JP2002138180A - Vinyl chloride resin plasisol composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin plastisol composition having excellent sol viscosity, thermal stability at processing and of molding, without causing bleeding of compounds possibly of sanitary concern. SOLUTION: This vinyl chloride resin plastisol composition comprises (a) 30 to 200 pts.wt. of a plasticizer, (b) 0.01 to 10 pts.wt. of at least a compound selected from the group consisting of an organic carboxylic acid magnesium salt, an organic carboxylic acid calcium salt and hydrotalcite, (c) 0.01 to 10 pts.wt. of at least a compound selected from an organic carboxylic acid zinc salt, and (d) 0.001 to 10 pts.wt. of at least a compound selected from a phosphite compound expressed by formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin plastisol composition, and more particularly, to a composition comprising a phosphite compound having a specific structure, which is excellent in hygiene, coloring and heat stability. The present invention relates to an excellent vinyl chloride resin plastisol composition.

[0002]

2. Description of the Related Art Gloves obtained from vinyl chloride resins have been used as cooking gloves because of their good water resistance. Such gloves are generally manufactured from a plastisol mainly composed of a vinyl chloride resin for paste and a plasticizer.

[0003] In such a plastisol, various additives, mainly metal-based stabilizers, are blended in order to prevent deterioration due to heat or light during processing or use. Among these additives, phosphite compounds exhibit an excellent effect of improving thermal stability during processing or use.

However, these additives are eluted (bleed) from the plastisol, causing adhesion and migration to foods and the like that come into contact with the additives, and this is a problem particularly when used as cooking gloves. In addition, nonylphenol produced by decomposing trisnonylphenyl phosphite, which is often used as a low-toxicity phosphite compound, is suspected as an estrogenic substance, and a phosphite compound having excellent sanitary properties has been demanded as an alternative. I was

[0005] On the other hand, toys such as dolls are also formed from a vinyl chloride resin plastisol. However, it is conceivable that children may directly touch their hands or sometimes hold their mouths, and thus there is a problem of hygiene as described above.

Accordingly, an object of the present invention is to provide a vinyl chloride resin plastisol composition which is excellent in sol viscosity, in processing and in heat stability of a molded product without elution of a compound which may be a problem in hygiene. It is in.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a vinyl chloride resin plastisol composition contains a phosphite compound having a specific structure to elute the phosphite compound. It has been found that heat resistance and coloring properties can be remarkably improved without occurrence of the odor, and the present invention has been achieved.

That is, the present invention relates to a vinyl chloride resin 100
(B) 30 to 200 parts by weight of a plasticizer, (b) 0.01 to 10 parts by weight of at least one selected from a magnesium salt of an organic carboxylic acid, a calcium salt of an organic carboxylic acid and a hydrotalcite compound, C) at least one selected from the group consisting of zinc salts of organic carboxylic acids 0.01 to 0.01
10 parts by weight, and (d) at least one phosphite compound represented by the following general formula (I):
The above object has been achieved by providing a vinyl chloride resin plastisol composition containing 001 to 10 parts by weight.

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[0009]

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

The vinyl chloride resin used in the present invention is obtained by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the polymerization method is not particularly limited.
For example, 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 Polymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride 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-methacrylic Acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride Chlorine-containing resins such as various vinyl ether copolymers, and their mutual blends or their chlorine-containing resins and other chlorine-free synthetic resins, for example, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene ternary Blends with copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, polyesters,
Block copolymers, graft copolymers and the like can be mentioned.

The plasticizer (A) used in the present invention includes, for example, dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate and the like. Phthalic acid diester plasticizers; adipic acid diester plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate; 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 and the like, and oxalic acid as a dibasic acid,
Use malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and use monohydric alcohol and monocarboxylic acid as stoppers if necessary Polyester plasticizers; benzoate plasticizers such as dipropylene glycol dibenzoate and ethylene glycol dibenzoate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, Phosphate plasticizers such as trioctyl phosphate, tri (butoxyethyl) phosphate and octyl diphenyl phosphate; phenyl n-octyl sulfonate;
Sulfonate plasticizers such as phenyl / hexadecane sulfonate and mesamol (mixed esters of phenol and cresol of alkylsulfonic acid); others, tetrahydrophthalic plasticizer, azelaic plasticizer, sebacic plasticizer, stearic acid Plasticizers, citric acid plasticizers, trimellitic acid plasticizers, pyromellitic acid plasticizers, biphenylene polycarboxylic acid plasticizers, and the like.

