Stabilizer composition for vinyl chloride resin for foam molding, vinyl chloride resin composition for foam molding containing the same, and foam molded article thereof

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

Technical Field

[0001] The present invention relates to a stabilizer composition for vinyl chloride-based resin for foam molding, a vinyl chloride-based resin composition for foam molding containing the stabilizer composition, and a foam molded article thereof.

Background Art

[0002] Vinyl chloride-based resins are excellent in flame retardancy, chemical resistance, mechanical stability, transparency, adhesiveness, printability, etc., and can be easily changed in hardness from hard to soft by adding a plasticizer. Therefore, they are used in various applications. In particular, hard vinyl chloride-based resin compositions that do not contain any plasticizer or semi-hard vinyl chloride-based resin compositions that contain a small amount of plasticizer (for example, contain 50 parts by mass or less of plasticizer with respect to 100 parts by mass of vinyl chloride-based resin) are widely used for boards, panels, building materials, etc. because of their excellent rigidity.

[0003] In particular, as building materials members aimed at boards, panels, synthetic woods, etc., the production of foam molded articles has been widely attempted. These foam molded articles require good processability and productivity. In terms of processability, it is necessary to be easily gelled (gelation property). In terms of productivity, long-term continuous operation of the processing machine (long run property) is required. However, when production is carried out continuously for a long time, the resin composition gradually accumulates in the processing machine, which thermally decomposes, and the thermal decomposition products adhere to the surface of the molded article, etc., resulting in a problem that defective products with deteriorated surface appearance of the molded article are generated. Further, when fine and uniform foam cells are not formed, the appearance of the foam molded article is inferior due to deterioration of surface properties such as surface roughness, and a vinyl chloride-based resin composition excellent in foamability and a foam molded article having an excellent appearance are required. In contrast, the use of acrylic polymers has been proposed (Patent Documents 1 and 2).

[0004] On the one hand, as stabilizers for vinyl chloride resins, conventionally, heavy metal stabilizers such as lead and cadmium have been used from the perspective of cost advantages and the like because they are inexpensive. However, in recent years, with the increasing concern for environmental protection and conservation, their use has become a problem due to the toxicity of heavy metals and their adverse effects on the environment. Also, tin-based stabilizers, which are organotin compounds, are not preferable from the perspective of their impact on the environment and toxicity.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

[0006] In the conventional technology, the processability of vinyl chloride resins for foam molding, particularly the gelling property, and the productivity, particularly the long-run property, are not sufficient. Further, the foaming property is also not sufficient, and the appearance of the obtained foam molded article is not satisfactory.

[0007] Therefore, an object of the present invention is to provide a stabilizer composition that can impart excellent processability and productivity to vinyl chloride resins for foam molding. Another object of the present invention is to provide a vinyl chloride resin composition having excellent processability, productivity, and foaming property. Furthermore, an object of the present invention is to provide a vinyl chloride resin foam molded article having an excellent appearance.

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a combination of a specific metal salt and polyethylene oxide wax, and have thus completed the present invention.

[0009] That is, the present invention provides a stabilizer composition for vinyl chloride resins for foam molding, which contains 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). (A) component: Zinc salt of organic acid (B) component: Metal salt selected from the group consisting of barium salt of organic acid, overbasic barium carbonate salt, calcium salt of organic acid, and overbasic calcium carbonate salt (C) component: Oxidized polyethylene wax

[0010] The present invention also provides the above-mentioned stabilizer composition for vinyl chloride resin for foam molding, characterized in that the acid value of the oxidized polyethylene wax as the (C) component is 1.0 mgKOH / g or more and 30.0 mgKOH / g or less. The present invention also provides a vinyl chloride resin composition for foam molding containing a vinyl chloride resin, a foaming agent, and the above-mentioned stabilizer composition.

[0011] The present invention also provides the above-mentioned vinyl chloride resin composition for foam molding, 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 the vinyl chloride resin. The present invention also provides the above-mentioned vinyl chloride resin composition for foam molding, wherein the foaming agent is azodicarbonamide.

[0012] The present invention also provides the above-mentioned vinyl chloride resin composition for foam molding, wherein 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 present invention also provides the above-mentioned 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 foam molded article of the above-mentioned vinyl chloride resin composition for foam molding.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, embodiments of the present invention will be described in detail. First, the stabilizer composition for 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). Component (A): Zinc salt of an organic acid Component (B): A metal salt selected from the group consisting of barium salts of organic acids, overbased barium carbonate salts, calcium salts of organic acids, and overbased calcium carbonate salts Component (C): Oxidized polyethylene wax

[0014] First, component (A) will be described. Component (A) of the present invention contains one or more zinc salts of organic acids. Examples of such zinc salts of organic acids include zinc salts of organic carboxylic acids, phenols, and organic phosphoric acids.

[0015] Examples of the organic carboxylic acid include monovalent aliphatic saturated carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, neodecanoic acid, capric acid, undecanoic acid, isoundecylic acid, lauric acid, isolauric acid, tridecanoic acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, versatic acid; monovalent aromatic carboxylic acids such as benzoic acid, monochlorobenzoic acid, 4-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, toluic acid, dimethylbenzoic acid, 2,4-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, 2,4,6-trimethylbenzoic acid, ethylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 2,4,6-triethylbenzoic acid, 4-isopropylbenzoic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid; monovalent aliphatic unsaturated carboxylic acids such as elaidic acid, oleic acid, linoleic acid, linolenic acid, myristoleic acid, palmitoleic acid, elaeostearic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, arachidonic acid, docosapentaenoic acid, docosahexaenoic acid, ricinoleic acid; monovalent sulfur atom-containing carboxylic acids such as thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic acid; divalent aliphatic saturated carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; divalent aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid; divalent or trivalent aliphatic unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid; divalent sulfur atom-containing carboxylic acids such as thiodipropionic acid; monoester or monoamide compounds of these divalent carboxylic acids;Examples of the di- or tri-ester compounds of trivalent or tetravalent carboxylic acids include dibutane tricarboxylic acid, butane tetracarboxylic acid, hemimellitic acid, trimellitic acid, mellophanic acid, pyromellitic acid, etc.

[0016] Examples of the phenols include tertiary butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, methyl tertiary octylphenol, etc.

