JP2000319468A - Stabilizer composition for vinyl chloride resin - Google Patents

Abstract

(57) [Problem] To provide a stabilizer composition for a vinyl chloride resin which is liquid and excellent in storage stability and heat stability. SOLUTION: The stabilizer composition for a vinyl chloride resin according to the present invention comprises (a) 1 to 80% by weight of a zinc carboxylate;
It contains 1 to 80% by weight of a calcium carboxylate and (C) 10 to 98% by weight of an epoxidized fatty acid monoester. The stabilizer composition of the present invention is used particularly for a vinyl chloride resin for food packaging. The stabilizer composition of the present invention further improves the stabilizing effect by further containing 1 to 50% by weight of a phenolic antioxidant. Further, the vinyl chloride resin composition of the present invention contains the above-mentioned stabilizer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizer composition for a vinyl chloride resin, and more particularly to a stabilizer composition for a vinyl chloride resin which is liquid and has excellent storage stability and heat stability.

[0002]

2. Description of the Related Art Polyvinyl chloride stretch films have excellent transparency, flexibility, gas barrier properties, food packaging properties, and packaging suitability.
Meat at food departments such as department stores and supermarkets,
It is widely used as a film for packaging foods such as fresh fish, fruits and vegetables, and side dishes.

Various additives for improving the resistance to light, heat, oxidation, etc., such as metal soap stabilizers, organic phosphite compounds, epoxy compounds, phenolic antioxidants, etc., are added to vinyl chloride resins. Is blended.

[0004] Among these stabilizers, metal soap-based stabilizers are almost always essential components for stabilization, but are in the form of powder. Since the powder stabilizer may cause problems at the processing site such as scattering, a liquid and one-pack stabilizer is preferred.

For example, JP-A-49-98445 discloses
JP-A-53-5246 proposes a liquid metallic soap-based stabilizer. However, in the case of a mixed solvent system of hydrocarbons and alcohols used as a solvent, a saturated aliphatic monohydric alcohol, and the like, the odor and the like when remaining in the product cause problems such as odor and the like. Was not preferred as a stabilizer.

[0006] Further, in particular, stabilizers for vinyl chloride resins for food packaging are limited to non-toxic or low-toxic components, so that satisfactory stability cannot be obtained at present. For this reason, there has been a demand for a stabilizer composition for vinyl chloride resin having more excellent heat resistance.

Accordingly, an object of the present invention is to provide a stabilizer composition for a vinyl chloride resin which is liquid and has excellent storage stability and heat stability.

[0008]

The present inventors have conducted intensive studies and as a result, have found that a composition containing an epoxidized fatty acid monoester together with two specific carboxylate salts can achieve the above object. Was found.

The present invention has been made on the basis of the above-mentioned findings, and comprises (a) 1-80% by weight of a zinc carboxylate, (b) 1-80% by weight of a calcium salt of a carboxylate, and (c) an epoxidized fatty acid monoester. An object of the present invention is to provide a stabilizer composition for vinyl chloride resin containing 10 to 98% by weight.

[0010]

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

The carboxylic acid which forms the zinc carboxylate of the component (a) used in the present invention includes, for example, caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid 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, araquine Acid, behenic acid, erucic acid, brassic acid and similar acids and mixtures of the above 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, p-tert-butylbenzoic acid Acid, ethyl benzoic acid, isopropyl benzoic acid, toluic acid, xy Le acid, salicylic acid, 5 - tert-octyl salicylic acid, naphthenic acid, cyclohexanecarboxylic acid, acrylic acid, monovalent carboxylic acids such as methacrylic acid,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid And divalent carboxylic acids such as citraconic acid, metaconic acid, itaconic acid and aconitic acid, and their monoesters.

The carboxylic acid forming the calcium carboxylate of the component (b) used in the present invention includes, for example, the compounds exemplified above as the carboxylic acid forming the component (a).