Among these plasticizers, adipic acid ester plasticizers such as adipic acid diester plasticizer or adipic acid polyester plasticizer using adipic acid as a dibasic acid component; It is preferable to use it because it does not dissolve and can be obtained with excellent heat resistance and coloring properties.

The content of the plasticizer (A) is 30 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount exceeds 200 parts by weight, bleeding may occur or heat resistance, weather resistance, etc. may decrease, which is not preferable.

The magnesium salt and calcium salt of the organic carboxylic acid (b) used in the present invention are salts of organic carboxylic acids of magnesium and calcium, respectively, and include normal salts, acidic salts, basic salts and overbased salts. Can be used.

Examples of the organic carboxylic acid include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic 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 mixtures of 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 And ethyl benzoic acid, isopropyl benzoic acid, toluic acid, xylic acid, salicylic acid, 5-tert-octyl salicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid and the like.

The (b) hydrotalcite compound used in the present invention is, as represented by the following general formula (II), a composite salt comprising magnesium or / and an alkali metal and aluminum or zinc, magnesium and aluminum. It may be a compound which is obtained by dehydrating water of crystallization.

[0017]

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The (b) hydrotalcite compound is
It may be a natural product or a synthetic product. Examples of the method for synthesizing the synthetic product include JP-B-46-2280, JP-B-50-30039, and JP-B-51-29.
No. 129, Japanese Patent Publication No. 3-36839, Japanese Unexamined Patent Publication No.
Known methods described in JP-A-174270, JP-A-5-17952 and the like can be exemplified. Further, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter, and the like.

The (b) 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, or an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate. It may be coated with a salt, a higher fatty acid amide, a higher fatty acid ester or a wax.

The content of at least one selected from the above (ii) magnesium organic carboxylate, calcium organic carboxylate and hydrotalcite compound is as follows:
0.01 to 1 based on 100 parts by weight of vinyl chloride resin
0 parts by weight, preferably 0.1 to 5 parts by weight. If the content is less than 0.01 part by weight, the effect of addition cannot be obtained and 1
Exceeding 0 parts by weight is not preferred because the degree of coloring may become too large.

The (c) zinc salt of an organic carboxylic acid used in the present invention is a salt of an organic carboxylic acid of zinc (the organic carboxylic acid is the same as that exemplified above).
Acid salts, basic salts or overbased salts can be used.

The content of the above-mentioned (c) the zinc salt of an organic carboxylic acid is 0.01 to 100 parts by weight of the vinyl chloride resin.
10 to 10 parts by weight, preferably 0.1 to 5 parts by weight. If the content is less than 0.01 part by weight, the effect of addition cannot be obtained. If the content exceeds 10 parts by weight, blackening due to heat history during processing or use may occur, which is not preferable.

In the phosphite compound represented by the above general formula (I) used in the present invention, in the general formula (I), as the alkyl group having 1 to 4 carbon atoms represented by R Examples include groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like. Examples of the alkyl group having 1 to 20 carbon atoms represented by R ′ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl,
2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
Examples include groups such as heptadecyl, octadecyl, nonadecyl, and icosyl. Examples of the aryl group represented by R ′ include groups such as phenyl and naphthyl.
Examples of the alkylaryl group represented by R ′ include a phenyl group or a naphthyl group substituted with 1 to 5 alkyl groups exemplified above. Examples of the arylalkyl group represented by R ′ include a benzyl group and α-
Examples include methylbenzyl, α, α-dimethylbenzyl, and phenylethyl groups. 1 to 1 carbon atoms represented by A
Examples of the alkylene group of 10 include linear or branched groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene, and have 1 to 10 carbon atoms.
Examples of the alkanetriyl group include linear or branched groups such as methanetriyl, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl, octanetriyl, nonanthryl, and decanetriyl.