[0017] Examples of the organic phosphoric acids include alkyl phosphoric acids such as mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di(nonylphenyl) phosphoric acid; and alkyl phosphonate esters such as nonylphenyl phosphonate ester, stearyl phosphonate ester, etc.

[0018] The zinc salt of the organic acid may be any of an acidic salt, a neutral salt, a basic salt, and a perbasic complex in which part or all of the base of the basic salt is neutralized with carbonic acid.

[0019] Also, the zinc salt of the organic acid may be composed of two or more organic acids. For example, in the case of a zinc salt of a monovalent organic acid, the same organic acid may form an anion site and form a salt with divalent zinc that forms a cation site, or two different monovalent organic acids may form an anion site and form a salt with divalent zinc that forms a cation site.

[0020] In the present invention, from the viewpoints of processability, productivity, and foaming properties, the component (A) is preferably a zinc salt of an organic acid selected from the group consisting of zinc acetate, zinc benzoate, zinc toluate, zinc 4-tert-butylbenzoate, zinc stearate, zinc laurate, zinc versatate, zinc octylate, zinc oleate, zinc palmitate, and zinc myristate. As the zinc salt of the organic acid which is the component (A), only one kind may be used, or two or more kinds may be used in combination.

[0021] Next, the component (B) will be described. The component (B) of the present invention is a metal salt selected from the group consisting of barium salts of organic acids, overbased barium carbonate salts, calcium salts of organic acids, and overbased calcium carbonate salts. The component (B) may contain two or more kinds of metal salts.

[0022] First, the barium salt of the organic acid will be described. Examples of such barium salts of organic acids include barium salts of organic carboxylic acids, phenols, organic phosphoric acids, and the like.

[0023] Examples of the organic carboxylic acid include monovalent aliphatic saturated carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, neodecanoic acid, capric acid, undecanoic acid, isoundecylic acid, lauric acid, isolauric acid, tridecanoic acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, versatic acid, etc.; monovalent aromatic carboxylic acids such as benzoic acid, monochlorobenzoic acid, 4-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, toluic acid, dimethylbenzoic acid, 2,4-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, 2,4,6-trimethylbenzoic acid, ethylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 2,4,6-triethylbenzoic acid, 4-isopropylbenzoic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, etc.; monovalent aliphatic unsaturated carboxylic acids such as elaidic acid, oleic acid, linoleic acid, linolenic acid, myristoleic acid, palmitoleic acid, elaeostearic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, arachidonic acid, docosapentaenoic acid, docosahexaenoic acid, ricinoleic acid, etc.; monovalent sulfur atom-containing carboxylic acids such as thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic acid, etc.; divalent aliphatic saturated carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.; divalent aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, etc.; divalent or trivalent aliphatic unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, etc.; divalent sulfur atom-containing carboxylic acids such as thiodipropionic acid, etc.; monoester or monoamide compounds of these divalent carboxylic acids;Examples of the di- or triesters of trivalent or tetravalent carboxylic acids include dibutane tricarboxylic acid, butane tetracarboxylic acid, hemimellitic acid, trimellitic acid, mellophanic acid, pyromellitic acid, etc.

[0024] Examples of the phenols include tertiary butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, methyl tertiary octylphenol, etc.

[0025] Examples of the organic phosphoric acids include alkyl phosphoric acids such as mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di(nonylphenyl) phosphoric acid; and alkyl phosphonate esters such as nonylphenyl phosphonate, stearyl phosphonate, etc.

[0026] 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 of a monovalent organic acid, the same organic acid may form an anion site and form a salt with divalent barium that forms a cation site, or two different monovalent organic acids may form an anion site and form a salt with divalent barium that forms a cation site. The barium salt of the organic acid may be used alone or in combination of two or more kinds. Also, the barium salt of the organic acid may be any of an acidic salt, a neutral salt, and a basic salt.

[0027] Next, the basic barium carbonate salt will be described. The basic barium carbonate salt is a liquid basic carboxylate / carbonate complex of barium. This complex is different from a simple mixture of the normal carboxylate salt of barium and barium carbonate. Instead, these substances form a complex through some kind of interaction. It has the characteristics of having a high metal content and showing a uniform liquid state in an organic solvent. This complex is composed of the normal carboxylate salt of barium, barium carbonate, and a composite salt of barium carboxylate and carbonate as its constituent components. With barium carbonate at the center, the normal carboxylate salt of barium and the composite salt of barium carboxylate and carbonate exist around it. By forming something like a micelle, it shows a uniform liquid state in an organic solvent.

[0028] The liquid basic carboxylate / carbonate complex of barium can be produced, for example, by the production method shown in JP-A-2004-238364.

[0029] As for the liquid basic carboxylate / carbonate complex of barium, various commercially available complexes can also be used as they are. Representative commercially available complexes include, for example, "PlastiStab TM 2116" (basic barium oleate / carbonate complex: specific gravity 1.42 - 1.53, Ba = 33 - 36%), "PlastiStab TM 2513" (basic barium oleate / carbonate complex: specific gravity 1.41 - 1.52, Ba = 33 - 36%), "PlastiStab TM 2508" (basic barium oleate / carbonate complex: specific gravity 1.39 - 1.51, Ba = 33 - 36%), etc. The basic barium carbonate salt may be used alone or in combination of two or more.

[0030] Next, the calcium salt of the organic acid will be described. Examples of such calcium salts of organic acids include calcium salts of organic carboxylic acids, phenols, or organic phosphoric acids.

[0031] Examples of the organic carboxylic acids include those exemplified in the description of the barium salts above. Examples of the phenols include those exemplified in the description of the barium salts above. Examples of the organic phosphoric acids include those exemplified in the description of the barium salts above.

[0032] The calcium salt of the organic acid may be composed of two or more organic acids. For example, in the case of a calcium salt formed by a monovalent organic acid, the same organic acid may form an anion site and form a salt with divalent calcium that forms a cation site, or two different monovalent organic acids may form an anion site and form a salt with divalent calcium that forms a cation site. Only one type of calcium salt of the organic acid may be used, or two or more types may be used in combination. Also, the calcium salt of the organic acid may be any of an acidic salt, a neutral salt, and a basic salt.

