JPH0681810B2 - Resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition in which leather powder is mixed with a synthetic resin, and to a leather-resin composition capable of injection molding, extrusion molding, calender molding and the like.

[Conventional technology]

Sheets, films, leathers, molded products, etc. made of synthetic resin molded products have the disadvantages of being inferior to natural products such as contamination due to electrification, poor moisture absorption and desorption, and unfriendly plastic feel. There is.

In order to improve this, a material in which leather powder is mixed with a synthetic resin (including rubber) has characteristics of natural leather such as its moisture absorption / release property and non-electrostatic property. However, although the cause is not clear, when the material mixed with this leather powder is melt-molded, it foams only by drying the raw material, especially at 150 ° C.
The above-mentioned kneading and molding which require high productivity of the resin requiring molding cannot be substantially performed, and the resin to be used is greatly limited, and the use thereof is also greatly limited. there were.

[Problems to be Solved by the Invention]

INDUSTRIAL APPLICABILITY The present invention does not foam even in melt molding at a relatively high temperature and 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. It is an object of the present invention to provide a resin composition containing leather powder.

[Means for Solving the Problems]

The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, have found that a resin composition containing leather powder and a metal deactivator in a synthetic resin is suitable for that purpose, and thus completed the present invention. I 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, either a thermoplastic resin or a thermosetting resin can be used. As the thermoplastic resin, polyethylene (low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer), polypropylene, polybutene-1
Polyolefin, polybutadiene, polystyrene, etc.
Polyvinyl chloride (including those containing a plasticizer), polycarbonate, polyester, polyamide, ethylene-
Vinyl alcohol copolymer, polyvinyl alcohol, gelatin; various rubbers such as ethylene-propylene rubber, urethane rubber, ethylene-propylene-diene rubber and the like can be mentioned. These resins may be used alone or as a mixture. As the thermosetting resin, phenol resin,
Examples thereof include epoxy resin, polyurethane, unsaturated polyester resin, various thermosetting rubbers, and the like.

When a thermoplastic resin is used as the synthetic resin, injection molding, extrusion molding, calender molding and the like can be applied, and various molded products can be obtained with high productivity. Further, even if the resin has a molding temperature of 150 ° C. or higher, a resin composition that can be molded can be obtained, so that the resin used is greatly expanded.

Plasticizer, stabilizer, talc,
Fillers such as calcium carbonate, colorants, curing agents, catalysts,
Including those used as a resin compound containing a reactive monomer, a solvent, a dispersant, and various other additives. The resin may be solid or liquid.

As the leather powder used in the present invention, those produced by the following method are preferably used.

Raw leather is cut into pieces of 5 to 30 mm or less and the temperature is 100 to 1
Steaming is performed for 10 to 60 minutes under conditions of 20 ° C. and a water content of about 40 to 60% by weight to swell, and then the steam-heated strip is dried until the water content becomes 3% by weight or less. Next, the dried fine pieces are crushed preferably using a fine Victory mill or the like, and sized using a sieve having a particle size of 40 mesh.

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

As the raw material leather, chrome tanned etc. have been treated,
Cowhide, pig skin, sheep skin and the like are preferably used. Further, floor skin, shaving waste, and the like can also 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 fatliquoring step when processing the leather, it is preferable to degrease the leather powder. This treatment is usually carried out by extraction with a solvent, but a method not accompanied by heating at high temperature is preferable for preventing alteration (gelatin addition) of leather powder. As the solvent, chloroform, benzene, acetone, carbon tetrachloride, trichloroethylene, dichloromethane, trichlorotolufluoroethane, dibromotetrafluoroethane, hexane, petroleum ether, petroleum fraction (DL
N) etc. are used.

The degreasing treatment preferably has an animal fat content of 2% by weight or less, preferably 0.05 to 1.5% by weight, and more preferably 0.1% by weight.
~ 1.0 wt%. When the content exceeds 2% by weight, the degree of foaming is low, but when compounded in a resin and heated and melted, a bad odor is generated and molding becomes difficult, and the obtained molded product has a dark color. It is not preferable because the oil and fat bleeds on the surface and becomes sticky. Also, 0.05
If it is less than wt%, foaming tends to occur, and it is preferable that the amount be within the above range.

The leather degreasing step for obtaining the modified leather powder of the present invention is not particularly limited. For example, after roughly crushing and drying the raw material leather, after steam heating and drying,
For example, after the pulverizing step and after sieving. If adopted in this case, although degreasing efficiency is low, solid-liquid separation after treatment is good, if adopted, although solid-liquid separation is low, degreasing efficiency is high, and depending on the selection of the extraction solvent, It has the feature that dehydration can be performed simultaneously.

From the viewpoint of the moldability of the resin composition and the appearance of the molded product, the particle size of the leather powder is preferably one that passes through a 40-mesh screen. More preferably, the one that has passed through a 60 mesh sieve is used (ASTM type standard sieve).