The epoxidized fatty acid monoester of the component (c) used in the present invention is, for example, one obtained by epoxidizing a fatty acid monoester obtained by transesterification of a natural fat or oil or a monoester of a synthetic fatty acid. For example, epoxidized butyl stearate, epoxidated octyl stearate, epoxidized butyl linoleate, epoxidized octyl ricinoleate, epoxidized linseed oil fatty acid butyl, epoxidized linseed oil fatty acid octyl, epoxidized tall oil fatty acid butyl, epoxidation Tall oil fatty acid octyl, epoxidized soybean oil fatty acid butyl,
And octyl epoxidized soybean oil fatty acid. These epoxidized fatty acid esters have an epoxy equivalent of 800
In the following, it is particularly preferable to use those having 100 to 500, because more excellent heat resistance can be imparted.

The stabilizer composition for a vinyl chloride resin of the present invention comprises 1 to 80% by weight, preferably 5 to 50% by weight, of a zinc carboxylate of the component (a), and 1 to 50% by weight of the calcium carboxylate of the component (b). To 80% by weight, preferably 5 to 50% by weight, and the epoxidized fatty acid ester compound (C).
It contains 98% by weight, preferably 20 to 90% by weight. If the content of the component (a) is less than 1% by weight, a satisfactory stabilizing effect cannot be obtained when the component is blended with a vinyl chloride resin, and if it exceeds 80% by weight, the component is blended with a vinyl chloride resin. Blackening occurs in a short time. When the content of the component (b) is less than 1% by weight, a satisfactory stabilizing effect cannot be obtained when blended with a vinyl chloride resin, and when the content exceeds 80% by weight, the compound is blended with a vinyl chloride resin. Coloring occurs. If the content of the component (c) is less than 10% by weight, a stable liquid stabilizer composition cannot be obtained, and 98% by weight.
If it exceeds 3, a satisfactory stabilizing effect cannot be obtained when blended with a vinyl chloride resin.

[0015] The stabilizer composition for vinyl chloride resin of the present invention is preferably further contained a phenolic antioxidant since the stabilizing effect can be improved.

These phenolic antioxidants include, for example, 2,6-di-tert-butyl-p-cresol, 2,6
-Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3 , 5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl- m-cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) ), Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidenebis (4,
6-di-tert-butylphenol), 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-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert. Tributyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl- 6- (2-Acroyloxy-3-tert-butyl-
5-methylbenzyl) phenol, 3,9-bis [2-
(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane], triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

The content of these phenolic antioxidants is
The amount is preferably 1 to 50% by weight, particularly 3 to 30% by weight, and if the amount is less than 1% by weight, the effect is not sufficiently exhibited. This is not preferable because coloring may occur.

Although the stabilizer composition of the present invention can provide a stable liquid stabilizer by using an epoxidized fatty acid monoester, other organic solvents may be used for the purpose of lowering the viscosity. And these other organic solvents include, for example, iso- or n-butanol, iso- or n-propanol, amyl alcohol, 1-octanol, 2-ethyl-1-hexanol, 3,5,5
5-trimethyl-1-hexanol, tridecanol,
Isodecanol, Oxocol 710 (Nissan Chemical: C
7-10 linear alcohol), isostearyl alcohol, isooctanol, dovanol 23-I (M12-13 branched chain alcohol manufactured by Mitsubishi Chemical Corporation), Epal61
0, Epal108, Epal810 (Ethyl I
C6-10 linear alcohol), propylene glycol, 1,3-butylene glycol, diethanolamine, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl carbitol, glycerin, ethylene glycol, dipropylene glycol, triethylene Glycol, benzyl alcohol, β-phenylethanol, cyclohexanol,
Alcohols such as 2,4,4-trimethylpentanol; ketones such as acetone, methyl isopropyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone; tetrahydrofuran, 1,2-dimethoxyethane, 1,2- Ethers such as diethoxyethane; esters such as ethyl acetate and n-butyl acetate; benzene, toluene, xylene, turpentine oil, D-limonene, pinene, mineral spirits, swazol # 310 (Cosmo Matsuyama Sekiyu KK), Solvesso # 100 (Exxon Chemical Co., Ltd.), Exol D-80 (Exxon Chemical), hydrocarbons such as liquid paraffin; halogenated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and chlorobenzene S; aniline, triethylamine, pyridine, dioxane, acetic acid, acetonitrile,
Carbon disulfide and the like. These solvents can be used alone or arbitrarily as a mixed solvent of two or more kinds. When used for food packaging, it is preferable to select a non-toxic solvent such as liquid paraffin. These solvent components can be used in any amount. However, if it is used in excess of 50% by weight, storage stability may be adversely affected, which is not preferred.

