JP2000290418A - Vinyl chloride resin composition for foam molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin composition for foam molding capable of improving the coloring resistance, particularly the heat coloring resistance of a vinyl chloride resin foam molded article obtained by using thermally expandable microcapsules. To do. SOLUTION: The vinyl chloride resin composition for foam molding of the present invention comprises (a) 0.01 to 10 parts by weight of thermally expandable microcapsules and (b) per 100 parts by weight of the vinyl chloride resin.
It is obtained by mixing 0.001 to 10 parts by weight of a perchlorate compound. The shell wall of the microcapsule of the component (A) is a nitrile resin or the like. Further, by adding (c) 0.001 to 10 parts by weight of a thioether-based antioxidant, coloring resistance is further improved. The component (c) is an ester compound of thiodipropionic acid or alkylmercaptopropionic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for foam molding, and more particularly, to a foamed composition comprising a heat-expandable microcapsule and a perchlorate compound. The present invention relates to a vinyl chloride resin composition for molding.

[0002]

BACKGROUND OF THE INVENTION In order to reduce the weight of molded articles, foaming of resins has been carried out. In the past, pyrolytic foaming agents such as azodicarbonamide were often used. Was. However, in foaming using these pyrolytic foaming agents, it is difficult to obtain a uniform foam cell, and foam decomposition remains, which causes various problems. In order to solve the problem of the foam using such a pyrolytic foaming agent, for example, Japanese Patent Application Laid-Open No.
JP-A-35-635 and JP-A-63-57665 propose a foamed composition of a chlorine-containing resin containing a liquid metal perchlorate salt, but a satisfactory composition has not yet been obtained. Did not.

[0003] On the other hand, foamed materials using heat-expandable microcapsules are expected to be widely used in the future because of their beautiful cells and excellent strength. The foam material used was
For example, Japanese Patent Application Laid-Open Nos. 7-113020 and 8-5
3567, JP-A-8-196309, JP-A-9-157427, JP-A-10-152575
Has been proposed.

A vinyl chloride resin is inexpensive and its hardness can be easily adjusted by using a plasticizer, so that it can be used for various applications. It is also being applied to foamed molded products.

[0005] However, in the case of applying a vinyl chloride resin to a foam molded product using a heat-expandable microcapsule,
There is a problem that coloring due to heat occurs during molding or the like. However, this problem does not occur when another thermoplastic resin is used in place of the vinyl chloride resin,
This is considered to be a specific problem when a vinyl chloride resin is used. Further, there is a problem that a resin used as a shell wall material of the heat-expandable microcapsules, in particular, a significant coloring which is considered to be derived from a nitrile resin which is an excellent shell wall material, and its use is currently limited. Was. In order to solve such a problem, it has been proposed to use an antioxidant, but the problem has not been solved yet.

[0006] Accordingly, an object of the present invention is to provide a vinyl chloride-based resin composition for foam molding capable of improving the coloring resistance, particularly the heat-resistant coloring property, of a vinyl chloride-based resin foam molded article obtained by using thermally expandable microcapsules. Is to provide.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object by blending a thermally expandable microcapsule and a perchlorate compound with a vinyl chloride resin. I knew that I could get it.

The present invention has been made on the basis of the above-mentioned findings. 100 parts by weight of a vinyl chloride resin is mixed with (a) 0.01 to 10 parts by weight of thermally expandable microcapsules and (b) a perchlorate compound 0. An object of the present invention is to provide a vinyl chloride resin composition for foam molding comprising 0.001 to 10 parts by weight.

[0009]

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

The vinyl chloride resin used in the present invention is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Examples thereof include polyvinyl chloride and 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 terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer , Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, salt Chlorine-containing resins such as vinyl-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their mutually blended products or the like Chlorine-containing resin and another chlorine-free synthetic resin such as acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer Polymer,
Examples thereof include blends with polyester and the like, block copolymers, graft copolymers, and the like.

The heat-expandable microcapsules of the component (a) used in the present invention have a structure similar to a shell wall composed of a polymer and a volatile liquid expanding agent contained in the shell wall. It is. Examples of the volatile liquid expanding agent include, for example, propane, propene, butane, isobutane, butene, pentane, isopentane, neopentane, hexane, trimethylethylmethane, heptane, petroleum ether, methyl chloride, methylene chloride, trichlorofluoromethane, dichlorodifluoro Methane, tetramethylsilane, trimethylethylsilane and the like can be mentioned. As the polymer used as the shell wall, for example, polyamide, polybutadiene, polyurethane resin, vinylidene chloride, acrylonitrile, acrylamide, acrylic acid, acrylate ester, methacrylonitrile, methacrylamide, methacrylic acid, methacrylic acid ester and the like alone Although a polymer and a copolymer are used, it is particularly preferable to use a nitrile-based resin, particularly a copolymer containing acrylonitrile as a monomer component, since a foam molded article having uniform cells and high strength can be obtained. Other monomer components capable of forming a polymer, for example, acrylic acid,
Examples include methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, vinyl acetate, vinylidene chloride, butadiene and the like. Further, these may be blended.

