JPH07118473A - Stabilized chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heat stability, suppressing occurrence of choking, loss of surface gloss, etc., by blending a chlorine-containing resin with a specific copper-containing hydrotalcite compound and a prescribed organic phosphoric acid zinc compound. CONSTITUTION:(A) 100 pts.wt. of a chlorine-containing resin is mixed with (B) 0.01-10 pts.wt. of a copper-containing hydrotalcite compound obtained by combining 0.001-5 pts.wt. of a copper compound (e.g. copper oxide) with 0.01-10 pts.wt. of a hydrotalcite compound of formula I (X1 and X2 are numbers satisfying 0<=X2<10 and 2<=X1+X2<20; m is real number) or by replacing Mg ion of the compound of formula I with copper ion and (C) an organic phosphoric acid zinc compound of formula II and/or formula III (R1 and R2 are 8-30C alkyl). The copper-containing hydrotalcite of the component B, for example, is obtained by dispersing synthetic hydrotalcite into water and ethyl alcohol, reacting with copper sulfate.pentahydrate at 60 deg.C for one hour, reacting with Na2CO3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a stabilized chlorine-containing resin composition, and more specifically, to a chlorine-containing resin, a copper compound and a hydrotalcite compound, or a copper-containing hydrotalcite compound, and an organic phosphorus. The present invention relates to a chlorine-containing resin composition which is excellent in thermal stability and suppresses occurrence of chalking upon exposure to the environment, loss of surface gloss and browning by adding a zinc acid compound.

[0002]

2. Description of the Related Art Chlorine-containing resin compositions have been used in various applications from soft applications to hard applications by incorporating a plasticizer. Hard to semi-rigid chlorine-containing resin compositions that do not contain plasticizers or have a small amount of plasticizers are particularly suitable for pipes, corrugated sheets, etc. because of their high heat distortion temperature, thermal stability, and excellent light resistance. It is used for outdoor use. However, this chlorine-containing resin composition has a drawback in that it is affected by heat and light derived from sunlight during use, oxygen in rainwater and air, and causes a whitening phenomenon called choking by blowing out a filler or the like.

It is known that a copper compound is effective for preventing this choking. For example, Japanese Patent Laid-Open No. 1-223148 proposes to add an organic copper phosphate to a chlorine-containing resin. JP-A-2-18744
JP-A-3-11440 proposes adding an organic acid metal salt and copper-containing hydrotalcite or copper glycine to a chlorine-containing resin, and JP-A-3-11440 discloses an inorganic copper compound and a hydrotalcite compound. It has been proposed to add it to a chlorine-containing resin, and in JP-A-4-88041,
It has been proposed to add a hydrotalcite compound treated with an inorganic copper aqueous solution and an alkali carbonate aqueous solution to a chlorine-containing resin, but the choking-preventing ability of these resin compositions was not substantially satisfactory. Furthermore,
Their loss of surface gloss and their ability to suppress brown discoloration were not yet fully satisfactory.

Therefore, an object of the present invention is to provide a chlorine-containing resin composition which is excellent in heat stability and in which occurrence of chalking upon exposure to the environment, loss of surface gloss and browning are suppressed.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a chlorine compound containing a copper compound and a specific hydrotalcite compound, or a specific copper-containing hydrotalcite compound, and The present inventors have found that a composition to which a specific organic zinc phosphate compound is added can achieve the above object, and have reached the present invention.

That is, the present invention is based on 100 parts by weight of a chlorine-containing resin, 0.001 to 5 parts by weight of at least one kind of (a) a copper compound as the component (a) and the following [Chemical formula 3] (the above [Chemical formula 1] The same) 0.01 to 10 parts by weight of the hydrotalcite compound represented by the general formula (I) or (b) the hydrotalcite compound represented by the general formula (I) At least 0.01 to 10 parts by weight of a copper-containing hydrotalcite compound obtained by substituting a part or all of magnesium ions with copper ions, and the following [Chemical formula 4] (Chemical formula 2) The same) of at least one of the organic zinc phosphate compounds represented by the general formula (II) and / or the general formula (III) of 0.01 to
A chlorine-containing resin composition obtained by adding 10 parts by weight.

[0007]

[Chemical 3]

[0008]

[Chemical 4]

The chlorine-containing resin composition of the present invention will be described in detail below.

