JP2017186441A - Stabilizer composition for vinyl chloride resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the heat stability and coloring resistance of vinyl chloride resin.SOLUTION: A liquid stabilizer composition for vinyl chloride resin comprises (A) component: β-diketone compound, (B) component: at least one fatty acid metal salt selected from aromatic fatty acid metal salt, branched fatty acid metal salt, and unsaturated fatty acid metal salt, (C) component: phosphite, and (D) component: organic solvent with a boiling point of 120°C or more.SELECTED DRAWING: None

Description

  The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition excellent in thermal stability, color resistance, and heat resistance colorability.

  Vinyl chloride resin is excellent in flame retardancy, chemical resistance, mechanical stability, transparency, adhesiveness, printability, etc., and the hardness can be easily changed from hard to soft by adding a plasticizer. Therefore, it is used for various purposes. In particular, a hard vinyl chloride resin composition containing no plasticizer or a semi-rigid vinyl chloride resin composition containing a small amount of plasticizer is widely used for building materials and the like because of its excellent rigidity. Therefore, they are required to have higher performance not only during processing exposed to high temperature and pressure but also in heat stability and weather resistance as a molded product.

  In addition, in the case of hard transparent molded products, it is also used for containers that require transparency for glass, industrial boards, decorative boards, films and sheets, etc., making it a highly versatile resin. On the other hand, in addition to insufficient stability to light and heat, vinyl chloride resins have the drawback of being prone to decomposition mainly due to dehydrohalogenation during thermoforming and product use. Are known. In order to improve such drawbacks, various stabilizers such as metal salts of organic acids, organic tin compounds, organic phosphite compounds, epoxy compounds, β-diketone compounds, antioxidants, ultraviolet absorbers and the like have been conventionally used. Attempts have been made to improve the stability of vinyl chloride resins by blending (Patent Documents 1, 2, 3, 4).

  However, these conventional techniques still have problems. Even with vinyl chloride resin compositions containing the above stabilizers, the degradation of the molecular weight of vinyl chloride resins during thermoforming and product use, and decomposition due to dehydrohalogenation are completely suppressed. Not. And the problem that the vinyl chloride resin composition color | colors by the fall of the molecular weight of such a vinyl chloride resin or generation | occurrence | production of hydrogen chloride is also discovered.

Japanese Patent No. 3660562 Japanese Patent No. 2623271 Special table 2008-535997 gazette JP 2000-309671 A

  An object of the present invention is to prevent quality deterioration associated with heating of such a vinyl chloride resin composition. The present invention provides a stabilizer composition capable of giving a vinyl chloride resin composition with further improved thermal stability and color resistance, and vinyl chloride resin molding with further improved thermal stability and color resistance. The purpose is to provide goods.

  Accordingly, as a result of intensive studies to solve the above problems, the present inventors have obtained a liquid stabilizer composition obtained by dissolving a β-diketone compound, a specific fatty acid metal salt, and a phosphite in a specific organic solvent. Has been found to be effective as a stabilizer for further improving the thermal stability and coloration resistance of the vinyl chloride resin, leading to the present invention. That is, the present invention is as follows.

  (Invention 1) Component (A): 10-40% by mass of β-diketone compound, Component (B): aromatic fatty acid metal salt represented by the following general formula (1), branch represented by the following general formula (2) Fatty acid metal salt, one or more fatty acid metal salts selected from unsaturated fatty acid metal salts represented by the following general formula (3) 3 to 40% by mass, (C) component: phosphite 20 to 80% by mass, ( D) Component: 1 to 30% by mass of an organic solvent having a boiling point of 120 ° C. or higher (however, the amount of each component is the total amount of the component (A), the component (B), the component (C), and the component (D)) relative to 100 parts by mass. A liquid stabilizer composition for vinyl chloride resin.

（Ｒ^１〜Ｒ^５は、水素、炭素数が１〜６のアルキル基、炭素数が２〜６のアルケニル基から選択される基を表し、それぞれ同じでもよく、異なってもよい。ｎは２以上の整数を表す。Ｍはｎ価の金属を表す。）

(R ^{1 to} R ⁵ each represents a group selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms, and may be the same or different. N is 2 (It represents an integer above. M represents an n-valent metal.)

（Ｒ^６は炭素数が５〜１７の分岐アルキル基を表す。ｎは２以上の整数を表す。Ｍはｎ価の金属を表す 。）

(R ⁶ represents a branched alkyl group having 5 to 17 carbon atoms. N represents an integer of 2 or more. M represents an n-valent metal.)

（Ｒ^７は炭素数が７〜２１の不飽和炭化水素基を表す。ｎは２以上の整数を表す。Ｍはｎ価の金属を表す。）

(R ⁷ represents an unsaturated hydrocarbon group having ⁷ to 21 carbon atoms. N represents an integer of 2 or more. M represents an n-valent metal.)

  (Invention 2) The stabilizer composition for vinyl chloride resins according to Invention 1, wherein the component (A) comprises an acetylacetone zinc salt.

