JPH01225665A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is prevented from foaming during melt molding at high temperature, is capable of extrusion or injection molding and gives a molding improved in appearance and heat resistance, by mixing a synthetic resin with a leather powder and a metal inactivator. CONSTITUTION:A leather material is finely divided into 5-30mm or smaller pieces, swollen by heating with steam for 10-60min under conditions of 100-120 deg.C and a water content of 40-60wt.%, dried to a water content <=3wt.% and ground. The obtained leather powder of an apparent specific gravity >=0.30 and a particle size of 40 mesh or smaller is defatted to obtain a leather powder (B) of an animal fat content of 0.05-1.5wt.%. 100pts.wt. composition comprising 20-98wt.% synthetic resin (A) (e.g., linear low-density PE) and 2-80wt.% component B is mixed with 0.5-15pts.wt. metal inactivator (C) [e.g., 3-(N-salicyloyl)- amino-1,2,4-triazole] and optionally 0.5-10pts.wt. antioxidant (D) [e.g., pentaerythritol tetrakis-(beta-lauryl-thiopropionate)].

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition in which leather powder is blended with a synthetic resin, and relates to a leather-resin composition that can be molded by injection molding, extrusion molding, calender molding, etc.

[Conventional technology]

Sheets, films, leather, molded products, etc. made of synthetic resin molded products have disadvantages that are inferior to natural products, such as contamination due to static charge, poor moisture absorption and desorption properties, and an uncomfortable plastic feel. There is.

In order to improve this, materials made by blending leather powder with synthetic resins (including rubber) are attracting attention because they have the characteristics of natural leather, such as moisture absorption and release properties and non-static properties. However, although the cause is not clear, when materials containing this leather powder are melt-molded, they foam when the raw materials are only dried.
It is virtually impossible to perform highly productive molding of resins that require kneading and molding at temperatures above °C, which is a major problem, as the resins that can be used are greatly restricted and their uses are also greatly limited. There was a point.

[Problem to be solved by the invention]

The present invention does not foam even in melt molding at relatively high temperatures, can be molded using highly productive extrusion molding, injection molding, etc., and the obtained molded product also has a good appearance and high heat resistance. An object of the present invention is to provide a resin composition containing leather powder.

[Means to solve the problem]

As a result of extensive studies to achieve the above object, the present inventor found that a resin composition containing a synthetic resin, leather powder and a metal deactivator was suitable for the purpose, and completed the present invention. It's arrived.

That is, the present invention provides a resin composition comprising a synthetic resin, leather powder, and a metal deactivator.

As the resin used in the present invention, various resins such as natural resins and synthetic resins are used. As the synthetic resin, both thermoplastic resins and thermosetting resins can be used. Thermoplastic resins include polyolefins such as polyethylene (low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer), polypropylene, polybutene-1, etc. Polybutadiene, polystyrene, polyvinyl chloride (including those containing plasticizers), polycarbonate, polyester, polyamide, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, gelatin; ethylene-propylene rubber, urethane rubber, ethylene-propylene-diene rubber Various rubbers such as These resins may be used alone or as a mixture. Thermosetting resins include phenolic resin, epoxy resin, polyurethane, unsaturated polyester resin,
Examples include various thermosetting rubbers.

When a thermoplastic resin is used as the synthetic resin, injection molding, extrusion molding, calendar molding, etc. can be applied, and various molded products can be obtained with high productivity. Moreover, since a moldable resin composition can be obtained even with a resin having a molding temperature of 150° C. or higher, the range of resins that can be used is greatly expanded.

Plasticizers, stabilizers, talc,
Fillers such as calcium carbonate, colored side, curing agent, catalyst,
Including those used as resin compounds containing reactivity-based Tsumer 1 solvents, dispersants, and various other additives. Moreover, the resin may be solid or liquid.

As the leather powder used in the present invention, for example, one manufactured by the following method is suitably used.

Cut the raw leather into pieces of 5 to 30 cm or less and heat them at a temperature of 10 cm.
Steam heating is performed for 10 to 60 minutes at a temperature of 0 to 120° C. and a moisture content of approximately 40 to 60% by weight to cause swelling, and then the steam-heated strips are dried until the moisture content is 3% by weight or less.

Next, the dried pieces are preferably ground using a fine victory mill or the like, and sized using a sieve to obtain particles having a particle size of 40 mesh passes.