[0033] Next, the overbased calcium carbonate salt will be described. The overbased calcium carbonate salt is a liquid overbased carboxylate / carbonate complex of calcium. This complex is different from a simple mixture of a normal calcium carboxylate and calcium carbonate. These are complexed by some interaction, and it has the characteristic of showing a uniform liquid state in an organic solvent while having a high metal content. This complex is composed of a normal calcium carboxylate of calcium, calcium carbonate, and a composite salt of a carboxylic acid and carbonate of calcium as constituent components. With calcium carbonate as the center, the normal calcium carboxylate of calcium and the composite salt of a carboxylic acid and carbonate of calcium exist around it, and by forming something like a micelle, it shows a uniform liquid state in an organic solvent.

[0034] The liquid overbased carboxylate / carbonate complex of calcium can be produced in the same manner as the liquid overbased carboxylate / carbonate complex of barium. Also, various commercially available complexes can be used as they are. Representative examples of commercially available complexes include, for example, "PlastiStab TM 2265" (overbased calcium oleate / carbonate complex: specific gravity 1.04 - 1.09, Ca = 10%) manufactured by AM STABILIZERS, USA. The overbased calcium carbonate salt may be used alone or in combination of two or more.

[0035] The barium salt of an organic acid, overbased barium carbonate salt, calcium salt of an organic acid, and overbased calcium carbonate salt used as component (B) of the stabilizer composition of the present invention may be used alone or in combination of two or more.

[0036] Component (B) of the stabilizer composition of the present invention is preferably at least one selected from the group consisting of the barium salt of an organic acid and the calcium salt of an organic acid from the viewpoints of processability, productivity, and foamability, and more preferably the calcium salt of an organic acid. As specific compounds, from the viewpoints of processability, productivity, and foamability, as the barium salt of an organic acid, barium stearate is preferable, and as the calcium salt of an organic acid, calcium stearate is preferable. Component (B) preferably contains calcium stearate among these.

[0037] The content of component (B) in the stabilizer composition of the present invention is preferably 5 - 700 parts by mass, more preferably 25 - 500 parts by mass, and particularly preferably 50 - 300 parts by mass with respect to 100 parts by mass of the zinc salt of the organic acid of component (A) from the viewpoints of processability, productivity, and foamability.

[0038] Next, component (C) of the stabilizer composition of the present invention will be described. Component (C) of the present invention contains one or more of polyethylene oxide waxes.

[0039] From the viewpoints of processability, productivity, and foamability, the acid value of the polyethylene wax is preferably 1.0 mgKOH / g or more and 30 mgKOH / g or less, more preferably 5.0 mgKOH / g or more and 25.0 mgKOH / g or less, still 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 in accordance with JIS K0070.

[0040] In the present invention, from the viewpoints of processability, productivity, and the appearance of the foam molded body, the melt viscosity of the polyethylene wax is preferably in the range of 50 to 10,000 mPa·s when measured at 140 °C with a B-type viscometer, and more preferably 100 to 9,000 mPa·s.

[0041] In the present invention, from the viewpoints of processability, productivity, and foamability, the number average molecular weight of the polyethylene wax is preferably 800 to 8,000, and more preferably 1,000 to 6,000.

[0042] The method for producing the polyethylene wax is not particularly limited. For example, the polyethylene wax obtained by a method such as polymerizing ethylene at low pressure with a Ziegler catalyst or reducing the molecular weight of polyethylene for general molding by thermal decomposition can be oxidized by a method such as air oxidation to produce it. Also, those modified with an alcohol or the like can be used.

[0043] Commercially available products may be used as the polyethylene wax. For example, polyethylene waxes such as the Hiwax series manufactured by Mitsui Chemicals, Inc., the Sunwax series manufactured by Sanyo Chemical Industries, Ltd., the Rubax series manufactured by Nippon Seiro Co., Ltd., and the A-C series manufactured by Honeywell can be mentioned.

[0044] The content of component (C) in the stabilizer composition of the present invention is preferably 5 to 200 parts by mass, more preferably 10 to 120 parts by mass, and particularly preferably 20 to 80 parts by mass with respect to 100 parts by mass of the zinc salt of the organic acid of component (A) from the viewpoints of processability, productivity, and foaming properties.

[0045] From the viewpoints of processability, productivity, and foaming properties, it is also preferable that the stabilizer composition of the present invention further contains a phenolic antioxidant. The phenolic antioxidant is preferably contained in an amount of 1 to 200 parts by mass, more preferably 2 to 150 parts by mass, and even more preferably 5 to 100 parts by mass with respect to 100 parts by mass of component (A).

[0046] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), bis [3,3-bis(4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl]-2,4,8,Examples include 10 - tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3 - tert - butyl - 4 - hydroxy - 5 - methylphenyl) propionate], etc. Only one type of phenolic antioxidant may be used, or two or more types may be used in combination.

[0047] Among these phenolic antioxidants, pentaerythritol tetrakis [3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionate] is preferred in terms of processability, productivity, and foaming properties.

[0048] From the viewpoints of processability, productivity, and foaming properties, it is also preferable for the stabilizer composition of the present invention to further contain a polyhydric alcohol compound. In terms of processability, productivity, and foaming properties, it is preferably contained in an amount of 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and even more preferably 20 to 100 parts by mass based on 100 parts by mass of component (A).

[0049] Examples of the polyhydric alcohol compound include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5 - tris(2 - hydroxyethyl) isocyanurate, polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, lactose, etc. Only one type of polyhydric alcohol compound may be used, or two or more types may be used in combination.

[0050] Among these polyhydric alcohol compounds, dipentaerythritol and 1,3,5 - tris(2 - hydroxyethyl) isocyanurate are preferred in terms of processability, productivity, and foaming properties.

[0051] From the viewpoints of processability, productivity, and foamability, the stabilizer composition of the present invention can further contain a β-diketone compound.

[0052] Examples of the β-diketone compound include acetylacetone, triacetylmethane, 2,4,6-heptatrienone, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, distearoylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis(4-octylbenzoyl)methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, ethyl acetoacetate, cyclohexane-1,3-dione, methyl 3,6-dimethyl-2,4-dioxocyclohexane-1-carboxylate, 2-acetylcyclohexanone, dimedone, 2-benzoylcyclohexane, etc. Metal salts thereof can also be used in the same manner. Examples of the metal salts include lithium salts, sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts, and aluminum salts. Examples of preferred metal salts include calcium acetylacetonate and zinc acetylacetonate. Only one type of β-diketone compound may be used, or two or more types may be used in combination.