  (Invention 3) According to Invention 1 or 2, the component (B) contains both the aromatic fatty acid metal salt represented by the general formula (1) and the unsaturated fatty acid metal salt represented by the general formula (3). A stabilizer composition for vinyl chloride resin.

  (Invention 4) A vinyl chloride resin composition comprising the vinyl chloride resin and the stabilizer composition for vinyl chloride resins according to any one of Inventions 1 to 3.

  (Invention 5) The vinyl chloride resin composition of Invention 4, wherein the amount of the stabilizer composition for vinyl chloride resin is in the range of 0.3 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  (Invention 6) A molded article comprising the vinyl chloride resin composition of Invention 4 or 5.

  ADVANTAGE OF THE INVENTION According to this invention, the stabilizer composition for providing the vinyl chloride-type resin composition excellent in heat stability and coloring resistance can be provided. The stabilizer of the present invention is suitable for obtaining a molded article of a vinyl chloride resin excellent in thermal stability and coloring resistance. Moreover, if the stabilizer of this invention is used, since the molded product to which high transparency was provided simultaneously can also be obtained, the use of a vinyl chloride-type resin can be expanded also to the use for which transparency is required.

Hereinafter, the stabilizer composition for vinyl chloride resin of the present invention and the vinyl chloride resin composition using the same will be described in detail.
[(A) component: β-diketone compound]
Component (A) constituting the stabilizer composition of the present invention: β-diketone compounds include, for example, acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetyl Methane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, stearoylbenzoylmethane, bis (4-octylbenzoyl) methane, benzoyldiacetylmethane, 4- Methoxybenzoylbenzoylmethane, bis (4-carboxymethylbenzoyl) methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, Cyclohexane-1,3-dione, 3,6-dimethyl-2,4-dioxy cyclohexane -1-carboxylate, 2-acetyl cyclohexanone, dimedone, and 2-benzoyl-cyclohexane are used.

  (A) The metal salt of the compound illustrated as said (beta) -diketone compound can also be used as a component. The metal species that can provide the β-diketone metal salt are, for example, alkali metals such as lithium, sodium and potassium; magnesium, calcium, strontium, zinc, aluminum and the like.

  As the component (A), one or more compounds selected from the β-diketone compounds can be used. For coloring resistance and transparency of the vinyl chloride resin in which the stabilizer composition of the present invention is blended, such β-diketone compounds include dibenzoylmethane, stearoylbenzoylmethane, acetylacetone zinc salt, acetylacetone calcium salt, and the like. Are preferred, and acetylacetone zinc salt is more preferred.

  The amount of the component (A) in the stabilizer composition of the present invention is 10 to 40% by mass of the total amount of the stabilizer composition of the present invention. When emphasizing color resistance, the amount of component (A) is preferably 13 to 35% by mass, more preferably 15 to 30% by mass. When the amount of the component (A) is less than 10% by mass of the total amount of the stabilizer composition, the coloring resistance of the vinyl chloride resin may not be sufficiently improved. When the amount of the component (A) exceeds 40% by mass of the total amount of the stabilizer composition, the thermal stability of the vinyl chloride resin may be rather lowered.

[(B) component: fatty acid metal salt]
The component (B) constituting the stabilizer composition of the present invention is one or more fatty acid metal salts selected from aromatic fatty acid metal salts, branched fatty acid metal salts, and unsaturated fatty acid metal salts.

  The aromatic fatty acid metal salt used as the component (B) is a compound represented by the following general formula (1).

（Ｒ^１〜Ｒ^５は、水素、炭素数が１〜６のアルキル基、炭素数が２〜６のアルケニル基から選択される基を表し、それぞれ同じでもよく、異なってもよい。ｎは２以上の整数を表す。Ｍはｎ価の金属を表す。）

(R ^{1 to} R ⁵ each represents a group selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms, and may be the same or different. N is 2 (It represents an integer above. M represents an n-valent metal.)

The alkyl group having 1 to 6 carbon atoms allowed as R ^{1 to} R ^{5 in} the general formula (1) is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, A pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, an isohexyl group, a cyclohexyl group, and the like. Such an alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.

The alkenyl group having 2 to 6 carbon atoms allowed as R ^{1 to} R ^{5 in} the general formula (1) is, for example, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, an isopentenyl group, Hexenyl group etc. Such an alkenyl group is preferably an alkenyl group having 2 to 4 carbon atoms.

  The metal accepted as M in the general formula (1) is, for example, a metal having a valence of 2 or more, such as calcium, barium, aluminum, zinc, and magnesium. Of these, zinc, calcium and barium are preferred.

  Preferred examples of the aromatic fatty acid metal salt represented by the general formula (1) include zinc o-toluate, zinc m-toluate, zinc p-toluate, calcium o-toluate, and m-toluic acid. Calcium, calcium p-toluate, barium o-toluate, barium m-toluate, barium p-toluate, zinc benzoate, calcium benzoate, barium benzoate, zinc 4-tert-butylbenzoate, 4-tert -Calcium butylbenzoate, barium 4-tert-butylbenzoate, zinc 2,4-dimethylbenzoate, calcium 2,4-dimethylbenzoate, barium 2,4-dimethylbenzoate, zinc 3,5-dimethylbenzoate , Calcium 3,5-dimethylbenzoate, barium 3,5-dimethylbenzoate, zinc 2-ethylbenzoate, 3-ethylantho Kosan zinc, 4-ethyl benzoic acid zinc, 2-ethyl calcium benzoate, 3-ethyl calcium benzoate, 4-ethyl calcium benzoate.

