JPH09104841A - Composition for forming leather-like surface layer excellent in elongation-following property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a leather-like surface layer-forming composition excellent in moldability, giving the surface of a molded product or sheet natural leather- like appearance and touch, by admixing an organic natural powder insoluble in organic solvents to a specific synthetic resin binder. SOLUTION: (A) An organic natural powder insoluble in organic solvents is mixed with (B) a binder made of a synthetic resin which is soluble in an organic solvent and has a modulus of <=80kgf/cm<2> at 100% elongation at a weight ratio of (10-200):100. A urethane resin is most suitable for component B and a purified collagen powder or a leather powder containing at least collagen is preferred as the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel leather-like surface layer forming agent. More specifically, a synthetic resin binder soluble in an organic solvent and having a specific physical property value in the surface layer forming agent, and an organic natural product powder insoluble in the organic solvent are added at a specific ratio to form a molded article or sheet. A leather-like surface layer forming agent that imparts a natural leather-like appearance and feel when the surface layer is formed by applying this to the surface of a substance or the like, and that is excellent in the elongation followability of the surface layer during molding after application. Regarding

[0002]

2. Description of the Related Art In recent years, sheets of vinyl chloride, synthetic leather, artificial leather, etc., and furniture using them, bags, interior materials for automobiles, etc., have become more and more popular. It is required to have the feel and function. This leather-like surface layer was formed on the surface of vinyl chloride sheets, containers, etc. using synthetic resins soluble in organic solvents such as urethane resins and acrylic resins as binders, and inorganic pigments such as silica, urethane resins and acrylic resins. It was done by applying a finishing agent mixed with powder such as, and further by processing the surface with a leather pattern such as grain, but with this, the appearance becomes glossy, the pattern is leather-like, but the feel and function are , Warmth, dry feeling,
It did not look like leather at all, such as moisture absorption and desorption.

In recent years, in order to meet these requirements, a surface layer forming agent using leather fiber powder or leather powder obtained by crushing leather scraps instead of the above-mentioned inorganic pigment and organic synthetic resin powder has been proposed. It is used as a coating agent for automobile interior materials, furniture, household electric appliances, etc., which gives properties close to those of natural leather. Several leather-like surface layer forming agents and leather-like surface layer forming methods using this leather powder have been proposed, and as prior examples thereof, for example, JP-A-49-7405 and JP-A-63-218286, 63-263663
6, JP-A-1-122775, and 1-256.
904 publication and the like.

A collagen powder obtained by purifying collagen in animal tissues by a special method, heat-stabilized, and finely powdered has also been proposed. When used as a surface layer forming agent, the above-mentioned leather powder is used. Excellent physical properties can be expressed as compared with. (JP-A-3-124800, JP-A-3-195800, JP-A-3-255200, etc.) A leather-like surface layer forming agent using these leather powders and collagen powders is a leather excellent for a coated object. Appearance, warmth,
Functions such as a feeling of dryness and moisture absorption / release can be imparted.

However, the above-mentioned leather powder, collagen powder, inorganic and organic resin powders, etc. are coated with vinyl chloride, synthetic leather, artificial leather coated with a leather-like surface forming agent added in an amount sufficient to obtain the intended effect. When a sheet of leather or the like is applied to a container and then molded by a vacuum molding method or the like, the powder added to the leather-like surface forming agent cannot follow the elongation at the time of molding, and the surface treatment layer is whitened. There was a problem. In general, do not use the post-coating molding method for this problem,
Alternatively, measures were taken by applying it only to the fields where high elongation at the time of molding is not required. However, this method has not been a fundamental solution to the problem, and only limits the range of application of the leather-like surface treatment forming agent.

[0006]

DISCLOSURE OF THE INVENTION The object of the present invention is to improve the above-mentioned problems of the prior art, and to solve the problems, vinyl chloride, synthetic leather,
A sheet of artificial leather or the like, which can be applied to the surface of furniture, bags, interior materials such as automobile interior materials using the same to impart properties close to those of natural leather, and is excellent in molding applicability. It is to provide a surface layer forming agent.

[0007]

[Means for Solving the Problems] As a result of various studies to achieve the above object, it was found that a suitable synthetic resin binder for a leather-like surface forming agent containing organic natural product powder, inorganic powder, organic powder, etc. The inventors have found that a leather-like surface layer forming agent that solves the problem of elongation followability during molding can be obtained by selecting a material having physical properties, and completed the present invention. The leather-like surface layer forming agent of the present invention is a synthetic resin binder blended with an organic natural product powder and / or an inorganic or organic powder for the purpose of imparting a leather-like appearance, feel and function. The surface of the base material is provided with smoothness and high moisture absorption / release properties to form a leather-like surface layer having properties close to those of natural leather. At the same time, the synthetic resin binder is provided with appropriate physical properties, so that the synthetic resin binder has elongation followability capable of supporting various molding methods.