The amount of these heat-expandable microcapsules is 0.01 to 100 parts by weight of the vinyl chloride resin.
10 to 10 parts by weight, preferably 0.1 to 5 parts by weight,
If the amount is less than 0.01 part by weight, a sufficient expansion ratio cannot be obtained. If the amount is more than 10 parts by weight, not only waste but also uniform foam cells cannot be obtained.

In the present invention, a thermally decomposable foaming agent can be used in combination with the thermally expandable microcapsules. Examples of the pyrolytic foaming agent that can be used in combination include dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, benzenesulfonylhydrazide, p-toluenesulfonylamide, and p, p ' -Oxybis (benzenesulfonylhydrazide), 3,3'-disulfonehydrazidediphenylsulfone, toluenedisulfonylhydrazide, p-toluenedisulfonylhydrazide, p-toluenesulfonylsemicarbazide, azobisisobutylnitrile, azodicarbonamide, diethylazodicarboxy Rate and the like.

These pyrolytic foaming agents are preferably used in an amount of less than 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.
More preferably any amount less than 5 parts by weight is used,
It is not preferable to use more than parts by weight because the cells may be roughened and the aesthetic appearance may be impaired.

The perchlorate compound of component (b) used in the present invention includes lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, barium perchlorate, perchloric acid. Zinc, aluminum perchlorate, lead perchlorate, ammonium perchlorate and the like,
At least one of these is used. These perchlorates may be anhydrous or hydrated salts, and may be those dissolved in alcohol-based or ester-based solvents such as butyl diglycol and butyl diglycol adipate, and their dehydrated products.

The amount of the perchlorate compound used is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
If the amount is less than 1 part by weight, a sufficient effect cannot be obtained.
Reduces the heat resistance of the composition.

It is preferable to further use a thioether-based antioxidant as the component (C) in the vinyl chloride-based resin composition of the present invention since coloring by heat can be further suppressed.

The thioether-based antioxidants include:
For example, thiodipropionate compounds such as dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl, stearyl, distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). Suitable compounds include alkylmercaptopropionate compounds such as β-alkylmercaptopropionate esters of polyols.

The amount of the thioether-based antioxidant to be used is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
-5 parts by weight. If the amount is less than 0.001 part by weight, a sufficient effect cannot be obtained, so that it is not preferable. If the amount is more than 10 parts by weight, not only wasteful but also coloring may be caused.

The composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, for example, organic acid metal salts, plasticizers, antistatic agents, hydrotalcite compounds. , Β-diketone compounds, zeolite compounds, organic phosphite compounds, phenolic antioxidants, epoxy compounds, polyols, ultraviolet absorbers,
A hindered amine-based light stabilizer, other inorganic metal compounds, and the like can also be blended.

Examples of the metal salts of organic acids include, for example, metals (Li, N) of carboxylic acids, phenols or organic phosphoric acids.
a, K, Ca, Mg, Ba, Sr, Cd, Zn, Al,
Sn, organic Sn) salts, which are normal salts, acidic salts,
It may be a basic salt or an overbased salt.

Examples of the carboxylic acid include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid,
Oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acids, coconut fatty acids,
Mixtures of the above naturally occurring acids such as tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5- Trioctylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid and the like, and the phenols include, for example,
Phenol, cresol, ethyl phenol, cyclohexyl phenol, nonyl phenol, dodecyl phenol and the like, and as the organic phosphoric acid, for example, mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di- (Nonylphenyl) phosphoric acid, nonylphenyl phosphonate, stearyl phosphonate and the like can be mentioned.

Examples of the plasticizer include dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate,
Phthalic acid-based plasticizers such as dicyclohexyl phthalate and dioctyl terephthalate; adipic acid-based plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di (butyldiglycol) adipate; ethylene glycol, diethylene glycol, and triethylene glycol as polyhydric alcohols , 1,2-
Propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol and the like, and as a dibasic acid,
Use oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and if necessary, monohydric alcohol and monocarboxylic acid. Polyester plasticizer used for the stopper: triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate And other phosphate ester plasticizers; other, tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, and trimellitic acid plasticizers. , Pyromellitic acid plasticizers include biphenylene polycarboxylic acid plasticizers.