  The branched fatty acid metal salt used as the component (B) is a compound represented by the following general formula (2).

（Ｒ^６は炭素数が５〜１７の分岐アルキル基を表す。ｎは２以上の整数を表す。Ｍはｎ価の金属を表す。）

(R ⁶ represents a branched alkyl group having 5 to 17 carbon atoms. N represents an integer of 2 or more. M represents an n-valent metal.)

Examples of the branched alkyl group having 5 to 17 carbon atoms allowed as R ^{6 in the} general formula (2) include an isopentyl group, an isohexyl group, an isoheptyl group, an isooctyl group, an isononyl group, an isodecyl group, an isodecyl group, an isododecyl group, and an isotridecyl group. Group, isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group and the like. Such a branched alkyl group is preferably a branched alkyl group having 5 to 13 carbon atoms.

  The metal accepted as M in the general formula (2) is, for example, a metal having a valence of 2 or more, such as calcium, barium, aluminum, zinc, and magnesium. Of these, zinc, calcium and barium are preferred.

  Preferred as the branched fatty acid metal salt represented by the general formula (2) are zinc 2-ethylhexanoate, calcium 2-ethylhexanoate, barium 2-ethylhexanoate, zinc versatate, calcium versatate, Versatic Barium, Zinc Isolaurate, Calcium Isolaurate, Barium Isolaurate, Zinc Isomyristate, Calcium Isomyristate, Barium Isomyristate, Zinc Isopalmitate, Calcium Isopalmitate, Barium Isopalmitate, Zinc Isostearate, Examples thereof include calcium isostearate and barium isostearate.

  The unsaturated fatty acid metal salt used as the component (B) is a compound represented by the following general formula (3).

（Ｒ^７は炭素数が７〜２１の不飽和炭化水素基を表す。ｎは２以上の整数を表す。Ｍはｎ価の金属を表す。）

(R ⁷ represents an unsaturated hydrocarbon group having ⁷ to 21 carbon atoms. N represents an integer of 2 or more. M represents an n-valent metal.)

The unsaturated hydrocarbon group permitted as R ^{7 in the} general formula (3) is preferably an unsaturated hydrocarbon group having 15 to 21 carbon atoms. The metal permitted as M in the general formula (3) is, for example, a metal having a valence of 2 or more, such as calcium, barium, aluminum, zinc, and magnesium. Of these, zinc, calcium and barium are preferred.

  Preferred as the unsaturated fatty acid metal salt represented by the general formula (3) are zinc palmitate, calcium palmitate, barium palmitate, zinc oleate, calcium oleate, barium oleate, zinc vacceate, Zinc linoleate, calcium linoleate, barium linoleate, (9,12,15) -zinc linolenate, (9,12,15) -calcium linolenate, (9,12,15) -barium linolenate, (6 , 9,12) -zinc linolenate, (6,9,12) -calcium linolenate, (6,9,12) -barenoleate, zinc eleostearate, calcium eleostearate, barium eleostearate, (8,11) -icosadienoic acid zinc, (8,11) -icosadienoic acid calcium, 5, 8, 11) - Ikosatorien zinc, (5,8,1 1, 14) - Ikosatetoraen zinc, docosapentaenoic acid zinc, zinc docosahexaenoic acid.

  As the component (B) of the present invention, one compound represented by any one of the general formulas (1), (2), and (3), two or more compounds represented by the general formula (1), Two or more compounds represented by formula (2), two or more compounds represented by formula (3), a compound represented by any one of formulas (1), (2), and (3) Any of these two or more compounds may be used. The advantage of the stabilizer composition of the present invention that a fatty acid metal salt stabilizer having a relatively low dispersibility with respect to the vinyl chloride resin can be applied to the vinyl chloride resin is that the components (B) are represented by the general formulas (1) and (2). ) And (3) are more effective when two or more kinds of compounds represented by at least one are used.

  The amount of the component (B) in the stabilizer composition of the present invention is 3 to 40% by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, heat stability, and coloration resistance in a balanced manner, the amount of component (B) is preferably 4 to 35% by mass, more preferably 5 to 30% by mass. When the amount of the component (B) is less than 1.5% by mass of the total amount of the stabilizer composition, the coloring resistance of the vinyl chloride resin may not be sufficiently improved. If the amount of the component (B) exceeds 40% by mass of the total amount of the stabilizer composition, the thermal stability of the vinyl chloride resin may rather decrease.

[(C) component: phosphite]
Examples of the component (C) constituting the stabilizer composition of the present invention include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio). ) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, Bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert Tributylphenyl) pentaerythritol diphosphite, bis (2,4-dic Ruphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) ) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4 6-tert-butylphenyl) -octadecyl phosphite, 2,2′-ethyl Bis (4,6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphos Fepin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol phosphite, tris (2,4-di-tert-butylphenyl) Phosphites such as phosphites are used. As the component (C), one type of phosphite is used alone, or a mixture of two or more types of phosphite is used.