Further, when the apparent specific gravity of the leather powder is small, the moldability is poor, and the appearance of the molded product is poor, and it may be difficult to mix the resin with a large amount, and preferably 0.3 g. / cm ³ or more, more preferably 0.35 to 0.
6 g / cm ³ is used.

The apparent specific gravity used here is the specific gravity (Aerated Bulk Density) due to the inclusion of air. After vibrating the sieve and passing the leather powder through the sieve into a 100 cc container, the upper part of the container is scraped off and weighed.
It is displayed at 100.

As the metal deactivator used in the present invention, those conventionally used as metal damage inhibitors in plastics are used. By using the metal deactivator, foaming does not occur even when melting at a relatively high temperature.

Oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives and others are known as metal deactivators, but any of them can be used in the present invention. For example, 3- (N-salicyloyl) -amino-1,2,4-triazole is used as a salicylic acid derivative.

In addition, 2,2'-oxaamino bis- [ethyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate], decamethylenedicarboxylic acid hydrazide
N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 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-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N'-bissalicyloylhydrazine, oxalobis (benzylidenehydrazide), N-salicylidene-N'-salicyloyl Examples thereof include hydrazine, benzotriazole and guanidines. These metal deactivators can be used alone or in combination.

The resin composition of the present invention may contain an antioxidant such as a phenol type, a phosphorus type, or a sulfur type. By including an antioxidant, it is possible to further improve the degree of foaming, the color tone, and further the deterioration of physical properties such as the decrease of elongation. Examples of these antioxidants include 2,6-
Di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol),
4,4'-butylidene bis (3-methyl-6-t-butylphenol), n-octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate,
1,1,3-tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, pentaristhitol tetoxys [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- {β- ( 3-t-butyl-4-hydroxy-5-
Methylphenyl] propionyl} ethyl] -2,4,8,10-
Phenolic antioxidants such as tetraoxaspiro [5,5] undecane and phosphorus antioxidants such as tris (nonylphenyl) phosphite and distearyl bentaerythritol diphosphite, dilaurylthiodipropionate, diristylthio Sulfuric acid inhibitors such as dipropionate, distearyl thiodipropionate and pentaerythritol-tetrakis (β-lauryl-thiopropionate) can be mentioned. These antioxidants can be used alone or in combination.

The composition ratio when the leather composition is blended with the resin to form a resin composition is determined by the use, shape and required characteristics of the molded product obtained by molding the resin composition. It is preferable to add 30 to 98% by weight (including the case of compound), preferably 40 to 95% by weight, and 2 to 70% by weight, preferably 5 to 60% by weight of leather powder. If the amount of leather powder is less than 2% by weight, the effect of adding leather powder cannot be obtained, and if it exceeds 70% by weight, it cannot be uniformly dispersed in the resin and the physical properties such as strength and abrasion resistance are greatly deteriorated. It is not preferable.

The metal deactivator is 0.2 to 15 per 100 parts by weight of the resin composition.
Part by weight, preferably 0.5 to 10 parts by weight. The antioxidant is added in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight.

Furthermore, in order to improve the adhesiveness between the resin and the leather powder, a coupling agent is added in an amount of 0.1 to 5% by weight based on the leather powder in the composition.
It is preferable to mix them.

As the coupling agent, those usually used for fiber reinforced plastics can be used, and examples thereof include silane coupling agents such as vinylsilane, alkoxysilane, aminosilane, chlorosilane and epoxysilane, and titanate coupling agents. Preferably, γ-aminopropyltriethoxysilane, N-β- (aminoethyl)
-Γ-aminopropyltrimethoxysilane, N-β-
An amino-based silane coupling agent such as (aminoethyl) -γ-aminopropyltriethoxysilane or N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane is used. Examples of titanate coupling agents include tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, isopropyl tri (N-aminoethyl) titanate, isopyropyrtris (dioctyl pyrophosphate titanate). Is used.

The above resin, leather powder, metal deactivator, antioxidant and coupling agent can be easily kneaded by a usual kneader such as roll, Banbury, and extruder, and the obtained resin composition is a calendar. It can be easily molded by ordinary resin molding methods such as molding, extrusion molding, injection molding, and compression molding. The obtained molded product has no appearance of bubbles even when molded at a relatively high temperature of 150 ° C. or higher, and has a good appearance. Further, the physical properties such as strength and elongation are not deteriorated and the color tone is stable.

In addition, the obtained molded product has excellent moisture absorption and desorption properties, antistatic properties, and abrasion properties, and with its excellent feel, it is a flexible film similar to natural leather, seat, chair armrest, wall material,
Widely used as furniture, console box, handle grip, etc. Further, the resin composition is expected to be used in various fields such as being able to be used as a coating material or a coating material that gives a leather-like appearance to the surface of metal products or resin molded products.