Examples of the chlorine-containing resin used in the present invention include polyvinyl chloride, chlorinated polyvinyl chloride,
Polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer,
Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride, styrene-acrylonitryl copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer , Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-
Chlorine-containing resins such as maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and the mutual or other chlorine-free resins Blended products with synthetic resins, block copolymers,
Examples thereof include a graft copolymer.

Examples of the copper compound (a) of the component (a) used in the present invention include copper oxide, copper hydroxide, copper halide,
Examples include (basic) inorganic acid copper and (basic) organic acid copper.

Examples of the above copper halide include copper chloride, copper fluoride, copper iodide, and the like, and examples of the above (basic) inorganic acid copper include copper nitrate, copper sulfate, copper phosphate, and copper perphosphate. , Copper phosphite, copper hypophosphite, copper pyrophosphate, copper silicate, copper hypochlorite, copper carbonate, copper borate, copper sulfamate, copper molybdate, copper chromate, and basic salts thereof. Etc.

As the organic acid to be the above (basic) organic acid copper, acetic acid, stearic acid, oleic acid, acrylic acid,
Methacrylic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, benzoic acid, salicylic acid,
Carboxylic acids such as phthalic acid, terephthalic acid and naphthenic acid, organic phosphoric acids such as lauryl phosphoric acid and stearyl phosphoric acid, phenols such as phenol, cresol and nonylphenol, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -2-hydroxybenzophenones such as octoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tertiary octylphenyl) benzotriazole, 2- (2'-hydroxy-
Examples thereof include 2- (2′-hydroxyphenyl) benzotriazoles such as 3′-tert-butyl-5′-methylphenyl) benzotriazole, and basic salts of these organic acids.

The amount of the above copper compound added is the chlorine-containing resin 1
The amount is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 00 parts by weight. If the addition amount is less than 0.001 part by weight, almost no effect is observed, and if it is more than 5 parts by weight, the effect is not enhanced, and the thermal stability of the chlorine-containing resin is significantly reduced.

The hydrotalcite compound represented by the above general formula (I), which is the component (a) used in the present invention, may be a natural product or a synthetic product. As a method for synthesizing the synthetic product, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, and Japanese Patent Publication No. 51-29 are available.
Known methods described in JP-A No. 129 and JP-A No. 61-174270 can be exemplified. Further, in the present invention, it can be used without being limited by its crystal structure, crystal grain size, presence or absence of crystal water, and the amount thereof.

On the surface of the hydrotalcite compound, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal salt such as alkali metal dodecylbenzene sulfonate, higher fatty acid amide. Those coated with higher fatty acid ester or wax can also be used.

The amount of the above-mentioned hydrotalcite compound added is 0.01 to 10 relative to 100 parts by weight of the chlorine-containing resin.
Parts by weight, preferably 0.05 to 5 parts by weight. If the addition amount is less than 0.01 part by weight, almost no effect is obtained, and if it is more than 10 parts by weight, the effect is not improved and the chlorine-containing resin composition is greatly colored.

The copper compound and the hydrotalcite compound may be added separately to the chlorine-containing resin, or they may be blended in advance and used. Further, for example, as shown in JP-A-4-88041. It is also possible to use a compound (copper-treated hydrotalcite) in which an inorganic copper compound is incorporated between layers of a hydrotalcite obtained by treating such a hydrotalcite compound with inorganic copper and a carbonate anion.

The copper-containing hydrotalcite compound (b) of the component (a) used in the present invention means a part or all of the magnesium ion of the hydrotalcite compound represented by the above general formula (I). It is formed by substituting for example, and is shown in, for example, Japanese Patent Laid-Open No. 2-187442.

The amount of the copper-containing hydrotalcite compound added is 0.01 to 100 parts by weight of the chlorine-containing resin.
10 parts by weight, preferably 0.05 to 5 parts by weight. If the addition amount is less than 0.01 parts by weight, almost no effect is observed, and if it is more than 10 parts by weight, the effect is not improved, and the chlorine-containing resin composition is greatly colored or the thermal stability is deteriorated. .

In the above general formulas (II) and (III), alkyl groups represented by R ₁ and R ₂ include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl. , Nonadecyl, eicosyl, henicosyl, docosyl, tetracosyl, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontyl and the like.