The stabilizer composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, for example, plasticizers, epoxy compounds, antifogging agents,
It may contain a β-diketone compound, an organic phosphite compound, a sulfur-based antioxidant, a polyol, an ultraviolet absorber and the like.

Examples of the plasticizer include dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate,
Phthalic acid plasticizers such as dicyclohexyl phthalate and dioctyl terephthalate; adipic acid plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate and di (butyldiglycol) adipate; ethylene glycol, diethylene glycol, and triethylene glycol as polyhydric alcohols , 1,2-
Propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol and the like, and as a dibasic acid,
Use 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., and if necessary, monohydric alcohol and monocarboxylic acid. Polyester plasticizer used for the stopper: triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate And other phosphate ester plasticizers; other, tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, and trimellitic acid plasticizers. , Pyromellitic acid plasticizers include biphenylene polycarboxylic acid plasticizers.

Examples of the epoxy compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, and the like. Epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, vinylcyclohexene diepoxide, dicyclohexenecarboxylate, 3,4
-Epoxycyclohexenemethylepoxycyclohexanecarboxylate and the like.

Examples of the antifogging agent include polyoxyethylene lauryl ether, -stearyl ether, and-
Nonylphenyl ether, polyethylene glycol monopalmitate, -monostearate, polyoxyethylene sorbitan monolaurate, -monopalmitate, glycerin monolaurate, -monopalmitate, -monostearate, -monooleate, pentaerythritol monolau Rate, sorbitan monopalmitate, -monobehenate, -distearate, diglycerindiolate sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride,
Dodecylamine hydrochloride, lauric lauramide ethyl phosphate, triethylcetyl ammonium iodide, oleylaminodiethylamine hydrochloride, dodecylpyridinium salt and the like can be mentioned.

Examples of the β-diketone compound include dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene and the like, and the like. Metal salts (lithium, sodium, potassium, calcium,
Magnesium, barium, zinc, etc.).

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) .ethyl Phosphite, diphenylacid phosphite, 2,2′-methylenebis (4,6-ditertbutylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyldiisodecyl phosphite, tributyl phosphite,
Tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexane dimethyldi Phosphite, bis (2,4-di-tert-butylphenyl)
Pentaerythritol diphosphite, bis (2,6-
Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol / pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) −4,4 ′ −
Isopropylidene diphenyl phosphite, bis [2,
2′-methylenebis (4,6-diamylphenyl)] • isopropylidenediphenylphosphite, 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 triphosphonite, 9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide, 2
-Butyl-2-ethylpropanediol 2,4,6-
Tri-tert-butylphenol monophosphite and the like can be mentioned.

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionates of polyols.

The polyols include, for example, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol half-ester stearic acid, bis (dipentaerythritol) adipate, Glycerin,
Tris (2-hydroxyethyl) isocyanurate, sorbitol, mannitol, trehalose and the like can be mentioned.

Examples of the ultraviolet absorber include, for example, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 '-(2-methacryloyloxyethoxyethoxy) benzophenone, 5,5'-methylenebis (2-hydroxy-4 2-hydroxybenzophenones such as -methoxybenzophenone); 2- (2-hydroxy-5-
Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-3-tert-butyl-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (2-hydroxy-
3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7
~ 9 mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; 2- (2-hydroxy-4
-Hexyloxyphenyl) -4,6-diphenyl-1,
3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6 -Bis (2,4-dimethylphenyl)-
1,3,5-triazine, 2- (2-hydroxy-4-
2- (2-hydroxyphenyl) -1,3,5- such as acryloyloxyethoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine
Triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-
3,5-di-tert-butyl-4-hydroxybenzoate,
2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5
Benzoates such as di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-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.

The stabilizer composition of the present invention is particularly suitable as a stabilizer for a vinyl chloride resin for food packaging, and preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of a vinyl chloride resin. Preferably 0.5 to 10 parts by weight are blended,
If the amount is less than 0.1 part by weight, a sufficient stabilizing effect may not be provided, and if the amount is more than 20 parts by weight, not only is it wasteful, but also coloring or bleeding occurs, or the physical properties are deteriorated. It is not preferable because there is a possibility of the like.