The product thus obtained has excellent kneadability with resin, moldability of the resin composition, and excellent appearance of the molded product obtained. However, the leather powder used in the present invention is not limited to this.

The raw material is leather that has been treated with chrome tanning, etc.
Cow skin, pig skin, sheep skin, etc. are preferably used. Also, floor skin, shaving waste, etc. can be used.

Since the raw material leather generally contains the base oil of the raw material leather and the fats and oils added in the fatliquing process when processing the leather, it is preferable to perform a degreasing treatment on the leather powder.

This treatment is usually carried out by extraction using a solvent, but
A method that does not involve high-temperature heating is the alteration of leather powder (gelatinization).
Preferable for prevention. Solvents include chloroform, benzene, acetone, carbon tetrachloride, trichloroethylene, dichloromethane, trichlorotolufluoroethane,
Dibromotetrafluoroethane, hexane, petroleum ether, petroleum fraction (DLN), etc. are used.

The degreasing treatment is carried out so that the content of animal fat and oil is preferably 2% by weight or less, preferably 0.05 to 1.5% by weight, and more preferably 0.1 to 1.0% by weight. If this content exceeds 2%, the degree of foaming will be low, but when it is mixed with a resin and heated and melted, it will generate a bad odor, making it difficult to mold, and the resulting molded product will be dark in color. , fats and oils bleed onto the surface, resulting in stickiness, which is undesirable. Further, if the amount is less than 0.05% by weight, foaming tends to occur, so it is preferable to keep it within the above range.

Note that the leather degreasing step for obtaining the modified leather powder of the present invention is not particularly limited. For example, ■ After coarsely crushing and drying raw leather, ■ After steam heating treatment and drying,
■After the fine grinding process, ■After the sieve edge, etc. In this case, if ■■ is adopted, the degreasing efficiency is low, but the solid-liquid separation after treatment is good, and if ■■ is adopted, the solid-liquid separability is low, but the degreasing efficiency is high, and the extraction solvent Depending on the selection, dehydration can be performed at the same time.

The particle size of the leather powder is preferably one that passes through a 40 mesh sieve in terms of the moldability of the resin composition and the appearance of the molded product. More preferably, the material that has passed through a 60 mesh sieve is used (ASTM standard sieve).

Furthermore, if the apparent specific gravity of the leather powder is low, the moldability and appearance of the molded product will be poor, and it may become impossible to increase the filling amount of the resin and mixing may become extremely difficult. 3 g/ct1 or more, more preferably 0.35 to 0.6 g/cd is used.

Note that the apparent specific gravity used here is the bulk specific gravity with air (
8erated Bulk Density),
After passing the leather powder through the sieve by vibrating it and putting it into a 100 cc container, the top of the container is cut off and weighed, and the value is expressed as the weight of the leather powder + 100.

As the metal deactivator used in the present invention, those conventionally used as metal damage inhibitors in plastics can be used. The use of metal deactivators prevents foaming even at relatively high melting temperatures.

As metal deactivators, ■Oxalic acid derivatives■Salicylic acid derivatives■Hydrazide derivatives■Others are known.
Any of these can be used in the present invention.

For example, 3-(N-salicyloyl)-amino-1°2.4-)riazole as a salicylic acid derivative is used.

In addition, 2,2'-oxaminobis-[ethyl-3-
(3,5-di-monobutyl-4-hydroxyphenyl)
propionate], decamethylene dicarboxylic acid hydrazide, N,N'-bis[3-(3,5-di-butyl-4-hydroxyphenyl)propionate 9 isophthalic acid bis(2-phenoxypropionyl hydrazide),
N,N'-dibenzoylhydrazine, N-benzoyl-
N'-salicyloylhydrazine, N,N-dibutyrylhydrazine, N,N'-distearoylhydrazine, N,
N'-bis(3-(3,5-di-L-butyl-4-hydroxyphenyl)propionyl)hydrazine, N,N'
-bissalicyloylhydrazine, oxalobis(benzylidene hydrazide), N-salicylidene-N'-salicyloylhydrazine, benzotriazole, guanidines and the like. These metal deactivators can be used alone or in combination.