[0053] From the viewpoints of processability, productivity, and foamability, the stabilizer composition of the present invention can further contain a phosphite compound.

[0054] Examples of the phosphite compound include trialkyl phosphite, dialkyl phosphite, dialkyl monoallyl phosphite, alkyl allyl phosphite, monoalkyl diallyl phosphite, diallyl phosphite, triallyl phosphite, etc.

[0055] In the present invention, either a triester or a diester can be used, but from the viewpoints of processability, productivity, and the appearance of the foam molded article, it is preferable to use a triester. Further, a thioester can also be used.

[0056] Examples of the phosphite compound include triphenyl phosphite, tricresyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(mono- and di-mixed nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, diphenyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite, octyldiphenyl phosphite, diphenyldecyl phosphite, diphenyl(2-ethylhexyl) phosphite, di(decyl) monophenyl phosphite, diphenyltridecyl phosphite, diphenyl(C12-C15 mixed alkyl) phosphite, phenyldiisodecyl phosphite, phenylbis(isotridecyl) phosphite, triethyl phosphite, tributyl phosphite, 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-cyclohexanedimethyl diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, di(tridecyl) pentaerythritol diphosphite, phenyl-4,4'-Isopropylidenediphenol pentaerythritol diphosphite, tetra(C12~15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis(octylphenyl)·bis[4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol)]·1,6-hexanediol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, hexa(tridecyl)·1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane triphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol·2,4,6-tri-tert-butylphenol monophosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tetra(tridecyl) isopropylidenediphenol diphosphite, tetrakis(2,4-di-tert-butylphenyl) biphenylene diphosphite, tris(2-[(2,4,8,10-tetrakis tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol, etc. can be mentioned., The phosphite compound may be used alone or in combination of two or more kinds.,

[0057] Among these phosphite compounds, from the viewpoints of processability, productivity, and foaming property, phosphite compounds having 12 to 80 carbon atoms are preferable, phosphite compounds having 12 to 46 carbon atoms are more preferable, phosphite compounds having 12 to 36 carbon atoms are still more preferable, and phosphite compounds having 18 to 30 carbon atoms are particularly preferable.,

[0058] From the viewpoints of processability, productivity, and foamability, the stabilizer composition of the present invention can further contain a hydrotalcite compound.

[0059] Examples of the hydrotalcite compound include compounds represented by the following general formula (1). Mg x1 Zn x2 Al2(OH) 2x1+2x2+4 (CO3) 1-y1 / 2 (ClO4) y1 mH2O (1)

[0060] In the formula (1), x1, x2, and y1 represent numbers that satisfy the conditions represented by 0 ≦ x2 / x1 < 10, 2 ≦ x1 + x2 < 20, and 0 ≦ y1 ≦ 2, and m represents 0 or an arbitrary integer.

[0061] As the hydrotalcite compound, a double salt compound composed of magnesium and aluminum, or zinc, magnesium, and aluminum is preferably used. Further, it may be one from which crystal water has been dehydrated, or one treated with perchloric acid. Such a hydrotalcite compound may be a natural product or a synthetic product. There are no restrictions on the crystal structure, crystal particle size, etc. of the hydrotalcite compound.

[0062] As the hydrotalcite compound, those whose surface is coated with a higher fatty acid such as stearic acid, a metal salt of a higher fatty acid such as an alkali metal salt of oleic acid, a metal salt of an organic sulfonic acid such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or wax can also be used. Only one type of hydrotalcite-based compound may be used, or two or more types may be used in combination.

[0063] From the viewpoints of processability, productivity, and foamability, the stabilizer composition of the present invention can further contain a hindered amine light stabilizer.

[0064] The hindered amine light stabilizer is not particularly limited as long as it is a conventionally known hindered amine light stabilizer. 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-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1,2,2,6,6-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=sebacate mixture, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / succinic acid diethyl polycondensate, 1,6-bis(2,2,6,6-Tetramethyl-4-piperidylamino)hexane / dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tri-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino-s-triazin-6-ylamino]undecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino-s-triazin-6-ylamino]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-tetramethylpiperidin-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., The hindered amine light stabilizer may be used alone or in combination of two or more kinds.,

[0065] From the viewpoints of processability, productivity, and foamability, the hindered amine light stabilizer is preferably a compound having a group represented by the following general formula (2).

[0066]

Chem.

[0067] In the general formula (2), R 1 represents 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, a hydroxyalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an oxy radical, and these alkyl groups, alkoxy groups, hydroxyalkyl groups, hydroxyalkoxy groups, and alkenyl groups may be interrupted by one or more oxygen atoms or carbonyl groups. Further, the group of the general formula (2) is bonded at the position of *. The group of the general formula (2) may be contained in plural in the compound.

[0068] Examples of the alkyl group having 1 to 30 carbon atoms that R 1 in the general formula (2) can take include a linear alkyl group or a branched alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, etc. Examples of the branched alkyl group include a group in which one or more of the above linear alkyl groups are substituted with an alkyl group having 1 to 9 carbon atoms.

[0069] Examples of the alkoxy group having 1 to 30 carbon atoms that R 1 in the general formula (2) can take include alkoxy groups corresponding to the above alkyl groups.

[0070] In the general formula (2), R 1Examples of the hydroxyalkyl group having 1 to 30 carbon atoms that can be taken include hydroxyalkyl groups corresponding to the above-described alkyl groups.

[0071] R in the general formula (2) 1 Examples of the hydroxyalkoxy group having 1 to 30 carbon atoms that can be taken include hydroxyalkoxy groups corresponding to the above-described alkoxy groups.

[0072] R in the general formula (2) 1 Examples of the alkenyl group having 2 to 30 carbon atoms that can be taken include, for example, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group, henicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, pentacosenyl group, hexacosenyl group, heptacosenyl group, octacosenyl group, nonacosenyl group, triacontenyl group, and corresponding alkadienyl groups and alkatrienyl groups thereof.

[0073] From the viewpoints of processability, productivity, and foamability, the group represented by the general formula (2) is preferably such that R 1 is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.

