JPH0820696A - Resin composition containing halogen and excellent in thermal stability - Google Patents

Abstract

PURPOSE:To obtain a resin composition, having high heat resistance without deteriorating the softening temperature by adding a stabilizer comprising a Ca salt of acetylacetone, an organotin and sulfur compound and a metallic salt of silicic acid to a resin containing a halogen and highly thermally stabilizing the resin containing the halogen. CONSTITUTION:This resin composition is obtained by blending 100 pts.wt. resin containing a halogen (e.g. vinyl chloride resin) with a stabilizer comprising (A) 0.01-5 pts. wt. Ca salt of acetylacetone, (B) 0.01-5 pts.wt. organotin and sulfur compound [e.g. a compound of the formula (R is a 1-18C straight-chain or branched chain alkyl; a 1-20C alkoxycarbonylethyl; R<1> is a 1-36C straight- chain or branched chain alkyl, alkenyl, etc.)] and (C) 0.01-5 pts.wt. metallic salt of silicic acid (e.g. zinc silicate) or the metallic salt treated with perchloric acid. The amount of the perchloric acid used in the component (C) is preferably 0.01-0.9equiv. based on the metallic oxide in the metallic salt of the silicic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a highly heat-stabilized halogen-containing resin composition.

[0002]

2. Description of the Related Art Since a halogen-containing resin lacks heat and light stability, it tends to undergo thermal decomposition due to dehydrohalogenation during heat molding. As a result, the molded product is colored, and the mechanical properties are deteriorated.

[0003]

In order to make up for the drawbacks of the halogen-containing resin which is unstable to heat and light, an invention using a metal silicate as a stabilizer (Japanese Patent Publication No. 52-30174), perchlorine. An invention has been proposed in which a metal silicate treated with an acid is used as a stabilizer (Japanese Patent Publication No. 4-49872), but it does not yet exhibit a satisfactory stabilizing effect against heat and light.

[0004]

Therefore, as a result of various investigations, the inventors of the present invention have found that halogen-containing resins include calcium salts of acetylacetone, organotin-containing sulfur compounds and metal salts of silicic acid (or silicic acid treated with perchloric acid). It was found that a halogen-containing resin composition having excellent thermal stability can be obtained by the combined use of (metal salt) as a stabilizer, and the present invention has been completed.

The present invention relates to (a) 0.01 to 5 parts by weight of a calcium salt of acetylacetone, (b) 0.01 to 5 parts by weight of an organotin-sulfur compound, and (c) a silica salt, relative to 100 parts by weight of a halogen-containing resin. A halogen-containing resin composition having excellent thermal stability, which contains 0.01 to 5 parts by weight of a silicic acid metal salt treated with an acid metal salt or perchloric acid.

Examples of the chlorine-containing resin to be stabilized by the present invention include vinyl halide homopolymers such as vinyl chloride resin and vinylidene chloride resin, vinyl halides such as vinyl acetate, ethylene, propylene, styrene, isobutylene, and chloride. Copolymers such as those formed by copolymerization with one or more comonomers such as vinylidene, maleic anhydride, butadiene, isoprene, methyl methacrylate, acrylonitrile, dialkyl maleates, post chlorination Examples thereof include vinyl chloride resin. In addition, halogen-containing resins and acrylonitrile / butadiene / styrene resins, methyl methacrylate / butadiene / styrene resins, acrylonitrile / chlorinated polyethylene / styrene copolymer resins, acrylic rubber / acrylonitrile / styrene copolymers, acrylic rubber / methyl Examples thereof include a polymer blend resin with an impact resistance improving resin such as a methacrylate / acrylonitrile copolymer resin, vinyl acetate / ethylene copolymer resin, chlorinated polyethylene, and chlorinated rubber.

The organotin sulfur compound added in the present invention is
It is a compound represented by the following general formulas [1] to [19].