  The amount of the component (C) in the stabilizer composition of the present invention is 20 to 80% by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, heat stability, and coloration resistance in a balanced manner, the amount of the component (C) is preferably 30 to 75% by mass, more preferably 35 to 70% by mass. When the amount of the component (C) is less than 30% by mass of the total amount of the stabilizer composition, the coloring resistance of the vinyl chloride resin may not be sufficiently improved. If the amount of the component (C) exceeds 80% by mass of the total amount of the stabilizer composition, the thermal stability of the vinyl chloride resin may rather decrease.

[(D) component: organic solvent]
Component (D) constituting the stabilizer composition of the present invention is an organic solvent having a boiling point of 120 ° C. or higher. Preferred organic solvents as component (D) are alcohol organic solvents such as 3-methoxy-n-butanol, 2-ethylhexanol, undecanol, tridecanol, and glycol organic solvents such as methyl diglycol, butyl diglycol, and methylpropylene glycol. Liquid paraffin, naphthenic solvents, aromatic hydrocarbon compounds and the like. As the component (D), such an organic solvent may be used alone, or a mixture of two or more organic solvents may be used.

  The stabilizer composition of the present invention is a liquid additive composition in which the aforementioned component (A), component (B), and component (C) are mixed and dissolved in component (D). In such a liquid stabilizer composition, it is presumed that the fatty acid metal salt contained in the component (B) forms a mixed acid metal salt.

When the stabilizer composition of the present invention is added to a vinyl chloride resin, the thermal stability and color resistance of the vinyl chloride resin can be significantly improved. The improvement effect cannot be achieved by adding the components (A), (B), and (C) alone or by adding a mixture of the components (A), (B), and (C). Is at a high level. Such an excellent vinyl chloride resin stabilizing function is presumed to be due to the mixed acid metal salt formed in the liquid stabilizer composition of the present invention.
The amount of the component (D) in the stabilizer composition of the present invention is 1 to 30% by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, thermal stability, and coloration resistance in a well-balanced manner, the amount of component (D) is preferably 1.5 to 25% by mass, more preferably 2 to 20% by mass. If the amount of the component (D) is less than 1% by mass of the total amount of the stabilizer composition, the mixed acid metal salt of the fatty acid metal salt may not be sufficiently produced, and thus the desired stabilizing function may not be obtained. When the amount of the component (D) exceeds 30% by mass of the total amount of the stabilizer composition, the thermal stability and color resistance of the vinyl chloride resin may rather be lowered.

[Consideration of mixed acid metal salts]
The presence of the mixed acid metal salt formed in the liquid stabilizer composition of the present invention is supported by the results of the following simple experiment.
-The benzoic acid and zinc hydroxide were made to react at 180-200 degreeC in the butyl diglycol (boiling point 231 degreeC) which is the solubility solvent with respect to the organic solvent of the zinc salt of benzoic acid (single). After completion of the reaction, dehydration was performed, and the reaction solution was cooled to room temperature, whereby zinc benzoate was precipitated. The saturated solubility of zinc benzoate in butyl diglycol was calculated to be less than 22.4% from the raw material charge.
Toluic acid and zinc hydroxide were reacted at 180 to 200 ° C. in butyl diglycol (boiling point 231 ° C.), which is a solubility solvent of zinc salt of toluic acid (single) in an organic solvent. After completion of the reaction, dehydration was performed, and the reaction solution was cooled to room temperature, whereby zinc toluate was precipitated. The saturated solubility of zinc toluate in butyl diglycol was calculated to be less than 25.0% from the raw material charge.
・ Reaction of benzoic acid, toluic acid, and zinc hydroxide in butyl diglycol (boiling point 231 ° C), which is a solution of zinc salt of benzoic acid and toluic acid (mixed acid) in organic solvent at 180-200 ° C I let you. After completion of the reaction, dehydration was performed, and when the reaction solution was cooled to room temperature, no precipitate was formed. Therefore, the total amount of the reaction product was dissolved in butyl diglycol at room temperature. The reaction of benzoic acid, toluic acid, and zinc hydroxide produces a zinc salt of a mixed acid consisting of benzoic acid and toluic acid, which is different from either the zinc salt of benzoic acid alone or the zinc salt of toluic acid alone. It can be presumed that no precipitate is formed due to the behavior and the solubility of this mixed acid zinc salt in butyl diglycol is extremely high.

  In the stabilizer composition of the present invention, the fatty acid metal salt is presumed to exist as a mixed acid metal salt. This assumption is that the stabilizer composition of the present invention forms a liquid composition by dissolving a relatively large amount of component (B): fatty acid metal salt in component (A), component (C), and component (D). In addition, the liquid stabilizer composition of the present invention is excellent in dispersibility with respect to the vinyl chloride resin, and is therefore consistent with the effect of improving the heat stability of the vinyl chloride resin. Based on this assumption, linear fatty acid salts that are solid and have low solubility in organic solvents are not suitable as components of the stabilizing composition of the present invention.