Therefore, as the organic zinc phosphate compound represented by the above general formulas (II) and (III) of the component (b) used in the present invention, for example, the following [Chemical formula 5] to [Chemical formula 10]
Compounds (No. 1 to N0.5) shown in 1) and the like can be mentioned.

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

The amount of the above-mentioned organic zinc phosphate compound added is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin. If the addition amount is less than 0.01 parts by weight, almost no effect is observed and 1
Even if it is more than 0 parts by weight, the effect is not improved and the thermal stability of the chlorine-containing resin composition is lowered.

The composition of the present invention may be added with a commonly used metal stabilizer, for example, a lead stabilizer,
Examples include calcium-based stabilizers, zinc-based stabilizers, magnesium-based stabilizers, barium-based stabilizers, organotin-based stabilizers, and composite stabilizers thereof.

Examples of the lead-based stabilizer include lead white,
Basic lead silicate, basic lead sulfate, dibasic lead sulfate, tribasic lead sulfate, basic lead sulfite, dibasic lead phosphite, silica gel co-precipitated lead silicate, dibasic lead phthalate, tribasic Lead maleate, lead salicylate, lead stearate, basic lead stearate, dibasic lead stearate, lead laurate,
Examples thereof include lead octylate, lead 12-hydroxystearate, lead behenate, and lead naphthenate.

Examples of the above-mentioned calcium-based, zinc-based, magnesium-based and barium-based stabilizers include metal oxides, hydroxides, carbonates, basic carbonates, (meth) s which constitute these stabilizers. Borate, (meth) silicate, (phosphite), basic phosphate, aluminate, titanate,
Inorganic compounds such as stannates and rhodanates, and metallic soaps with organic carboxylic acids are mentioned. Examples of the organic carboxylic acid include acetic acid, lactic acid, stearyl lactic acid, caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic acid, palmitic acid, undecylenic acid, ricinoleic acid, linoleic acid, linoleic acid, neodecanoic acid. , Oleic acid, stearic acid, isodecanoic acid, isostearic acid, 12-hydroxystearic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid, arachidic acid, behenic acid, erucic acid, brassic acid and the like. Acids and mixtures of naturally occurring acids such as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, p-tert-butyl. Benzoic acid, 5-tertiary octyl salicylic acid, naphthene , Xylyl acid, ethyl benzoate, isopropyl benzoate, di-tert-butylbenzoic acid, bromobenzoic acid, maleic acid, adipic acid, phthalic acid, monobutyl maleate,
Examples thereof include monodecyl phthalate and cyclohexanedicarboxylic acid.

Examples of the above-mentioned organic tin stabilizers include methylstannoic acid, butylstannoic acid, octylstannoic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dimethyltin sulfide, Dibutyltin sulfide, dioctyltin sulfide, monobutyltin oxide sulfide, methylthiostannoic acid, butylthiostannoic acid, octylthiostannoic acid, dibutyltin dilaurate, dibutyltin distearate, dioctyltin dioleate, dibutyltin basic Laurate, dibutyltin dicrotonate, dibutyltin bis (butoxydiethylene glycol malate), dibutyltin methyl octyl neopentyl glycol malate, dibutyltin isooctyl 1,4-butanedi Rumalate, dibutyltin dimethacrylate, dibutyltin dicinnamate, dioctyltin bis (oleyl maleate), dibutyltin bis (stearyl malate), dibutyltin itaconate, dioctyltin malate, dimethyltin dicrotonate, dioctyltin bis (butylmalate), dibutyltin Dimethoxide, dibutyltin dilauroxide, dioctyltin ethyleneglycoxide, pentaerythritol / dibutyltin oxide condensate, dibutyltin bis (lauryl mercaptide), dimethyltin bis (stearyl mercaptide), monobutyltin tris (lauryl mercaptide) , Dibutyltin-β
-Mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, monobutyltin tris (isooctylmercaptoacetate), monooctyltin tris (2-ethylhexylmercaptoacetate), dibutyltin bis (isooctylmercapto) Acetate), dioctyl tin bis (isooctyl mercapto acetate), dioctyl tin bis (2
-Ethylhexyl mercaptoacetate), dimethyl tin bis (isooctyl mercapto acetate), dimethyl tin bis (isooctyl mercapto propionate), monobutyl tin tris (isooctyl mercapto propionate), bis [monobutyl di (isooctoxy carbonyl methylene thio) ) Tin] sulfide, bis [dibutylmono (isooctoxycarbonylmethylenethio) tin] sulfide, monobutylmonochlorotin bis (isooctylmercaptopropionate), monobutylmonochlorotin bis (isooctylmercaptoacetate), monobutylmonochlorotin Bis (lauryl mercaptide), butyltin bis (ethylcellosolbumarate), bis (dioctyltin butylmalate) malate, bis (methyltin diisooctyltilg) Cholate) disulfide, bis (methyl / dimethyltin mono / diisooctylthioglycolate) disulfide, bis (methyltin diisooctylthioglycolate) trisulfide, bis (butyltin diisooctylthioglycolate) trisulfide , 2-butoxycarbonylethyltin tris (butylthioglycolate), and the like.

The amount of the metallic stabilizer used is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The composition of the present invention may further contain an organic phosphorus compound such as an organic phosphite compound and / or an epoxy compound, whereby the composition of the present invention exhibits an excellent synergistic effect.

Examples of the above-mentioned organic phosphorus compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl).
Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenylacid phosphite, 2,2′-methylenebis (4,6-ditertiarybutylphenyl) octylphosphite, Diphenyldecylphosphite, phenyldiisodecylphosphite, tributylphosphite,
Tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexanedimethyldi Phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-
4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, hydrogenated-4,4'-isopropylidenediphenol poly Phosphite, bis (octylphenyl)
Bis [4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, tetratridecyl-4,4'-butylidene bis (2-tert-butyl- 5-methylphenol) diphosphite, hexa (tridecyl) -1,1,
3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphite, 9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like can be mentioned.

The amount of the organic phosphite compound added is
It is preferably 0.0 with respect to 100 parts by weight of the chlorine-containing resin.
It is 1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil. Fatty acid butyl, epoxy methyl stearate,
-Butyl, 2-ethylhexyl or -stearyl,
Tris (epoxypropyl) isocyanurate, 3-
(2-xenoxy) -1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, etc. Is mentioned.

The amount of the epoxy compound added is preferably 0.01 to 20 with respect to 100 parts by weight of the chlorine-containing resin.
Parts by weight, more preferably 0.5 to 10 parts by weight.

A light stabilizer such as an ultraviolet absorber or a hindered amine compound may be used in combination with the composition of the present invention.

Examples of the light stabilizer include 2,4-
2-hydroxybenzophenones such as dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2 '-Hydroxy-5'
-Methylphenyl) benzotriazole, 2- (2'-
Hydroxy-5′-tertiary octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditertiarybutylphenyl) benzotriazole, 2- (2′-
Hydroxy-3 ', 5'-di-tert-butylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-dicumylphenyl) benzotriazole,
2- (2′-hydroxyphenyl) benzotriazoles such as 2,2′-methylenebis (4-tertiary octyl-6-benzotriazolyl) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiary Butylphenyl-3 ', 5'-di-tert-butyl-4'-
Hydroxybenzoate: Benzoates such as hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-
Substituted oxanilides such as ethoxy-4′-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3-
Cyanoacrylates such as (p-methoxyphenyl) acrylate; 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2, 2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2
2,6,6-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-)
Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2)
2,6,6-pentamethyl-4-piperidyl) -1,
2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,3
5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-
Tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis ( 2,2,6,6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tertiaryoctylamino-s-triazine polycondensate, 1,6-bis (2,2,6,6) 6-tetramethyl-4
-Piperidylamino) hexane / 2,4-dichloro-6
And hindered amine compounds such as morpholino-s-triazine polycondensate.

The amount of the above-mentioned light stabilizer added is the chlorine-containing resin 1
It is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, relative to 00 parts by weight.

In the composition of the present invention, β-aminocrotonates such as 1,4-butanediol bis (β-aminocrotonate) and thiodiglycol bis (β-aminocrotonate); diphenylurea , Urea such as diphenylthiourea; indole such as α-phenylindole and α- (octylphenyl) indole; 2,6-dimethyl-3,5-dicarbococtoxy-1,4-dihydropyridine, 2 , 6-Dimethyl-3,5-dicarblauryloxy-1,4-dihydropyridine and other dihydropyridines; dibenzoylmethane, benzoylacetone,
Β-diketone compounds such as stearoylbenzoylmethane, caproylbenzoylmethane and dehydroacetic acid; trimethylolpropane, glycerin, tris (hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, mannite, sorbit, pentaerythritol stearate , Dipentaerythritol / adipate, dipentaerythritol / pyrrolidone carboxylic acid ester, and other polyhydric alcohols; dilaurylthiodipropionate, distearylthiodipropionate, pentaerythritol tetra (laurylmercaptopropionate), etc. Organic sulfur compounds of bisphenol A, 2,6-di-tert-butyl-p
-Cresol, stearyl-3,5-di-tert-butyl-4
-Phenols such as hydroxyphenylpropionate or melamines can be used in combination.

Further, the composition of the present invention contains calcium carbonate, silica, clay, glass beads, mica, sericite, glass flakes, asbestos, wollastonite,
Potassium titanate, PMF, gypsum fiber, zonotolite, MO
S, phosphate fiber, glass fiber, carbon fiber,
Fillers such as aramid fibers can be used.

Furthermore, pigments such as titanium oxide, red iron oxide, yellow lead, ultramarine blue, carbon black, azo pigments, phthalocyanine pigments, quinacridone pigments and dioxazine pigments can be used in the composition of the present invention.

In addition, if necessary, the composition of the present invention may include, for example, a crosslinking agent, a foaming agent, an antistatic agent, an antifogging agent, an antiplateout agent, a surface treatment agent, a lubricant, a flame retardant, a fluorescent agent, Antifungal agents, bactericides, metal deactivators, photodegradants, processing aids, release agents, reinforcing agents and the like can be included.

[0047]

EXAMPLES The chlorine-containing resin composition of the present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

First, the copper-containing hydrotalcite compound (stabilizer-A) used in the examples was prepared as described in JP-A-4-88.
It was synthesized according to Japanese Patent Publication No. 041.

Synthesis of Stabilizer-A 10 g of Alkamizer 1 (synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.), 350 g of water and 50 g of ethyl alcohol were stirred and uniformly dispersed, and copper sulfate / pentahydrate was added thereto. Add 4.97 g, warm to 60 ° C. and stir for 1 hour. Then, 2.09 g of sodium carbonate was added, and the mixture was added at room temperature to 2
Stir for hours. Then, it filtered, washed with water, and dried, and the stabilizer-A was obtained. This was used in Examples 1-4 below.

Example 1 After kneading with the following composition at 190 ° C. for 5 minutes, 1
A test piece having a thickness of 1 mm was prepared by pressing for 5 minutes at 70 ° C. and 200 kg / cm ² . This test piece was rained at 63 ℃
It was put in a sunshine weatherometer (SWOM) and the blackening time was measured. Further, the blackening time was measured in an oven at 190 ° C., and a heat stability test (HS) was performed.

The test pieces were accelerated by a UV tester, and the test pieces after 480 hours and 840 hours were visually evaluated for chalking (whitening) on a 10-point scale. The results are shown in [Table 1] below.

In the evaluation criteria, 1 represents a state in which no whitening has occurred, and shows that whitening increases as the numerical value increases. The setting conditions of the UV tester are as follows. Black panel temperature 50 ℃ Light intensity 60mw / cm ² (at
365nm) Humidity 50%

(Combination) Polyvinyl chloride (average molecular weight 1050) 100 parts by weight Tribasic lead sulfate 0.5 Lead stearate 1.5 Dibasic lead stearate 0.3 Calcium stearate 0.3 Calcium carbonate 2. 0 Titanium oxide 0.2 Carbon black 0.01 Stabilizer-A (copper-containing hydrotalcite compound) 0.2 Organic zinc phosphate compound (shown in [Table 1] below) 0.1

[0054]

[Table 1]

Example 2 A test piece was prepared in the same manner as in Example 1 with the following composition, and this test piece was used as a sunshine weatherometer (SW).
OM), the blackening time was measured, and the choking (whitening) generation time (visual) was measured with a UV tester. Also,
A thermal stability test (HS) at 190 ° C. was also performed. The results are shown in [Table 2] below. The settings were the same as in Example 1.