[0074] Examples of the hindered amine light stabilizer having the group represented by the general formula (2) include, for example, R in the general formula (2) 1As those having a hydrogen atom, 2,2,6,6 - tetramethyl - 4 - piperidyl stearate, 2,2,6,6 - tetramethyl - 4 - piperidyl benzoate, 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 - tert - octylamino - s - triazine polycondensate, 1,5,8,12 - tetrakis[2,4 - bis(N - butyl - N - (2,2,6,6 - tetramethyl - 4 - piperidyl)amino) - s - triazin - 6 - yl] - 1,5,8,12 - tetraazadodecane, 1,6,11 - tris[2,4 - bis(N - butyl - N - (2,2,6,6 - tetramethyl - 4 - piperidyl)amino - s - triazin - 6 - ylamino]undecane, 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, 2,2,6,6 - tetramethyl - 4 - piperidyl hexadecanoate, 2,2,6,6 - tetramethyl - 4 - piperidyl octadecanoate, etc. may be mentioned, and R of the general formula (1) 1Examples of those in which R is a methyl group include 1,2,2,6,6-pentamethyl-4-piperidyl stearate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 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) = decanedioate / methyl = 1,2,2,6,6-pentamethyl-4-piperidyl = sebacate mixture, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino-s-triazin-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-piperidyl hexadecanoate, 1,2,2,6,6-pentamethyl-4-piperidyl octadecanoate, etc. The R in the general formula (1) 1 Examples of those in which R is an alkoxy group having 1 to 30 carbon atoms include bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, etc. Among these, from the viewpoints of processability, productivity, and foaming properties, R in the group represented by the general formula (2) 1 is preferably a hindered amine light stabilizer in which R is a hydrogen atom or a methyl group, and more preferably a hindered amine light stabilizer in which R in the group represented by the general formula (2) 1 is a methyl group.

[0075] The stabilizer composition of the present invention can also contain a solvent as long as the effects of the present invention are not impaired. From the viewpoint of the 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, still more preferably an organic solvent having a boiling point of 120 °C or higher, and particularly preferably an organic solvent having a boiling point of 150 °C or higher. Examples of preferred organic solvents include alcohol-based organic solvents such as 3-methoxy-n-butanol, 2-ethylhexanol, undecanol, and tridecanol; glycol-based organic solvents such as methyl diglycol, butyl diglycol, and methylpropylene glycol; hydrocarbon-based solvents such as liquid paraffin, naphthenic solvents, normal paraffin solvents, isoparaffin solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and mineral oil. Only one type of solvent may be used, or two or more types may be used in combination.

[0076] To obtain the stabilizer composition of the present invention, the essential components (A) to (C) and, if necessary, the above-mentioned preferred compounding components and optional components that can be compounded may be mixed, and various mixers can be used for mixing. Heating may be performed during mixing. Examples of mixers that can be used include tumbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, and Nauta mixers. Further, the above components may be directly compounded into the vinyl chloride-based resin, either individually or simultaneously in two or more types, to prepare a vinyl chloride-based resin composition.

[0077] Next, the vinyl chloride-based 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.

[0078] First, the vinyl chloride resin will be described. The vinyl chloride resin may be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. For example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers and other vinyl chloride resins, and blends thereof, other synthetic resins not containing chlorine, for example, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth)acrylate copolymer, blends with polyester, etc., block copolymers, graft copolymers, etc. These vinyl chloride resins may be a mixture of two or more kinds, or a mixture with other synthetic resins. The vinyl chloride resin used in the present invention is preferably polyvinyl chloride from the viewpoints of processability, productivity, and the appearance of the foamed molded article.

[0079] Next, the foaming agent will be described. As the foaming agent, those conventionally known can be used, for example, thermal decomposition type organic foaming agents and thermal decomposition type inorganic foaming agents. Examples of the thermal decomposition type organic foaming agents include azo-based foaming agents such as azodicarbonamide, azobisisobutyronitrile, diazoaminobenzene, diethyl azodicarboxylate, diisopropyl azodicarboxylate, azobis(hexahydrobenzonitrile); nitroso-based foaming agents such as N,N'-dinitropentamethylenetetramine, N,N'-dimethyl-N,N'-dinitroterephthalamide; hydrazide-based foaming agents such as benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, 3,3'-disulfohydrazide phenyl sulfone, toluene disulfonyl hydrazone, thiobis(benzenesulfonyl hydrazide), toluene esulfonyl azide, toluene sulfonyl semicarbazide, p,p'-bis(benzenesulfonyl hydrazide) ether; carbazide-based foaming agents such as p-toluenesulfonyl semicarbazide, 4,4'-oxybis(sulfonyl semicarbazide); triazine-based foaming agents such as trihydrazinotriazine, 1,3-bis(o-biphenyltriazine), etc. Examples of the decomposition type inorganic foaming agents include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compounds, sodium borohydride, etc. Only one type of foaming agent may be used, or two or more types may be used in combination.

[0080] From the viewpoint that the foaming agent has excellent foamability and can form fine and uniform foam cells, resulting in excellent appearance of the foam molded body, thermal decomposition type organic foaming agents are preferred, and azodicarbonamide is particularly preferred.

[0081] From the viewpoints of compatibility and dispersibility with vinyl chloride resins and forming fine and uniform foam cells, it is preferably contained in an amount of 0.05 to 10.0 parts by mass, more preferably 0.1 to 8.0 parts by mass, based on 100 parts by mass of the vinyl chloride resin. The foaming agent may be compounded with the vinyl chloride resin, or may be compounded in the stabilizer composition before being compounded with the vinyl chloride resin.

[0082] 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 blended into the stabilizer composition before being blended into the vinyl chloride resin.

