JPH02277891A - Synthetic leather - Google Patents

Abstract

PURPOSE:To provide a synthetic leather having excellent permanent surface smoothness by forming a polyurethane surface-treated layer containing a silicone oil and/or a modified silicone oil and a specific diol on the surface of polyurethane surface layer. CONSTITUTION:A polyurethane surface layer 4 (preferably having a 100% modulus of 20-200kg/cm<2>) is formed on a fiber substrate 2 comprising natural, regenerated or synthetic fibers through a polyurethane adhesive 3, on whose surface a polyurethane surface-treated layer 5 containing a silicone oil and/or a modified silicone oil (e.g. dimethylpolysiloxane) and prepared from a polyol component (e.g. polycarbonate polyol) containing a siliconediol is further formed to provide a synthetic leather 1 having excellent surface smoothness and not generating any unpleasant abrasion noise.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to synthetic leather with excellent surface smoothness.

[Conventional technology and Problems that the invention attempts to solve]

Synthetic leather used for furniture, vehicle seats, door linings, shift lever boots, etc. is produced by forming a polyurethane skin layer on a fiber base material such as nonwoven fabric, woven fabric, or knitted fabric using a wet or dry process. However, this type of synthetic leather tends to generate unpleasant scraping sounds when the polyurethane skin layer is rubbed.This is due to the lack of lubricity on the surface of the skin layer. Conventional synthetic leather uses methods such as adding silicone oil to the polyurethane that makes up the skin layer or spraying silicone oil onto the surface of the skin layer to form a silicone oil film in order to give the surface lubricity. It had been. However, these methods do not provide sufficient lubricity, or the surface lubricity obtained is temporary and lacks sustainability, and is still insufficient for applications that require permanent surface lubricity. It was something.

[Means to solve the problem]

The present invention was made in view of the above points, and an object of the present invention is to provide a synthetic leather that has a long-lasting surface smoothness effect and can permanently prevent the occurrence of scratching sounds.

That is, the present invention provides a synthetic leather characterized by having a surface treatment layer formed of polyurethane containing silicone oil and/or modified silicone oil and containing silicone diol in the polyol component on the surface of the polyurethane skin layer. This is a summary.

〔Example〕

Hereinafter, one embodiment of the present invention will be described based on the drawings.

FIG. 1 shows an embodiment of the synthetic leather 1 of the present invention, in which a polyurethane skin layer 4 is provided on the surface of a fiber base material 2 via an adhesive N3, and a polyurethane skin layer N4 is further provided on the surface of a fiber base material 2.
It has a structure in which a surface treatment layer 5 is provided on the surface.

As the fiber base material 2, for example, natural fibers such as cotton and linen,
Knitted fabrics, woven fabrics, non-woven fabrics, etc., which are knitted, woven, or intertwined with single or various blended fibers such as recycled fibers such as rayon, staple fiber, and acetate, and synthetic fibers such as polyester, polyamide, and polyacrylonitrile, are used.

The adhesive constituting the adhesive layer 3 may be any adhesive as long as it can bond the fiber base material 1 and the polyurethane skin layer 4, but a urethane adhesive is usually used. As a urethane adhesive, the 100% modulus is 10 to 100.
kg/cl is preferable, and examples of the polyurethane in this urethane adhesive include polycarbonate polyurethane, polytetramethylene ether polyurethane,
Examples include polypropylene ether polyurethane, polyester ether polyurethane, and polyester polyurethane. Trimethylolpropane (TMP) is a crosslinking agent for polyurethane used in urethane adhesives.
) and TDI, an adduct of TMP and HMD I, an adduct of TMP and IPDI, a trimer of HMD I, and the like.

The amount of crosslinking agent added is polyurethane (polyurethane solid content)
The amount is 5 to 30 parts by weight per 100 parts by weight. If the amount of crosslinking agent is too small, the adhesive strength will be insufficient, and if it is too large, it will become too hard. Further, an amine catalyst may be added to the urethane adhesive as a crosslinking promoter, if necessary. The thickness of the adhesive layer 3 is preferably 10 to 1° Oμ. The adhesive layer 3 can also be colored if necessary.

The polyurethane constituting the polyurethane skin layer 4 is 100%
The polyurethane preferably has a % modulus of 20 to 200 kg/cm, and examples of the polyurethane include polycarbonate polyurethane, polytetramethylene ether polyurethane, polyester ether polyurethane, and polyester polyurethane. The thickness of this epidermis N4 is 10~
100μ is preferred. Further, a thin film layer made of polyurethane may be further provided on the surface of this skin layer 4 if necessary.

The polyurethane constituting this thin film layer has a 100% modulus of 60 to 600 kg/c+fl, especially 200 to 60
A polyurethane having a yield value of 0 kg/c++1 is preferable, and examples of the type of polyurethane include those similar to the polyurethane constituting the skin layer 4. Polyurethane skin layer 4
For example, a polyurethane liquid for forming a skin layer is applied and dried on the surface of a release paper with a diaphragm, to form a film, an adhesive is applied to the surface of this film, and then laminated with the fiber base material 2,
It can be formed by a dry method in which the release paper is peeled off and transferred after the adhesive has solidified.