The phosphite compound represented by the above general formula (I) is more specifically shown below. However, the phosphite compound used in the present invention is not limited to these.

[0025]

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[0026]

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[0027]

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[0028]

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The content of (d) the phosphite compound represented by the general formula (I) used in the present invention is 0.001 to 10 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of the vinyl chloride resin. 0.01 to 5 parts by weight, 0.00
If the amount is less than 1 part by weight, the effect of use cannot be obtained, and if the amount is more than 10 parts by weight, not only is it wasteful, but there is a possibility that the coloring may be reduced, which is not preferable.

Further, the composition of the present invention comprises
In addition to the components of (d), various additives that are usually used as additives for vinyl chloride resins, for example,
Epoxy compounds, β-diketone compounds, zeolite compounds, phenolic or sulfuric antioxidants, polyols,
An ultraviolet absorber, a hindered amine-based light stabilizer, other inorganic metal compounds and the like can also be blended.

It is preferable to mix an epoxy compound with the composition of the present invention since a more excellent stabilizing effect can be obtained. 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, and epoxidized safflower oil; Methyl, -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, vinyl Cyclohexene diepoxide, dicyclohexene carboxylate, 3,4-epoxycyclohexene methyl epoxy cyclohexane carboxylate,
Bisphenol type or novolak type epoxy resin and the like can be mentioned.

Particularly, epoxidized animal and vegetable oils, especially epoxidized soybean oil, are preferable because they have an excellent stabilizing effect and are safe from natural fats and oils.

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, zinc, etc.) and the like.

The zeolite compound is an alkali or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure.
, X-, Y- and P-type zeolites, monodenite, analsite, sodalite aluminosilicates, clinobutyrolite, erionite, chabazite and the like. Crystal water of these zeolite compounds (so-called Either a hydrate containing water (zeolite) or an anhydride from which water of crystallization has been removed may be used.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,3 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] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

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.

Examples of the polyols include 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.

As the above-mentioned ultraviolet absorber, for example,
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-C ₇
~ 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)-
2- (2-hydroxyphenyl) -1,3,5-triazines such as 1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-di-tert. Tributyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-
3,5-di-tert-butyl-4-hydroxybenzoate,
Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2'-
Substituted oxanilides such as ethoxy oxanilide and 2-ethoxy-4'-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-
And cyanoacrylates such as 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, , 2,6,6-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) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2
2,6,6-pentamethyl-4-piperidyl) -1,
2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,
2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (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-morpholino- s
Triazine polycondensate, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane /
2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,
4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-
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-
Triazin-6-ylamino] undecane, 1,6,1
1-tris [2,4-bis (N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane.

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

Further, in addition to the above-mentioned various additives, a stabilizing aid usually used for a vinyl chloride resin can be added to the composition of the present invention. Examples of such a stabilizing aid include diphenylthiourea, diphenylurea, 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, crosslinking agents, antistatic agents, anti-fogging agents, plate-out inhibitors, surface treatment agents, lubricants, flame retardants, fluorescent agents,
An antifungal agent, a bactericide, a metal deactivator, a release agent, a pigment, a processing aid, an antioxidant, a light stabilizer and the like can be added.

The use of the vinyl chloride resin plastisol composition of the present invention is not particularly limited, but is excellent in hygiene and is suitable for molding of toys such as vinyl gloves and dolls.

[0044]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples.

[Examples 1-1 to 1-5 and Comparative Example 1-
1) Use the following Formulation 1 and prepare 30
The mixture was kneaded for 1 minute to prepare a plastisol composition, which was applied to a ferro-plate at a thickness of 0.7 mm, and placed in a gear oven at 180 ° C. for 5 minutes to form a test piece. The following evaluation tests were performed using the obtained test pieces.
Table 1 shows the results.

(Blend 1) Parts by weight Vinyl chloride resin (ZEST P-21 manufactured by Shin-Daiichi PVC) 100 diisononyl adipate 60 titanium dioxide 0.5 magnesium octylate 1.0 zinc octylate 0.5 Test compounds (Table below) 1.0) 1.0

(Evaluation Test) <Elubility> Test pieces were immersed in distilled water, 4% acetic acid, 20% ethanol and n-heptane, respectively, left in a gear oven at 40 ° C. for 10 days, and then tested from the test pieces. The elution amount of the compound was examined.

