JPH09208777A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the above composition excellent in thermal stability and colorability, especially the colorability, by adding a β-diketone compound and a cobalt compound or a nickel compound in specific amounts, respectively, to a vinyl chloride resin. SOLUTION: This vinyl chloride resin composition comprises (A) 100 pts.wt. of a vinyl chloride resin, (B) 0.001-10 pts.wt. of a β-diketone compound (e.g. dibenzoylmethane) and (C) a cobalt compound or a nickel compound (preferably the organic carboxylate or β-diketonate of cobalt or nickel). The component B and the component C are preferably added in amounts of 0.01-1 pt.wt. and 0.001-0.1 pt.wt., respectively, in a B/C weight ratio of 1/0.005 to 1/0.1 to 100 pts.wt. of the component A. The further addition of an alkaline earth metal perbasic phenolate or carboxylate/carbonate complex of the formula: R2 M- zMCO3 [R is a phenol residue or a carboxylic acid residue; M is an alkaline earth metal; (z) is a positive integer] is preferable because of remarkably improving the thermal stability of the resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized vinyl chloride resin composition, and more specifically, a vinyl chloride resin composition excellent in heat coloring property by adding together a β-diketone compound and an iron group metal compound. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resins are inexpensive and can be easily adjusted in hardness by using a plasticizer. Therefore, vinyl chloride resins should be used for various purposes. You can

However, it is known that a vinyl chloride resin is difficult to be stable against light and heat, and is liable to be decomposed mainly due to dehydrohalogenation at the time of heat molding processing and use of a product. For this reason, various stabilizers such as a metal salt of an organic acid, an organic tin compound, an organic phosphite compound, an epoxy compound, a β-diketone compound, an antioxidant and an ultraviolet absorber are blended to stabilize the vinyl chloride resin. Have been tried to improve.

Among these stabilizers, the β-diketone compound is particularly excellent in the effect of suppressing coloration when blended with a vinyl chloride resin, and the method of using it is described in, for example, JP-A-54-56645. Various reports can be found in the gazette and the like. However, when this β-diketone compound was used, the effect of suppressing the coloration immediately after processing was excellent, but the effect of suppressing the coloration after heat history was quite insufficient.

If there is a large difference between the coloring immediately after processing (initial coloring) and the coloring after heat history (thermal coloring), too much heat is applied during processing, or the quality may deteriorate when stored for a long period of time. May occur, which is not preferable.

Further, iron group metal compounds such as nickel compounds and cobalt compounds are known as weather resistance improvers for vinyl chloride resins together with copper compounds. For example, JP-A-56-22342 discloses chlorides. It has been proposed to add those acetates, chlorides, resinates and sulfanates to vinyl resins, and JP-A-55-13103.
No. 6, it is proposed to add the oxyketo complex, naphthenic acid, long-chain fatty acid or nitrate to a vinyl chloride resin. However, when these are simply used, coloring or heat It had a defect that the stability was rather lowered.

Therefore, an object of the present invention is to provide a vinyl chloride resin composition having excellent heat stability and colorability.

[0008]

As a result of intensive studies, the present inventors have found that the above object can be achieved by adding a β-diketone compound and a specific iron group metal compound in combination. .

The present invention has been made on the basis of the above findings. 100 parts by weight of a vinyl chloride resin, (a) at least 0.001 to 10 parts by weight of a β-diketone compound and (b) a cobalt compound or nickel. It is intended to provide a vinyl chloride resin composition containing 0.0001 to 1 part by weight of at least one compound.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the vinyl chloride resin composition of the present invention will be described in detail.

Examples of the β-diketone compound which is the component (a) used in the present invention include dibenzoylmethane,
Benzoylacetone, stearoylbenzoylmethane,
Examples include caproylbenzoylmethane and dehydroacetic acid.

The amount of the β-diketone compound is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and particularly preferably 0.01 to 1 part by weight, based on 100 parts by weight of the vinyl chloride resin. It is a department. If the blending amount is less than 0.001 part by weight, a sufficient effect cannot be obtained, and if the blending amount is more than 10 parts by weight, the effect is not improved and the coloring property may be lowered.