The resin composition of the present invention can contain antioxidants such as phenolic, phosphorus, and sulfur antioxidants. By containing an antioxidant, it is possible to further improve the degree of foaming, color tone, and deterioration of physical properties such as deterioration of elongation. Examples of these antioxidants include 2,6
-di-t-butyl-4-methylphenol, 2.2'-
Methylenebis(4-methyl-6-butylphenol), 4.41-butylidenebis(3-methyl-6-butylphenol)
butylphenol), n-octadecyl-3-(3,5
-di-t-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-butylphenyl)butane, pentaerythritol tetrakis(3-(3,5- dibutyl-4-hydroxyphenyl)propionate], 3.9
-bis(1,1-dimethyl-2-(β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyl)ethyl)-2,4,8,10-tetraoxaspiro(5,5 ) Phenolic antioxidants such as undecane, phosphorus antioxidants such as tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, dilaurylthiodipropionate, silistylthiodipropionate, distearylthio Examples include sulfur-based acid antioxidants such as dipropionate and pentaerythritol-tetrakis (β-lauryl-thiopropionate).These antioxidants can be used alone or in combination.

The composition ratio when blending leather powder with resin to make a resin composition depends on the use, shape, and shape of the molded product obtained by molding the resin composition.
It is determined by the required properties, but usually a resin (
It is preferable to mix the leather powder so that it contains 30 to 98% by weight, preferably 40 to 95% by weight (including the case of a compound), and 2 to 70% by weight, preferably 5 to 60% by weight of leather powder. If the amount of leather powder blended is less than 2% by weight, the effect of adding leather powder will not be obtained, and if it exceeds 70% by weight, it will not be possible to uniformly disperse it in the resin, and physical properties such as strength and abrasion resistance will be significantly reduced. I don't like it.

The metal deactivator is used in an amount of 0.0% per 100 parts by weight of the resin composition.
2 to 15 parts by weight, preferably 0.5 to 10 parts by weight. Further, the antioxidant is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight.

Furthermore, in order to improve the adhesion between the resin and the leather powder, it is preferable to blend a coupling agent in an amount of 0.1 to 5% by weight based on the leather powder in the composition.

As the coupling agent, those commonly used for fiber-reinforced plastics can be used, including silane coupling agents such as vinylsilane, alkoxysilane, aminosilane, chlorosilane, and epoxysilane, and titanate coupling agents. Preferably, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-T-aminopropyltrimethoxysilane, N-β
An amino-based silane coupling agent such as -(aminoethyl)-γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-r-aminopropylmethyldimethoxysilane is used. Titanate coupling agents include tetraoctyl bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, isopropyl tri(
N-aminoethyl) titanate, isopropyl tris(
Dioctyl pyrophosphate titanate and the like are used.

The above resin, leather powder, metal deactivator, antioxidant, and coupling agent can be easily kneaded with a common kneader such as a roll, Banbury, or extruder, and the resulting resin composition is It can be easily molded using common resin molding methods such as calendar molding, extrusion molding, injection molding, and compression molding. The obtained molded product has no fear of foaming even when molded at a relatively high temperature of 150° C. or higher, and has a good appearance. Furthermore, the color tone is stable without deterioration of physical properties such as strength and elongation.

In addition, the molded products obtained have excellent moisture absorption and desorption properties, antistatic properties, and abrasion resistance, and in addition to their excellent feel, they can also be used as flexible films similar to natural leather, seats, chair armrests, wall materials, etc.
Widely used for furniture, console boxes, handle grips, etc. Furthermore, the resin composition is expected to be used in various fields, such as being able to be used as a paint or coating material that gives a leather-like appearance to the surface of metal products or resin molded products.

[Examples] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.

Example 1 and Comparative Example 1 A piece of chrome-tanned leather (10 mm or less) was treated with steam, dried, and crushed in a mill, and the oil content was 2.2% by weight.
, passed through a 4"0 mesh sieve, and obtained a leather powder with an apparent specific gravity of 0.42 g/cd. Acetone was added to this for extraction treatment, and the oil and fat contents were 0.05% by weight, 0.3% by weight, 1. A 2% by weight leather powder was obtained.

Next, linear low density polyethylene (ethylene-butene-
1 copolymer) MI=25g/10min, density 0.91
5 g/cTa (Idemitsu polyethylene-L2024G) 8
Leather powder 20 with various oil and fat contents obtained above to 0 parts by weight
Part by weight and manufactured by Adeka Argus Chemical Co., Ltd., product name MARK
CDA-1 (3-(N-salicyloyl)amino-1
, 2,4-triazole in the proportions shown in Table 1,
Knead with a twin-screw kneader at 180°C to create pellets,
Using these pellets, a sheet having a thickness of one size was obtained by compression molding. Table 1 shows the evaluation results of the foaming state of the obtained sheet.