[0008]

Embedded image (In each formula, R is an alkyl group having 1 to 18 carbon atoms or a straight chain or branched chain, or an alkoxycarbonylethyl group having 1 to 20 carbon atoms, and R ¹ is a straight chain or branched chain having 1 to 36 carbon atoms. R ² represents a residue of a fatty acid having 1 to 22 carbon atoms or a residue of an aromatic acid, each of which has an alkyl group, an alkenyl group or an aralkyl group)

In the general formulas [13] to [17], specific examples of the group -OOCR ² are, for example, formic acid, acetic acid, propionic acid, butyric acid, bivalic acid, valeric acid, caprylic acid, caproic acid and decanoic acid. , Lauric acid, myristic acid, palmitic acid, 2-ethylhexylic acid, stearic acid, eicosanoic acid, oleic acid, linoleic acid, linolenic acid, tall oil acid, soybean oil acid, cottonseed oil acid, hardened cottonseed oil acid, peanut oily acid, palm oil Residues of oil acid, corn oil acid, castor oil acid, hardened castor oil acid, benzoic acid and t-butylbenzoic acid (o-, m-, p-) are mentioned.

Examples of the organotin-sulfur compounds represented by the general formulas [1] to [19] include monomethyltin sulfide, monobutyltin sulfide, monooctyltin sulfide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide and dilauryl. Tin sulfide, monomethyltin tris (2-ethylhexyl mercaptoacetate), monomethyltin tris (isooctyl mercaptoacetate), monobutyltin tris (2-ethylhexyl mercaptoacetate), monobutyltin tris (isooctyl mercaptoacetate), monobutyltin tris (iso) Nonylmercaptoacetate), monooctyltin tris (2-ethylhexylmercaptoacetate), monooctyltin tris (isoo Tilmercaptoacetate), monooctyltin tris (dodecyl mercaptoacetate), monooctyltin tris (tetradecyl mercaptoacetate), monooctyltin tris (hexadecyl mercaptoacetate), monooctyltin tris (octadecyl mercaptoacetate), butoxycarbonyl Ethyl tin tris (2-ethylhexyl mercapto acetate), butoxycarbonyl ethyl tin tris (isooctyl mercapto acetate), monolauryl tin tris (2-ethyl hexyl mercapto acetate), dimethyl tin bis (2-ethyl hexyl mercapto acetate), dimethyl tin bis (Isooctyl mercaptoacetate), dibutyltin bis (2-ethylhexyl mercaptoacetate), dibutyl Tin bis (isooctyl mercaptoacetate), dioctyltin bis (2-ethylhexyl mercaptoacetate),
Dioctyl tin bis (isooctyl mercapto acetate), dioctyl tin bis (isononyl mercapto acetate), dioctyl tin bis (decyl mercapto acetate), dioctyl tin bis (dodecyl mercapto acetate), dioctyl tin bis (tetradecyl mercapto acetate), dioctyl tin bis (hexadecyl mercaptoacetate), dioctyltin bis (octadecyl mercaptoacetate), (mercaptoacetate of C ₁₀ ~ ₁₈ mixed alcohols) dioctyltin bis,
Dilauryl tin bis (2-ethylhexyl mercapto acetate), dilauryl tin bis (isooctyl mercapto acetate), bis (butoxycarbonylethyl) tin bis (isooctyl mercapto acetate),
Monomethyl tin tris (2-ethylhexyl mercapto propionate), monobutyl tin tris (isooctyl mercapto propionate), monooctyl tin tris (dodecyl mercapto propionate), ethoxycarbonyl ethyl tin tris (tetradecyl mercapto propionate) ), Monolauryl tin tris (isooctyl mercapto propionate), dimethyl tin bis (2-ethylhexyl mercapto propionate), dimethyl tin bis (isooctyl mercapto propionate), dibutyl tin bis (2-ethylhexyl mercapto propionate) ), Dibutyltin bis (isooctyl mercaptopropionate), dibutyltin bis (isononyl mercaptopropionate), dioctyltin bis (2-ethylhexyl) Le mercaptopropionate),
Dioctyl tin bis (isooctyl mercapto propionate), dioctyl tin bis (isononyl mercapto propionate), dilauryl tin bis (isooctyl mercapto propionate), dilauryl tin bis (2
-Ethylhexylpropionate), bis (butoxycarbonylethyl) tin bis (isooctylmercaptopropionate), monomethyltin (tridecylmercaptoacetate) sulfide, monobutyltin bis (isooctylmercaptoacetate) sulfide,
Monooctyl tin bis (isooctyl mercapto acetate) sulfide, monolauryl tin bis (isononyl mercapto acetate) sulfide, butoxycarbonylethyl tin bis (2-ethylhexyl mercapto propionate) sulfide, bis [monomethyl tin bis (isooctyl mercapto) Acetate)] sulfide, bis [monooctyltin bis (2-ethylhexylmercaptoacetate)] sulfide, bis [monolauryltin bis (decylmercaptoacetate)]
Sulfide, bis [dimethyltin (isooctylmercaptoacetate)] sulfide, bis [dibutyltin (isononylmercaptoacetate)] sulfide, bis [dioctyltin (2-ethylhexylmercaptoacetate)] sulfide, monobutyltin (decylmercaptopropionate) sulfide , Monolauryl tin (stearyl mercaptopropionate) sulfide, bis [monomethyl tin bis (isooctyl mercapto propionate)] sulfide, bis [monooctyl tin bis (2-ethylhexyl mercapto propionate)] sulfide, bis [dimethyl tin (Nonylmercaptopropionate)] sulfide,
Bis [dioctyltin (isooctylmercaptopropionate)] sulfide, bis [dilauryltin (isooctylmercaptopropionate)] sulfide, bis [bis (butoxycarbonylethyl) tin (isononylmercaptopropionate)] sulfide, Monomethyltin tris (2-mercaptoethyl oleic acid), monobutyltin tris (2-mercaptoethyl capric acid), monooctyltin tris (2-mercaptoethyl tall oil acid), monolauryl tin tris (2
-Mercaptoethylstearic acid), butoxycarbonylethyltin tris (2-mercaptoethyloctylic acid), dimethyltinbis (2-mercaptoethyllinoleic acid), dibutyltinbis (2-mercaptoethyllauric acid), dioctyltinbis (2 -Mercaptoethyl oleic acid), dilauryltin bis (2-mercaptoethyl linolenic acid), bis (octoxycarbonylethyl) tin bis (2-mercaptoethyl coconut acid), monomethyltin (2-mercaptoethyl oleic acid) ) Sulfide, monobutyltin (2-mercaptoethyloctylic acid) sulfide, monooctyltin bis (2-mercaptoethyltoluic acid) sulfide, bis [monomethyltin bis (2-mercaptoethyl oleic acid)] sulfide, bis Monobutyltin bis (2-mercaptoethyl soybean oil acid)] sulfide, bis [monooctyltin bis (2-mercaptoethyl tall oil acid)] sulfide, bis [monolauryltin bis (2-mercaptoethyloctyl acid)] sulfide, Bis [dimethyltin (2-mercaptoethyl tall oil acid)] sulfide, bis [dibutyltin (2-mercaptoethyl castor oil acid)] sulfide, bis [dioctyltin (2-mercaptoethyl palmitate)] sulfide, dibutyltin 3-mercaptopropio And dioctyl tin mercapto acetate.