The polycarbonate-based polyurethane is a polymer of a polycarbonate-based polyol, a diisocyanate compound, and a chain extender, and the polycarbonate-based polyol is generally preferably a polyalkylene polycarbonate-based polyol, particularly preferably a 1,6-hexane polycarbonate-based polyol. Furthermore, a mixture of the polyalkylene polycarbonate polyol and polyether polyol can also be used. The diisocyanate compounds to be reacted with this polycarbonate polyol include tolylene diisocyanate (TDr), diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDl), and isophorone diisocyanate (
IPDI), hydrogenated diphenylmethane diisocyanate, etc. can be used. Chain extenders include low molecular weight glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol, or piperazine, ethylenediamine, hexamethylenediamine, propylene-1,2-diamine, N- Methyl-
Bis(3-aminopropyl)amine, 1,4-diaminocyclohexane, 1-amino-3-aminomethyl-3,
Primary or secondary such as 5,5-trimethylcyclohexane
A class aliphatic amine can be used. Polytetramethylene ether polyurethane uses polytetramethylene ether glycol as a polyol component, and polypropylene ether polyurethane uses polypropylene ether glycol as a polyol component. In addition, polyester-ether polyurethane is used as a polyol component.
For example, ethylene oxide is added to a polyester glycol consisting of a glycol having 4 or more carbon atoms and a dicarboxylic acid.
Propylene oxide or a polyol obtained by addition polymerization of a mixture of these, a polyester glycol consisting of a glycol having 4 or more carbon atoms and a dicarboxylic acid, and a mixed polyol of polypropylene glycol or polypropylene/ethylene glycol are used, and polyester polyurethane is a polyol. As a component, a polyester polyol obtained by reacting a hydroxyl compound having 6 or more carbon atoms with a dibasic acid, an ε-caprolactone polyester polyol, or a polymethylvalerolactone polyester polyol is used. As the diisocyanate compound and chain extender used in each of these polycarbonate-based, polytetramethylene ether-based, polypropylene ether-based, polyester-ether-based, and polyester-based polyurethanes, the same ones used in the polycarbonate-based polyurethane can be mentioned. . Various additives such as antioxidants, light stabilizers, ultraviolet absorbers, and hydrolysis inhibitors can be added to these polyurethanes as necessary.

The synthetic leather 1 of the present invention is provided with a surface treatment layer 5 for imparting surface smoothness to the surface of the skin layer 4. This surface treatment layer 5 is made of polyurethane containing silicone oil and/or modified silicone oil, and further uses a polyurethane whose polyol component is a mixture of silicone diol and other polyol. Examples of polyols used in combination with silicone diols include polycarbonate polyols, polytetramethylene ether polyols, polyester ether polyols, and polyester polyols. The content of silicone diol in the polyol component is 5 to 40% by weight, since no lubricity effect can be obtained if it is less than 5% by weight, and the lubricity cannot be further improved even if it exceeds 40% by weight.
It is preferable to use the polyol in combination with the other polyols mentioned above. Further, as the diisocyanate and chain extender constituting the polyurethane used in the surface treatment layer 5, the same ones as the diisocyanate and chain extender constituting the polyurethane used in the adhesive N3 and the skin layer 4 are used.

The silicone oil and modified silicone oil contained in this surface treatment layer 5 include dimethylpolysiloxane,
Examples include alcohol-modified dimethylpolysiloxane. The content of these is preferably 1 to 50 parts by weight based on 100 parts by weight of polyurethane (solid content) constituting surface treatment N5. Surface treatment layer 5 may be formed by gravure printing or the like using the above polyurethane solution. It is preferable that the surface treatment layer 5 is formed by applying a polyurethane resin solution such that the dry coating amount is 0.1 to 5 g/nf.

In the synthetic leather 1 of the present invention, a polyurethane intermediate layer 6 may be provided between the skin layer 4 and the adhesive layer 3, as shown in FIG. As the polyurethane constituting the intermediate layer 6, the same polyurethane as the polyurethane constituting the skin layer 4 is used. This intermediate layer 6 may have a foamed structure. The intermediate layer 6 can be formed by transferring simultaneously with the skin layer 4 by a dry method. The thickness of the intermediate layer 6 is 10 to 100μ in the case of a non-foamed structure, and 50 to 100μ in the case of a foamed structure.
0μ is preferred. By providing such an intermediate layer 6 between the skin layer 4 and the adhesive N3, it is possible to obtain synthetic leather with excellent frictional strength and a rich sense of volume. Furthermore, in the synthetic leather 1 of the present invention, the fiber base material 2 can be impregnated with polyurethane, and as shown in FIG. 7 can also be provided. The wet microporous layer 7 is formed by applying a solution of polyurethane in a water-soluble organic solvent similar to that used for the film layer, and then immersing it in water to dissolve and remove the water-soluble organic solvent in water to solidify the polyurethane. I can do it. Furthermore, although not particularly shown, a polyurethane foam layer formed by a dry method may be provided instead of the wet microporous polyurethane layer N7. The thickness of the wet microporous layer 7 or the foam layer formed by the dry method is 100 to 200
0 μ is preferable, and by providing such a wet microporous layer 7 or a foamed layer formed by a dry method, the flexibility of the synthetic leather will be improved and the texture will be even better.