[Optional components: (E) component, (F) component]
In view of the effect of further improving the heat resistance and coloring resistance of the vinyl chloride resin, the stabilizer composition of the present invention may further contain a phenolic antioxidant (component (E)). Examples of the phenolic antioxidant that can be added to the stabilizer composition of the present invention include 2,6-ditert-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, thiodiethylene glycol bis [(3,5-di-tert-butyl-4- Hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl- 4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methyl Bis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) Butyric acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondary butyl-6-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-butyl) Yl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4) -Hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-Ditert-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-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10 Tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like are used.

  The amount of the component (E) in the stabilizer composition of the present invention: phenolic antioxidant is 0.01 to 10% by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, heat stability, and coloration resistance in a balanced manner, the amount of the component (E) is preferably 0.03 to 8% by mass, more preferably 0.05 to 7% by mass. When the amount of the component (E) is less than 0.01% by mass of the total amount of the stabilizer composition, the coloring resistance of the vinyl chloride resin may not be sufficiently improved. When the amount of the component (E) exceeds 10% by mass of the total amount of the stabilizer composition, the transparency of the vinyl chloride resin may be lowered.

In consideration of the processability, heat resistance and coloration resistance of the vinyl chloride resin, the stabilizer composition of the present invention further contains a hydrotalcite compound (component (F)) represented by the following general formula (4). It is also possible to make it.
Mg _x1 Zn _x2 Al ₂ (OH) _{2x1 + 2x2 + 4} (CO ₃ ) _{1-y1 / 2} (ClO ₄ ) _y1 mH ₂ O
... (4)
(In the formula [4], x1, x2 and y1 represent numbers satisfying the conditions represented by the following formulas, 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 <20, 0 ≦ y1 ≦ 2, respectively, Represents 0 or any integer).

  As such a hydrotalcite compound, magnesium and aluminum, or a double salt compound composed of zinc, magnesium and aluminum is preferably used. Moreover, what dehydrated crystal water may be used. Such a hydrotalcite compound may be a natural product or a synthetic product. There is no restriction | limiting in the crystal structure of the said hydrotalcite compound, a crystal particle diameter, etc.

  Further, as the hydrotalcite compound, the surface thereof is higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal salt such as alkali metal dodecylbenzenesulfonate, higher fatty acid amide, Those coated with higher fatty acid esters or waxes can also be used.

  In the present invention, the hydrotalcite-based compound may be used alone or in combination of two or more. The amount of the component (F) in the stabilizer composition of the present invention: hydrotalcite compound is 0.1 to 50% by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, heat stability, and coloration resistance in a well-balanced manner, the amount of the component (E) is preferably 0.3 to 45% by mass, more preferably 0.5 to 30% by mass. When the amount of the component (E) is less than 0.1% by mass of the total amount of the stabilizer composition, the thermal stability of the vinyl chloride resin cannot be sufficiently improved. When the amount of the component (E) exceeds 50% by mass of the total amount of the stabilizer composition, the coloring resistance of the vinyl chloride resin may rather be lowered.

[Vinyl chloride resin]
There is no restriction | limiting in the vinyl chloride-type resin which is the application object of the stabilizer composition of this invention. As such a vinyl chloride resin, those obtained by any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used without limitation. Examples of such vinyl chloride resins include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride- Propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile Copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic ester Copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylic ester Rononitrile copolymers, vinyl chloride resins such as vinyl chloride-various vinyl ether copolymers, and their blends or other synthetic resins not containing chlorine, such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene Copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, blends with polyesters, block copolymers, graft copolymers, and the like can be used.

[Other additives for vinyl chloride resin]
When the stabilizer composition of the present invention is added to the vinyl chloride resin, a lubricant can be further added in consideration of processability. Examples of the lubricant include hydrocarbon lubricants such as low molecular wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, and fluorocarbon; natural wax lubricants such as carnauba wax and candelilla wax; lauric acid, stearic acid, and behenic acid Fatty acid lubricants such as higher fatty acids such as oxyfatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, oleylamide, or alkylenebisfats such as methylenebisstearylamide, ethylenebisstearylamide Aliphatic amide lubricants such as aliphatic amides; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, distearyl phthalate, glycerin tristearate, sorbitan tristearate Fatty acid polyhydric alcohol ester compounds such as rate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, polyglycerin polyricinoleate, hydrogenated castor oil, or monovalent like adipic acid / stearic acid ester of dipentaerythritol Fatty acid alcohol-based lubricants such as fatty acid and polybasic organic acid and polyhydric alcohol compound ester compounds; fatty alcohol-based lubricants such as stearyl alcohol, lauryl alcohol, palmityl alcohol; metal soaps; partially saponified montanic acid esters Montanic acid type lubricants such as; acrylic type lubricants; silicone oils and the like are used. Only one kind of these lubricants may be used, or two or more kinds of lubricants may be used in combination.

  The addition amount of the lubricant with respect to the vinyl chloride resin is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and preferably 0.05 to 3.0 parts by mass from the viewpoint of workability. If the content of the lubricant is less than 0.01 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, the processability of the vinyl chloride resin may be insufficient. When the content of the lubricant exceeds 5.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, there is a decrease in performance such as a decrease in transparency.