Examples of the metal silicate used in the present invention include zinc silicate, aluminum silicate, aluminum hydrosilicate, potassium aluminum silicate,
Aluminum calcium silicate, sodium aluminum silicate, potassium silicate, calcium silicate (meta), sodium calcium silicate, strontium silicate, sodium silicate, magnesium silicate, magnesium calcium silicate, lithium silicate (meta), Magnesium aluminate silicate, kaolin, activated clay, talc, perlite, bentonite (montmorillonite), wollastonites, tobermorites, gyrolites, aluminosilicate having zeolite crystal structure, Kyoward 700 (Al ₂ O) ₃ · 9SiO ₂ ·
nH ₂ O) [Kyowa Chemical Industry Co., Ltd.], Kyoward 600
(2MgO · 6SiO ₂ · nH ₂ O) [manufactured by Kyowa Chemical Industry Co., Ltd.] and the like.

Further, the metal salt of silicic acid treated with perchloric acid used in the present invention is prepared by mixing the metal salt of silicic acid with perchloric acid or an aqueous solution of perchloric acid at room temperature, or by heating the mixture. By doing so, it can be easily prepared.

The amount of perchloric acid used in the above treatment is preferably in the range of 0.01 to 0.9 equivalent with respect to the metal oxide in the metal silicate salt.