Hereinafter, the present invention will be explained in more detail by giving specific examples.

Example 1 100% modulus is 50 kg on the surface of release paper with aperture
/cffl polycarbonate polyurethane (manufactured by Dainippon Ink & Chemicals ■: Crisbon NY331) was applied using a knife coater so that the dry thickness was 20μ,
A polyurethane film (skin layer) was formed by drying with hot air at 100°C for 2 minutes, and then a two-component urethane adhesive (large) made of polytetramethylene ether polyurethane with a 100% modulus of 15 kg/ci was applied on top of this film. (manufactured by Nippon Ink Kagaku Kogyo ■: Crisbon TA-290) was applied using a knife coater to a dry thickness of 30μ, and the adhesive-applied surface was in contact with the raised surface of the fiber base material made of Tetron-rayon blended suede. superimposed on io
After drying with hot air at O'C for 5 minutes and further aging at 70°C for 48 hours to react and solidify the adhesive, the release paper is peeled off to form a skin layer on the surface of the fiber base material via the adhesive layer. were laminated. Next, 100 parts by weight of polyurethane (solid content) was added to an organic solvent solution of polycarbonate-based polyurethane containing silicone diol as a polyol component (Rezaroid 5P-300, manufactured by Dainichiseika Chemical Industries, Ltd.). 5F
-8427) and 15 parts by weight of dimethylpolysiloxane-polyoxyalkylene copolymer (5H-28PA manufactured by Tou μ Silicone) were added, and this solution was coated with a dry coating amount of 2 g/rrf. A surface treatment layer was formed by coating using a gravure printing method to obtain synthetic leather.

The resulting synthetic leather has a slimy feel and has excellent surface lubricity that does not produce abrasive noise even when the surface is rubbed.It also has excellent hydrolysis resistance and light resistance, and has a natural texture and appearance. It closely resembles leather and was suitable for use in furniture, vehicles, etc.

Comparative Example 1 A synthetic leather having the same structure as in Example 1 was obtained by the same method except that the surface treatment layer did not contain alcohol-modified silicone and dimethylpolysiloxane-polyoxyalkylene copolymer.

Comparative Example 2 Polycarbonate-based polyurethane (manufactured by Dainichiseika Kogyo ■:
A surface treatment layer was formed using a polyurethane solution prepared by adding the same amounts of alcohol-modified silicone and dimethylpolysiloxane-polyoxyalkylene copolymer as in Example 1 to Retheroid Lu4003 (which does not contain silicone diol as a polyol component). Synthetic leather was obtained in the same manner as in Example 1 in other respects.

Comparative Example 3 After forming a polyurethane skin layer on a fiber base material via an adhesive layer by the same method as in Example 1, the same alcohol-modified silicone and dimethylpolysiloxane-polyoxyalkylene as used in Example 1 were added. A solution of the polymer simply dissolved in toluene was applied and dried to obtain synthetic leather.

The amounts of alcohol-modified silicone and dimethylpolysiloxane-polyoxyalkylene copolymer that adhere to the surface of this skin layer are the same as those of the alcohol-modified silicone and dimethylpolysiloxane-polyoxyalkylene contained in the surface treatment layer in Example 1. The amount was made to be the same as the amount of alkylene copolymer.

Table 1 shows the results of testing the friction noise prevention effect of the synthetic leather obtained in Example 1 and Comparative Examples 1 to 3 under the following conditions.

D. Using a single vibration type friction fastness tester, the surface of the composite comparison was
After rubbing the synthetic leather with a cotton cloth the number of times shown in Table 1 under a load of 0 g, the surface of the synthetic leather was rubbed together to check whether a scratching sound was generated.

○...No frictional noise occurred.

Δ: A slight scraping sound was generated.

×: Severe frictional noise is generated.

It was evaluated as

Table 1 (Effects of the Invention) As explained above, the synthetic leather of the present invention contains silicone oil and/or modified silicone oil on the surface of the polyurethane skin layer, and contains silicone diol in the polyol component. By having a surface treatment layer formed using synthetic leather, it has excellent surface lubricity, and unlike conventional synthetic leather, there is no possibility of generating unpleasant scratching sounds when the surface is rubbed, and the surface lubricity is long-lasting. Because of its superior properties, a permanent friction sound prevention effect can be obtained.

[Brief explanation of drawings]

The drawings show examples of the present invention, and FIG. 1 is a longitudinal cross-sectional view showing one embodiment of the synthetic leather of the present invention, and FIGS. 2 and 3 are longitudinal cross-sectional views showing other embodiments of the synthetic leather of the present invention, respectively. It is a front view.

Claims (1)

[Claims] A synthetic leather comprising, on the surface of a polyurethane skin layer, a surface treatment layer formed of polyurethane containing silicone oil and/or modified silicone oil and containing silicone diol in the polyol component.