  When the stabilizer composition of the present invention is added to the vinyl chloride resin, a processing aid can be further added in consideration of processability. The processing aid can be appropriately selected from known processing aids. A preferred processing aid is an acrylic acid processing aid. As such processing aids, for example, homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; co-polymerization of the above alkyl methacrylates with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate Copolymer; Copolymer of the above alkyl methacrylate with an aromatic vinyl compound such as styrene, α-methyl styrene, vinyl toluene; Copolymer of the above alkyl methacrylate with a vinyl cyan compound such as acrylonitrile, methacrylonitrile, etc. Can be used. Only one type of these processing aids may be used, or two or more processing aids may be used in combination.

The amount of the processing aid added to the vinyl chloride resin is preferably 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. If the content of the processing aid is less than 0.01 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, the processability of the vinyl chloride resin may be insufficient. When the content of the processing aid exceeds 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, there is a decrease in performance such as a decrease in transparency.
In addition to the stabilizer composition, other additives usually used in vinyl chloride resins such as plasticizers, polyethers, organic acid metal salts other than the above metal soaps, zeolite compounds, perchlorates, epoxy Compounds, antioxidants such as phenols and sulfurs, ultraviolet absorbers, hindered amine light stabilizers, fillers, flame retardants, flame retardant aids and the like can also be blended within a range that does not impair the effects of the present invention.

  Examples of the plasticizer include phthalate plasticizers such as dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; dioctyl adipate, diisononyl adipate , Diisodecyl adipate, di (butyl diglycol) adipate and other adipate plasticizers; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (Butoxyethyl) phosphate, octyl diphenyl phosphate, etc. Sulfate plasticizer; 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 other polyhydric alcohols, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid Polyester plasticizers using dibasic acids such as acids and using monohydric alcohols and monocarboxylic acids as stoppers if necessary; tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid plasticizers, stearin Acid plasticizer, citric acid plasticizer, toner Trimellitate-based plasticizers, pyromellitic acid plasticizers, and biphenylene polycarboxylic acid plasticizer used. These plasticizers may be used alone or in combination of two or more.

  Examples of the polyether include pentaerythritol, dipentaerythritol, polypentaerythritol, sorbitol, mannitol, maltitol, lactitol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, lactose, trimethylolpropane, ditritol. Methylolpropane, pentaerythritol or stearic acid partial ester of dipentaerythritol, bis (dipentaerythritol) adipate, glycerin, diglycerin, tris (2-hydroxyethyl) isocyanurate, and the like are used. These may be used alone or in combination of two or more.

  As the organic acid metal salt other than the metal soap, metal (sodium, potassium, calcium, barium, aluminum, magnesium, zinc) salts of phenols and organic phosphoric acids are used.

  Examples of the phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexyl. Phenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofuxylphenol, methyl tertiary octylphenol and the like are used.

  Examples of the organic phosphoric acid include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, and the like. Used.

  The metal salts of the phenols and organic phosphoric acids may be acid salts, neutral salts, basic salts, or overbased complexes obtained by neutralizing a part or all of the bases of the basic salts with carbonic acid.

  The zeolite compound is an alkali or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure. Typical examples are A-type, X-type, Y-type and P-type zeolites, monodenite, analsite, sodalite group aluminosilicate, clinoptilolite, erionite and chabasite. These zeolitic compounds may be either a hydrate containing crystal water (so-called zeolite water) or an anhydride from which crystallization water has been removed. As these zeolite compounds, those having a particle size of 0.1 to 50 μm can be used, and those having a particle size of 0.5 to 10 μm are particularly preferable.

  Examples of the perchlorates include metal perchlorate, ammonium perchlorate, perchloric acid-treated hydrotalcite, and perchloric acid-treated silicate. Examples of the metal constituting the perchloric acid metal salt include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum. The perchloric acid metal salt may be an anhydride or a hydrated salt, and may be a solution dissolved in an alcohol or ester solvent such as butyl diglycol or butyl diglycol adipate, or a dehydrate thereof.

  Examples of the epoxy compound include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, Epoxidized tall oil fatty acid octyl, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, -2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2- Epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate And bis (3,4-epoxycyclohexyl) adipate.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Propionic acid esters are used.

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

  Examples of the hindered amine light stabilizer include 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 ( , 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-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis ( N-butyl- -(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-triazin-6-ylamino ] Undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino A hindered amine compound such as undecane is used.

  Examples of the filler include calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium aluminate silicate, hydrokarma Ito, aluminum silicate, magnesium silicate, calcium silicate, silicate metal salts such as zeolite, activated clay, talc, clay, bengara, asbestos, antimony trioxide, silica, glass beads, mica, sericite, glass flakes, Asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber, aramid fiber, etc. are used.

  Examples of the flame retardant and flame retardant aid include triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogen flame retardants, silicon flame retardants, phosphate ester flame retardants, condensed phosphate ester flame retardants, Intomesent flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, organic flame retardant aids, and the like are used.