The cobalt compound or nickel compound which is the component (b) used in the present invention (hereinafter, both may be collectively referred to as "iron group metal compound") means an organic compound containing cobalt and nickel or Inorganic compounds such as oxides, hydroxides, chlorides, carbonates, basic carbonates, (meth) borates, (meth) silicates, (sub) phosphates, basic ( Inorganic compounds such as hypophosphate, aluminate, titanate, stannate, and rhodate; 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, isodecanic acid, isostearic acid, 12-hydroxys Theariic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid,
Arachidic acid, behenic acid, erucic acid, brassic acid and similar acids as well as mixtures of the above mentioned naturally occurring acids such as tallow fatty acid, coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid , Chlorobenzoic acid, toluic acid, salicylic acid, p-tertiary butyl benzoic acid, 5-tertiary octyl salicylic acid, naphthenic acid, xylyl acid, ethyl benzoic acid, isopropyl benzoic acid, ditertiary butyl benzoic acid, bromobenzoic acid, Organic carboxylic acids such as maleic acid, adipic acid, phthalic acid, monobutyl maleate, monodecyl phthalate, cyclohexanedicarboxylic acid, adipic acid, maleic acid, acrylic acid methacrylic acid; phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol , Pheno with dodecylphenol, etc. An organic phosphate with a mono- or dioctyl phosphoric acid, a mono- or didodecyl phosphoric acid, a mono- or di-octadecyl phosphoric acid, a mono- or di- (nonylphenyl) phosphoric acid, a phosphonic acid nonylphenyl ester, a phosphonic acid stearyl ester, etc .; Dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid,
Β-diketonates with acetylacetone and the like; organic compounds such as benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid and other organic sulfonates, and the like. Among these, it is particularly preferable to use an organic carboxylic acid of cobalt or nickel or β-diketonate because a remarkable effect can be obtained.

The amount of the iron group metal compound blended is 0.0001 to 1 part by weight, preferably 0.0005 to 0.5 part by weight, and more preferably 0.001 part by weight per 100 parts by weight of the vinyl chloride resin.
001 to 0.1 parts by weight. The blending amount is 0.0001
If it is less than 1 part by weight, a sufficient effect cannot be obtained, and even if it is more than 1 part by weight, the expected effect is not improved, and rather the coloring property and heat resistance are deteriorated.

In the present invention, the weight ratio (former / latter) of the β-diketone compound as the component (a) and the iron group metal compound as the component (b) is 1/0. ．
001 to 1 / 0.1, especially 1 / 0.005 to 1 / 0.1
Is preferred, and within this range the component (a) and (b)
By using the components, it is possible to obtain a vinyl chloride resin composition which is particularly excellent in heat colorability.

The vinyl chloride resin used in the present invention is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Examples thereof include polyvinyl chloride and chlorinated polyvinyl chloride. , Polyvinyl 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-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer , Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Chlorine-containing resins such as nyl-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their blends or other products Chlorine-free synthetic resin, for example, acrylonitrile-styrene copolymer,
Examples thereof include an ethylene-vinyl acetate copolymer, an ethylene-ethyl (meth) acrylate copolymer, a blend with polyester and the like, a block copolymer, a graft copolymer and the like.

In addition, the composition of the present invention contains the metal (Li, Na, or carboxylic acid, organic phosphoric acid or phenol).
K, Ca, Mg, Ba, Sr, Cd, Zn, Al, S
n, organic Sn, etc.) is preferable because the thermal stability is improved, and examples of the carboxylic acid include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, and undecylene. acid,
Lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachidic acid, Behenic acid, erucic acid, brassic acid and similar acids and naturally occurring mixtures of the above acids such as tallow fatty acid, coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid,
p-tert-Butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylyl acid, salicylic acid, 5
-Tertiary octyl salicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid,
Methacrylic acid and the like may be mentioned, and as the organic phosphoric acid, mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester. , Phosphonic acid stearyl ester and the like, and examples of the phenols include normal salts such as phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol and dodecylphenol, acidic salts, basic salts or overbased salts. can give.

Among these metal salts, the use of an alkaline earth metal overbased phenolate or carboxylate / carbonate complex represented by the following general formula (I) significantly improves the thermal stability. preferable.

R ₂ MzMCO ₃ (I) (wherein R represents a residue of a phenol or a carboxylic acid, M represents an alkaline earth metal, and z represents an excess amount of metal and is a positive value larger than 0). Indicates the number.)

