequentially laminated on the surface of the leather. 100 ~ modulus of, respectively 10 ~
50 Kg/cm ² , 40 to 100 Kg/cm ² and 80 to 200 Kg/cm ² can improve the peel strength between the polyurethane layers, and the polyurethane layers are sequentially formed from coarse to dense; In the synthetic leather of the present invention, each of the above-mentioned structural layers interacts with each other at the interface, so it exhibits not only cushioning properties but also excellent flexibility with rich drapability, and the texture, feel, and wrinkle properties are more natural. A product that closely resembles leather is obtained.

Moreover, the synthetic leather of the present invention not only has a texture that closely resembles that of natural leather, but also has hydrolysis resistance, light resistance, and heat resistance that can withstand high temperatures of 100 to 120°C for a long period of time. Can be done.

Example 1 Polyester fiber (manufactured by Teijin and Toray Industries,
100% modulus 50Kg/cm ² 1,6-
A mixture of 100 parts by weight of a hexanediol polycarbonate-based polyurethane solvent solution (solvent DMF) and 3 parts by weight of a nonionic surfactant was coated with a doctor knife coater to such an extent that the raised fabric was not visible (approximately 400 g/m ² coating weight). It was coated and subjected to wet coagulation treatment in water to obtain a microporous composite fiber base material.

On the other hand, on the spun release paper, 100% modulus 120
Dry 100 parts by weight of a 1,6-hexane carbonate-based polyurethane solvent solution (containing 15 parts by weight of titanium oxide) of Kg/cm ² with a doctor knife coater to a thickness of 30 μm.
The polyurethane film layer is formed by applying the polyurethane film and drying it by heating at 100°C for 3 minutes, which is used as the skin layer.

Next, apply 100% Modulus 80 to the surface of the epidermis layer.
Kg/cm ² of polyester (adipic acid) polyurethane is applied in the same manner as above to a dry thickness of 30 μm, dried to form a polyester polyurethane film layer, and this is used as the intermediate skin layer.

Furthermore, on the surface of the mesothelial layer, 100% Modulus 20
Kg/cm ² of 1,6-hexane carbonate-tetramethylene ether copolymer polyurethane adhesive was applied to a dry thickness of 30 μm, and after drying with hot air at 120°C for 5 minutes, the upper surface of the adhesive layer was coated as described above. The raised surfaces of the microporous composite fiber base materials were bonded together by thermocompression at 100°C, and after the adhesive had hardened, the release paper was peeled off to obtain synthetic leather. The obtained synthetic leather had excellent flexibility with excellent heat resistance, hydrolysis resistance, light resistance, cushioning properties, and drapability.

Example 2 Both sides of a cotton base fabric were brushed, and 100 parts by weight of a 1,6-hexane carbonate polyurethane solvent solution (solvent DMF) with a 100% modulus of 50 kg/cm ² , 5 parts by weight of carbon black, and a nonionic surfactant were added. Synthetic leather was prepared in the same manner as in Example 1, except that it was impregnated with 1 part by weight of the agent, squeezed with Nitzprol at a squeezing rate of 100%, wet-coagulated in water, and used as a microporous composite fiber base material. Obtained. The obtained synthetic leather has heat resistance, hydrolysis resistance,
In addition to light resistance, this synthetic leather has excellent cushioning properties and excellent flexibility with excellent drapability.

Claims (1)

[Scope of Claims] 1 The surface of a fibrous base material is brushed, the polycarbonate polyurethane is impregnated with a polycarbonate polyurethane solvent solution, and the polycarbonate polyurethane forms a microporous body through wet coagulation treatment. 100% modulus 10 on microporous composite fiber material
~50Kg/cm ² , 10~80μ thick polycarbonate polyurethane adhesive layer, 100% modulus 40~100
Kg/cm ² , thickness 10~50μ, non-foamed polyester polyurethane medium layer made of -(CH ₂ -) number 4 or higher glycol dicarboxylic acid, 100% modulus 80~
A flexible synthetic leather for vehicles characterized by sequentially laminated polycarbonate polyurethane skin layers weighing 200Kg/cm ² and having a thickness of 10 to 50μ. 2. A microporous composite fiber base material is coated with a polycarbonate polyurethane solvent solution on the raised surface of the raised fibrous base material so as to cover the raised layer, and the microporous material is applied to the raised surface by wet coagulation treatment. The flexible synthetic leather for vehicles according to claim 1, characterized in that the flexible synthetic leather is laminated thereon. 3. The flexible synthetic leather for vehicles according to claim 1, characterized in that the skin layer of the polycarbonate polyurethane contains a coloring pigment and a filler having light-shielding properties.