The vinyl chloride resin is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Examples thereof include polyvinyl chloride, chlorinated polyvinyl chloride, and 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-chloride Vinylidene copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer,
Vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer, Vinyl chloride-methacrylate copolymer, vinyl chloride-
Chlorine-containing resins such as acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and their blended products or their chlorine-containing resins and other chlorine-free synthetic resins, such as acrylonitrile-styrene copolymers Acrylonitrile-styrene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blends with polyester, etc., block copolymers, graft copolymers and the like. be able to.

The vinyl chloride resin composition containing the stabilizer composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, such as those exemplified above. When done, plasticizer, epoxy compound,
An antifogging agent, a β-diketone compound, an organic phosphite compound, a sulfur-based antioxidant, a polyol, an ultraviolet absorber and the like can be used in combination. Furthermore, for example, hydrotalcite compounds, perchlorates, zeolite compounds, other inorganic metal compounds, and the like can be used in combination.

The hydrotalcite compound is a complex salt compound comprising magnesium and / or an alkali metal and aluminum or zinc, magnesium and aluminum as represented by the following general formula (I), and is obtained by dehydrating water of crystallization. It may be.

Ia _x1 Mg _x2 Zn _x3 Al _y (OH) _{x1 + 2 (x2 + x3) + 3y-2} (CO ₃ ) _{1-z / 2} (ClO ₄ ) mH ₂ O (I) (wherein Ia Represents an alkali metal atom, x1, x
2, x3, y, and z each represent a number that satisfies the condition represented by the following equation, and m represents a real number. 0 ≦ x1 ≦ 10,0 ≦
x2 ≦ 10, 0 ≦ x3 ≦ 10, 0 ≦ y ≦ 10, 0 ≦ z ≦
10. However, x1 and x2 are never 0 at the same time. )

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.
Gazette, Japanese Patent Publication No. 3-36839, JP-A-61-174
Known methods described in, for example, Japanese Patent Application Laid-Open No. 270, JP-A-5-17952 and the like can be exemplified. Further, the above hydrotalcite compound can be used without being limited by its crystal structure, crystal particle system and the like.

The above-mentioned hydrotalcite compound may have a surface formed of a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, or a higher salt thereof. It may be one coated with a fatty acid amide, a higher fatty acid ester or a wax.

The above perchlorates include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, barium perchlorate, zinc perchlorate,
Aluminum perchlorate, lead perchlorate, ammonium perchlorate and the like, and these perchlorates may be anhydrous or hydrated salts, and butyl diglycol, alcohols such as butyl diglycol adipate and the like. It may be one dissolved in an ester solvent or the like and a dehydrated product thereof.

The zeolite compound is an alkali or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure.
Type, X type, Y type, and P type zeolite, monodenite,
Analsite, sodalite group aluminosilicate, clinbutyrolite, erionite, chabazite and the like can be mentioned, and hydrated water containing crystallization water of these zeolite compounds (so-called zeolite water) or water of crystallization is removed. Any of anhydrides may be used.

The other inorganic metal compounds mentioned above include:
Examples include calcium silicate, calcium phosphate, calcium oxide, calcium hydroxide, magnesium silicate, magnesium phosphate, magnesium oxide, magnesium hydroxide and the like.

The vinyl chloride resin composition containing the stabilizer composition of the present invention may contain other stabilizing aids usually used for vinyl chloride resins. Such stabilizing aids include, for example, diphenylthiourea, diphenylurea, anilinodithiotriazine,
Melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid and the like can be mentioned.

In addition, the above-mentioned vinyl chloride resin composition may contain, if necessary, additives usually used for vinyl chloride resins, for example, fillers, coloring agents, crosslinking agents, plate-out preventing agents, surface treatment agents. , A lubricant, a flame retardant, a fluorescent agent, a fungicide, a bactericide, a metal deactivator, a release agent, a pigment, a processing aid, a foaming agent, and the like.

The vinyl chloride resin composition containing the stabilizer composition of the present invention can be used irrespective of the processing method of the vinyl chloride resin.
Calendar processing, roll processing, inflation processing,
It can be suitably used for extrusion molding, melt rolling, pressure molding, powder molding and the like.