Furthermore, if necessary, the halogen-containing resin composition of the present invention may contain an antioxidant, an epoxy compound,
Organic phosphite, UV absorber, boric acid, borate ester, borate, antimony trioxide, lubricant, pigment,
Fillers, antistatic agents, flame retardants, processing aids, plasticizers and the like can be added.

[0015]

EXAMPLES Next, the present invention will be described with reference to examples, but parts in the examples indicate parts by weight.

Examples 1 to 6 100 parts by weight of vinyl chloride resin (Geon 103EP-8 manufactured by Nippon Zeon Co., Ltd.), 1.0 part by weight of dioctyltin bis (isooctyl mercaptoacetate), 0.5 part by weight of calcium salt of acetylacetone. And a metal silicate of Table 1 below were added and kneaded with a kneading roll at 190 ° C. for 3 minutes, and the obtained sheet having a thickness of 0.5 mm was placed in an oven at 195 ° C. for thermal stability. Was conducted to measure the time until blackening.

[0017]

[Table 1]

Examples 7 to 16 100 parts by weight of vinyl chloride resin (Geon 103EP-8, manufactured by Nippon Zeon Co., Ltd.), impact strengthening agent (Kaneace B-5)
2 Kanebuchi Chemical Industry Co., Ltd.) 10 parts by weight, acetylacetone calcium salt 1.0 parts by weight, aluminum silicate salt (Kyoward 700 Kyowa Chemical Industry Co., Ltd.) 2.0 parts by weight and the organic tin content shown in Table 2 below. The sulfur compound (3.0 parts by weight) was added, and the same operation as in Examples 1 to 6 was carried out for evaluation.

[0019]

[Table 2]

Examples 17 to 21 100 parts by weight of post-chlorinated vinyl chloride resin (HA-15F manufactured by Tokuyama Sekisui Chemical Co., Ltd.), an impact resistance enhancer (metabrene C)
-150S Mitsubishi Rayon Co., Ltd.) 15 parts by weight, dioctyl tin bis (isooctyl mercaptoacetate) 2.0
Parts by weight, 1.0 part by weight of magnesium silicate (Kyoward 600 manufactured by Kyowa Chemical Industry Co., Ltd.), 0.5 parts by weight of lubricant (SL-02 manufactured by Riken Vitamin Co., Ltd.) and a calcium salt of acetylacetone shown in Table 3 below. The same operations as in Examples 1 to 6 were performed and evaluated.

[0021]

[Table 3]

Examples 22 to 25 100 parts by weight of vinyl chloride resin (Geon 103EP-8, manufactured by Nippon Zeon Co., Ltd.), an impact resistance enhancer (Kane Ace B-3)
1 Kanefuchi Chemical Industry Co., Ltd.) 5.0 parts by weight, processing aid (Metabrene P-551A Mitsubishi Rayon Co., Ltd.) 1.0 part by weight, acetylacetone calcium salt 2.0 parts by weight, dioctyltin bis (isooctyl mercapto) acetate)
1.0 parts by weight, monobutyltin sulfide 0.2 parts by weight, lubricant (SL-02 manufactured by Riken Vitamin Co., Ltd.) 0.5 parts by weight, and metal salt of silicate treated with perchloric acid shown in Table 4 below (metal silicate). 0.2 parts by weight of perchloric acid (0.5 equivalent per 1 equivalent of salt) was added, and the same operation as in Examples 1 to 6 was performed for evaluation.

[0023]

[Table 4]

[0024]

[Effect] As is clear from the heat stability tests of Examples 1 to 25, a stabilizer comprising a calcium salt of acetylacetone, an organotin sulfur compound and a metal silicate (or a metal silicate treated with perchloric acid). It can be seen that when is added to the halogen-containing resin, it has an effect of highly stabilizing the heat of the resin. As described above, the halogen-containing resin composition of the present invention has high heat resistance and does not lower the softening temperature, and thus is suitable for thermal stabilization of light, thin, short and small products.

Claims (1)

[Claims] (1) 0.01 to 5 parts by weight of a calcium salt of acetylacetone, (b) 0.01 to 5 parts by weight of an organotin-sulfur compound, and (c) a metal silicate with respect to 100 parts by weight of a halogen-containing resin. A halogen-containing resin composition having excellent thermal stability, which comprises a stabilizer comprising 0.01 to 5 parts by weight of a metal silicate treated with a salt or perchloric acid.