Examples of the antistatic agent include polyoxyethylene lauryl ether, -stearyl ether, -nonylphenyl ether, polyethylene glycol monopalmitate, -monostearate, polyoxyethylene sorbitan monolaurate, -monopalmitate. , Glycerin monolaurate, -monopalmitate,
-Monostearate,-monooleate, pentaerythritol monolaurate, sorbitan monopalmitate,
-Monobehenate,-distearate, diglycerindiolate sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauric lauramide ethyl phosphate, triethylcetylammonium iodide Oleylaminodiethylamine hydrochloride, dodecylpyridinium salt and the like.

The hydrotalcite compound is a complex salt compound comprising magnesium and / or an alkali metal and aluminum or zinc, magnesium and aluminum as represented by the following general formula (I), and is obtained by dehydrating water of crystallization. It may be.

Ia _X1 Mg _X2 Zn _X3 Al _y (OH) _{X1 + 2 (X2 + X3) + 3y-2} (CO ₃ ) _{1-z / 2} (ClO ₄ ) mH ₂ O (I) (wherein Ia Represents an alkali metal atom, x1, x
2, x3, y, and z each represent a number that satisfies the condition represented by the following equation, and m represents a real number. 0 ≦ x1 ≦ 10,0 ≦
x2 ≦ 10, 0 ≦ x3 ≦ 10, 0 ≦ y ≦ 10, 0 ≦ z ≦
10. However, x1 and x2 are never 0 at the same time. )

The hydrotalcite compound may be a natural product or a synthetic product. The method for synthesizing the synthetic product is described in JP-B-46-2280, JP-B-50-30039, and JP-B-51-29129.
Gazette, Japanese Patent Publication No. 3-36839, JP-A-61-174
Known methods described in, for example, Japanese Patent Application Laid-Open No. 270, JP-A-5-17952 and the like can be exemplified. Further, the above hydrotalcite compound can be used without being limited by its crystal structure, crystal particle system and the like.

The surface of the hydrotalcite compound may be a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, or a higher salt thereof. It may be one coated with a fatty acid amide, a higher fatty acid ester or a wax.

Examples of the β-diketone compound include dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene, and the like, and the like. Metal salts (lithium, sodium, potassium, calcium,
Magnesium, barium, zinc, etc.).

The zeolite compound is an alkali or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure.
Type, X type, Y type, and P type zeolite, monodenite,
Analsite, sodalite group aluminosilicate, clinbutyrolite, erionite, chabazite and the like can be mentioned, and the hydrate or crystallization water containing crystal water of these zeolite compounds (so-called zeolite water) is removed. Any of anhydrides may be used.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono- and di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) .ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di Tributylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite,
Dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol)
1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-)
Methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C
12-15 mixed alkyl) -4,4'-isopropylidenediphenyl phosphite, bis [2,2'-methylenebis (4,6-diamylphenyl)] isopropylidene diphenyl phosphite, hydrogenated-4,4 ' -Isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (
2-tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl •
4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphonite,
Examples thereof include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,3 5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m -Cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) , Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidenebis (4,
6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3
-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) Phenyl] terephthalate, 1,3,5-
Tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert. Tributyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl- 6- (2-Acroyloxy-3-tert-butyl-
5-methylbenzyl) phenol, 3,9-bis [2-
(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the epoxy compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, and the like. Epoxidized methyl stearate, -butyl, -2-
Ethylhexyl, -stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, vinylcyclohexene diepoxide, dicyclohexene carboxylate, 3,
4-epoxycyclohexenemethylepoxycyclohexanecarboxylate, bisphenol A diglycidyl ether and the like.

The polyols include, for example, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol half-ester stearic acid, bis (dipentaerythritol) adipate, Glycerin,
Tris (2-hydroxyethyl) isocyanurate, sorbitol, mannitol, trehalose and the like can be mentioned.