The above-mentioned alkaline earth metal overbased phenolate or carboxylate / carbonate complex is
As described above, it is a compound represented by the above general formula (I), but is completely different from a simple mixture of an alkaline earth metal normal salt of a phenol or a carboxylic acid and an alkaline earth metal carbonate. However, these are formed into a complex by some kind of interaction, and have a characteristic of showing a uniform liquid state in an organic solvent while having a high alkaline earth metal content.

Since the above-mentioned alkaline earth metal overbased phenolate or carboxylate / carbonate complex forms such a complex, it exhibits an excellent stabilizing effect which cannot be achieved by a simple mixture. Is.

The above-mentioned alkaline earth metal overbased phenolate or carboxylate / carbonate complex is
For example, a method of reacting the phenol or the carboxylic acid with a stoichiometric excess of an alkaline earth metal carbonate, the phenol or the carboxylic acid and a stoichiometric excess of an alkaline earth metal oxide. Or a conventionally known method such as a method of reacting with a hydroxide and then treating with carbon dioxide, or a method of reacting the alkaline earth metal normal salt of the phenol or the carboxylic acid with an alkaline earth metal carbonate Can be manufactured in. The alkaline earth metal overbased phenolate or carboxylate / carbonate complex thus prepared is characterized by the type of metal, the type of acid, the content of metal, the metal ratio and the like. Here, the term "metal ratio" is a term indicating the total chemical equivalent of the metal in the salt with respect to the equivalent amount of the metal forming a neutral salt, and z + in the above general formula (I).
This is equivalent to 1.

Further, the above-mentioned alkaline earth metal overbased phenolate or carboxylate / carbonate complex can be easily produced by the above-mentioned method, but various commercially available complexes are used as they are. You can also Typical examples of the commercially available complex include, for example, “LZ-2” manufactured by Lubrizol Co., Ltd. in the United States.
106 "(overbased barium phenolate / carbonate complex: specific gravity 1.3, Ba = 27.5%)," LZ-2
116 "(overbased barium oleate / carbonate complex: specific gravity 1.47, Ba = 34%)," LZ-211
7 "(overbased calcium oleate / carbonate complex: specific gravity 1.07, Ca = 14.2%)," LZ-53
41 ”(overbased calcium oleate / carbonate complex: specific gravity 1.16, Ca = 14.3%) and the like.

The amount of these metal salts compounded is preferably 0.01 to 10 relative to 100 parts by weight of the vinyl chloride resin.
Parts by weight, more preferably 0.05 to 5 parts by weight.

In addition, it is preferable to add perchlorates to the composition of the present invention because the heat aging property is remarkably improved. Examples of the perchlorates are lithium perchlorate, sodium perchlorate, Potassium perchlorate, strontium perchlorate, barium perchlorate, zinc perchlorate, cadmium perchlorate, lead perchlorate, aluminum perchlorate, ammonium perchlorate, etc. are listed. May be an anhydride or a hydrous salt, or may be one dissolved in an alcohol or ester solvent such as butyl diglycol or butyl diglycol adipate, or its dehydrated product.

The amount of the above-mentioned perchlorates is preferably 0.01 to 1 with respect to 100 parts by weight of the vinyl chloride resin.
It is 0 part by weight, and more preferably 0.05 to 5 parts by weight.

Further, it is preferable to add a hydrotalcite compound to the composition of the present invention because the thermal stability is improved. The hydrotalcite compound is represented by the following general formula (II): It is a double salt compound composed of magnesium and aluminum, or zinc, magnesium and aluminum, and may be one obtained by dehydrating crystal water.

Mg _x1 Zn _x2 Al ₂ · (OH) _{2x1 + 2x2 + 4} · (CO ₃ ) _{1-y1 / 2} (ClO ₄ ) _y1 · mH ₂ O (II) (wherein x ₁ , x ₂ and y ₁ is a number satisfying the condition represented by the following formula, and m is 0 or any positive number: 0 ≦ x ₂ / x ₁ <10, ₂ ≦ x ₁ + x ₂ <20, 0
≤y ₁ ≤2)

The hydrotalcite compound may be a natural product or a synthetic product. The method for synthesizing the synthetic product is described in JP-B-46-2280, JP-B-50-30039, and JP-B-51-29129.
Japanese Laid-Open Patent Publication No. 3-36839, Japanese Patent Laid-Open No. 61-1
A known method described in, for example, Japanese Patent No. 74270 can be exemplified. Further, the hydrotalsalt compound can be used without being limited by its crystal structure, crystal particle size and the like.

