JP6871682B2 - Stabilizer composition for vinyl chloride resin - Google Patents

Description

The present invention relates to a vinyl chloride-based resin composition, and more particularly to a vinyl chloride-based resin composition having excellent thermal stability, coloring resistance, and heat-resistant coloring property.

Vinyl chloride resin has excellent 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-hard vinyl chloride resin composition containing a small amount of plasticizer is widely used as a building material because of its excellent rigidity. Therefore, they are required to have higher performance not only during processing exposed to high temperature and high pressure, but also in thermal stability and weather resistance as molded products.

In the case of hard transparent molded products, it is also used for containers, industrial boards, decorative boards, films, sheets, etc. that require transparency for glass, making it a highly versatile resin. On the other hand, vinyl chloride-based resins have a drawback that they are not sufficiently stable against light and heat, and that they are prone to decomposition mainly due to hydrogen dehalogenation during heat molding 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, and ultraviolet absorbers have been conventionally used. Attempts have been made to improve the stability of vinyl chloride-based resins by blending them (Patent Documents 1, 2, 3, and 4).

However, these conventional techniques still have problems. Even in the vinyl chloride resin composition containing the above stabilizer, the decrease in the molecular weight of the vinyl chloride resin during heat molding and the use of the product and the decomposition due to hydrogen dehalogenation are completely suppressed. Not. Then, it has been found that the vinyl chloride resin composition is colored due to the decrease in the molecular weight of the vinyl chloride resin and the generation of hydrogen chloride.

Japanese Patent No. 3660562 Japanese Patent No. 2623271 Japanese Patent Application Laid-Open No. 2008-535997 Japanese Unexamined Patent Publication No. 2000-309671

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

Therefore, as a result of diligent studies to solve the above problems, the present inventors have made a liquid stabilizer composition obtained by dissolving a β-diketone compound, a specific fatty acid metal salt, and a phosphite ester in a specific organic solvent. However, they have found that they are effective as a stabilizer for further improving the thermal stability and color resistance of vinyl chloride resins, and have reached the present invention. That is, the present invention is as follows.

(Invention 1) Component (A): 10 to 40 parts 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, 3 to 40 parts by mass of one or more fatty acid metal salts selected from unsaturated fatty acid metal salts represented by the following general formula (3), component (C): 20 to 80 parts by mass of phosphite ester, ( D) Component: 1 to 30 parts by mass of an organic solvent having a boiling point of 120 ° C. or higher (However, the amount of each of the above components is the total amount of (A) component, (B) component, (C) component, and (D) component : with respect to 100 parts by mass. shows the percentage.) including, a vinyl chloride resin for liquid stabilizer composition,
The component (D) is an alcohol-based organic solvent having a boiling point of 120 ° C. or higher.
From an alcohol-based organic solvent having a boiling point of 120 ° C. or higher, a liquid paraffin having a boiling point of 120 ° C. or higher, a naphthenic solvent having a boiling point of 120 ° C. or higher, and one or more organic solvents selected from aromatic hydrocarbon compounds having a boiling point of 120 ° C. or higher. Mixture,
Glycol-based organic solvent with boiling point of 120 ° C or higher and 231 ° C or lower,
One or more organic solvents selected from glycol-based organic solvents with a boiling point of 120 ° C. or higher and 231 ° C. or lower, liquid paraffins with a boiling point of 120 ° C. or higher, naphthenic solvents with a boiling point of 120 ° C. or higher, and aromatic hydrocarbon compounds with a boiling point of 120 ° C. or higher. And a mixture of
A liquid stabilizer composition for a vinyl chloride resin, which is one of the above .

（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 represent 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, respectively. N is 2. Represents the above integer. 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 a vinyl chloride resin according to Invention 1, wherein the component (A) contains an acetylacetone zinc salt.

(Invention 3) The component (B) of Invention 1 or 2 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). Stabilizer composition for vinyl chloride resin.

(Invention 4) A vinyl chloride resin composition containing a vinyl chloride resin and a stabilizer composition for a vinyl chloride resin 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 a 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 product comprising the vinyl chloride resin composition of Invention 4 or 5.

According to the present invention, it is possible to provide a stabilizer composition for providing a vinyl chloride resin composition having excellent thermal stability and color resistance. The stabilizer of the present invention is suitable for obtaining a molded product of a vinyl chloride resin having excellent thermal stability and color resistance. Further, by using the stabilizer of the present invention, it is possible to obtain a molded product having high transparency at the same time, so that the use of the vinyl chloride resin can be expanded to the use requiring transparency.

Hereinafter, the stabilizer composition for a vinyl chloride resin of the present invention and the vinyl chloride resin composition using the same will be described in detail.
[Component (A): β-diketone compound]
The 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. Methan, stearoyl acetyl methane, phenyl acetyl acetyl methane, dicyclohexyl carbonyl methane, benzoyl formyl methane, benzoyl acetyl methane, dibenzoyl methane, octyl benzoyl methane, stearoyl benzoyl methane, bis (4-octyl benzoyl) methane, benzoyl diacetyl methane, 4- Methoxybenzoylbenzoylmethane, bis (4-carboxymethylbenzoyl) methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, cyclohexane-1,3-dione, 3,6-dimethyl-2,4-dioxycyclohexane-1 Methyl carboxylate, 2-acetylcyclohexanone, dimedone, 2-benzoylcyclohexane and the like are used.

As the component (A), a metal salt of the compound exemplified as the β-diketone compound can also be used. 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 above β-diketone compounds can be used. For the color resistance and transparency of the vinyl chloride resin to 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. Is preferable, and acetylacetone zinc salt is more preferable.

The amount of the component (A) in the stabilizer composition of the present invention is 10 to 40 parts by mass of the total amount of the stabilizer composition of the present invention. When emphasis is placed on color resistance, the amount of the component (A) is preferably 13 to 35 parts by mass, more preferably 15 to 30 parts by mass. If the amount of the component (A) is less than 10 parts 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 (A) exceeds 40 parts by mass of the total amount of the stabilizer composition, the thermal stability of the vinyl chloride resin may be rather lowered.

[Component (B): 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 represent 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, respectively. N is 2. Represents the above integer. M represents an n-valent metal.)

^{The alkyl group having 1 to 6 carbon atoms allowed as R 1 to} R ⁵ of 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, and the like. A pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, an isohexyl group, a cyclohexyl group and the like. As such an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable.

^{The alkenyl group having 2 to 6 carbon atoms allowed as R 1 to} R ⁵ of 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, and the like. Hexenyl groups are equal. As such an alkenyl group, an alkenyl group having 2 to 4 carbon atoms is preferable.

The metal permitted as M in the general formula (1) is a metal having a divalent value or higher, such as calcium, barium, aluminum, zinc, and magnesium. Of these, zinc, calcium and barium are preferable.

Preferred aromatic fatty acid metal salts represented by the general formula (1) are o-zinc o-toluic acid, zinc m-toluic acid, zinc p-toluic acid, calcium o-toluic acid, and m-toluic acid. Calcium, calcium p-toluic acid, barium o-toluic acid, barium m-toluic acid, barium p-toluic acid, zinc benzoate, calcium benzoate, barium benzoate, 4-tert-butyl zinc benzoate, 4-tert -Calcium butyl benzoate, barium 4-tert-butyl benzoate, zinc 2,4-dimethyl benzoate, calcium 2,4-dimethyl benzoate, barium 2,4-dimethyl benzoate, zinc 3,5-dimethyl benzoate , Calcium 3,5-dimethylbenzoate, barium 3,5-dimethylbenzoate, zinc 2-ethylbenzoate, zinc 3-ethylbenzoate, zinc 4-ethylbenzoate, calcium 2-ethylbenzoate, 3-ethyl Calcium benzoate, 4-ethyl calcium benzoate and the like.

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.)

Branched alkyl group having a carbon number of 5-17, which is acceptable R ⁶ in formula (2) are, for example, isopentyl group, isohexyl group, isoheptyl group, isooctyl group, an isononyl group, an isodecyl group, isoundecyl group, isododecyl group, isotridecyl Group, isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group and the like. As such a branched alkyl group, a branched alkyl group having 5 to 13 carbon atoms is preferable.

The metal permitted as M in the general formula (2) is a metal having a divalent value or higher, such as calcium, barium, aluminum, zinc, and magnesium. Of these, zinc, calcium and barium are preferable.

Preferred as the branched fatty acid metal salt represented by the general formula (2) are zinc 2-ethylhexanate, calcium 2-ethylhexanoate, barium 2-ethylhexanoate, zinc versaticate, calcium versaticate, and the like. Barium Versatic Acid, Zinc Isolaurate, Calcium Isolaurate, Barium Isolaurate, Zinc Isomiristate, Calcium Isomiristinate, Barium Isomylistate, Zinc Isopalmitate, Calcium Isopalmitate, Barium Isopalmitate, Zinc Isostearate, Calcium isostearate, barium isostearate and the like.

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.)

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 a metal having a divalent value or higher, such as calcium, barium, aluminum, zinc, and magnesium. Of these, zinc, calcium and barium are preferable.

Preferable unsaturated fatty acid metal salts represented by the general formula (3) are zinc palmitereate, calcium palmitereate, barium palmitereate, zinc oleate, calcium oleostear, barium oleate, zinc baxenoate, and the like. Zinc linoleate, calcium linoleate, barium linolenate, (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) -Barium linolenate, Zinc eleostearate, Calcium eleostearate, Barium eleostearate, (8,11) -Zinc icosadienate, (8,11) -Calcium icosadientate, (5,8,11) -Zinc icosatorienate, (5,8,11,14) -Zinc icosatetetraenoate, docosapentaenoic acid Zinc, zinc docosahexaene, etc.

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

The amount of the component (B) in the stabilizer composition of the present invention is 3 to 40 parts by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, thermal stability, and color resistance in a well-balanced manner, the amount of the component (B) is preferably 4 to 35 parts by mass, more preferably 5 to 30 parts by mass. If the amount of the component (B) is less than 1.5 parts 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 parts by mass of the total amount of the stabilizer composition, the thermal stability of the vinyl chloride resin may be rather lowered.

[Component (C): Phosphite ester]
As the component (C) constituting the stabilizer composition of the present invention, for example, trisnonylphenyl phosphite, tris [2-third butyl-4- (3-third butyl-4-hydroxy-5-methylphenylthio) )-5-Methylphenyl] Phosphite, Tridecylphosphite, Octyldiphenylphosphite, Di (decyl) monophenylphosphite, Di (tridecyl) pentaerythritol diphosphite, Di (nonylphenyl) pentaerythritol diphosphite, Bis (2,4-ditertiary butylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiary butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,5-trith) Tributylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropyridene diphenol diphosphite, tetra (tridecyl) -4,4'-n- Butyldenbis (2-tertiary butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-third butylphenyl) butanetriphosphite, tetrakis (2) , 4-Ditertiary Butylphenyl) Biphenylenediphosphonite, 9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide, 2,2'-Methylenebis (4,6-3rd Butyl) Phenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-tertiary butylphenyl) -octadecylphosphite, 2,2'-ethylidenebis (4,6-ditrith butylphenyl) fluorophos Fight, Tris (2-[(2,4,8,10-tetrax tertiary butyldibenzo [d, f] [1,3,2] dioxaphosfepin-6-yl) oxy] ethyl) amine, 2 Subphosphate esters such as phosphite of -ethyl-2-butylpropylene glycol and 2,4,6-tritriternal butylphenol and tris (2,4-di-3-butylphenyl) phosphite are used. As the component (C), one kind of phosphite ester is used alone, or a mixture consisting of two or more kinds of phosphite ester is used.

The amount of the component (C) in the stabilizer composition of the present invention is 20 to 80 parts by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, thermal stability, and color resistance in a well-balanced manner, the amount of the component (C) is preferably 30 to 75 parts by mass, more preferably 35 to 70 parts by mass. If the amount of the component (C) is less than 30 parts 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 parts by mass of the total amount of the stabilizer composition, the thermal stability of the vinyl chloride resin may be rather lowered.

[(D) component: organic solvent]
The 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 the component (D) are alcohol-based organic solvents such as 3-methoxy-n-butanol, 2-ethylhexanol, undecanol, and tridecanol, and glycol-based organic solvents such as methyldiglycol, butyldiglycol, and methylpropylene glycol. , Liquid paraffin, naphthenic solvent, aromatic hydrocarbon compound, etc. Such an organic solvent may be used alone as the component (D), or a mixture of two or more kinds of organic solvents may be used.

The stabilizer composition of the present invention is a liquid additive composition in which the above-mentioned components (A), (B) and (C) are mixed and dissolved in the 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 remarkably improved. The improving effect cannot be achieved by adding the above-mentioned components (A), (B) and (C) alone or by adding a mixture of the above-mentioned components (A), (B) and (C). At a high level. It is presumed that such an excellent vinyl chloride resin stabilizing function is 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 parts by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, thermal stability, and color resistance in a well-balanced manner, the amount of the component (D) is preferably 1.5 to 25 parts by mass, more preferably 2 to 20 parts by mass. If the amount of the component (D) is less than 1 part 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 therefore the desired stabilizing function may not be obtained. If the amount of the component (D) exceeds 30 parts by mass of the total amount of the stabilizer composition, the thermal stability and color resistance of the vinyl chloride resin may be rather deteriorated.

[Discussion on mixed acid metal salt]
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 experiments.
-Solubility of zinc salt of benzoic acid (alone) in an organic solvent In butyl diglycol (boiling point 231 ° C), benzoic acid and zinc hydroxide were reacted at 180 to 200 ° C. After the reaction was completed, dehydration was performed and the reaction solution was cooled to room temperature to precipitate zinc benzoate. The saturated solubility of zinc benzoate in butyl diglycol was calculated to be less than 22.4% from the amount of raw material charged.
-Solubility of zinc salt of toluic acid (alone) in an organic solvent In butyl diglycol (boiling point 231 ° C), toluic acid and zinc hydroxide were reacted at 180 to 200 ° C. After the reaction was completed, dehydration was performed and the reaction solution was cooled to room temperature to precipitate zinc toluate. The saturated solubility of zinc toluate in butyl diglycol was calculated to be less than 25.0% from the amount of raw material charged.
-Reacts benzoic acid, p-toluic acid, and zinc hydroxide in butyl diglycol (boiling point 231 ° C), which is a solvent for dissolving a zinc salt (mixed acid) of benzoic acid and toluic acid in an organic solvent, at 180 to 200 ° C. I let you. After the reaction was completed, dehydration was performed and the reaction solution was cooled to room temperature, and no precipitate was formed. Therefore, the entire 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, and this zinc mixed acid salt is different from the zinc salt of benzoic acid alone and the zinc salt of toluic acid alone. It can be inferred that the behavior is shown and that no precipitate is formed because the solubility of this zinc mixed acid salt in butyl diglycol is extremely high.

It is presumed that the fatty acid metal salt also exists as a mixed acid metal salt in the stabilizer composition of the present invention. This speculation is that in the stabilizer composition of the present invention, a relatively large amount of the component (B): fatty acid metal salt is dissolved in the component (A), the component (C), and the component (D) to form a liquid composition. This is consistent with the fact that the liquid stabilizer composition of the present invention is excellent in dispersibility with respect to the vinyl chloride resin and therefore has an excellent effect of improving the heat resistance stability of the vinyl chloride resin. Based on this speculation, straight chain fatty acid salts, which are solid and have low solubility in organic solvents, are not suitable as components of the stabilizing composition of the present invention.

[Optional component: (E) component, (F) component]
It is also possible to further add a phenolic antioxidant (component (E)) to the stabilizer composition of the present invention in anticipation of the effect of further improving the heat resistance and color resistance of the vinyl chloride resin. Examples of the phenolic antioxidant that can be added to the stabilizer composition of the present invention include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,). 5-Ditertiary Butyl-4-Hydroxyphenyl) -Propionate, Distearyl (3,5-Ditertiary Butyl-4-Hydroxybenzyl) Phosphonate, Thiodiethylene Glycolbis [(3,5-Ditertiary Butyl-4-) (Hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditertiary butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditertiary butyl-) 4-Hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tertiary butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tertiary butylphenol), 2,2' -Methylenebis (4-ethyl-6-tertiary butylphenol), bis [3,3-bis (4-hydroxy-3-third butylphenyl) butyl acid] glycol ester, 4,4'-butylidenebis (6-th) Tributyl-m-cresol), 2,2'-etylidenebis (4,6-di-tertiary butylphenol), 2,2'-etylidenebis (4-second butyl-6-third butylphenol), 1,1 , 3-Tris (2-Methyl-4-hydroxy-5-third Butylphenyl) Butan, Bis [2-Third Butyl-4-Methyl-6- (2-Hydroxy-3-3rd Butyl-5-Methyl) Benzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tertiary butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditriary butyl) -4-Hidolxibenzyl) isocyanurate, 1,3,5-tris (3,5-ditriary butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-Ditertiary Butyl-4-hydroxyphenyl) Propionyloxyethyl] Isocyanurate, Tetrax [Methylene-3- (3', 5'-Ditertiary Butyl-4'-Hydroxyphenyl) Propionate] Methane , 2-3rd Butyl-4-Methyl-6- (2-Acryloyloxy-3-3rd Butyl-5-Methylbenzyl) Phenol, 3,9-Bis [1,1-Dimethyl-2-{(3-) Tertiary Butyl-4-Hydroxy-5-Methylphenyl) Propionyloxy} Ethyl] -2, 4,8,10-Tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate] and the like are used.

The amount of the component (E): phenolic antioxidant in the stabilizer composition of the present invention is 0.01 to 10 parts by mass of the total amount of the stabilizer composition of the present invention. In order to exhibit transparency, thermal stability, and color resistance in a well-balanced manner, the amount of the component (E) is preferably 0.03 to 8 parts by mass, and more preferably 0.05 to 7 parts by mass. If the amount of the component (E) is less than 0.01 parts 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 (E) exceeds 10 parts by mass of the total amount of the stabilizer composition, the transparency of the vinyl chloride resin may decrease.

Considering the processability, heat resistance, and color 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, and m is 0 or any integer).

As such a hydrotalcite compound, a compound salt compound composed of magnesium and aluminum, or zinc, magnesium and aluminum is preferably used. Further, the water of crystallization may be dehydrated. Such hydrotalcite compounds may be natural products or synthetic products. There are no restrictions on the crystal structure, crystal particle size, etc. of the hydrotalcite compound.

Further, as the hydrotalcite compound, higher fatty acids such as stearic acid, higher fatty acid metal salts such as oleic acid alkali metal salt, organic sulfonic acid metal salts such as dodecylbenzene sulfonic acid alkali metal salt, and higher fatty acid amides are used on the surface thereof. Those coated with a higher fatty acid ester or wax can also be used.

In the present invention, the hydrotalcite-based compound may be used alone or in a mixture of two or more. The amount of the component (F): hydrotalcite compound in the stabilizer composition of the present invention is 0.1 to 50 parts by mass of the total amount of the stabilizer composition of the present invention. Transparency, thermal stability, the amount of component (E) in order to exert a well-balanced coloring resistance is preferably 0.3 to 45 parts by weight, more preferably 0.5 to 30 parts by weight. If the amount of the component (E) is less than 0.1 parts by mass of the total amount of the stabilizer composition, the thermal stability of the vinyl chloride resin cannot be sufficiently improved. If the amount of the component (E) exceeds 50 parts by mass of the total amount of the stabilizer composition, the color resistance of the vinyl chloride resin may be rather lowered.

[Vinyl chloride resin]
There is no limitation on the vinyl chloride resin to which the stabilizer composition of the present invention is applied. As such a vinyl chloride-based 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-based resins include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and vinyl chloride-. Propropylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonitrile Copolymer, Vinyl Chloride-butadiene Copolymer, Vinyl Chloride-Isoprene Copolymer, Vinyl Chloride-Chlorinated propylene Copolymer, Vinyl Chloride-Vinylidene Chloride-Vinyl Acetate Tripartite Copolymer, Vinyl Chloride-Maleic Acid Ester Does not contain copolymers, vinyl chloride-based resins such as vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and blends of them or other chlorine. Synthetic resin, for example, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blended product with polyester, etc., block common weight Combined, 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 a vinyl chloride resin, a lubricant can be further added in consideration of processability. Examples of the lubricant include hydrocarbon-based lubricants such as low-molecular-weight wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, and fluorocarbon; natural wax-based lubricants such as carnauba wax and candelilla wax; lauric acid, stearic acid, and behenic acid. Higher fatty acids such as, or fatty acid-based lubricants such as oxy fatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, oleylamide or alkylenebis fats such as methylenebisstearylamide, ethylenebisstearylamide. Fatty acid amide-based lubricants such as group amides; fatty acid monovalent alcohol ester compounds such as stearyl stearate, butyl stearate, and distearyl phthalate, or glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, dipentaerythritol. Fatty acid polyhydric alcohol ester compounds such as hexastearate, polyglycerin polylysinolate, and hardened castor oil, or monovalent fatty acids such as dipentaerythritol adipic acid / stearic acid ester, and polybasic organic acids and polyhydric alcohols. Fatty acid alcohol ester-based lubricants such as composite ester compounds; Stearic acid-based lubricants such as steearic acid, lauryl alcohol, and palmityl alcohol; Metal soaps; Montanic acid-based lubricants such as partially saponified montanic acid ester; Acrylic lubricants; Silicone oil or the like is used. Only one kind of these lubricants may be used, or two or more kinds of lubricants may be used in combination.

The amount of the lubricant added 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 is preferably 0.05 to 3.0 parts by mass from the viewpoint of processability. 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. If 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 a vinyl chloride resin, a processing aid may 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-based processing aid. As such a processing aid, for example, a homopolymer or copolymer of alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; the copolymerization of the above alkyl methacrylate and an alkyl acrylate such as methyl acrylate, ethyl acrylate, and butyl acrylate. Combined; Copolymer of the above alkyl methacrylate with an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene; Copolymer of the above alkyl methacrylate with a vinyl cyan compound such as acrylonitrile or methacrylonitrile, etc. Can be used. Only one kind of these processing aids may be used, or two or more kinds of 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. If 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.
Further, in addition to the stabilizer composition, other additives usually used for vinyl chloride resins, such as plasticizers, polyethers, organic acid metal salts other than the above metal soaps, zeolite compounds, perchlorates, and epoxies. Compounds, phenolic and sulfur-based antioxidants, ultraviolet absorbers, hindered amine-based 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 above-mentioned plasticizers include phthalate plasticizers such as dibutylphthalate, butylhexylphthalate, diheptylphthalate, dioctylphthalate, diisononylphthalate, diisodecylphthalate, dilaurylphthalate, dicyclohexylphthalate and dioctylterephthalate; dioctyl adipate and 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 Phosphate plasticizers such as (butoxyethyl) phosphate, octyldiphenyl phosphate; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4- Polyhydric alcohols such as butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentylglycol, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid. , Sebatic acid, phthalic acid, isophthalic acid, terephthalic acid and other dibasic acids, and if necessary, monohydric alcohol and monocarboxylic acid as stoppers; polyester plasticizers; other tetrahydrophthalic acid plasticizers, azelaic acid System plasticizers, sebatic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, trimellitic acid plasticizers, pyromellitic acid plasticizers, biphenylene polycarboxylic acid plasticizers and the like are used. These plasticizers may be used alone or in a mixture of two or more.

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

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

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

Examples of the organic phosphoric acids 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 phenols and organic phosphates may be a hyperbasic complex in which some or all of the bases of an acidic salt, a neutral salt, a basic salt or a basic salt are neutralized with carbonic acid.

The zeolite compound is an alkaline 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 zeolite, monodenite, analsite, sodalite aluminosilicate, clinobtyrolite, erionite and chavasite. These zeolite compounds may be either a hydrous having water of crystallization (so-called zeolite water) or an anhydride from which water of crystallization 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 perchlorate salts include metal perchloric acid salts, ammonium perchlorate, hydrotalcite treated with perchloric acid, and silicates treated with perchloric acid. Examples of the metal constituting the perchlorate metal salt include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead and aluminum. The metal perchloric acid salt may be an anhydride or a hydrous salt, or may be dissolved in an alcohol-based or ester-based solvent such as butyl diglycol or butyl diglycol adipate, or a dehydrated product thereof.

Examples of the epoxy compound include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized flaxseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef fat oil, epoxidized castor oil, and epoxidized safflower oil. Epoxy toll oil fatty acid octyl, epoxidized flaxseed oil fatty acid butyl, epoxy stearate methyl, -butyl, -2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2- Epoxy propane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxyside, dicyclopentadiene diepoxyside, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate Etc. are used.

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-third octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Di-tertiary butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tertiary butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5) -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-thioctyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-3-third butyl-5-carboxyphenyl) benzotriazole 2- (2-Hydroxyphenyl) benzotriazoles such as polyethylene glycol ester; phenylsalicylate, resorcinol monobenzoate, 2,4-ditertiary butylphenyl-3,5-ditertiary butyl-4-hydroxybenzoate, hexadecyl Benzoates such as -3,5-ditertiary butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl- Cyano acrylates such as α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate are used.

Examples of the hindered amine-based 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 , Tetraquis (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) -2-Butyl-2- (3,5-ditertiary butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / kohaku Diethyl acid polycondensate, 1,6-bis (2,2,6,6-tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetra) Methyl-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-tertiary 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-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11 -Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6-ylamino] undecane, 1,6,11- Hindered amine compounds such as tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-ylamino] undecane are 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 alumina silicate, and hydrokarma. Metal silicates such as ite, aluminum silicate, magnesium silicate, calcium silicate, zeolite, activated white clay, talc, clay, red iron oxide, asbestos, antimony trioxide, silica, glass beads, mica, sericite, glass flakes, Asbestos, walastonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber, aramid fiber and the like are used.

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

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

As the metal hydroxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide and the like are used.

Examples of the phosphoric acid ester flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyldiphenyl. Phosphate, trixylenyl phosphate, octyldiphenyl phosphate, xylenyldiphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyldiphenyl phosphate, t-butylphenyldiphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t) -Butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate and the like are used.

Examples of the condensed phosphate ester-based 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 flame retardant, ammonium salts and amine salts of (poly) phosphate such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate are used.

As the other inorganic flame retardant aid, for example, inorganic compounds such as zinc oxide, titanium oxide, aluminum oxide, magnesium oxide, and talc, and various commercially available products such as surface-treated products thereof can be used.

Further, in addition to the stabilizer composition of the present invention, a stabilizing aid usually used for vinyl chloride-based resins 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, silicic acid, p-tertiary butylbenzoic acid and the like are used.

Furthermore, if necessary, additives usually used for vinyl chloride resins, such as cross-linking agents, antistatic agents, antifogging agents, plate-out inhibitors, surface treatment agents, fluorescent agents, fungicides, fungicides, foaming agents. Agents, metal deactivators, mold release agents, pigments, antioxidants, light stabilizers and the like can be blended within a range that does not impair the effects of the stabilizer composition of the present invention.

[Vinyl chloride resin composition]
The vinyl chloride-based resin composition of the present invention includes a vinyl chloride-based resin and the above-mentioned stabilizer composition of the present invention. The content of the stabilizer composition of 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 with respect to 100 parts by mass of the vinyl chloride resin. Is 0.8 to 5 parts by mass.

〔Molding〕
The vinyl chloride resin composition of the present invention can be molded by any of known molding methods such as extrusion molding, melt casting, pressure molding, and calendar molding. The vinyl chloride resin composition of the present invention can be used particularly for sheet-shaped 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 with reference to Examples. However, the present invention is not limited to the following examples. In the following examples and the like, "%" is based on mass unless otherwise specified. The formulation in 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]
A liquid composition was produced by dissolving various compounds in an organic solvent according to the formulations shown in Table 1. In this way, the stabilizer composition of the present invention (Examples 1 to 5) and the stabilizer composition for comparison (Comparative Examples 1 and 2) were produced.

[Production and Evaluation of Vinyl Chloride Resin Compositions: Examples 6 to 10 and Comparative Examples 3 and 4]
The vinyl chloride resin, the stabilizer composition, and other additives were blended with a Henschel mixer according to the formulation shown in Table 2. In this way, the vinyl chloride resin composition of the present invention (Examples 6 to 10) and the vinyl chloride resin composition for comparison (Comparative Examples 3 and 4) were obtained. The blend was calendar-molded to create a sheet. (Roll kneading condition: 180 ° C. × 30 rpm × 0.6 mm) The obtained sheet was evaluated by the following test method. 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 does not peel 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. Sheets with a disassembly 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 collection time at which blackening was first observed on the collected sheet 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 the start of roll kneading at 180 ° C. This 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., respectively. The time from the start of heating until the sheet sample in each gear oven was blackened (blackening time) was measured. The longer the blackening time, the better the thermal stability of the sheet in the 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 taken 3 minutes after the start of roll kneading at 80 ° C. Sheet samples were analyzed according to JIS K7373 and Y. The I value (Yellowness Index) was calculated. Y. The smaller the I value, the better the color resistance of the sheet. Y. Sheets with an I value of more than 10 cannot withstand actual use.

Notes in Table 1 * 1: Octyldiphenylphosphite * 2: Tridecylphosphite * 3: 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5, 5] Undecane

Note in Table 2 * 4: TK-700 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 5: PA-20 (made by Kaneka)
* 6: G-72 (manufactured by Emery Oreo Chemicals Japan)
* 7: Tetrakis [methylene-3- (3', 5'-ditertiary 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 which do not contain the stabilizer composition of the present invention are inferior in both thermal stability and color resistance. In Comparative Example 3, calcium laurate and zinc stearate, which are linear fatty acid salts, are blended, and the fact that both thermal stability and color resistance are inferior means that the linear fatty acid salt forms a mixed acid metal salt. Support the speculation that it is difficult.

[Manufacturing and Evaluation of Vinyl Chloride Resin Composition: Comparative Example 5]
First, stabilizer compositions 5-1, 5-2, 5-3, and 5-4 were prepared according to the formulations shown in Table 4. Next, the vinyl chloride resin, the stabilizer composition, and other additives were kneaded according to the formulations 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 notes. Pellets 5-1, 5-2, 5-3, 5-4 were blended in equal proportions. In this way, a vinyl chloride resin composition for comparison (Comparative Example 5) was obtained. This vinyl chloride resin composition was molded by the same method as in Examples 6 to 10 and Comparative Examples 3 and 4. The evaluation results of the obtained sheets are shown in Table 6.

The vinyl chloride resin composition of Comparative Example 5 contains all of the compounds corresponding to the component (A), the component (B), the component (C), and the component (D) of the present invention. However, in the vinyl chloride resin composition of Comparative Example 5, a part of the component (B) was liquefied together with the components (A), (C), and (D) to form a vinyl chloride resin composition. It is compounded. Surprisingly, the vinyl chloride resin composition of Comparative Example 5 is significantly inferior in thermal stability to Examples 6 to 10. It is presumed that the stabilizer composition 5-1, 5-2, 5-3, 5-4 used in Comparative Example 5 did not form a sufficient mixed acid of fatty acids to exhibit an excellent stabilizer effect. To.

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

Although the stabilizer composition of the present invention is a compound whose raw material has been conventionally used as a stabilizer, it has an extremely high vinyl chloride resin stabilizing function that could never be achieved by a conventional method of blending a stabilizer. Have. Such a stabilizer composition of the present invention is an epoch-making additive for a vinyl chloride resin. The vinyl chloride resin composition of the present invention exhibits extremely high resistance to thermal history during processing and use. Therefore, from the vinyl chloride resin composition of the present invention, advantages such as strength and flexibility of the vinyl chloride resin are maintained, and a molded product having a good color tone can be obtained. The present invention is expected to improve the quality of various products using vinyl chloride resins, especially sheet materials.

Claims (6)

(A) component: 10 to 40 parts by mass of β-diketone compound, (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), 3 to 40 parts by mass of one or more fatty acid metal salts selected from unsaturated fatty acid metal salts represented by the following general formula (3), component (C): 20 to 80 parts by mass of phosphite ester, component (D): 1 to 30 parts by mass of an organic solvent having a boiling point of 120 ° C. or higher (However, the amounts of each of the above components indicate the ratio of the components (A), (B), (C), and (D) to 100 parts by mass in total). A liquid stabilizer composition for a vinyl chloride resin containing
The above component (D) is
Alcohol-based organic solvent with a boiling point of 120 ° C or higher,
A mixture consisting of an alcohol-based organic solvent having a boiling point of 120 ° C. or higher and one or more organic solvents selected from liquid paraffin, naphthenic solvent, and aromatic hydrocarbon compounds.
Glycol-based organic solvent with boiling point of 120 ° C or higher and 231 ° C or lower,
A mixture consisting of a glycol-based organic solvent having a boiling point of 120 ° C. or higher and 231 ° C. or lower and one or more organic solvents selected from liquid paraffin, naphthenic solvent, and aromatic hydrocarbon compounds.
Der any of is,
The vinyl chloride resin is a vinyl chloride resin that does not contain the component (B).
The fatty acid metal salt contained in the component (B) forms a mixed acid metal salt in a state where the component (A), the component (B), and the component (C) are mixed and dissolved in the component (D). ing,
Liquid stabilizer composition for vinyl chloride resin.

(R ^{1 to} R ⁵ represent 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, respectively. N is 2. Represents the above integer. 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 liquid stabilizer composition for a vinyl chloride resin according to claim 1, wherein the component (A) contains an acetylacetone zinc salt. The chloride according to claim 1 or 2, wherein 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). Liquid stabilizer composition for vinyl resins. A vinyl chloride resin composition comprising a vinyl chloride resin and the liquid 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 liquid stabilizer composition for a 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 product comprising the vinyl chloride resin composition according to claim 4 or 5.