  Examples of the triazine ring-containing compound include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Dimelamine, tetramethylene dimethylamine, hexamethylene dimethylamine, 1,3-hexylene dimeramine and the like are used.

  As the metal hydroxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide or the like is used.

  Examples of the phosphate ester flame retardant include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl Phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t -Butylphenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (isopropylphosphate) Le) diphenyl phosphate, tris - (isopropyl phenyl) phosphate is used.

  Examples of the condensed phosphate ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. As the system flame retardant, an ammonium salt or amine salt of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, piperazine pyrophosphate, or the like is used.

  As said other inorganic type flame retardant adjuvant, various commercial items, such as inorganic compounds, such as a zinc oxide, a titanium oxide, aluminum oxide, magnesium oxide, a talc, and its surface treatment products, can be used, for example.

  Furthermore, in addition to the stabilizer composition of the present invention, a stabilizing aid usually used for a vinyl chloride resin can be added within a range that does not impair the effect of the stabilizer composition of the present invention. As such a stabilizing aid, for example, diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid and the like are used.

  Furthermore, additives usually used for vinyl chloride resins as required, such as crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents, surface treatment agents, fluorescent agents, antifungal agents, bactericides, foaming An agent, a metal deactivator, a release agent, a pigment, an antioxidant, a light stabilizer and the like can be blended within a range not impairing the effect of the stabilizer composition of the present invention.

[Vinyl chloride resin composition]
The vinyl chloride resin composition of the present invention includes a vinyl chloride resin and the above-described stabilizer composition of the present invention. The content of the stabilizer composition in the vinyl chloride resin composition of the present invention is 0.3 to 10 parts by mass, preferably 0.5 to 8 parts by mass, more preferably 100 parts by mass of the vinyl chloride resin. Is 0.8-5 parts by mass.

〔Molding〕
The vinyl chloride resin composition of the present invention can be molded by any known molding method such as extrusion molding, melt casting, pressure molding, calendar molding, and the like. The vinyl chloride resin composition of the present invention can be used particularly for sheet-like molded products, and the obtained sheets are widely used as building materials, building interior products, daily necessities, stationery, miscellaneous goods and the like.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited by the following examples. In the following examples and the like, “%” is based on mass unless otherwise specified. The formulation of each table is indicated by the amount (mass) of the materials and compounds used.

[Production of Stabilizer Composition: Examples 1 to 5 and Comparative Examples 1 and 2]
Various compounds were dissolved in an organic solvent according to the formulation shown in Table 1 to produce a liquid composition. Thus, the stabilizer composition of the present invention (Examples 1 to 5) and the comparative stabilizer composition (Comparative Examples 1 and 2) were produced.

[Production and Evaluation of Vinyl Chloride Resin Composition: Examples 6 to 10 and Comparative Examples 3 and 4]
A vinyl chloride resin, a stabilizer composition, and other additives were blended with a Henschel mixer according to the formulation shown in Table 2. Thus, a vinyl chloride resin composition of the present invention (Examples 6 to 10) and a comparative vinyl chloride resin composition (Comparative Examples 3 and 4) were obtained. The blend was calendered to create a sheet. (Roll kneading conditions: 180 ° C. × 30 rpm × 0.6 mm) The obtained sheets were evaluated by the following test methods. The evaluation results are shown in Table 3.

Decomposition test The time (decomposition time) from the start of roll kneading at 180 ° C. until the sheet no longer peeled off from the roll due to thermal decomposition of the sheet was measured. The longer the decomposition time, the better the thermal stability of the sheet. A sheet having a decomposition time of 20 minutes or less cannot withstand actual use.

-Dynamic thermal stability test Roll kneading was started at 180 ° C, and sheet samples were taken every 3 minutes. The sampling time at which blackening was first observed in the collected sheets was defined as the blackening time (minutes). The longer the blackening time, the better the thermal stability of the sheet in the dynamic environment. Sheets with a blackening time of 15 minutes or less cannot withstand actual use.

・ Static thermal stability test
A sheet sample was taken 3 minutes after starting roll kneading at 180 ° C. The sheet sample was heated in a gear oven having an internal temperature of 190 ° C and a gear oven having an internal temperature of 200 ° C. The time (blackening time) from the start of heating to the blackening of the sheet sample in each gear oven was measured. The longer the blackening time, the better the thermal stability of the sheet in a static environment. A sheet having a blackening time of 40 minutes or less when heated at 190 ° C. cannot withstand actual use. A sheet having a blackening time of 20 minutes or less when heated at 200 ° C. cannot withstand actual use.

Color resistance test A sheet sample was collected 3 minutes after starting roll kneading at 80 ° C. The sheet sample was analyzed according to JIS K7373. I value (Yellowness Index) was calculated. Y. The smaller the I value, the better the color resistance of the sheet. Y. A sheet having an I value exceeding 10 cannot withstand actual use.