[0083] Examples of the lubricant include hydrocarbon lubricants such as low molecular weight wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, and fluorocarbon; natural wax lubricants such as carnauba wax and candelilla wax; fatty acid lubricants such as higher fatty acids like lauric acid, stearic acid, behenic acid, and oxy fatty acids like hydroxystearic acid; aliphatic amide lubricants such as aliphatic amide compounds like stearylamide, laurylamide, and oleylamide, and alkylene bis aliphatic amides like methylene bis stearylamide and ethylene bis stearylamide; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, and distearyl phthalate, fatty acid polyhydric alcohol ester compounds such as glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, polyglycerin polyricinoleate, and hydrogenated castor oil, and fatty acid alcohol ester lubricants such as composite ester compounds of monobasic fatty acids and polybasic organic acids and polyhydric alcohols like adipic acid·stearic acid ester of dipentaerythritol; aliphatic alcohol lubricants such as stearyl alcohol, lauryl alcohol, and palmityl alcohol; metal soaps; montanic acid lubricants such as partially saponified montanic acid esters; acrylic lubricants; silicone oil, etc. Only one type of lubricant may be used, or two or more types may be used in combination.

[0084] When using the lubricant, the addition amount is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 4.0 parts by mass, and even more preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of processability.

[0085] When adding the stabilizer composition of the present invention to a vinyl chloride-based resin, it is preferable to further add a processing aid in consideration of processability. The processing aid may be blended into the stabilizer composition before being blended into the vinyl chloride-based resin.

[0086] 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; copolymers of the alkyl methacrylate and alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the alkyl methacrylate and aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; copolymers of the alkyl methacrylate and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, etc. Only one type of processing aid may be used, or two or more types may be used in combination.

[0087] When using the processing aid, the addition amount is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the vinyl chloride-based resin.

[0088] In addition to the stabilizer composition of the present invention, other additives usually used in vinyl chloride-based resins, such as sulfur-based antioxidants, epoxy compounds, plasticizers, ultraviolet absorbers, impact modifiers, reinforcing materials, fillers, zeolite compounds, perchlorates, magnesium salts of organic acids, overbased magnesium carbonate salts, flame retardants, flame retardant aids, etc., can also be blended within a range that does not impair the effects of the present invention. These various additives may be blended into the stabilizer composition before being blended into the vinyl chloride-based resin.

[0089] Examples of the sulfur-based antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, myristyl stearyl thiodipropionate, and distearyl thiodipropionate, and β-alkyl mercaptopropionic acid esters of polyols such as pentaerythritol tetra(β-dodecyl mercaptopropionate). Only one type of sulfur-based antioxidant may be used, or two or more types may be used in combination.

[0090] Examples of the epoxy compound include epoxidized vegetable and animal oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil; epoxidized tall oil fatty acid esters such as epoxidized octyl tall oil fatty acid; epoxidized linseed oil fatty acid esters such as epoxidized butyl linseed oil fatty acid; epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, and epoxidized stearyl stearate; epoxidized polybutadiene; tris(epoxypropyl) isocyanurate; 3-(2-xenoxy)-1,2-epoxypropane; epoxidized polybutadiene; bisphenol-A diglycidyl ether; bisphenol type and novolac type epoxy resins; vinylcyclohexene diepoxide; dicyclohexene diepoxide; dicyclopentadiene diepoxide; 3,4-epoxycyclohexyl-6-methyl epoxycyclohexanecarboxylate; bis(3,4-epoxycyclohexyl) adipate; 3,4-epoxycyclohexylmethyl epoxycyclohexanecarboxylate, etc. Only one type of epoxy compound may be used, or two or more types may be used in combination.

[0091] Examples of the plasticizer include phthalate plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(butyldiglycol) adipate; phosphate plasticizers such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri(butoxyethyl) phosphate, and octyldiphenyl phosphate; polyester plasticizers prepared by using polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, and neopentyl glycol and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid, and optionally using monohydric alcohols and monocarboxylic acids as stoppers; and other plasticizers such as tetrahydrophthalic acid-based plasticizers, azelaic acid-based plasticizers, sebacic 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.

[0092] From the viewpoints of processability, productivity, foamability, and obtaining a molded article with excellent appearance, the vinyl chloride resin composition for foam molding is preferably a rigid vinyl chloride resin composition that does not contain a plasticizer or a semi-rigid vinyl chloride resin composition that contains 0 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of the vinyl chloride resin, and more preferably a rigid vinyl chloride resin.

[0093] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxyphenyl)benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol, and polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl α-cyano-β,β-diphenylacrylate and methyl 2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. Only one type of ultraviolet absorber may be used, or two or more types may be used in combination.

[0094] Examples of the impact improver include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, 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, etc. Examples of the diene of the ethylene-propylene-diene copolymer rubber (EPDM) include 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene, etc. Only one type of impact improver may be used, or two or more types may be used in combination.

[0095] As the reinforcing agent, fibrous, plate-shaped, granular, or powdery materials commonly used for reinforcing synthetic resins can be used. Specifically, inorganic fibrous reinforcing materials such as glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, slag fiber, zonolite, elestadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and boron fiber; organic fibrous reinforcing agents such as polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, manila hemp, sugarcane, wood pulp, paper scraps, waste paper, and wool; and plate-shaped or granular reinforcing agents such as glass flake, non-swelling mica, graphite, metal foil, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silica, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dacite, and clay can be mentioned. These reinforcing agents may be coated or aggregated with thermoplastic resins such as ethylene / vinyl acetate copolymer or thermosetting resins such as epoxy resin, or may be treated with coupling agents such as aminosilane and epoxy silane. Only one type of reinforcing agent may be used, or two or more types may be used in combination.

[0096] Examples of the filler include metal silicates such as calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium aluminosilicate, hydrocalumite, aluminum silicate, magnesium silicate, calcium silicate, zeolite, activated clay, talc, clay, red iron oxide, antimony trioxide, silica, glass beads, mica, sericite, glass flakes, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber, aramid fiber, and the like. Only one type of filler may be used, or two or more types may be used in combination.

[0097] The zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure. Representative examples thereof include A-type, X-type, Y-type, and P-type zeolites, mordenite, analcite, sodalite group aluminosilicates, clinoptilolite, erionite, and chabazite. Any of a hydrate having crystal water (so-called zeolite water) of these zeolite compounds or an anhydride obtained by removing crystal water may be used, and those having a particle size of 0.1 to 50 μm can be used, and particularly, those having a particle size of 0.5 to 10 μm are preferable. Only one type of zeolite compound may be used, or two or more types may be used in combination.