In the present invention, the surface of the hydrotalcite compound is a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal salt of oleic acid, or an organic sulfone such as an alkali metal salt of dodecylbenzenesulfonic acid. Those coated with acid metal salts, higher fatty acid amides, higher fatty acid esters or waxes can also be used.

The blending amount of the above hydrotalcite compound 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 vinyl chloride resin.
Parts by weight.

Further, the composition of the present invention further comprises various additives which are usually used as additives for vinyl chloride resins, such as plasticizers, zeolite compounds, organic phosphite compounds, phenol compounds or sulfur compounds. Antioxidants, epoxy compounds, polyols, ultraviolet absorbers, hindered amine light stabilizers, other inorganic metal compounds, foaming agents and the like can also be added.

As the above-mentioned plasticizer, any plasticizer usually used in vinyl chloride resins can be optionally used. Examples thereof include dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl. Phthalate plasticizers such as phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; dioctyl adipate, diisononyl adipate,
Adipate plasticizers such as diisodecyl adipate and di (butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri ( Butoxyethyl) phosphate phosphate plasticizers such as octyldiphenylphosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-
Propylene glycol, 1,3-butanediol, 1,
4-butanediol, 1,5-hexanediol, 1,
6-hexanediol, neopentyl glycol, etc. and dibasic acids as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. A polyester plasticizer using a monohydric alcohol or monocarboxylic acid as a stopper if necessary; other, a tetrahydrophthalic acid plasticizer, an azelaic acid plasticizer, a sebacic acid plasticizer, a stearic acid plasticizer, Examples thereof include citric acid plasticizers, trimellitic acid plasticizers, pyromellitic acid plasticizers, and biphenylene polycarboxylic acid plasticizers.

The amount of the plasticizer added can be appropriately used within the range of 0 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

The above-mentioned zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and typical examples thereof include A type, X type, Y type and P type. Zeolite, monodenite, analsite, aluminosilicate of the sodalite group, clinobuchilorite, erionite, chabazite, etc. can be mentioned, and a hydrate or crystal water having crystal water of these zeolite compounds (so-called zeolite water). Any of the anhydrides from which is removed may be used.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,
4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenylacid phosphite,
2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, tridecyl phosphite Lauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite,
Bis (neopentyl glycol) / 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite,
Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-4,4 '
-Isopropylidene diphenol pentaerythritol diphosphite, tetra (C12-15 mixed alkyl)-
4,4'-isopropylidenediphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (2-tert-butyl) -5
-Methylphenol)] ・ 1,6-hexanediol ・
Diphosphite, tetratridecyl-4,4'-butylidenebis (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-1
0-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol,
2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-
Di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylenebis [(3,5-di-tert-butyl-4
-Hydroxyphenyl) propionate], 4,4'-
Thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-)
(Hydroxyphenoxy) -s-triazine, 2,2′-
Methylene bis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl Butyl-m
-Cresol), 2,2′-ethylidenebis (4,6-
Di-tert-butylphenol), 1,1,3-tris (2-
Methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-
Hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6
-Dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-
4-hydroxyphenyl) propionyloxyethyl]
Isocyanurate, tetrakis [methylene-3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6-
(2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5 , 5] undecane-bis [β-
(3-tert-butyl-4-hydroxy-5-butylphenyl) propionate] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the sulfur-based antioxidants include dilauryl thiodipropionate, dimyristyl,
Examples thereof include dialkylthiodipropionates such as myristyl stearyl and distearyl esters, and β-alkylmercaptopropionic acid esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil. Animal and vegetable oil, epoxidized methyl stearate, -butyl,
-2-ethylhexyl, -stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide , 3,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate, bisphenol type or novolak type epoxy resin.