As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 '-(2-methacryloyloxyethoxyethoxy) benzophenone, 5,5'-methylenebis (2-hydroxy-4 2-hydroxybenzophenones such as -methoxybenzophenone); 2- (2-hydroxy-5-
Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-3-tert-butyl-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (2-hydroxy-
3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7
~ 9 mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; 2- (2-hydroxy-4
-Hexyloxyphenyl) -4,6-diphenyl-1,
3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6 -Bis (2,4-dimethylphenyl)-
2- (2-hydroxyphenyl) -1,3,5-triazines such as 1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert. Tributyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-
3,5-di-tert-butyl-4-hydroxybenzoate,
Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2'-
Substituted oxanilides such as ethoxy oxanilide and 2-ethoxy-4'-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-
And cyanoacrylates such as cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, , 2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2
2,6,6-pentamethyl-4-piperidyl) -1,
2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,
2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-
Hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6- Tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino- s
Triazine polycondensate, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane /
2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,
4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-
6-yl] -1,5,8,12-tetraazadodecane,
1,5,8,12-Tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-
Piperidyl) amino) -s-triazin-6-yl]-
1,5,8,12-tetraazadodecane, 1,6,11
-Tris [2,4-bis (N-butyl-N- (2,2,
6,6-tetramethyl-4-piperidyl) amino-s-
Triazin-6-ylamino] undecane, 1,6,1
1-tris [2,4-bis (N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane.

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

The composition of the present invention may further contain other stabilizing aids usually used for vinyl chloride resins. Examples of such a stabilizing aid include diphenylthiourea, diphenylurea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, and the like.

In addition, the composition of the present invention may contain, if necessary, additives usually used for vinyl chloride resins, for example,
Fillers, colorants, cross-linking agents, antistatic agents, plate-out inhibitors, surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides,
A bactericide, a metal deactivator, a release agent, a pigment, a processing aid, an antioxidant, a light stabilizer, a foaming agent, and the like can be added.

The composition of the present invention can be used irrespective of the method for processing a vinyl chloride resin.
For example, it can be suitably used for calendering, roll processing, extrusion molding, injection molding, paste processing, melt rolling, pressure molding, powder molding, and the like.

The composition of the present invention includes building materials such as wall materials, floor materials, window frames, and wallpaper; electric wire coating materials; interior and exterior materials for automobiles;
Agricultural materials such as tunnels; fish food packaging materials such as wraps and trays; paints, hoses, pipes, sheets, toys and other miscellaneous goods.

[0042]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1 The following composition was calendered at 120 ° C. to prepare a 0.7 mm sheet. The sheet and the sheet at 140 ° C. for 20 minutes and 200 ° C.
And the yellowness after heating for 10 minutes was measured. Further, the presence or absence of bloom in the sheet was visually evaluated. In addition, extrusion foaming was performed at 210 ° C. using the same composition, the yellowness of the molded product was measured, and the state of the foam cells was visually observed.

(Blending) Parts by weight Vinyl chloride resin (degree of polymerization 800) 100 Dioctyl phthalate 50 Titanium dioxide (rutile type) 1.5 Zinc stearate 0.2 Alkamizer 1 0.7 (manufactured by Kyowa Chemical Co., Ltd .; synthesis) Hydrotalcite) Stearoyl benzoylmethane 0.1 EXPANCEL 6.0 (manufactured by Akzo Nobel; heat-expandable microcapsules) Test compounds (described in Table 1) Table 1

[0045]

[Table 1]

[0046]

[Table 2]

As is clear from the results shown in Tables 1 and 2, the vinyl chloride resin composition for foam molding using the heat-expandable microcapsules is colored by heat, and the foam molding material obtained therefrom is severe. It becomes colored (Comparative Example 1-1). This was hardly improved by using ordinary phenolic or phosphorus antioxidants (Comparative Example 1-
2,1-3), although the thioether-based antioxidants show some improvement effects, they are still insufficient (Comparative Example 1--1).
Four ).

On the other hand, by adding the perchlorate compound according to the present invention, coloring due to heat is suppressed, whereby a foamed molding material having excellent coloring resistance can be obtained (all Examples). By using a thioether-based antioxidant in combination therewith, a more excellent effect of suppressing coloration can be exhibited (Examples 1-4 to 1-8).

[0049]

The vinyl chloride resin composition for foam molding of the present invention can provide a foam molding material having significantly improved coloring properties.

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Claims (4)

[Claims] 1. 100 parts by weight of a vinyl chloride resin,
(B) A vinyl chloride resin composition for foam molding, comprising 0.01 to 10 parts by weight of thermally expandable microcapsules and (b) 0.001 to 10 parts by weight of a perchlorate compound. 2. The vinyl chloride resin composition for foam molding according to claim 1, wherein the shell wall of the microcapsule of the component (a) is a nitrile resin. 3. The composition according to claim 1, further comprising (C) 0.001 to 10 parts by weight of a thioether-based antioxidant.
The vinyl chloride resin composition for foam molding according to the above. 4. The vinyl chloride resin composition for foam molding according to claim 3, wherein the component (c) is an ester compound of thiodipropionic acid or alkylmercaptopropionic acid.