<Colorability> The test pieces were placed in a gear oven at 200 ° C., and the coloring over time was visually evaluated. The evaluation of the coloring property was visually performed, and the one having little coloring was set to 1, and the larger the numerical value, the lower the coloring property.

[0049]

[Table 1]

[Examples 2-1 to 2-5 and Comparative Example 2-
1] Except for using the following formulation 2 instead of the above formulation 1,
A test piece was prepared in the same manner as in Example 1-1. About the obtained test piece, the said coloring property was evaluated similarly. Table 2 shows the results.

(Blend 2) parts by weight Vinyl chloride resin (ZEST P-21 manufactured by Shin-Daiichi PVC) 100 Polyester plasticizer 50 (adipic acid / propylene glycol / n-octanol, viscosity 200 cp) Mesamol (manufactured by Bayer AG; Sulfone) Acid-based plasticizer) 50 Reelegyl (manufactured by Tokuyama Soda Co., Ltd .; silicon dioxide) 0.5 Calcium octylate 1.0 Zinc octylate 0.5 Test compound (see Table 2 below) 1.0

[0052]

[Table 2]

[Examples 3-1 to 3-5 and Comparative Example 3-
1] Except that the following formulation 3 was used instead of the above formulation 1,
A test piece was prepared in the same manner as in Example 1-1. About the obtained test piece, the said coloring property was evaluated similarly. Table 3 shows the results.

(Blending 3) parts by weight vinyl chloride resin (ZEST P-21 manufactured by Shin-Daiichi PVC) 100 polyester plasticizer 60 (adipic acid / 1,4-butanediol / lauric acid, viscosity 280 cp) DHT-4A ( (Kyowa Chemical Co., Ltd. synthetic hydrotalcite) 0.2 Zinc stearate 0.2 Test compound (see Table 3 below) 1.0

[0055]

[Table 3]

As is clear from Tables 1 to 3, when a general-purpose trisnonylphenyl phosphite was used as the phosphite compound (Comparative Examples 1-1, 2-1 and 3).
-1) When formed into a molded product, it is easily eluted by water, alcohol, or the like, and is inferior in elution. Further, the coloring property was poor, and the heat stability was insufficient.

On the other hand, the plastisol compositions of the present invention obtained by using a phosphite compound having a specific structure are described in Examples 1-1 to 1-5,
-1 to 2-5 and 3-1 to 3-5), when formed, the phosphite compound is not eluted by water, alcohol, or the like, and is excellent in colorability and thermal stability.

[0058]

The vinyl chloride resin plastisol composition of the present invention does not cause bleeding of the molded product over time, and is excellent in coloring property and heat stability. Therefore, the vinyl chloride resin plastisol composition of the present invention can be suitably used for gloves and toys requiring hygiene and the like.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 5/524 C08K 5/524 F term (reference) 2C150 AA03 BC02 FB13 FB14 FB43 FD31 4J002 BB241 BD031 BD041 BD061 BD071 BD081 BD101 BD181 DE287 EG037 EG057 EG058 EH046 EH096 EH146 EV246 EW046 EW069 FD026 FD030 FD050 FD070 GC00

Claims (4)

[Claims] 1. 100 parts by weight of a vinyl chloride resin,
(A) 30 to 200 parts by weight of a plasticizer, (b) 0.01 to 10 parts by weight of at least one selected from magnesium salts of organic carboxylic acids, calcium salts of organic carboxylic acids and hydrotalcite compounds, (c) organic carboxylic acids 0.01 to 10 parts by weight of at least one selected from zinc acid salts, and (d) at least one of 0.001 to 0.001 selected from phosphite compounds represented by the following general formula (I)
A vinyl chloride resin plastisol composition containing 10 parts by weight. Embedded image 2. The plastisol composition according to claim 1, wherein (a) the plasticizer is selected from an adipic acid ester plasticizer and a sulfonic acid ester plasticizer. 3. The plastisol composition according to claim 1, which is used for forming gloves. 4. The plastisol composition according to claim 1, which is used for toy molding.