Examples of the above-mentioned polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentalithritol, polypentaerythritol, pentaerythritol or stearic acid half ester of dipentalithritol,
Bis (dipentaerythritol) adipate, glycerin, tris (2-hydroxyethyl) isocyanurate, trehalose and the like can be mentioned.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-.
2-hydroxybenzophenones such as 4-octoxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole,
-(2-hydroxy-5-tert-octylphenyl) 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′-methylenebis (4-tert-octyl-
2- (2-hydroxyphenyl) benzotriazoles such as 6-benzotriazolylphenol) and polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; phenyl salicylate; Benzoates such as resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2- Substituted oxanilides such as ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-
and cyanoacrylates such as β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizer include, for example, 2,2,6,6-tetramethyl-4-
Piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6
-Tetramethyl-4-piperidylbenzoate, bis (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) butanetetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) 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- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,
2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6
-Tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane /
2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6- Trioctylamino-s-triazine polycondensate,
1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl]- 1,
5,8,12-tetraazadodecane, 1,5,8,12
-Tetrakis [2,4-bis (N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12
-Tetraazadodecane, 1,6,11-tris [2,4
-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6
-Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,
Hindered amine compounds such as 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane.

Examples of the other inorganic metal compounds include calcium silicate, calcium phosphate, calcium oxide, calcium hydroxide, magnesium silicate, magnesium phosphate, magnesium oxide, magnesium hydroxide and the like.

Examples of the foaming agent include azodicarbonamide, azobisisobutylnitrile, diazoaminobenzene, diethylazodicarboxylate,
Azo foaming agents such as diisopropyl azodicarboxylate and azobis (hexahydrobenzonitrile);
N'-dinitropentamethylenetetramine, N, N'-
Nitroso-based blowing agents such as dimethyl-N, N'-dinitroterephthalamine, benzenesulfonylhydrazide, p
Hydrazides such as -toluenesulfonylhydrazide, 3,3'-disulfonhydrazidephenylsulfone, toluenedisulfonylhydrazone, thiobis (benzenesulfonylhydrazide), toluenesulfonylazide, toluenesulfonylsemicarbazide, p, p'-bis (benzenesulfonylhydrazide) ether; System foaming agent, p-
Carbazide-based blowing agents such as toluenesulfonyl semicarbazide and 4,4′-oxybiz (sulfonyl semicarbazide), trihydrazinotriazine, 1,3-bis (o
-Biphenyltriazine) and the like.

Further, the composition of the present invention may contain other stabilizing aids which are usually used in vinyl chloride resins. Such stabilizing aids include, for example, diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid and the like.

In addition, the composition of the present invention may contain, if necessary, additives usually used for vinyl chloride resins, for example,
Fillers, colorants, cross-linking agents, antistatic agents, anti-fog agents, anti-plateout agents, surface treatment agents, lubricants, flame retardants, anti-fog agents,
Fluorescent agents, antifungal agents, bactericides, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers and the like can be added.

Further, the composition of the present invention can be used irrespective of the processing method of the vinyl chloride resin,
For example, calendar processing, roll processing, extrusion processing,
It can be suitably used for the melt rolling method, pressure molding process, powder molding and the like.

The composition of the present invention is used for building materials such as wall materials, floor materials, window frames and wallpaper; interior materials for automobiles; covering materials for electric wires;
It can be suitably used as agricultural materials such as tunnels; food packaging materials such as wraps and trays; paints; miscellaneous goods such as hoses, pipes, sheets and toys.

[0049]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1 The following formulation was used to roll-knead at 170 ° C. to prepare a sheet, which was pressed at 180 ° C. for 5 minutes and 30 minutes, and the yellowness of the pressed sheet was measured using a Hunter colorimeter. . The results are shown in Table 1 below.

[Compounding] Parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 Di-2-ethylhexyl phthalate 40 Epoxidized soybean oil 2 Titanium dioxide 1 Zinc stearate 0.5 Barium stearate 1.0 DHT-4A ^{* 1} 0 .5 Dibenzoylmethane 0.3 Metal compound (See [Table 1] below) 0.005 * 1: Synthetic hydrotalcite manufactured by Kyowa Chemical Co., Ltd. Compositional formula: Mg _4.5 Al ₂ · (OH) ₁₃ · CO ₃ · 3.5H ₂ O

[0052]

[Table 1]

Example 2 Using the following formulation, a roll-up sheet of 1 mm was prepared at 180 ° C., a press sheet of 180 ° C. for 5 minutes, and 180 ° C.
A press sheet was prepared at 30 ° C. for 30 minutes, the yellowness was measured with a Hunter colorimeter, and the color difference was determined. The results are shown in Table 2 below.