Notes to Table 1 * 1: Octyl diphenyl phosphite * 2: Tridecyl phosphite * 3: 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5 5] Undecane

Note 2 in Table 2 * 4: TK-700 (Shin-Etsu Chemical Co., Ltd.)
* 5: PA-20 (manufactured by Kaneka)
* 6: G-72 (made by Emery Oleo Chemicals Japan)
* 7: Tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane * 8: Zinc-modified hydrotalcite

  As the results in Table 3 show, the vinyl chloride resin compositions of Examples 6 to 10 containing the stabilizer composition of the present invention are excellent in both thermal stability and color resistance. On the other hand, the vinyl chloride resin compositions of Comparative Examples 3 and 4 that do not contain the stabilizer composition of the present invention are inferior in both thermal stability and color resistance. In Comparative Example 3, the linear fatty acid salt calcium laurate and zinc stearate are blended, and both the thermal stability and the color resistance are inferior. The linear fatty acid salt forms a mixed acid metal salt. Support the guess that it is difficult.

[Production and Evaluation of Vinyl Chloride Resin Composition: Comparative Example 5]
First, the stabilizer composition 5-1, 5-2, 5-3, 5-4 was manufactured by the prescription shown in Table 4. Next, a vinyl chloride resin, a stabilizer composition, and other additives were kneaded according to the formulation shown in Table 5 to produce pellets 5-1, 5-2, 5-3, and 5-4. * 1 to * 10 in Tables 4 and 5 follow the above-mentioned comments. Pellets 5-1, 5-2, 5-3, and 5-4 were blended in the same amount ratio. Thus, a comparative vinyl chloride resin composition (Comparative Example 5) was obtained. This vinyl chloride resin composition was molded in the same manner as in Examples 6 to 10 and Comparative Examples 3 and 4. Table 6 shows the evaluation results of the obtained sheet.

  The vinyl chloride resin composition of Comparative Example 5 contains all the compounds corresponding to the (A) component, (B) component, (C) component, and (D) component of the present invention. However, in the vinyl chloride resin composition of Comparative Example 5, a part of the component (B) is converted into a vinyl chloride resin composition without going through a state of being liquefied together with the components (A), (C), and (D). It is blended. Surprisingly, the vinyl chloride resin composition of Comparative Example 5 is greatly inferior in thermal stability as compared with Examples 6-10. It is speculated that the stabilizer composition 5-1, 5-2, 5-3, 5-4 used in Comparative Example 5 is not formed with a sufficient mixed acid of fatty acids to exhibit an excellent stabilizer effect. The

  From the results of Examples and Comparative Examples, the stabilizer composition of the present invention is a mixture of a predetermined amount of (A) component, (B) component, (C) component, and (D) component to form a liquid composition. As a result, it can be seen that the excellent stabilizing action of the vinyl chloride resin, which could not be achieved by the conventional stabilizer, is exhibited.

  The stabilizer composition of the present invention has an extremely high vinyl chloride resin stability function that could never be achieved by a conventional stabilizer blending method, even though the raw material is a compound that has been conventionally used as a stabilizer. Have. Such a stabilizer composition of the present invention is an innovative additive for a vinyl chloride resin. The vinyl chloride resin composition of the present invention exhibits extremely high resistance to heat history during processing and use. Therefore, the vinyl chloride resin composition of the present invention maintains the advantages such as strength and flexibility of the vinyl chloride resin, and a molded product with good color tone can be obtained. The present invention is expected to improve the quality of various products using a vinyl chloride resin, particularly sheet materials.

Claims (6)

(A) component: β-diketone compound 10 to 40% by mass, (B) component: aromatic fatty acid metal salt represented by the following general formula (1), branched fatty acid metal salt represented by the following general formula (2), One or more fatty acid metal salts selected from unsaturated fatty acid metal salts represented by the following general formula (3) 3 to 40% by mass, (C) component: phosphite 20 to 80% by mass, (D) component: 1-30 mass% of organic solvents having a boiling point of 120 ° C. or higher (however, the amounts of the above components indicate the total amount of component (A), component (B), component (C), component (D)) based on 100 parts by mass. A liquid stabilizer composition for vinyl chloride resin.

(R ^{1 to} R ⁵ each represents a group selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms, and may be the same or different. N is 2 (It represents an integer above. M represents an n-valent metal.)

(R ⁶ represents a branched alkyl group having 5 to 17 carbon atoms. N represents an integer of 2 or more. M represents an n-valent metal.)

(R ⁷ represents an unsaturated hydrocarbon group having ⁷ to 21 carbon atoms. N represents an integer of 2 or more. M represents an n-valent metal.) The stabilizer composition for vinyl chloride resins according to claim 1, wherein the component (A) comprises an acetylacetone zinc salt. The component (B) contains both of the aromatic fatty acid metal salt represented by the general formula (1) and the unsaturated fatty acid metal salt represented by the general formula (3). A stabilizer composition for vinyl resins. A vinyl chloride resin composition comprising a vinyl chloride resin and a stabilizer composition for a vinyl chloride resin according to any one of claims 1 to 3. The vinyl chloride resin composition according to claim 4, wherein the amount of the stabilizer composition for vinyl chloride resin is in the range of 0.3 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.   A molded article comprising the vinyl chloride resin composition according to claim 4 or 5.