〔Example〕

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 Chrome-tanned leather pieces (10 mm or less) were steamed, dried, and then crushed by a mill to give a fat / oil content of 2.2% by weight, a 40 mesh sieve, and an apparent specific gravity of 0.42 g / cm ³ . Got the powder. Acetone was added to this and extraction treatment was carried out to obtain a leather powder having fat and oil contents of 0.05% by weight, 0.3% by weight and 1.2% by weight.

Next, linear low-density polyethylene (ethylene-butene-
1 copolymer) MI = 25 g / 10 min, density 0.915 g / cm ³ [Idemitsu Polyethylene-L 2024G] 20 parts by weight of the above-obtained leather powder having various oil and fat contents in 80 parts by weight and Adeka Argus Chemical Co., Ltd. Product name: MARK CDA-1 (3- (N-salicyloyl) amino-1,2,4-triazole was mixed in the proportion shown in Table 1 and kneaded with a biaxial kneader at 180 ° C to prepare pellets. Then, a sheet having a thickness of 1 mm was obtained by compression molding using the pellets, and the evaluation results of the foaming state of the obtained sheet are shown in Table 1.

Example 2 and Comparative Example 2 Polyvinyl chloride compound (100 parts by weight of PVC, DOP 8
0 parts by weight, 5 parts by weight of stabilizer) 50 parts by weight of 50 parts by weight of the above-obtained leather powder and 5 parts by weight of CDA-1 are mixed and kneaded in a kneader at 170 ° C., and a sheet having a thickness of 0.8 mm Was obtained by compression molding. Table 2 shows the evaluation results of the foaming state.

Example 3 and Comparative Example 3 In the same manner as in Example 1, leather powder having an oil and fat content of 0.32% by weight was obtained.

Next, linear low-density polyethylene (ethylene-butene-
1 copolymer) MI = 25 g / 10 minutes, density 0.915 g / cm ³ [Idemitsu Polyethylene-L 2024G] 20 parts by weight of the above-obtained leather powder and 80 parts by weight of ADEKA ARGUS CHEMICAL CORPORATION, trade name MARK
CDA-1 (3- (N-salicyloyl) amino-1,2,4-
1 part by weight of triazole was mixed and kneaded with a twin-screw kneader at 180 ° C to prepare pellets.
A thick sheet was obtained by compression molding. A sample containing no MARK CDA-1 was used as a comparative example. The physical property measurement results are shown in Table 3.

Example 4 and Comparative Example 4 50 parts by weight of polyvinyl chloride compound TEZ-4950 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 50 parts by weight of the leather powder obtained above and the above
CDA 15 5 parts by weight, 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) pyropionyl} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane) 0.5 part by weight, MARK AO-412S
(Adeka Argus Chemical Co., Pentaerythritol-
Tetrakis- (β-lauryl-thiopropionate) 0.
5 parts by weight were blended and kneaded with a kneader at 170 ° C. to obtain a 0.8 mm-thick sheet by compression molding. The results of measuring physical properties are shown in Table 4.

[Effect of the Invention] The resin composition according to claim 1 can prevent foaming and can be melt-molded. Further, the obtained product has excellent heat resistance, and a product having a bright and stable color tone can be obtained.

The resin composition according to claim 2 has a significantly excellent effect of preventing foaming.

The resin composition according to claim 3 can be applied to injection molding, extrusion molding, calender molding and the like, and is excellent in productivity.

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

In the resin composition according to the fifth aspect, the resin and the leather powder can be easily mixed and kneaded, and a thin-walled molded product and a thin-walled coating can be obtained.

The resin composition according to claims 6 and 7 has an excellent effect of preventing foaming.

Further, the above resin composition is excellent in moldability, appearance of molded products, and abrasion resistance. Further, the molded product is also excellent in moisture absorption and desorption characteristics, and can be widely used not only as a pseudo-leather product but also as many synthetic resin products for various purposes.

Claims (7)

[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, wherein the synthetic resin is a thermoplastic resin. 4. The resin composition according to claim 1, wherein the animal fat content of the leather powder is 0.05 to 1.5% by weight. 5. The resin composition according to claim 1 or 2, wherein the leather powder has a particle size capable of passing through a 40-mesh screen, and has an apparent specific gravity of 0.30 or more. 6. A metal deactivator based on 100 parts by weight of a composition comprising 20 to 98% by weight of synthetic resin and 2 to 80% by weight of leather powder.
The resin composition according to claim 1, which contains 0.5 to 10 parts by weight. 7. A metal deactivator per 100 parts by weight of a composition comprising 20 to 98% by weight of synthetic resin and 2 to 80% by weight of leather powder.
The resin composition according to claim 2, wherein 0.5 to 15 parts by weight and 0.05 to 5 parts by weight of an antioxidant are blended.