[0098] Examples of the perchlorates include metal perchlorates, ammonium perchlorate, perchloric acid-treated silicate, 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 perchlorate may be an anhydride or a hydrate, and may also be a solution in an alcohol-based or ester-based solvent such as butyl diglycol or butyl diglycol adipate and its dehydrate. Perchlorates may be used alone or in combination of two or more.

[0099] Examples of the magnesium salts of the organic acids include magnesium salts of organic carboxylic acids, phenols, or organic phosphoric acids.

[0100] Examples of the organic carboxylic acids include those exemplified in the description of the barium salts. Examples of the phenols include those exemplified in the description of the barium salts. Examples of the organic phosphoric acids include those exemplified in the description of the barium salts.

[0101] The magnesium salts of the organic acids may be composed of two or more organic acids. For example, in the case of a magnesium salt of a monovalent organic acid, the same organic acid may form an anion site and form a salt with divalent magnesium that forms a cation site, or two different monovalent organic acids may form an anion site and form a salt with divalent magnesium that forms a cation site. The magnesium salts of the organic acids may be used alone or in combination of two or more. Also, the magnesium salts of the organic acids may be any of acidic salts, neutral salts, and basic salts.

[0102] The overbasic magnesium carbonate salt is a liquid overbasic carboxylate / carbonate complex of magnesium. This complex is different from a simple mixture of magnesium, a normal carboxylate of magnesium, and magnesium carbonate. These are complexed by some interaction and have the characteristic of showing a uniform liquid state in an organic solvent while having a high metal content. This complex is composed of a normal carboxylate of magnesium, magnesium carbonate, and a complex salt of a carboxylic acid and carbonate of magnesium as constituent components. With magnesium carbonate as the center, the normal carboxylate of magnesium and the complex salt of a carboxylic acid and carbonate of magnesium exist around it, and a micelle-like structure is formed, whereby it shows a uniform liquid state in an organic solvent.

[0103] The liquid overbased carboxylate / carbonate complex of magnesium can be produced in the same manner as the liquid overbased carboxylate / carbonate complex of barium. Also, a commercially available complex can be used as it is. Only one type of overbased magnesium carbonate salt may be used, or two or more types may be used in combination.

[0104] 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, phosphate ester-based flame retardants, condensed phosphate ester-based flame retardants, intumescent-based flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, organic flame retardant aids, and the like.

[0105] Examples of the triazine ring-containing compounds include melamine, ammeline, benzoguanamine, acetoguanamine, phthalodiguamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, 1,3-hexylenedimelamine, and the like.

[0106] Examples of the metal hydroxides include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kisuma 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.), and the like.

[0107] Examples of the phosphate-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, trixylenyl phosphate, octyldiphenyl phosphate, xylenyl diphenyl phosphate, tris(isopropylphenyl) 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.

[0108] Examples of the condensed phosphate-based flame retardants include 1,3-phenylenebis(diphenyl phosphate), 1,3-phenylenebis(dixylenyl phosphate), bisphenol A bis(diphenyl phosphate), and the like. Examples of the intumescent flame retardants 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.

[0109] Examples of the other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof. For example, various commercially available products such as TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.) and Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.) can be used. Only one type of flame retardant and flame retardant aid may be used, or two or more types may be used in combination.

[0110] In addition to the stabilizer composition of the present invention, within a range that does not impair the effects of the stabilizer composition of the present invention, a stabilizing aid usually used for vinyl chloride resins can be added. Examples of such stabilizing aids include diphenylthiourea, anilinodithiothiazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, and the like. Further, if necessary, additives usually used for vinyl chloride resins, such as crosslinking agents, antistatic agents, antifogging agents, anti-plating agents, surface treatment agents, fluorescent agents, antifungal agents, bactericides, metal deactivators, release agents, white pigments such as titanium dioxide, and pigments such as blue pigments such as ultramarine blue and phthalocyanine blue can be blended within a range that does not impair the effects of the present invention. Only one type of these optional components may be used, or two or more types may be used in combination. These stabilizing aids and optional components may be blended into the stabilizer composition before being blended into the vinyl chloride resin.

[0111] Among the metal-based stabilizers used for vinyl chloride resins, it is not preferable to add lead-based stabilizers, cadmium-based stabilizers, and tin-based stabilizers which are organotin compounds from the viewpoints of environmental impact and toxicity.

[0112] The vinyl chloride resin composition of the present invention contains a vinyl chloride resin and the above-described stabilizer composition of the present invention. The content of the above-described stabilizer composition in the vinyl chloride resin composition of the present invention is preferably 0.3 to 15.0 parts by mass, more preferably 0.3 to 10.0 parts by mass, and even more preferably 0.5 to 8.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

[0113] 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-run property). Further, since fine and uniform foam cells are formed, the surface roughness of the molded body is eliminated and the surface property is good, and the appearance of the foam molded body is excellent.

[0114] The vinyl chloride resin composition for foam molding of the present invention can be molded by known molding methods such as roll processing, extrusion molding, melt casting, pressure molding, injection molding, powder molding, paste coating molding, rotary screen molding, calender molding, etc. to obtain a foam molded body. The foam molded body of the present invention has good surface properties without surface roughness or the like and is excellent in appearance.

[0115] The foam molded body obtained from the vinyl chloride resin composition of the present invention can be suitably used as building materials such as wall materials, floor materials, window frames, wallpapers, boards, etc.; interior materials for automobiles; agricultural materials; food packaging materials such as trays; sundries such as leather, sheets, hoses, toys, boards, panels, etc. It is particularly preferably used for building materials, boards, panels, etc.

Examples

[0116] Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited by the following examples.

[0117] 〔Examples 1 to 13 and Comparative Examples 1 to 3〕 (Production of stabilizer composition) Various components were mixed in the blending amounts shown in Table 1 to produce the stabilizer composition of the present invention (Examples 1 to 13) and the comparative stabilizer composition (Comparative Examples 1 to 3). The blending ratios shown in Table 1 are in parts 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 the same applies to the stabilizer compositions obtained in Examples 3 to 13. The comparative stabilizer composition obtained in Comparative Example 1 was designated as "Comparative Stabilizer Composition - 1", the comparative stabilizer composition obtained in Comparative Example - 2 was designated as "Comparative Stabilizer Composition - 2", and the comparative stabilizer composition obtained in Comparative Example 3 was designated as "Comparative Stabilizer Composition - 3".