(Compounding) Polyvinyl chloride (average molecular weight 1050) 100 parts by weight Epoxidized soybean oil 0.5 Zinc stearate 1.0 Calcium stearate 1.0 DHT-4A ^{* 1} 0.5 Dipentaerythritol 0.5 Bisphenol A 0.2 Calcium carbonate 10 Titanium oxide 0.2 Carbon black 0.1 Compound No. 3 0.05 Compound No. 6 0.05 Copper compound (shown in [Table 2] below) 0.1 * 1: Kyowa Chemical Synthetic hydrotalcite manufactured by Kogyo Co., Ltd.

[0057]

[Table 2]

Example 3 A test piece was prepared in the same manner as in Example 1 with the following composition, and a thermal stability test (HS) at 190 ° C. was carried out. Further, an outdoor exposure test (Urawa City, Saitama Prefecture) was conducted using this. ),
The gloss of the surface was visually evaluated by sampling every 3 months. The results are shown in [Table 3] below.

The evaluation standard is 10 steps, 1 indicates that the gloss is the same as that of the unexposed product, the gloss is lost due to occurrence of chalking as the numerical value increases, and 10 indicates the worst state. Represent

(Compounding) Polyvinyl chloride (average molecular weight 1050) 100 parts by weight Calcium stearate 1.0 Zinc stearate 1.0 Dipentaerythritol 0.7 Bisphenol A 0.4 Oxidized polyethylene wax 0.5 Calcium carbonate 4. 0 Titanium oxide 4.0 Compound No. 3 0.05 Compound No. 6 0.05 Cupric acetate 0.05 Test compound (shown in [Table 3] below) 0.3

[0061]

[Table 3]

Example 4 A test piece was prepared in the same manner as in Example 1 with the following composition, and the blackening time was measured (HS) in a gear oven at 190 ° C., and an outdoor exposure test was conducted using this. The
The occurrence of choking was visually evaluated by sampling every 3 months. The results are shown in [Table 4] below.

The evaluation criterion of 10 out of 10 indicates that no chalking phenomenon is observed at all, and that the occurrence of chalking is remarkable as the numerical value increases.

[0064]

(Compounding) Polyvinyl chloride (average molecular weight 1050) 100 parts by weight dibasic lead phosphite 2.0 lead stearate 1.0 tribasic lead sulfate 0.5 calcium stearate 0.5 acrylic modification Agent 5.0 Calcium carbonate 4.0 Titanium oxide 4.0 Compound No. 3 0.1 Compound No. 6 0.1 Cupric acetate 0.05 Test compound (shown in [Table 4] below) 0.1

[0066]

[Table 4]

As is clear from the above results, the composition in which the copper compound is used alone in the chlorine-containing resin has some effect on weathering resistance such as prevention of chalking.
Remarkably reduces the thermal stability. In addition, the composition obtained by using the organic zinc phosphate compound alone in the chlorine-containing resin has a small effect of improving the weather resistance such as prevention of chalking because the adverse effect on the thermal stability is small. On the other hand, the chlorine-containing resin composition of the present invention in which the copper compound, the organic zinc phosphate compound and the hydrotalcite compound are added to the chlorine-containing resin has excellent thermal stability, does not have a brown color change during weathering, and prevents chalking. It is very effective.

[0068]

EFFECT OF THE INVENTION The chlorine-containing resin composition of the present invention is excellent in thermal stability, and suppressed occurrence of chalking upon exposure to the environment, loss of surface gloss and browning.

Claims (1)

[Claims] 1. To 100 parts by weight of a chlorine-containing resin, 0.001 to 0.001 of (a) a copper compound as component (a).
5 parts by weight and 0.01 to at least one of the hydrotalcite compounds represented by the following general formula (I)
10 parts by weight or (b) at least a copper-containing hydrotalcite compound obtained by substituting a part or all of magnesium ions of the hydrotalcite compound represented by the general formula (I) of the following [Chemical Formula 1] with copper ions Type 0.01 ~
10 parts by weight, and as a component (b), 0.01 to 10 parts by weight of at least one zinc organophosphate compound represented by the following general formula (II) and / or general formula (III) is added. A stabilized chlorine-containing resin composition obtained from the above. [Chemical 1] [Chemical 2]