The organic solvent-insoluble organic natural product powder used in the present invention includes collagen powder, leather powder, chitin or chitosan powder, keratin powder, silk powder,
Cellulose powder is used, but it looks like natural leather,
For the purpose of obtaining a tactile sensation, it is preferable to use purified collagen powder or leather powder containing at least collagen. Examples include purified collagen prepared by the method described in JP-A-3-255200, but it may be one produced by other methods.
The term "insoluble in organic solvent" as used in the present invention means that an organic natural product powder is added to an organic solvent that dissolves a synthetic resin binder of a leather-like surface layer forming agent, and a homogeneous liquid is visually observed even when well mixed with stirring. It means a state in which the organic natural product powder exists separately in the organic solvent without being a mixture of

The organic solvent-soluble synthetic resin binder used in the present invention is generally a urethane resin,
100% of synthetic resin such as acrylic resin, vinyl chloride resin, epoxy resin, polyolefin resin
It is preferable that the modulus value is 80 kgf / cm ² or less. More preferably, it is 50 kgf / m ² . 100% modulus value is 80kgf / cm ²
The use of a synthetic resin binder exceeding 5 is not preferable because the stretch-following property of the skin layer is deteriorated at the time of molding after coating such as vacuum molding, and the soft feel like natural leather is impaired.

The elongation of the synthetic resin binder is 40
It is preferably 0% or more, more preferably 5
It is at least 00%. The elongation rate of the skin layer needs to be at least about 300% when applied to, for example, automobile interior materials. Since the elongation rate of the skin layer is reduced by adding the organic natural product powder or the like, when the elongation rate of the synthetic resin used as the binder is less than 400%, the skin layer after the addition of the organic natural product powder or the like is used. The elongation rate is less than the target of 300%, which is not preferable.

As the synthetic resin binder, synthetic resins such as urethane resin, acrylic resin, vinyl chloride resin, epoxy resin and polyolefin resin are generally used. Among them, urethane resin is the most suitable. As the urethane resin, a general linear resin can be used, but one having an aliphatic structure is particularly preferable. Particularly, as the polyol component, an aliphatic polyester polyol component, an aliphatic polycarbonate polyol component, a polybutadiene polyol component, a polysiloxane polyol component are preferable, and particularly preferably an aliphatic polyester polyol component is mainly used, or a homopolymer or the above-mentioned copolymer or Used as a mixture.

The aliphatic polyester polyol component is a constituent component that can be preferably used to obtain the above-mentioned 100% modulus value and elongation, and in addition to this, for the purpose of giving other surface physical properties and surface characteristics. A polyol component can be used in combination. For example, a polycarbonate polyol component may be used for the purpose of improving the surface properties, and a polysiloxane polyol component may be used for the purpose of improving the surface properties and the feel of the surface. Further, as constituent components of the aliphatic polyester polyol, 1,2-ethylene glycol component, 1,4-butylene glycol component, 1,6-hexanediol, neopentyl glycol component, 2-methyl-1,3-pentanediol component ,
Using a diol component such as a 3-methyl-1,5-pentanediol component and a dicarboxylic acid ester such as adipic acid, succinic acid, malonic acid or citraconic acid, and
Ring-opening esters of lactones such as -caprolactone, δ-valerolactone and γ-butyrolactone can be used. Further, the isocyanate component is not particularly limited, but an aliphatic isocyanate component is more preferable, and for example, a hexamethylene diisocyanate component can be used.

The resin as the bander must be soluble in an organic solvent in the state of a surface layer forming agent, and the solvent of these resins can be selected from non-polar solvents such as toluene and xylene, butyl acetate and acetic acid. Esters and ketones such as ethyl, butyl cellosolve acetate, methyl isobutyl ketone, methyl ethyl ketone and acetone, ethers such as butyl cellosolve, butyl carbitol and tetrahydrofuran, alcohols such as ethanol, 2-propanol and butyl alcohol, or N, N-dimethyl. There are high boiling point solvents such as formamide and N-methylpyrrolidone, and a mixed solvent thereof may be used.

The term "soluble in an organic solvent" as used herein means that when a synthetic resin is added to any one of the above organic solvents or a mixed solvent thereof and mixed well, it becomes a visually homogeneous liquid mixture. Says the condition. Further, in the above, the reference "in the state of the surface layer forming agent" means that in the case of urethane resin or epoxy resin, although it is soluble in an organic solvent in the state of the surface layer forming agent, that is, in the state before curing, This is because some resins are insoluble in the above organic solvent in the state where the crosslinked structure after curing is formed.