[0118] As the polyethylene wax oxide of component (C) in the examples, the following polyethylene wax oxides 1 to 5 were used. The acid value of the polyethylene wax oxide was measured in accordance with JIS K0070. The melt viscosity was measured at 140 ° C with a B-type viscometer. Polyethylene wax - 1 oxidized: Acid value = 15 mg KOH / g, melt viscosity = 200 mPa·s Polyethylene wax - 2 oxidized: Acid value = 16 mg KOH / g, melt viscosity = 8500 mPa·s Polyethylene wax - 3 oxidized: Acid value = 1 mg KOH / g, melt viscosity = 80 mPa·s Polyethylene wax - 4 oxidized: Acid value = 12 mg KOH / g, melt viscosity = 500 mPa·s Polyethylene wax - 5 oxidized: Acid value = 20 mg KOH / g, melt viscosity = 440 mPa·s

[0119] In the comparative example, instead of the oxidized polyethylene wax, a non - oxidized polyethylene wax (acid value = 0) was used as a comparative product. Its melt viscosity was measured at 140 °C with a B - type viscometer. Comparative product of polyethylene wax - 1: Melt viscosity = 350 mPa·s Comparative product of polyethylene wax - 2: Melt viscosity = 80 mPa·s

[0120] [Table 1]

[0121] [Examples 14 - 30, Comparative Examples 4 - 6] (Manufacture and evaluation of vinyl chloride - based resin composition for foam molding) To 100 parts by mass of the vinyl chloride - based resin, the stabilizer compositions - 1 to - 13 obtained in Examples 1 - 13 and azodicarbonamide as a foaming agent were blended in the blending amounts (parts by mass) shown in Table 2.

[0122] Furthermore, 0.1 part by mass of a phenol-based antioxidant, 0.5 part by mass of dipentaerythritol as a polyhydric alcohol compound, 1 part by mass of 1,3,5-tris(2-hydroxyethyl)isocyanurate, 0.1 part by mass of a lubricant (paraffin wax, Roxiol 2050 manufactured by Emery Oleochemicals), and 5.0 parts by mass of an acrylic processing aid (Kaneka Ace PA-40 manufactured by Kaneka Corporation) were blended, and they were mixed with a Henschel mixer to produce a vinyl chloride resin composition for foam molding. Using the comparative stabilizer compositions -1 to -3 obtained in Comparative Examples 1 to 3, a comparative vinyl chloride resin composition was similarly produced.

[0123] Using the obtained vinyl chloride resin composition for foam, the following processability test was conducted to evaluate the processability (gelation property).

[0124] <Processability (Gelation Property) Evaluation Test Method> Using a Laboplast Mill (manufactured by Toyo Seiki Seisaku-sho, Ltd.), the time until the first peak top of the torque value at 170 °C was measured as the gelation time. The shorter the gelation time, the better the gelation property and the better the processability.

[0125] Next, using the obtained vinyl chloride resin composition for foam, a foam board as a foam molded body was continuously produced using an extruder. The productivity (long-run property) and the foaming property were evaluated by the following evaluation methods.

[0126] <Productivity (Long-Run Property) Evaluation Test Method> The surface state of the foam board was visually confirmed, and those with deposits such as thermal decomposition products adhering to the surface, unevenness, roughness, coloring, or burning on the surface were regarded as defective products. The time when the ratio of defective products per 6 hours exceeded 3% was defined as the continuous operation possible time. The longer the continuous operation possible time, the better the productivity (long-run property).

[0127] <Foaming Property Evaluation Test Method> The state of the foam cells of the foam board was microscopically photographed and evaluated in 10 grades. Evaluation 10 indicates that uniform and fine foam cells are formed, being the best. The quality deteriorates as the numerical value decreases, and evaluation 1 is the worst.

[0128]

Table 2

[0129] From the results shown in Table 1 and Table 2, it is clear that the stabilizer composition for vinyl chloride-based resin for foam molding of the present invention can impart excellent processability, productivity, and foamability to the vinyl chloride-based resin for foam molding. Also, it is clear that the vinyl chloride-based resin composition for foam molding of the present invention is excellent in processability, productivity, and foamability, and can efficiently provide a foam molded body with excellent appearance.

Industrial Applicability

[0130] According to the present invention, it is possible to provide a stabilizer composition that can impart excellent processability and productivity to a vinyl chloride-based resin for foam molding. Also, according to the present invention, it is possible to provide a vinyl chloride-based resin composition having excellent processability, productivity, and foamability. Further, according to the present invention, it is possible to provide a vinyl chloride-based resin foam molded body having excellent appearance.

Claims

1. A stabilizer composition for a vinyl chloride-based resin for foam molding, which contains 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 an organic acid Component (B): A metal salt selected from the group consisting of barium salts of organic acids, overbasic barium carbonate salts, calcium salts of organic acids, and overbasic calcium carbonate salts Component (C): Oxidized polyethylene wax A stabilizer composition for a vinyl chloride-based resin for foam molding, wherein the acid value of the oxidized polyethylene wax as component (C) is 13.0 mgKOH / g or more and 20.0 mgKOH / g or less.

2. A vinyl chloride-based resin composition for foam molding, which contains a vinyl chloride-based resin, a foaming agent, and the stabilizer composition according to Claim 1.

3. The vinyl chloride-based resin composition for foam molding according to Claim 2, which contains 0.05 to 10.0 parts by mass of a foaming agent and 0.3 to 15.0 parts by mass of the stabilizer composition with respect to 100 parts by mass of the vinyl chloride-based resin.

4. The vinyl chloride-based resin composition for foam molding according to Claim 2 or 3, wherein the foaming agent is azodicarbonamide.

5. The vinyl chloride-based resin composition for foam molding according to any one of Claims 2 to 4, wherein the vinyl chloride-based resin composition is a rigid vinyl chloride-based resin composition that does not contain a plasticizer, or a semi-rigid vinyl chloride-based resin composition that contains 0 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of the vinyl chloride-based resin.

6. The vinyl chloride-based resin composition for foam molding according to any one of Claims 2 to 5, which does not contain a lead-based stabilizer, a cadmium-based stabilizer, and a tin-based stabilizer.

7. A foam molded article of the vinyl chloride-based resin composition for foam molding according to any one of Claims 2 to 6.

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