[Composition] Parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 Di-2-ethylhexyl phthalate 20 Epoxidized soybean oil 3 Titanium oxide 10 LZ-2106 0.5 Barium oleate 0.5 Zinc benzoate 0. 8 monophenyl ditridecyl phosphite 0.5 nickel acetate 0.001 β-diketone compound (see Table 2 below) 0.1

[0055]

[Table 2]

Example 3 The following formulation was calendered at 190 ° C.
A 0.5 mm sheet was prepared. Initial coloring and 190
Coloring after 60 minutes in a gear oven at ℃ was measured using a colorimeter to determine the color difference. The results are shown in Table 3 below.

(Combined) parts by weight polyvinyl chloride resin (Geon 103EP) 100 MBS resin 15 acrylic processing aid 2 titanium oxide 2 epoxidized soybean oil 3 LZ-2116 0.3 barium oleate 0.3 barium benzoate 0 .3 Zinc stearate 0.5 Dibenzoylmethane 0.2 Metal compound (see Table 3 below) 0.01

[0058]

[Table 3]

Example 4 A vinyl chloride resin composition having the following composition was dried up in a gear oven at 110 ° C. for 1 hour and then stirred for 15 minutes using a raider to prepare a compound. Approximately 1 chrome mirror plate in a 300 ° C gear oven
After putting it in for 5 minutes and taking it out, when the mirror plate reached 240 ° C., the compound was rapidly spread to a uniform thickness.
Let stand for a second. The mold was turned upside down, left as it was for 30 seconds, then immersed in a water tank and cooled to prepare a sheet.

Urethane foam was injected into the above-prepared sheet with a constant thickness to prepare a urethane-backed sheet.
This sheet was placed in an oven at 120 ° C., and the yellowness of the sheet was measured after 200 hours and 300 hours. The results are shown in [Table 4] below.

[Parts] By Weight Suspension Polymerized PVC 90 Paste PVC 10 Di (C9-11 mixed alkyl) phthalate 65 Epoxidized soybean oil 5 Zinc stearate 0.3 Alkamizer 4 ^{* 2} 1.0 Sodium A type zeolite 2.0 Barium perchlorate 0.6 Tetra (C12-15 mixed alkyl) bisphenol A 1.0 Diphosphite dibenzoylmethane 0.1 Metal compound (see Table 4 below) 0.001 * 2: Kyowa Chemical Co., Ltd. ) Zinc-modified synthetic hydrotalcite Compositional formula: Mg ₃ ZnAl ₂ · (OH) ₁₂ · CO ₃ · 3H ₂ O

[0062]

[Table 4]

From the above results, the following is clear. When only β-diketone compound is used for vinyl chloride resin (Comparative Examples 1-1,2-3,3-1,4-1), the effect of improving thermal coloring is small and only iron group metal compound is used. In the case of using (Comparative Examples 1-3, 2-1), almost no effect of suppressing the thermal coloring property is observed, and in the case of using other metal compounds in combination with the β-diketone compound (Comparative Example 3- 2,3-3,4-2,4-3) has no remarkable effect.

On the other hand, β-
When used in combination with a diketone compound and an iron group metal compound (Examples 1-1 to 1-5, 2-1 to 2-3, 3-1 to 3-4, 4-1 to 4-
5) shows a remarkable improvement effect on the heat coloring property.

[0065]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition of the present invention is excellent in coloring property, particularly in heat coloring property, and can be suitably used for all purposes.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/138 KHA C08K 5/138 KHA (72) Inventor Osamu Yoshiguchi 5 Shirahata, Urawa City, Saitama Prefecture 2-13 No. 13 Asahi Denka Kogyo Co., Ltd.

Claims (5)

[Claims] 1. A vinyl chloride resin in 100 parts by weight of (a)
At least one β-diketone compound 0.001-10
A vinyl chloride resin composition, which comprises 0.001 to 1 part by weight of (b) at least one cobalt compound or nickel compound. 2. The vinyl chloride resin composition according to claim 1, wherein the component (b) is at least one of cobalt or nickel organic carboxylic acid salts or β-diketonates. 3. The vinyl chloride resin composition according to claim 2, further comprising 0.01 to 10 parts by weight of at least one overbased phenolate or carboxylate / carbonate complex of an alkaline earth metal. 4. The vinyl chloride resin composition according to claim 2, further comprising 0.01 to 10 parts by weight of at least one kind of perchlorates. 5. The vinyl chloride resin composition according to claim 2, further comprising 0.01 to 10 parts by weight of at least one hydrotalcite compound.