The surface layer forming agent of the present invention is used in a state in which the synthetic resin binder is dissolved in the organic solvent or dissolved or dispersed in water. The addition amount of the binder synthetic resin and the organic natural product powder is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the binder resin solid content. If the amount added is less than 10 parts by weight, the effects such as matte appearance and soft touch of natural leather will not be sufficiently exhibited, and if it exceeds 200 parts by weight, the surface layer will become hard and brittle, and the desired elongation followability will be obtained. Is difficult to obtain.

The optimum particle size of the organic natural product powder blended in the surface layer forming agent is determined by the desired surface feel and the film thickness of the surface layer, so it cannot be generally stated, but in general it cannot be said. The content of particles having a particle size of 40 μm or less is preferably 85% by weight or more. This has a particle size of 40μ
If the content of particles that are less than or equal to m is less than 85% by weight,
This is because the surface of the coating film becomes rough, the touch is impaired, and a smooth feeling of smoothness cannot be obtained.

In addition to the organic natural product powder, it is also possible to add other organic solvent-insoluble inorganic powder, organic synthetic resin powder, or the like. The addition compounding ratio of the organic natural product powder is 20 to
80% by weight, total of inorganic powder and organic synthetic resin powder is 80
The range of -20% by weight is preferred. When the addition ratio of the organic natural product powder is 20% by weight or less, the functionality derived from the natural product such as moisture absorption and desorption is hardly expressed, which is not preferable. Further, as the inorganic powder and the organic synthetic resin powder which can be used together with the organic natural product powder in the present invention,
It is possible to use a commercially available powder having an average particle diameter of a comma number to several tens of microns.

The types of powder include alumina, titania, zirconia, magnesia and other metal oxides, silica,
Silicon oxide and its salts such as talc, kaolin and wollastonite, inorganic salts such as calcium carbonate, barium carbonate and barium sulfate, urethane resin, acrylic resin, nylon resin, phenol resin, melamine resin, urea resin, silicone resin, Teflon Powders of resins, polyester resins, polyolefin resins and chlorinated products thereof can also be used.

When an organic natural product powder and / or an inorganic powder, an organic synthetic resin powder or the like is added to the surface layer forming agent, the powder is precipitated in the surface layer forming agent to cause caking, thereby improving coatability. May significantly reduce. In that case, it can be solved by adding an appropriate amount of a polymer dispersant. In particular, a silicone resin anti-caking agent is suitable for preventing caking of collagen powder. Similarly, the above polymer dispersant may be added for the purpose of improving blocking resistance and slipping property.

[0020]

The present invention will be described below with reference to specific examples. Example 1 N, N-dimethylformamide / methyl ethyl ketone =
A 100% modulus value of 30 kgf / cm dissolved in a mixed solvent of 30/70 (wt%) at a ratio of about 15 wt%.
² , average particle size of about 8μm, 40μm for 100 parts by weight of solid content of urethane resin binder with elongation of 800%
10 purified collagen powders (Triazet CX260-1 manufactured by Showa Denko) containing less than 1% of powder having the above particle size were used.
0 part by weight was dispersed to prepare a leather-like surface layer forming agent. This was applied twice to a 0.5 mm thick vinyl chloride sheet using a gravure coater with 100 mesh.

The leather-like surface layer forming agent-coated vinyl chloride sheet prepared as described above has an elongation whitening resistance of 300% according to the test conditions using a JISK7113 No. 1 test piece by a tensile tester (Tensilon). Pulling
The surface layer of the test piece was visually observed and evaluated. Regarding the appearance, according to the method of JIS Z8741, the glossiness of the silver surface was measured at a reflection angle of 75 degrees with respect to the sheet surface at an incident angle of 75 degrees, and the matte property was evaluated. Regarding the tactile sensation, the softness when the surface layer was stroked with the finger pad was evaluated. Table 1 shows the evaluation results.