Example 2 and Comparative Example 2 Polyvinyl chloride compound (PVC 100 parts by weight, D
OP 80 parts by weight, stabilizer 5 parts by weight) 50 parts by weight of the leather powder obtained above and the CDA-15
Mix parts by weight, knead in a kneader at 170°C, and make 0.8
A sheet with a thickness of m was obtained by compression molding. Table 2 shows the evaluation results of the foaming state.

Example 3 and Comparative Example 3 Leather powder with an oil and fat content of 0.32% by weight was obtained in the same manner as in Example 1.

Next, linear low density polyethylene (ethylene-butene-
1 copolymer) MI=25g/10min, density 0.91
5 g/cij (Idemitsu polyethylene-L2024G)
80 parts by weight, 20 parts by weight of the leather powder obtained above and MARK CDA-1 (trade name, manufactured by Adeka Argus Chemical Co., Ltd.)
1 part by weight of 3-(N-salicyloyl)amino-1,2,4-triazole was blended and kneaded in a twin-screw kneader at 180°C to create pellets, and the pellets were used to make a sheet with a thickness of 1 mm. was obtained by compression molding. MARK CDA
A comparative example was one in which -1 was not blended. Table 3 shows the physical property measurement results.

Example 4 and Comparative Example 4 50 parts by weight of polyvinyl chloride compound TEZ-4950 (Shin-Etsu Chemical), 50 parts by weight of the leather powder obtained above, 5 parts by weight of the ODA 1, and MARK AO-
80 (manufactured by Adeka Argus Chemical Co., Ltd., 3.9-bis [1,
1-di-methyl-2-(β-(3-t-butyl-4-hydroxy-5=methylphenyl)propionyl)ethyl)-2°4.8.10-tetraoxaspiro(5,5)
undecane) 0.5 parts by weight, MARK AO-412
3 (manufactured by Adeka Argus Chemical Co., Ltd., pentaerythritol-tetrakis-(β-lauryl-thiopropionate)
0.5 parts by weight was blended and kneaded in a mixer at 170″C,
A sheet with a thickness of 0.8 m was obtained by compression molding. The physical property measurement results are shown in Table 4.

〔Effect of the invention〕

The resin composition according to claim 1 can prevent foaming and can be melt-molded. In addition, the obtained product has excellent heat resistance and has a bright and stable color tone.

The resin composition according to claim 2 has an extremely excellent foaming prevention effect.

The resin composition according to claim 3 can be applied to injection molding, extrusion molding, calender molding, etc., and has excellent productivity.

The resin composition according to claim 4 can prevent the surface from becoming sticky due to bleeding of oil and fat.

In the resin composition according to claim 5, the resin and leather powder can be easily blended and kneaded, and thin-walled molded products and thin-walled coatings can be produced.

The resin compositions according to claims 6 and 7 have an excellent foaming prevention effect.

Furthermore, the resin composition has excellent moldability, appearance of molded articles, and abrasion resistance. In addition, molded products have excellent moisture absorption and desorption properties, and can be used not only as raw leather products but also as many synthetic resin products for a wide variety of applications.

Claims (1)

[Scope of Claims] 1. A resin composition comprising a synthetic resin, leather powder, and a metal deactivator. 2. A resin composition comprising a synthetic resin, leather powder, a metal deactivator, and an antioxidant. 3. The resin composition according to claim 1 or 2, wherein the synthetic resin is a thermoplastic resin. 4. The animal fat content of the leather powder is 0.05 to 1.5% by weight.
The resin composition according to claim 1 or 2. 5. The resin composition according to claim 1 or 2, wherein the leather powder has a particle size that allows it to pass through a 40 mesh sieve, and has an apparent specific gravity of 0.30 or more. 6. The resin composition according to claim 1, wherein 0.5 to 10 parts by weight of a metal deactivator is blended to 100 parts by weight of a composition consisting of 20 to 98% by weight of synthetic resin and 2 to 80% by weight of leather powder. . 7. 0.5-15 parts by weight of a metal deactivator and 0.05-5 parts by weight of an antioxidant per 100 parts by weight of a composition consisting of 20-98% by weight of synthetic resin and 2-80% by weight of leather powder. 3. The resin composition according to claim 2, further comprising: