WO2021193372A1 - Stabilizer composition of vinyl chloride-based resin for foam molding, vinyl chloride-based resin composition for foam molding containing same, and foam-molded article thereof - Google Patents

Abstract

The purpose of the present invention is to provide a stabilizer composition capable of imparting, to a vinyl chloride-based resin for foam molding, superior processability and high producibility.　The stabilizer composition for a vinyl chloride-based resin for foam molding according to the present invention contains, with respect to 100 parts by mass of component (A), 5-700 parts by mass of component (B) and 5-200 parts by mass of component (C). Component (A): A zinc salt of an organic acid. Component (B): A metal salt selected from the group consisting of barium salts of organic acids, barium salts of overbased carbonic acids, calcium salts of organic acids, and calcium salts of overbased carbonic acids. Component (C): An oxidized polyethylene wax.

Description

Stabilizer composition of vinyl chloride resin for foam molding, vinyl chloride resin composition for foam molding containing this, and foam molded product thereof.

The present invention relates to a stabilizer composition of a vinyl chloride resin for foam molding, a vinyl chloride resin composition for foam molding containing the stabilizer composition, and a foam molded product thereof.

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 rigid vinyl chloride resin composition containing no plasticizer at all or a semi-rigid semi-rigid resin composition containing a small amount of plasticizer (for example, containing 50 parts by mass or less of a plasticizer with respect to 100 parts by mass of a vinyl chloride resin) is rigid. It is widely used for boards, panels, building materials, etc. because of its excellent properties.

In particular, the production of foam molded products has been widely attempted as a building material member oriented toward boards, panels, synthetic wood and the like. These foam molded products are required to have good workability and productivity. In terms of processability, it is required that it is easily gelled (gelling property). In terms of productivity, long-term continuous operation (long-running property) of the processing machine is required, but when continuous production is performed for a long time, the resin composition gradually accumulates in the processing machine, which is thermally decomposed. , There is a problem that the thermally decomposed product adheres to the surface of the molded product, resulting in a defective product in which the surface appearance of the molded product is deteriorated. Further, when a fine and uniform foam cell is not formed, the appearance of the foamed molded product is deteriorated due to deterioration of surface properties such as surface roughness, and the vinyl chloride resin composition having excellent foamability has an excellent appearance. There is a demand for a foam molded product to have.
On the other hand, the use of an acrylic polymer has been proposed (Patent Documents 1 and 2).

On the other hand, as a stabilizer for vinyl chloride resin, heavy metal stabilizers such as lead and cadmium have been conventionally used from the viewpoint of cost advantage because they are inexpensive. However, in recent years, there has been increasing interest in environmental protection and conservation, and the use of these has become a problem due to the toxicity of heavy metals and the adverse effects on the environment. Further, a tin-based stabilizer, which is an organic tin compound, is also not preferable from the viewpoint of environmental influence and toxicity.

US6391976 JP2012-140638A

With the conventional technology, the processability of the vinyl chloride resin for foam molding, especially the gelling property, and the productivity, especially the long-running property, are not sufficient, and the foamability is not sufficient, and the appearance of the obtained foamed molded product is also satisfactory. It wasn't a good thing.

Therefore, an object of the present invention is to provide a stabilizer composition capable of imparting excellent processability and productivity to a vinyl chloride resin for foam molding. Another object of the present invention is to provide a vinyl chloride resin composition having excellent processability, productivity and foamability. Further, an object of the present invention is to provide a vinyl chloride resin foam molded article having an excellent appearance.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a specific metal salt in combination with polyethylene oxide wax, and have completed the present invention.

That is, the present invention is a vinyl chloride resin for foam molding containing 5 to 700 parts by mass of the following component (B) and 5 to 200 parts by mass of the following component (C) with respect to 100 parts by mass of the following component (A). To provide a stabilizer composition of the above.
(A) Component: Zinc salt of organic acid (B) Component: Barium salt of organic acid, barium carbonate perbasic carbonate, calcium salt of organic acid and metal salt (C) selected from the group of calcium perbasic carbonate Ingredients: Polyethylene oxide wax

Further, the present invention is characterized in that the acid value of the polyethylene oxide wax of the component (C) is 1.0 mgKOH / g or more and 30.0 mgKOH / g or less, and the stabilizer composition of the vinyl chloride resin for foam molding. It provides things.
The present invention also provides a vinyl chloride resin composition for foam molding containing a vinyl chloride resin, a foaming agent and the stabilizer composition.

Further, in the present invention, the vinyl chloride for foam molding containing 0.05 to 10.0 parts by mass of a foaming agent and 0.3 to 15.0 parts by mass of a stabilizer composition with respect to 100 parts by mass of a vinyl chloride resin. It provides a based resin composition.
The present invention also provides the vinyl chloride resin composition for foam molding in which the foaming agent is azodicarbonamide.

Further, in the present invention, the vinyl chloride-based resin composition is a rigid vinyl chloride-based resin composition containing no plasticizer, or a semi-hardened vinyl chloride-based resin composition containing 0 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of the vinyl chloride-based resin. The present invention provides the vinyl chloride-based resin composition for foam molding, which is a vinyl chloride-based resin composition.
The present invention also provides the vinyl chloride resin composition for foam molding, which does not contain a lead-based stabilizer, a cadmium-based stabilizer, and a tin-based stabilizer.
The present invention also provides a foamed molded product of the vinyl chloride resin composition for foam molding.

Hereinafter, embodiments of the present invention will be described in detail.
First, the stabilizer composition of the vinyl chloride resin for foam molding of the present invention will be described.
The stabilizer composition of the present invention contains the following components (A), (B) and (C).
(A) Component: Zinc salt of organic acid (B) Component: Barium salt of organic acid, barium carbonate perbasic carbonate, calcium salt of organic acid, metal salt (C) selected from the group of calcium perbasic carbonate Ingredients: Polyethylene oxide wax

First, the component (A) will be described.
The component (A) of the present invention contains one or more zinc salts of organic acids. Examples of the zinc salt of such an organic acid include zinc salts of organic carboxylic acids, phenols, organic phosphoric acids and the like.

Examples of the organic carboxylic acid include acetic acid, propionic acid, butyric acid, benzoic acid, caproic acid, enanthic acid, capric acid, pelargonic acid, 2-ethylhexic acid, neodecanoic acid, capric acid, undecanoic acid, isoundecic acid and lauric acid. , Isolauric acid, tridecanoic acid, myristic acid, isomyristic acid, palmitic acid, isoparmic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, versatic acid and other monovalent aliphatic saturated carboxylic acids. Acids; benzoic acid, monochlorobenzoic acid, 4-tert-butyl benzoic acid, dimethylhydroxybenzoic acid, 3,5-ditertiary butyl-4-hydroxybenzoic acid, o-toluic acid, m-toluic acid, p-toluyl Acid, toluic acid, dimethyl benzoic acid, 2,4-dimethyl benzoic acid, 3,5-dimethyl benzoic acid, 2,4,6-trimethyl benzoic acid, ethyl benzoic acid, 2-ethyl benzoic acid, 3-ethyl benzoic acid , 4-Ethyl Benzoic Acid, 2,4,6-Triethyl Benzoic Acid, 4-Isobenzoic Acid, n-propyl Benzoic Acid, Amino Benzoic Acid, N, N-DimethylAmino Benzoic Acid, Acetoxy Benzoic Acid, Salicylic Acid, p- Monovalent aromatic carboxylic acids such as tertiary octylsalicylic acid; ellaic acid, oleic acid, linoleic acid, linolenic acid, myristoleic acid, palmitoleic acid, eleostearic acid, ecocenoic acid, ecosadienoic acid, ecosatrienoic acid, eiko Monovalent aliphatic unsaturated carboxylic acids such as satetetraenoic acid, arachidonic acid, docosapentaenoic acid, docosahexaenoic acid and ricinoleic acid; containing monovalent sulfur atoms such as thioglycolic acid, mercaptopropionic acid and octyl mercaptopropionic acid Carboic acid; divalent aliphatic saturated carboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid; phthalic acid, isophthalic acid, terephthalic acid, hydroxy Divalent aromatic carboxylic acids such as phthalic acid, chlorphthalic acid and aminophthalic acid; divalent or trivalent aliphatic unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid and benzoic acid; Divalent sulfur atom-containing carboxylic acids such as thiodipropionic acid; monoesters or monoamide compounds of these divalent carboxylic acids; butanetricarboxylic acid, butanetetracarboxylic acid, hemmellitic acid, trimellitic acid, merophanic acid, pyromerit Three such as acid Di or triester compounds of valent or tetravalent carboxylic acids can be mentioned.

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

Examples of the organic phosphoric acids include alkyl phosphates such as mono or dioctyl phosphate, mono or didodecyl phosphate, mono or dioctadecyl phosphate, mono or di (nonylphenyl) phosphate; phosphonic acid nonylphenyl ester, phosphonic acid. Examples thereof include phosphonic acid alkyl esters such as stearyl esters.

The zinc salt of the organic acid may be any of an acidic salt, a neutral salt, a basic salt, and a hyperbasic complex in which a part or all of the base of the basic salt is neutralized with carbonic acid.

Further, the zinc salt of the organic acid may be composed of two or more kinds of organic acids. For example, in the case of a zinc salt made of a monovalent organic acid, the same organic acid may form an anion moiety and form a salt with a divalent zinc forming a cation moiety, and different monovalent organic acids 2 may be formed. The seed may form a salt with a divalent zinc that forms an anionic moiety and forms a cation moiety.

In the present invention, from the viewpoint of processability, productivity and foamability, the component (A) is zinc acetate, zinc benzoate, zinc tolulate, 4-tert-butyl zinc benzoate, zinc stearate, zinc laurate. , Zinc versaticate, zinc octylate, zinc oleate, zinc palmitin and zinc myristine are preferably zinc salts of organic acids selected from the group.
As the zinc salt of the organic acid as the component (A), only one type may be used, or two or more types may be used in combination.

Next, the component (B) will be described.
The component (B) of the present invention is a metal salt selected from the group consisting of a barium salt of an organic acid, a perbasic barium carbonate salt, a calcium salt of an organic acid, and a perbasic calcium carbonate salt. The component (B) may contain two or more kinds of metal salts.

First, the barium salt of an organic acid will be described.
Examples of the barium salt of such an organic acid include barium salts such as organic carboxylic acids, phenols and organic phosphoric acids.

Examples of the organic carboxylic acid include acetic acid, propionic acid, butyric acid, benzoic acid, caproic acid, enanthic acid, capric acid, pelargonic acid, 2-ethylhexic acid, neodecanoic acid, capric acid, undecanoic acid, isoundecic acid and lauric acid. , Isolauric acid, tridecanoic acid, myristic acid, isomyristic acid, palmitic acid, isoparmic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, versatic acid and other monovalent aliphatic saturated carboxylic acids. Acids; benzoic acid, monochlorobenzoic acid, 4-tert-butyl benzoic acid, dimethylhydroxybenzoic acid, 3,5-ditertiary butyl-4-hydroxybenzoic acid, o-toluic acid, m-toluic acid, p-toluyl Acid, toluic acid, dimethyl benzoic acid, 2,4-dimethyl benzoic acid, 3,5-dimethyl benzoic acid, 2,4,6-trimethyl benzoic acid, ethyl benzoic acid, 2-ethyl benzoic acid, 3-ethyl benzoic acid , 4-Ethyl Benzoic Acid, 2,4,6-Triethyl Benzoic Acid, 4-Isobenzoic Acid, n-propyl Benzoic Acid, Amino Benzoic Acid, N, N-DimethylAmino Benzoic Acid, Acetoxy Benzoic Acid, Salicylic Acid, p- Monovalent aromatic carboxylic acids such as tertiary octylsalicylic acid; ellaic acid, oleic acid, linoleic acid, linolenic acid, myristoleic acid, palmitoleic acid, eleostearic acid, ecocenoic acid, ecosadienoic acid, ecosatrienoic acid, eiko Monovalent aliphatic unsaturated carboxylic acids such as satetetraenoic acid, arachidonic acid, docosapentaenoic acid, docosahexaenoic acid and ricinoleic acid; containing monovalent sulfur atoms such as thioglycolic acid, mercaptopropionic acid and octyl mercaptopropionic acid Carboic acid; divalent aliphatic saturated carboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid; phthalic acid, isophthalic acid, terephthalic acid, hydroxy Divalent aromatic carboxylic acids such as phthalic acid, chlorphthalic acid and aminophthalic acid; divalent or trivalent aliphatic unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid and benzoic acid; Divalent sulfur atom-containing carboxylic acids such as thiodipropionic acid; monoesters or monoamide compounds of these divalent carboxylic acids; butanetricarboxylic acid, butanetetracarboxylic acid, hemmellitic acid, trimellitic acid, merophanic acid, pyromerit Three such as acid Di or triester compounds of valent or tetravalent carboxylic acids can be mentioned.

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

Examples of the organic phosphoric acids include alkyl phosphates such as mono or dioctyl phosphate, mono or didodecyl phosphate, mono or dioctadecyl phosphate, mono or di (nonylphenyl) phosphate; phosphonic acid nonylphenyl ester, phosphonic acid. Examples thereof include phosphonic acid alkyl esters such as stearyl esters.

The barium salt of the organic acid may be composed of two or more kinds of organic acids. For example, in the case of a barium salt made of a monovalent organic acid, the same organic acid may form an anion moiety and form a salt with a divalent barium forming a cation moiety, and different monovalent organic acids 2 may be formed. The seed may form a salt with a divalent barium that forms an anionic moiety and forms a cation moiety.
Only one type of barium salt of an organic acid may be used, or two or more types may be used in combination.
The barium salt of the organic acid may be any of an acidic salt, a neutral salt and a basic salt.

Next, the hyperbasic barium carbonate salt will be described. The perbasic barium carbonate salt is a liquid barium superbasic carboxylate / carbonate complex of barium. This complex is different from a simple mixture of a positive barium carboxylic acid salt and barium carbonate, which is a complex by some interaction, and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid. This complex is composed of barium carboxylic acid positive salt, barium carbonate, and a composite salt of barium carboxylic acid and carbonic acid as constituents, and barium carboxylic acid positive salt and barium carboxylic acid centering on barium carbonate. A complex salt of carbonic acid and carbonic acid exists around it, and by forming something like micelles, it shows a uniform liquid in an organic solvent.

The liquid perbasic carboxylate / carbonate complex of barium can be produced, for example, by the production method shown in JP-A-2004-238364.

As the liquid perbasic carboxylate / carbonate complex of barium, various commercially available complexes can be used as they are. Typical commercially available complexes include, for example, "PlastiStab ^TM 2116" (perbasic barium oleate / carbonate complex: specific gravity 1.42 to 1.53, Ba = 33 to 36) manufactured by AM STABILIZERS in the United States. %), "PlastiStab ^TM 2513" (hyperbasic barium oleate / carbonate complex: specific density 1.41 to 1.52, Ba = 33 to 36%), "PlastiStab ^TM 2508" (hyperbasic barium oleate / carbonate complex: Specific gravity 1.39 to 1.51, Ba = 33 to 36%) and the like.
Only one type of perbasic barium carbonate may be used, or two or more types may be used in combination.

Next, the calcium salt of the organic acid will be described.
Examples of the calcium salt of such an organic acid include calcium salts of organic carboxylic acids, phenols, organic phosphoric acids and the like.

Examples of the organic carboxylic acid include those exemplified in the description of the barium salt. Examples of the phenols include those exemplified in the description of the barium salt. Examples of the organic phosphoric acids include those exemplified in the description of the barium salt.

The calcium salt of the organic acid may be composed of two or more kinds of organic acids. For example, in the case of a calcium salt made of a monovalent organic acid, the same organic acid may form an anion moiety and form a salt with a divalent calcium forming a cation moiety, and different monovalent organic acids 2 may be formed. The seed may form a salt with a divalent calcium that forms an anionic moiety and forms a cation moiety.
Only one type of calcium salt of the organic acid may be used, or two or more types may be used in combination.
Further, the calcium salt of the organic acid may be any of an acidic salt, a neutral salt and a basic salt.

Next, the hyperbasic calcium carbonate salt will be described. The perbasic calcium carbonate salt is a liquid perbasic carboxylate / carbonate complex of calcium. This complex is different from a simple mixture of a positive carboxylic acid salt of calcium and calcium carbonate, which is a complex by some interaction, and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid. This complex is composed of calcium carboxylic acid positive salt, calcium carbonate, and a composite salt of calcium carboxylic acid and carbonic acid as constituents, and is composed mainly of calcium carbonate, calcium carboxylic acid positive salt and calcium carboxylic acid. A complex salt of calcium and carbonic acid exists around it, and by forming something like micelles, it shows a uniform liquid in an organic solvent.

The liquid perbasic carboxylate / carbonate complex of calcium can be produced in the same manner as the liquid superbasic liquid carboxylate / carbonate complex of barium. Moreover, various commercially available complexes can also be used as they are. As a typical commercially available complex, for example, "PlastiStab ^TM 2265" (perbasic calcium oleate / carbonate complex: specific gravity 1.04 to 1.09, Ca = 10%) manufactured by AM STABILIZERS in the United States. ).
Only one type of perbasic calcium carbonate salt may be used, or two or more types may be used in combination.

The organic acid barium salt, perbasic barium carbonate, organic acid calcium salt and perbasic calcium carbonate used as the component (B) of the stabilizer composition of the present invention may be used alone. Two or more types may be used together.

The component (B) of the stabilizer composition of the present invention may be at least one selected from the group consisting of a barium salt of an organic acid and a calcium salt of an organic acid from the viewpoint of processability, productivity and foamability. It is preferably a calcium salt of an organic acid, more preferably. As the specific compound, barium stearate is preferable as the barium salt of the organic acid, and calcium stearate is preferable as the calcium salt of the organic acid from the viewpoint of processability, productivity and foamability. Among these, the component (B) preferably contains calcium stearate.

The content of the component (B) in the stabilizer composition of the present invention is preferably 5 to 700 parts by mass with respect to 100 parts by mass of the zinc salt of the organic acid of the component (A). From the viewpoint of productivity and foamability, it is more preferably 25 to 500 parts by mass, and particularly preferably 50 to 300 parts by mass.

Next, the component (C) of the stabilizer composition of the present invention will be described.
The component (C) of the present invention contains one or more kinds of polyethylene oxide wax.

The acid value of the polyethylene oxide wax is preferably 1.0 mgKOH / g or more and 30 mgKOH / g or less, and 5.0 mgKOH / g or more and 25.0 mgKOH / g or less from the viewpoint of processability, productivity and foamability. It is more preferably 10.0 mgKOH / g or more and 20.0 mgKOH / g or less, and most preferably 13.0 mgKOH / g or more and 20.0 mgKOH / g or less.
In the present invention, the acid value is measured according to JIS K0070.

In the present invention, the melt viscosity of the polyethylene oxide wax is in the range of 50 to 10000 mPa · s when measured at 140 ° C. with a B-type viscometer, which is the processability, productivity, and appearance of the foamed molded product. From this point of view, it is preferable, and more preferably 100 to 9000 mPa · s.

In the present invention, the number average molecular weight of the polyethylene oxide wax is preferably 800 to 8000, more preferably 1000 to 6000, from the viewpoint of processability, productivity and foamability.

The method for producing the polyethylene oxide wax is not particularly limited, and for example, a polyethylene wax obtained by polymerizing ethylene at a low pressure with a Ziegler catalyst, reducing the molecular weight of polyethylene for general molding by thermal decomposition, or the like can be used. It can be produced by oxidizing by a method such as air oxidation. Further, those modified with alcohol or the like can also be used.

A commercially available product may be used as the polyethylene oxide wax. Examples thereof include polyethylene oxide waxes such as high wax series manufactured by Mitsui Chemicals, Inc., sun wax series manufactured by Sanyo Chemical Industries, Ltd., Rubacs series manufactured by Nippon Seiro Co., Ltd., and AC series manufactured by Honeywell Co., Ltd.

The content of the component (C) in the stabilizer composition of the present invention is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the zinc salt of the organic acid of the component (A). From the viewpoint of productivity and foamability, it is more preferably 10 to 120 parts by mass, and particularly preferably 20 to 80 parts by mass.

The stabilizer composition of the present invention preferably further contains a phenolic antioxidant from the viewpoint of processability, productivity and foamability. From the viewpoint of processability, productivity, and foamability, the phenolic antioxidant is preferably contained in an amount of 1 to 200 parts by mass, preferably 2 to 150 parts by mass, based on 100 parts by mass of the component (A). More preferably, it is contained in an amount of 5 to 100 parts by mass.

Examples of the phenolic antioxidant include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-ditertiary butyl-4-4). Hydroxyphenyl) -propionate, distearyl (3,5-dithiary butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycolbis [(3,5-ditritiary 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) butyric acid] glycol ester, 4,4'-butylidenebis (6-tertiary butyl-m-cresol), 2 , 2'-Etilidenebis (4,6-di-tertiary butylphenol), 2,2'-Echilidenbis (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-Third Butyl-5-Methylbenzyl) Phenyl] Telephthalate, 1,3 , 5-Tris (2,6-dimethyl-3-hydroxy-4-third butylbenzyl) isocyanurate, 1,3,5-Tris (3,5-di-three-butyl-4-hydroxybenzyl) isocia Nurate, 1,3,5-tris (3,5-di-tertiary butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-third) Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3', 5'-ditertiary butyl-4'-hydroxyphenyl) propionate] methane, 2-third butyl-4- Methyl-6- (2-acryloyloxy-3-3 butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-3 butyl-4-hydroxy-5) -Methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspi (B) [5.5] Undecane, triethylene glycol bis [(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate] and the like can be mentioned.
Only one type of phenolic antioxidant may be used, or two or more types may be used in combination.

Among these phenolic antioxidants, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferable from the viewpoint of processability, productivity, and foamability.

The stabilizer composition of the present invention preferably further contains a polyhydric alcohol compound from the viewpoint of processability, productivity and foamability. From the viewpoint of processability, productivity, and foamability, the polyhydric alcohol compound is preferably contained in an amount of 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, based on 100 parts by mass of the component (A). It is preferably contained in an amount of 20 to 100 parts by mass, and more preferably.

Examples of the polyhydric alcohol compound include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, and 1,3,5-tris (2-hydroxyethyl). Examples thereof include isocyanurate, polyethylene glycol, glycerin, diglycerin, mannitol, martitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose (sucrose), trehalose, inositol, fructose, maltose, lactose and the like.
Only one type of polyhydric alcohol compound may be used, or two or more types may be used in combination.

Among these polyhydric alcohol compounds, dipentaerythritol and 1,3,5-tris (2-hydroxyethyl) isocyanurate are preferable from the viewpoint of processability, productivity and effervescence.

The stabilizer composition of the present invention may further contain a β-diketone compound from the viewpoint of processability, productivity and foamability.

Examples of the β-diketone compound include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and distearoylmethane. Stearoyl acetyl methane, phenyl acetyl acetyl methane, dicyclohexyl carbonyl methane, benzoyl formyl methane, benzoyl acetyl methane, dibenzoyl methane, octyl benzoyl methane, bis (4-octyl benzoyl) methane, benzoyl diacetyl methane, 4-methoxybenzoyl benzoyl methane, bis (4-Carboxymethylbenzoyl) methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, ethyl acetoacetate, cyclohexane-1,3-dione, 3,6-dimethyl-2,4-dioxycyclohexane-1carboxylic acid Methyl, 2-acetylcyclohexanone, dimedone, 2-benzoylcyclohexane and the like can be mentioned, and metal salts thereof can be used in the same manner. Examples of metal salts include lithium salts, sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts and aluminum salts. Examples of preferable metal salts include acetylacetone calcium salt, acetylacetone zinc salt and the like.
Only one type of β-diketone compound may be used, or two or more types may be used in combination.

The stabilizer composition of the present invention may further contain a phosphite ester compound from the viewpoint of processability, productivity and foamability.

Examples of the phosphite ester compound include phosphite trialkyl ester, phosphite dialkyl ester, phosphite dialkyl monoallyl ester, phosphite alkyl allyl ester, phosphite monoalkyl diallyl ester, and phosphite diallyl ester. , Triallyl ester of phosphite and the like.

In the present invention, either a triester or a diester can be used, but it is preferable to use the triester from the viewpoint of processability, productivity, and appearance of the foamed molded product. Thioesters can also be used.

Examples of the phosphite ester compound include triphenyl phosphite, tricresyl phosphite, tris (2,4-ditertiary butylphenyl) phosphite, tris (nonylphenyl) phosphite, and tris (dinonylphenyl). ) Phosphite, Tris (mono- and di-mixed nonylphenyl) phosphite, Tris (2,4-di-tertiary butylphenyl) phosphite, diphenylphosphite, 2,2'-methylenebis (4,6-di) Tertiary Butylphenyl) Octylphosphite, 2,2'-Methylenebis (4,6-3rd Butylphenyl) -2-ethylhexylphosphite, 2,2'-Methylenebis (4,6-3rd Butylphenyl) -Octadecyl Phosphite, 2,2'-Etilidenebis (4,6-ditertiary butylphenyl) fluorophosphite, octyldiphenylphosphite, diphenyldecylphosphite, diphenyl (2-ethylhexyl) phosphite, di (decyl) monophenyl Phosphite, diphenyltridecylphosphite, diphenyl (C12-C15 mixed alkyl) phosphite, phenyldiisodecylphosphite, phenylbis (isotridecyl) phosphite, triethylphosphite, tributylphosphite, tris (2-ethylhexyl) phosphite, Tris (decyl) phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, diethyl phosphite, dibutyl phosphite, dilauryl phosphite, bis (2-ethylhexyl) phosphite , Dioleyl phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertiary butylphenyl) pentaerythritol diphosphite, bis (2) , 6-Di3 butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritrith butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) penta Erislitol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, di (tridecyl) pentaerythritol diphosphite, phenyl-4,4'-isopropyridendiphenol pentaerythritol di Phosphite, Tetra (C12-15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, hydrogenation-4,4'-isopropyridendiphenol polyphosphite, bis (octylphenyl) bis [4, 4'-n-butylidenebis (2-third butyl-5-methylphenol)], 1,6-hexanediol, diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-third butyl-5) -Methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-3 butylphenyl) butanetriphosphite, hexa (tridecyl) 1,1,3-tris (2-Methyl-5-Triary Butyl-4-Hydroxyphenyl) Butan triphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethyl Propanediol 2,4,6-tritrith butylphenol monophosphite, tris [2-tertiary butyl-4- (3-third butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] Phosphite, Tetra (Tridecyl) Isopropyridene diphenol Diphosphite, Tetrax (2,4-ditertiary butylphenyl) Biphenylenediphosphite, Tris (2-[(2,4,8,10-Tetrakiss tertiary butyl) Dibenzo [d, f] [1,3,2] dioxaphosfepine-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tritertiary butylphenol Examples include phosphite.
Only one type of phosphite ester compound may be used, or two or more types may be used in combination.

Among these phosphite ester compounds, the phosphite ester compound having 12 to 80 carbon atoms is preferable, and the phosphite ester compound having 12 to 46 carbon atoms is preferable from the viewpoint of processability, productivity and foamability. More preferably, a phosphite ester compound having 12 to 36 carbon atoms is further preferable, and a phosphite ester compound having 18 to 30 carbon atoms is particularly preferable.

The stabilizer composition of the present invention may further contain a hydrotalcite compound from the viewpoint of processability, productivity and foamability.

Examples of the hydrotalcite compound include compounds represented by the following general formula (1).
Mg _x1 Zn _x2 Al ₂ (OH) _{2x1 + 2x2 + 4} (CO ₃ ) _{1-y1 / 2} (ClO ₄ ) _y1 mH ₂ O (1)

In the formula (1), x1, x2 and y1 represent numbers satisfying the conditions represented by 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 <20, and 0 ≦ y1 ≦ 2, and m is 0 or Represents an arbitrary integer.

As the hydrotalcite compound, a double salt compound composed of magnesium and aluminum, or zinc, magnesium and aluminum is preferably used. Further, the water of crystallization may be dehydrated or treated with perchloric acid. 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.

As the hydrotalcite compound, the surface thereof is surfaced with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as oleic acid alkali metal salt, an organic sulfonic acid metal salt such as dodecylbenzene sulfonic acid alkali metal salt, a higher fatty acid amide, and a higher grade. Those coated with fatty acid ester or wax can also be used.
Only one type of hydrotalcite compound may be used, or two or more types may be used in combination.

The stabilizer composition of the present invention may further contain a hindered amine-based light stabilizer from the viewpoints of processability, productivity and foamability.

The hindered amine-based light stabilizer is not particularly limited as long as it is a conventionally known hindered amine-based light stabilizer, and for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1, 2, 2 , 6,6-Pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6) -Tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl), bis (tridecyl) -1,2,3,4-butane tetracarboxylate, bis (1,2,2,6) 6-Pentamethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl- 2- (3,5-ditertiary butyl-4-hydroxybenzyl) malonate, 1,2,2,6,6-tetramethyl-4-piperidyl methacrylate, poly [{6- (1,1,3,3) -Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6) 6-Tetramethyl-4-piperidyl) imino}], 1,2,3,4-butanecarboxylic acid / 2,2-bis (hydroxymethyl) -1,3-propanediol / 3-hydroxy-2,2- Dimethylpropanal / 1,2,2,6,6-pentamethyl-4-piperidinyl ester polycondensate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) = decandioate / methyl = 1,2,2,6,6-pentamethyl-4-piperidyl = sebacato mixture, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1- (2-hydroxyethyl) -2,2,6 6-Tetramethyl-4-piperidinol / diethyl polycondensate succinate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromo Ethan 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-6-3 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-tetraaza Dodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6- Il] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl]) ) Amino-s-triazine-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl)) Amino-s-triazine-6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2-{tris (1,2,2,6,6-pentamethyl-) 4-Piperidyloxycarbonyl) Butylcarbonyloxy} Ethyl] -2,4,8,10-Tetraoxaspiro [5.5] Undecane, Bis (1-undecyloxy-2,2,6,6-tetramethylpiperidine) -4-yl) carbonate, 2,2,6,6-tetramethyl-4-piperidyl hexadecanoate, 2,2,6,6-tetramethyl-4-piperidyl octadecanoate and the like can be mentioned.
Only one type of hindered amine light stabilizer may be used, or two or more types may be used in combination.

The hindered amine-based light stabilizer is preferably a compound having a group represented by the following general formula (2) from the viewpoint of processability, productivity, and foamability.

In the general formula (2), R ¹ is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, and a carbon atom. It represents a hydroxyalkoxy group of 1 to 30, an alkenyl group having 2 to 30 carbon atoms, or an oxyradic, and these alkyl groups, alkoxy groups, hydroxyalkyl groups, hydroxyalkoxy groups and alkenyl groups are oxygen atoms or carbonyl groups. It may be interrupted by one or more. Further, the groups of the general formula (2) are bonded at the points marked with * in the general formula (2). A plurality of groups of the general formula (2) may be contained in the compound.

Examples of the alkyl group having 1 to 30 carbon atoms that can be taken ^{by R 1} of the general formula (2) include a linear alkyl group and a branched alkyl group. Linear alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadesyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group and the like. Examples of the branched alkyl group include a group in which one or two or more of the linear alkyl groups are substituted with an alkyl group having 1 to 9 carbon atoms.

Examples of the alkoxy group having 1 to 30 carbon atoms that can be taken ^{by R 1} of the general formula (2) include an alkoxy group corresponding to the above-mentioned alkyl group.

Examples of the hydroxyalkyl group having 1 to 30 carbon atoms that can be taken ^{by R 1} of the general formula (2) include a hydroxyalkyl group corresponding to the above-mentioned alkyl group.

Examples of the hydroxyalkoxy group having 1 to 30 carbon atoms that can be taken ^{by R 1} of the general formula (2) include a hydroxyalkoxy group corresponding to the above-mentioned alkoxy group.

^{Examples of the alkenyl group having 2 to 30 carbon atoms that can be taken by R 1} of the general formula (2) include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group and a nonenyl group. , Decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadesenyl group, icosenyl group, henicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group Examples thereof include a group, a heptacosenyl group, an octacosenyl group, a nonacosenyl group and a triacontenyl group, and the corresponding alkazienyl group and an alkatoenyl group are also mentioned.

From the viewpoint of processability, productivity, and foamability, the group represented by the general formula (2) preferably ^{has R 1} as a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, preferably having 1 to 30 carbon atoms. It is more preferably an alkyl group of 1 to 30, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.

As the hindered amine-based photostabilizer having a group represented by the general formula (2), for example, when R ¹ of the general formula (2) is a hydrogen atom, 2,2,6,6-tetramethyl-4. -Piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) bis (tridecyl) -1,2,3 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1 , 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) ) Hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro- 6-Third octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-)) Piperidil) 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, 3,9-bis [1,1-dimethyl-2-{tris (2,2,6,6-tetra) Methyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2,6,6-tetramethyl-4-piperidylhexadecano benzoate, 2,2,6,6-tetramethyl-4-piperidyl octadecanoate, and the like, as ^{R 1} in the general formula (1) is a methyl group, 1,2,2,6,6 -Pentamethyl-4-piperidyl stearate, bis (1, 2, 2, 2) 6,6-Pentamethyl-4-piperidyl) sebacate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6) 2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl)- 2-Butyl-2- (3,5-ditertiary butyl-4-hydroxybenzyl) malonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,3,4-butanecarbonate Acid / 2,2-bis (hydroxymethyl) -1,3-propanediol / 3-hydroxy-2,2-dimethylpropanal / 1,2,2,6,6-pentamethyl-4-piperidinyl ester polycondensation Thing, bis (1,2,2,6,6-pentamethyl-4-piperidyl) = decandioate / methyl = 1,2,2,6,6-pentamethyl-4-piperidyl = sebacart mixture, 1,5 8,12-Tetrakiss [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- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s- Triazine-6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl]- 2,4,8,10-Tetraoxaspiro [5.5] undecane, 1,2,2,6,6-pentamethyl-4-piperidylhexadecanoate, 1,2,2,6,6-pentamethyl- Examples thereof include 4-piperidyl octadecanoate, and examples ^{of the alkoxy group in which R 1} of the general formula (1) has 1 to 30 carbon atoms include bis (1-octoxy-2,2,6,6-tetramethyl). Examples thereof include -4-piperidyl) sebacate and bis (1-undecyloxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate.
Among these, processability, productivity, in terms of foaming, R ¹ groups are preferably a hindered amine light stabilizer of hydrogen atom or a methyl group represented by the general formula (2), the general formula (2) R ¹ of the groups represented more preferably a hindered amine light stabilizer of methyl groups.

The stabilizer composition of the present invention may also contain a solvent as long as the effects of the present invention are not impaired. From the viewpoint of solubility of the stabilizer component, the solvent is preferably an organic solvent, more preferably an organic solvent having a boiling point of 100 ° C. or higher, further preferably an organic solvent having a boiling point of 120 ° C. or higher, and an organic solvent having a boiling point of 150 ° C. or higher. Solvents are particularly preferred. Examples of preferable organic solvents include 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. Examples thereof include liquid paraffin, naphthenic solvent, normal paraffin solvent, isoparaffin solvent, aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent, and hydrocarbon solvent such as mineral oil.
Only one type of solvent may be used, or two or more types may be used in combination.

In order to obtain the stabilizer composition of the present invention, the essential components (A) to (C) and, if necessary, the above-mentioned preferable compounding components and any compoundable components may be mixed, and the mixture may be mixed. Can use various mixers. It may be heated at the time of mixing. Examples of the mixer that can be used include a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a super mixer, a nouter mixer, and the like. Further, the components may be directly blended with the vinyl chloride resin individually or at the same time in two or more kinds to prepare a vinyl chloride resin composition.

Next, the vinyl chloride resin composition for foam molding of the present invention will be described.
The vinyl chloride-based resin composition for foam molding of the present invention contains a vinyl chloride-based resin, the stabilizer composition of the present invention, and a foaming agent.

First, a vinyl chloride resin will be described.
The vinyl chloride-based resin may be produced by any polymerization method such as massive copolymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and may be produced by, for example, polyvinyl chloride, chlorinated polyvinyl chloride, or polychloride. Vinylidene, 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 ternary copolymer, vinyl chloride-styrene-acrylonilittle copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride -Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, Vinyl chloride-based resins such as vinyl chloride-various vinyl ether copolymers and their mutual blends, other synthetic resins that do not contain chlorine, such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, ethylene -Vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blended product with polyester and the like, block copolymer, graft copolymer and the like can be mentioned. These vinyl chloride resins may be a mixture of two or more kinds, or may be a mixture with other synthetic resins. The vinyl chloride resin used in the present invention is preferably polyvinyl chloride from the viewpoint of processability, productivity, and appearance of the foam molded product.

Next, the foaming agent will be described.
As the foaming agent, conventionally known ones can be used, and examples thereof include a thermal decomposition type organic foaming agent and a thermal decomposition type inorganic foaming agent. Examples of the thermally decomposable organic foaming agent include, for example, azodicarbonamide, azobisisobutylnitrile, diazoaminobenzene, diethylazodicarboxylate, diisopropylazodicarboxylate, azobis (hexahydrobenzonitrile) and the like. Azo-based foaming agents, nitroso-based foaming agents such as N, N'-dinitropentamethylenetetramine, N, N'-dimethyl-N, N'-dinitroterephthalamine, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 3,3 Hydrazide-based foaming agents such as'-disulfone hydrazidephenylsulfone, toluenedisulfonylhydrazone, thiobis (benzenesulfonylhydrazide), tolueneesulfonylazido, toluenesulfonylsemicarbazide, p, p'-bis (benzenesulfonylhydrazide) ether, p-toluene Examples thereof include sulfonyl semicarbazide, a carbazide-based effervescent agent such as 4,4'-oxybis (sulfonyl semi-carbazide), trihydrazine triazine, and a triazine-based effervescent agent such as 1,3-bis (o-biphenyltriazine). Examples of the decomposition type inorganic foaming agent include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compound, sodium borohydride and the like.
Only one type of foaming agent may be used, or two or more types may be used in combination.

The foaming agent is preferably a pyrolytic organic foaming agent, and azodicarbonamide is particularly preferable, because it has excellent foamability and can form fine and uniform foam cells, so that the foamed molded product obtained is excellent in appearance.

The foaming agent is 0.05 to 10.0 with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of compatibility and dispersibility with the vinyl chloride resin and from the viewpoint of forming fine and uniform foam cells. It is preferably contained in parts by mass, and more preferably 0.1 to 8.0 parts by mass.
The foaming agent may be blended in the vinyl chloride resin, but may be blended in the stabilizer composition before being blended in the vinyl chloride resin.

When adding the stabilizer composition of the present invention to a vinyl chloride resin, it is preferable to further add a lubricant in consideration of processability. The lubricant may be added to the stabilizer composition before being added to the vinyl chloride resin.

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 behenin. Higher fatty acids such as acids, and fatty acid-based lubricants such as oxy fatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide and oleylamide, and alkylene such as methylenebisstearylamide and ethylenebisstearylamide. Fatty acid amide-based lubricants such as bis-aliphatic amide; fatty acid monovalent alcohol ester compounds such as stearyl stearate, butyl stearate, and distearyl phthalate, glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, and dipenta. Fatty acid polyhydric alcohol ester compounds such as erythritol hexastearate, polyglycerin polylysinolate, hardened castor oil, monovalent fatty acids such as adipic acid / stearic acid ester of dipentaerythritol, and polybasic organic acids and polyhydric alcohols. Fatty acid alcohol ester-based lubricants such as composite ester compounds of Examples include silicone oil.
Only one type of lubricant may be used, or two or more types may be used in combination.

When the lubricant is used, the amount added is preferably 0.01 to 5.0 parts by mass, and 0.05 to 4.0 parts by mass from the viewpoint of processability with respect to 100 parts by mass of the vinyl chloride resin. It is more preferable, and 0.1 to 3.0 parts by mass is even more preferable.

When adding the stabilizer composition of the present invention to a vinyl chloride resin, it is preferable to further add a processing aid in consideration of processability. The processing aid may be added to the stabilizer composition before being added to the vinyl chloride resin.

The processing aid can be appropriately selected from known processing aids. Examples of the processing aid include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; the common weight of the alkyl methacrylate and alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate. Combined; Copolymer of the alkyl methacrylate with an aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene; Polymer of the alkyl methacrylate and a vinyl cyan compound such as acrylonitrile or methacrylonitrile, etc. Can be mentioned.
Only one type of processing aid may be used, or two or more types may be used in combination.

When the processing aid is used, the amount added is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. ..

In addition to the stabilizer composition of the present invention, the vinyl chloride resin includes other additives usually used for vinyl chloride resins, such as sulfur-based antioxidants, epoxy compounds, plasticizers, and ultraviolet absorbers. Impact improvers, reinforcing materials, fillers, zeolite compounds, perchlorates, magnesium salts of organic acids, perbasic magnesium carbonates, flame retardants, flame retardant aids, etc., as long as the effects of the present invention are not impaired. It can also be blended. These various additives may be added to the stabilizer composition before being added to the vinyl chloride resin.

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl ester, dimyristyl ester, myristylstearyl ester, and distearyl ester of thiodipropionic acid, and pentaerythritol tetra (β-dodecyl mercaptopropio). Examples thereof include β-alkyl mercaptopropionic acid esters of polyols such as Nate).
Only one type of sulfur-based antioxidant may be used, or two or more types may be used in combination.

Examples of the epoxidized compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized flaxseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef fat oil, epoxidized castor oil, and epoxidized safflower oil, and epoxidized tall. Epoxidized tall oil fatty acid ester such as oil fatty acid octyl, epoxidized flaxseed oil fatty acid ester such as epoxidized flaxseed oil fatty acid butyl, epoxidized stearic acid methyl ester, epoxidized stearic acid butyl ester, epoxidized stearic acid 2-ethylhexyl ester, Epoxidized stearic acid stearyl ester, epoxidized polybutadiene, tris (epoxide propyl) isocyanurate, 3- (2-xenoxy) -1,2-epoxide propane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, bisphenol type and novolak type Epoxide resin, vinylcyclohexene diepoxide, dicyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, bis (3,4-epoxidecyclohexyl) adipate, 3,4- Examples thereof include epoxycyclohexylmethyl and epoxycyclohexanecarboxylate.
Only one type of epoxy compound may be used, or two or more types may be used in combination.

Examples of the plasticizer include phthalate plasticizers such as dibutylphthalate, butylhexylphthalate, diheptylphthalate, dioctylphthalate, diisononylphthalate, diisodecylphthalate, dilaurylphthalate, dicyclohexylphthalate, and dioctylterephthalate; dioctyl adipate, diisononyl adipate, and the like. Adipate plasticizers such as diisodecyl adipate, di (butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri ( Butoxyethyl) Phosphate, octyldiphenyl phosphate and other phosphate plasticizers; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butane Polyhydric alcohols such as diols, 1,5-hexanediols, 1,6-hexanediols, neopentyl glycols, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, Polyester-based plasticizer using dibasic acids such as sebatic acid, phthalic acid, isophthalic acid, and terephthalic acid, and using monohydric alcohol and monocarboxylic acid as stoppers if necessary; other tetrahydrophthalic acid-based plasticizers, azelaic acid-based Examples thereof include plasticizers, sebatic acid-based plasticizers, stearic acid-based plasticizers, citric acid-based plasticizers, trimellitic acid-based plasticizers, pyromellitic acid-based plasticizers, and biphenylene polycarboxylic acid-based plasticizers.
Only one type of plasticizer may be used, or two or more types may be used in combination.

The vinyl chloride resin composition for foam molding of the present invention does not contain a plasticizer in terms of processability, productivity, foamability, and from the viewpoint of obtaining a molded product having excellent appearance. A rigid vinyl chloride resin composition or a semi-rigid vinyl chloride resin composition containing 0 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of the vinyl chloride resin is preferable. More preferably.

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-Ditertiary Butylphenyl) -5-Chlorobenzotriazole, 2- (2-Hydroxy-3-3rd Butyl-5-Methylphenyl) -5-Chlorobenzotriazole, 2- (2-Hydroxy-3,5) -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-third octyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-3-third butyl-5-carboxyphenyl) benzotriazole 2- (2-Hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of , 4-Di-tertiary amylphenyl-3,5-di-tertiary butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tertiary butyl-4-hydroxybenzoate and other benzoates; 2-ethyl-2'- Substituted oxanilides such as ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-) Cyanoacrylates such as methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dithiary butylphenyl) -s-triazine, 2- (2- (2-) Hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-ditertiary butylphenyl) )-S-Triaryl triazines and the like can be mentioned.
Only one type of ultraviolet absorber may be used, or two or more types may be used in combination.

Examples of the impact improver include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene graft. Copolymer, acrylonitrile-styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber, styrene-ethylene -Butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone / acrylic composite rubber graft copolymer, silicone rubber And so on. Examples of the ethylene-propylene-diene copolymer rubber (EPDM) diene include 1,4-hexanediene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, propenylnorbornene and the like.
Only one type of impact improver may be used, or two or more types may be used in combination.

As the reinforcing agent, fibrous, plate-shaped, granular, or powder-like ones that are usually used for strengthening synthetic resins can be used. Specifically, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wallastenite, sepiolite, slag fiber, zonolite, elestadite, gypsum fiber, Inorganic fibrous reinforcing materials such as silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton , Jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper scraps, waste paper and organic fibrous reinforcing agents such as wool, glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, clay , Mica, sericite, zeolite, bentonite, dolomite, kaolin, fine powder silicic acid, Nagaishi powder, potassium titanate, silas balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, Examples thereof include plate-like or granular strengthening agents such as silicon oxide, gypsum, novacurite, dosonite and white clay. These strengthening agents may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, and may be coated or focused with a coupling agent such as aminosilane or epoxysilane. It may have been processed.
Only one type of fortifier may be used, or two or more types may be used in combination.

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 the like. Hydrocarbamite, aluminum silicate, magnesium silicate, calcium silicate, metal silicates such as zeolite, active white clay, talc, clay, red iron oxide, antimony trioxide, silica, glass beads, mica, sericite, glass flakes, Examples thereof include walastonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber, and aramid fiber.
Only one type of filler may be used, or two or more types may be used in combination.

The zeolite compound is an alkaline or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure, and typical examples thereof are A-type, X-type, Y-type and P-type zeolite, monodenite, and anal. Sights, sodalite aluminosilicates, clinobtyrolites, erionites, chavasites, etc. can be mentioned, and hydrates having crystalline water (so-called zeolite water) of these zeolite compounds or anhydrides from which crystalline water has been removed. Any of these may be used, and 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.
Only one type of zeolite compound may be used, or two or more types may be used in combination.

Examples of the perchlorate salts include metal perchloric acid salts, ammonium perchlorate, perchloric acid-treated silicates and the like. Examples of the metal constituting these metal salts include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, aluminum and the like. 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.
Only one type of perchlorate may be used, or two or more types may be used in combination.

Examples of the magnesium salt of the organic acid include magnesium salts of organic carboxylic acids, phenols, organic phosphoric acids and the like.

Examples of the organic carboxylic acid include those exemplified in the description of the barium salt. Examples of the phenols include those exemplified in the description of the barium salt. Examples of the organic phosphoric acids include those exemplified in the description of the barium salt.

The magnesium salt of the organic acid may be composed of two or more kinds of organic acids. For example, in the case of a magnesium salt made of a monovalent organic acid, the same organic acid may form an anion moiety and form a salt with a divalent magnesium forming a cation moiety, and different monovalent organic acids 2 may be formed. The seed may form a salt with a divalent magnesium that forms an anionic moiety and forms a cation moiety.
Only one type of magnesium salt of organic acid may be used, or two or more types may be used in combination.
Further, the magnesium salt of the organic acid may be any of an acidic salt, a neutral salt and a basic salt.

The perbasic magnesium carbonate salt is a liquid perbasic carboxylate / carbonate complex of magnesium. This complex is different from a simple mixture of magnesium, a positive carboxylic acid salt, and magnesium carbonate, and is a complex formed by some kind of interaction, and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid. This complex is composed of magnesium carboxylic acid positive salt, magnesium carbonate, and a composite salt of magnesium carboxylic acid and carbonic acid as constituents, and is composed mainly of magnesium carbonate, magnesium carboxylic acid positive salt, and magnesium carboxylic. A complex salt of acid and carbonic acid exists in the vicinity thereof, and a so-called micelle-like substance is formed to show a uniform liquid state in an organic solvent.

The liquid perbasic carboxylate / carbonate complex of magnesium can be produced in the same manner as the liquid superbasic liquid carboxylate / carbonate complex of barium. Alternatively, a commercially available complex can be used as it is.
Only one type of perbasic magnesium carbonate may be used, or two or more types may be used in combination.

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

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. Examples thereof include dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1,3-hexylene melamine.

Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and Kismer 5A (magnesium hydroxide: manufactured by Kyowa Kagaku Kogyo Co., Ltd.).

Examples of the phosphate 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-butyl) Examples thereof include phenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate and the like.

Examples of the condensed phosphoric acid ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Examples of the mescent flame retardant include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.

Examples of the other inorganic flame retardant aid include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof. For example, TIPAQUE R-680 (titanium oxide: Ishihara Sangyo). Various commercially available products such as Kyowa Mug 150 (magnesium oxide: manufactured by Kyowa Kagaku Kogyo Co., Ltd.) can be used.
Only one kind of flame retardant and flame retardant auxiliary may be used, or two or more kinds may be used in combination.

In addition to the stabilizer composition of the present invention, a stabilizing aid usually used for vinyl chloride resins can be added as long as the effect of the stabilizer composition of the present invention is not impaired. 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, bactericides, etc. A metal deactivator, a mold release agent, a white pigment such as titanium dioxide, a pigment such as a blue pigment such as ultramarine blue and phthalocyanine blue, and the like can be blended within a range that does not impair the effects of the present invention.
Only one kind of these optional components may be used, or two or more kinds thereof may be used in combination. These stabilizing aids and optional components may be added to the stabilizer composition before being added to the vinyl chloride resin.

Of the metal stabilizers used in vinyl chloride resins, it is preferable to add lead stabilizers, cadmium stabilizers, and tin stabilizers, which are organic tin compounds, from the viewpoint of environmental impact and toxicity. No.

The vinyl chloride-based resin composition of the present invention contains a vinyl chloride-based resin and the above-mentioned stabilizer composition of the present invention. The content of the above-mentioned stabilizer composition in the vinyl chloride resin composition of the present invention is preferably 0.3 to 15.0 parts by mass, preferably 0.3 to 15.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. 10.0 parts by mass is more preferable, and 0.5 to 8.0 parts by mass is even more preferable.

The vinyl chloride resin composition for foam molding of the present invention is excellent in processability and productivity because it is easy to gel (good gelling property) and can be continuously operated for a long time (good long-running property). Further, since fine and uniform foam cells are formed, the surface of the molded product is not roughened and the surface properties are good, and the appearance of the foamed molded product is excellent.

The vinyl chloride resin composition for foam molding of the present invention is, for example, roll processing, extrusion molding processing, melt casting method, pressure molding processing, injection molding processing, powder molding, paste coating molding, rotary screen molding, calendar. A foam molded product can be obtained by molding by a known molding method such as molding.
The foam molded product of the present invention has good surface properties without surface roughness and is excellent in appearance.

The foam molded product obtained from the vinyl chloride resin composition of the present invention is a building material such as a wall material, a floor material, a window frame, a wallpaper, and a board; an interior material for an automobile; an agricultural material; a food packaging material such as a tray; a leather. , Seats, hoses, toys, boards, panels and other miscellaneous goods. Especially, it is preferably used for building materials, boards, panels and the like.

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited by the following examples.

[Examples 1 to 13 and Comparative Examples 1 to 3]
(Manufacturing of stabilizer composition)
Various components were mixed in the blending amounts shown in Table 1 to produce the stabilizer compositions of the present invention (Examples 1 to 13) and the comparative stabilizer compositions (Comparative Examples 1 to 3). The blending ratio shown in Table 1 is by mass. The stabilizer composition obtained in Example 1 was designated as "stabilizer composition-1", the stabilizer composition obtained in Example 2 was designated as "stabilizer composition-2", and obtained in Examples 3 to 13. The same applies to the obtained stabilizer composition. The comparative stabilizer composition obtained in Comparative Example 1 is "Comparative Stabilizer Composition-1", and the comparative stabilizer composition obtained in Comparative Example-2 is "Comparative Stabilizer Composition-2". The comparative stabilizer composition obtained in Example 3 is referred to as "comparative stabilizer composition-3".

As the polyethylene oxide wax of the component (C) of the example, the following polyethylene oxide waxes 1 to 5 were used. The acid value of polyethylene oxide wax was measured according to JIS K0070. The melt viscosity was measured at 140 ° C. with a B-type viscometer.
Polyethylene oxide wax-1:
Acid value = 15 mgKOH / g, melt viscosity = 200 mPa · s
Polyethylene oxide wax-2:
Acid value = 16 mgKOH / g, melt viscosity = 8500 mPa · s
Polyethylene oxide wax-3:
Acid value = 1 mgKOH / g, melt viscosity = 80 mPa · s
Polyethylene oxide wax-4:
Acid value = 12 mgKOH / g, melt viscosity = 500 mPa · s
Polyethylene oxide wax-5:
Acid value = 20 mgKOH / g, melt viscosity = 440 mPa · s

In the comparative example, instead of the polyethylene oxide wax, a polyethylene wax not subjected to the oxidation modification treatment (acid value = 0) was used as a comparative product. The melt viscosity of this was measured with a B-type viscometer at 140 ° C.
Polyethylene wax comparative product-1: Melt viscosity = 350 mPa · s
Polyethylene wax comparative product-2: Melt viscosity = 80 mPa · s

[Examples 14 to 30, Comparative Examples 4 to 6]
(Manufacturing and evaluation of vinyl chloride resin composition for foam molding)
In 100 parts by mass of the vinyl chloride resin, the stabilizer compositions-1 to the stabilizer compositions-13 obtained in Examples 1 to 13 and the azodicarbonamide as a foaming agent are blended in the amounts shown in Table 2 ( By mass).

Further, 0.1 part by mass of a fanol-based antioxidant as an antioxidant, 0.5 part by mass of dipentaerythritol as a polyhydric alcohol compound, and 1 part by mass of 1,3,5-tris (2-hydroxyethyl) isocyanurate as an antioxidant. 0.1 parts by mass of a lubricant (paraffin wax, Loxyol 2050 manufactured by Emery Oleo Chemicals) and 5.0 parts by mass of an acrylic processing aid (Kaneace PA-40 manufactured by Kaneka Co., Ltd.) are mixed. To produce a vinyl chloride resin composition for foam molding.
Using the Comparative Stabilizer Composition-1 to Comparative Stabilizer Composition-3 obtained in Comparative Examples 1 to 3, a comparative vinyl chloride resin composition was produced in the same manner.

Using the obtained vinyl chloride resin composition for foaming, the following processability test was performed to evaluate the processability (gelling property).

<Processability (gelling property) evaluation test method>
The gelation time was measured using a lab plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 170 ° C. with the time to the first peak top of the torque value as the gelation time. It can be said that the shorter the gelling time, the better the gelling property and the better the processability.

Next, using the obtained vinyl chloride resin composition for foaming, a foamed board, which is a foamed molded product, was produced by continuous operation using an extruder. Productivity (long-running property) and foamability were evaluated by the following evaluation methods.

<Productivity (long run) evaluation test method>
Visually check the surface condition of the foam board, and if there is adhesion such as pyrolysis on the surface, unevenness, roughness, or coloring is seen on the surface, or if the surface is burnt, it is considered as a defective product. bottom. The time when the ratio of defective products per 6 hours exceeded 3% was defined as the continuous operation possible time. It can be said that the longer the continuous operation time is, the better the productivity (long run property) is.

<Effervescent evaluation test method>
The state of the foam cell of the foam board was photographed under a microscope and evaluated on a scale of 10. Evaluation 10 is the best because uniform and fine foam cells are formed, and it is inferior as the numerical value decreases, and the evaluation of the numerical value 1 is the worst.

From the results shown in Tables 1 and 2, the stabilizer composition of the vinyl chloride resin for foam molding of the present invention imparts excellent processability, productivity and foamability to the vinyl chloride resin for foam molding. It is clear that it can be done. Further, it is clear that the vinyl chloride resin composition for foam molding of the present invention is excellent in processability, productivity and foamability, and it is clear that a foam molded product having excellent appearance can be efficiently provided. be.

According to the present invention, it is possible to provide a stabilizer composition capable of imparting excellent processability and productivity to a vinyl chloride resin for foam molding. Further, according to the present invention, it is possible to provide a vinyl chloride resin composition having excellent processability, productivity and foamability. Further, according to the present invention, it is possible to provide a vinyl chloride resin foam molded article having an excellent appearance.

Claims (8)

1. Stabilizer composition of vinyl chloride resin for foam molding containing 5 to 700 parts by mass of the following component (B) and 5 to 200 parts by mass of the following component (C) with respect to 100 parts by mass of the following component (A). ..
   Component (A): Zinc salt of organic acid (B) Component: Metal salt (C) selected from the group consisting of barium salt of organic acid, barium carbonate perbasic, calcium salt of organic acid and calcium carbonate perbasic. ) Ingredients: Polyethylene oxide wax
2. The stabilizer composition of a vinyl chloride resin for foam molding according to claim 1, wherein the acid value of the polyethylene oxide wax of the component (C) is 1.0 mgKOH / g or more and 30.0 mgKOH / g or less.
3. A vinyl chloride resin composition for foam molding containing a vinyl chloride resin, a foaming agent, and the stabilizer composition according to claim 1 or 2.
4. The vinyl chloride for foam molding according to claim 3, which contains 0.05 to 10.0 parts by mass of a foaming agent and 0.3 to 15.0 parts by mass of a stabilizer composition with respect to 100 parts by mass of a vinyl chloride resin. System resin composition.
5. The vinyl chloride resin composition for foam molding according to claim 3 or 4, wherein the foaming agent is azodicarbonamide.
6. The vinyl chloride resin composition is a rigid vinyl chloride resin composition containing no plasticizer, or a semi-rigid vinyl chloride resin composition containing 0 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin composition for foam molding according to any one of claims 3 to 5.
7. The vinyl chloride resin composition for foam molding according to any one of claims 3 to 6, which does not contain a lead-based stabilizer, a cadmium-based stabilizer, and a tin-based stabilizer.
8. A foamed molded product of the vinyl chloride resin composition for foam molding according to any one of claims 3 to 7.