Example 2 N, N-dimethylformamide / methyl ethyl ketone /
Dissolved in a mixed solvent of toluene / 2-propanol / methyl isobutyl ketone / ethyl acetate = 12/27/21/27/6/7 (wt%) at a ratio of about 13 wt% 10
0% modulus value is 35 kgf / cm ² , elongation rate is 600
% Of the urethane resin binder solid content of 100% by weight, purified collagen powder having an average particle size of about 8 μm and a particle size of 40 μm or more is 1% or less (Triazet C
25 parts by weight of X260-1 (Showa Denko) were dispersed to prepare a leather-like surface layer forming agent. Using a gravure coater on a vinyl chloride sheet with a thickness of 0.5 mm, this is 10
It was applied twice with 0 mesh. The leather-like surface layer forming agent-coated vinyl chloride sheet prepared as described above was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 N, N-dimethylformamide / methyl ethyl ketone /
Toluene / 2-propanol / methyl isobutyl ketone / ethyl acetate = 14/30/24/15 / 8.5 / 8.
A urethane resin binder solid content 100 having a 100% modulus of 50 kgf / cm ² and an elongation of 500% dissolved in a mixed solvent of 5 (wt%) at a ratio of about 12 wt%.
30 parts by weight of the same purified collagen powder as in Example 1 and 25 parts by weight of silica powder (Mizukasil P526, manufactured by Mizusawa Chemical Co., Ltd.) were dispersed in parts by weight to prepare a leather-like surface layer forming agent. Using a gravure coater on a 0.5 mm thick vinyl chloride sheet, use a 100 mesh to
Coated once. The leather-like surface layer forming agent-coated vinyl chloride sheet prepared as described above was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 The same solvent and urethane resin binder as in Example 1 were used, and the content of powder having an average particle size of about 6 μm and 40 μm or more was 1 part with respect to 100 parts by weight of the resin binder solid content.
% Of cellulose powder (Avicel Asahi Kasei) 50% by weight or less was dispersed to prepare a leather-like surface layer forming agent. This was applied twice to a 0.5 mm thick vinyl chloride sheet using a gravure coater with 100 mesh. The leather-like surface layer forming agent-coated vinyl chloride sheet prepared as described above was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 A leather-like surface treatment forming agent was prepared in the same manner as in Example 1 except that the purified collagen powder was not added, and was applied and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Comparative Example 2 A leather-like surface layer forming agent was prepared in the same manner as in Example 1 except that a urethane resin binder having a 100% modulus value of about 100 kgf / cm ² and an elongation of 350% was used. It was applied and evaluated in the same manner as in 1. Table 1 shows the evaluation results.

Comparative Example 3 Purified collagen powder was mixed with urethane resin binder solid content 1
A leather-like surface layer forming agent was prepared by the same method as in Example 1 except that 220 parts by weight was used with respect to 00 parts by weight, and the same was applied as in Example 1 and evaluated. Table 1 shows the evaluation results.

[0028]

[Table 1] Elongation whitening resistance: JIS by tensile tester (Tensilon)
According to the test conditions using the K7113 No. 1 type test piece, the elongation was pulled to 300% and the surface layer of the test piece was visually observed and evaluated. ○ If no whitening is observed
And Appearance: According to the method of JISZ8741, the silver surface glossiness of 10 or less measured by the reflection angle of 75 ° of the light irradiated to the sheet surface at the incident angle of 75 ° was evaluated as ○, and the value exceeding 10 was evaluated as ×. . Tactile sensation: Softness when the surface layer was rubbed with a finger pad was evaluated. A sample with natural leather-like softness was evaluated as ○, a sample having a slightly inferior property was evaluated as Δ, and a sample having a completely inferior product was evaluated as ×.

[0029]

EFFECTS OF THE INVENTION It is possible to form a leather-like surface layer which imparts a matte appearance and soft touch like natural leather and has improved stretch-whitening property of the surface layer at the time of molding after coating.

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Claims (6)

[Claims] 1. A synthetic resin soluble in an organic solvent and having a 100% modulus value of 80 kgf / cm ² or less is used as a binder, and an organic natural product powder insoluble in the organic solvent is added to 100 parts by weight of the synthetic resin binder solid content. 10-2
A leather-like surface layer forming composition comprising 100 parts by weight. 2. The leather-like surface layer forming agent composition according to claim 1, wherein the organic natural product powder comprises at least collagen. 3. The leather-like surface layer forming agent composition according to claim 1, wherein an organic natural product powder having a particle size of 40 μm or less and a content of particles of 85% by weight or more is used. 4. The leather-like surface layer forming agent composition according to claim 1, wherein the synthetic resin binder is a urethane resin or an acrylic resin. 5. The leather-like surface layer forming composition according to claim 1, wherein a synthetic resin having an elongation of 400% or more is used as a binder. 6. In addition to organic natural product powder, at least one selected from silica powder insoluble in organic solvents, urethane resin powder, acrylic resin powder and vinyl chloride resin powder,
The addition ratio of the organic natural product powder is 20 to 80% by weight of the organic natural product powder, and the total of the above powders is 80 to 20% by weight.
The leather-like surface layer forming agent composition according to claim 1, which is contained in the range of