The vinyl chloride resin composition containing the stabilizer composition of the present invention is not limited to its use, but is particularly used as a food packaging material such as a stretch film, a tray or a container. can do.

[0042]

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 A stabilizer composition was prepared by mixing the following components while heating at 100 ° C. The obtained stabilizer composition is placed in a 100 cc sealed sample bottle with a stopper, and closed in a closed system at room temperature, an open system at room temperature, a closed system at low temperature (5 ° C) and a closed system at high temperature (70 ° C).
The state after standing for a week was visually evaluated. Table 1 shows the results.

(Composition) Parts by weight Calcium benzoate 10 Zinc oleate 10 Test compound (described in Table 1) 80

[0045]

[Table 1]

Example 2 The stabilizer composition of the present invention can contain additives and other solvents commonly used for vinyl chloride resins. To show this, the same storage stability as in Example 1 was evaluated for the stabilizer compositions having the compositions shown in Tables 2 and 3. The results are shown in Tables 2 and 3. In the table, “の” means “uniform dissolution”.

[0047]

[Table 2]

[0048]

[Table 3]

Example 3 The following components were kneaded at 180 ° C. for 5 minutes, 10 minutes and 20 minutes, extruded at 190 ° C. by a T-die, and a film having a thickness of 18 μm was produced by a conventional method using a take-up machine. It was made into a roll. The scroll obtained at this time (about 1 cm thick)
Was visually evaluated. The evaluation criteria are 10 levels,
1 represents a state where there is almost no coloring, and the coloring increases as the numerical value increases. Table 4 shows the results.

[Blending] Parts by weight Vinyl chloride resin (ZEST 1400Z, manufactured by Zeon Corporation) 100 Diisononyl adipate 40 Epoxidized soybean oil 8 Glycerin monooleate 1.5 Polyoxyethylene (s) alkyl ether 0.5 Liquid stable Agent composition (described in Table 4) 2

[0051]

[Table 4]

As is clear from the above Examples, when the zinc carboxylate and the calcium carboxylate are liquefied with liquid paraffin (Comparative Example 1-1), precipitation occurs even at room temperature. When epoxidized soybean oil was used (Comparative Examples 1-2, 2-1 and 2-2), storage stability at room temperature was improved, but gelled at low temperature and gelled at high temperature. It hardens and storage stability is not satisfactory.

On the other hand, when the epoxidized fatty acid ester of the component (c) according to the present invention was used (Example 1-
1 to 1-7, 2-1 to 2-12) have excellent storage stability at normal temperature, low temperature, or high temperature, and also have the effect of improving the stabilizing effect when other solvents are used in combination to reduce the viscosity. Therefore, when various additives are contained, the composition exhibits excellent storage stability. Furthermore, when compounded with a vinyl chloride resin (Example 3
-1 to 3-4) have the same thermal stability and coloration resistance improvement effects as when a general-purpose epoxidized soybean oil is used,
In particular, by containing a phenolic antioxidant, the stabilizing effect can be further improved (Example 3-
3, 3-4).

[0054]

The stabilizer composition for a vinyl chloride resin according to the present invention is a liquid and excellent in storage stability, and furthermore has excellent heat resistance and coloring resistance only by a non-toxic component. The vinyl chloride resin composition can be suitably used as a food packaging material such as a stretch film.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Dai Nishimura 5-2-13-Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. F-term (reference) 4J002 BD031 BD041 BD081 BD091 BD101 EG037 EG046 EG056 EG057 EG066 EG067 EG076 EG077 EG086 EG087 EG096 EG097 EG106 EG107 EJ029 EJ039 EL028 EU189 EU199 EV099 EW129 FD020 FD036 FD037 FD050 FD068 FD070 FD200

Claims (4)

[Claims] 1. (a) 1-80% by weight of a zinc carboxylate, (b) 1-80% by weight of a calcium salt of a carboxylic acid, and (c) 10-98% by weight of an epoxidized fatty acid monoester.
A stabilizer composition for a vinyl chloride resin, comprising: 2. The stabilizer composition according to claim 1, which is used for a vinyl chloride resin for food packaging. 3. The stabilizer composition according to claim 1, further comprising 1 to 50% by weight of a phenolic antioxidant. 4. A vinyl chloride resin composition comprising the stabilizer composition according to claim 1.