JP2001342361A - Chlorine containing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chlorine containing resin composition having an excellent flexibility, cold resistance, heat resistance, etc. without using any compound with a risk of estrogenic activity, by selecting a plasticizer with excellent plasticizing efficiency, cold resistance, heat resistance, etc. SOLUTION: The chlorine-containing resin composition comprises a chlorine- containing resin, a plasticizer and other additives, wherein the plasticizer comprises from 5 to 95 wt.% glycol diester of dibenzoic acid of formula (I) (wherein G is a 2-10C alkylene group; and p is 1-10) and from 95 to 5 wt.% polyester plasticizer having a number average molecular weight of from 500 to 2,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chlorine-containing resin composition, and more particularly, to a chlorine-containing resin composition having excellent flexibility, cold resistance, heat aging resistance and the like.

[0002]

2. Description of the Related Art Chlorine-containing resins are inexpensive and excellent in various properties such as transparency, heat resistance, weather resistance and flame retardancy, and use plasticizers. Since the hardness can be easily adjusted by this, it can be used for various applications.

Hitherto, plasticizers for chlorine-containing resins have been excellent in plasticization efficiency, cold resistance, heat resistance, etc.
Phthalic acid-based plasticizers such as di (2-ethylhexyl) phthalate, adipate-based plasticizers such as di (2-ethylhexyl) adipate, and the like have been frequently used. However, in recent years, it has been suspected that these phthalic acid-based or adipic acid-based plasticizers are compounds that may have estrogenic activity. I was

[0004] As an alternative plasticizer, polyester-based plasticizers and the like can be cited. However, since these have relatively low compatibility with chlorine-containing resins, there is a problem that bleeding occurs when they are blended in large amounts. Therefore, its use is limited.

Accordingly, an object of the present invention is to find a plasticizer excellent in plasticization efficiency, cold resistance, heat resistance and the like without using a compound having a possibility of having estrogen activity, and to obtain flexibility, cold resistance and heat resistance. An object of the present invention is to provide a chlorine-containing resin composition having excellent properties and the like.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object by using glycol dibenzoic acid diester and a polyester plasticizer having a number average molecular weight of 500 to 2,000 in combination. And reached the present invention.

That is, the present invention provides a chlorine-containing resin, a plasticizer,
And a chlorine-containing resin composition comprising: (A) 5-95% by weight of a glycol dibenzoic acid diester represented by the following general formula (I); and (B) a number average molecular weight of 500. It is intended to provide a chlorine-containing resin composition comprising from 95 to 5% by weight of a polyester plasticizer of from 2000 to 2000%.

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[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the chlorine-containing resin composition of the present invention will be described in detail.

The chlorine-containing 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.
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, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, Vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymer Chlorine-containing resins such as bodies, and their mutual blends or their chlorine-containing resins and other chlorine-free synthetic resins, such as acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene terpolymer, Ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer,
Examples thereof include blends with polyester and the like, block copolymers, graft copolymers, and the like.

The plasticizer used in the present invention comprises (a) 5 to 95% by weight, preferably 5 to 60% by weight, particularly preferably 10 to 60% by weight of glycol dibenzoic diester represented by the above general formula (I). 50% by weight and (b) number average molecular weight 50
95 to 5% by weight of a polyester plasticizer of 0 to 2000,
Preferably 15 to 95% by weight, particularly preferably 50 to 9% by weight.
When the amount of the component (a) is large, physical properties such as cold resistance may be deteriorated, and when the amount of the component (b) is large, bleeding may occur. There is not preferred.

In the above general formula, the number of carbon atoms represented by G is 2
Examples of the alkylene group of 10 to 10 include straight-chain or branched groups such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene, and p is 1 to 10, and preferably 1 to 10.
5 Each of these may be used alone, or may be a mixture of those having different degrees of polymerization.

In the present invention, the glycol dibenzoic acid diester represented by the above formula (I) as the component (a) includes, for example, ethylene glycol dibenzoic acid ester, diethylene glycol dibenzoic acid ester, triethylene glycol dibenzoic acid ester , Polyethylene glycol dibenzoate, propylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, 1,3-butanediol dibenzoate, 1,
4-butanediol dibenzoate, 1,6-hexanediol dibenzoate, 3-methyl-1,5
-Pentanediol dibenzoate, 1,8-octanediol dibenzoate and the like are preferred.

In the present invention, as the polyester plasticizer having a number average molecular weight of 500 to 2,000 as the component (b),
It is a polyester plasticizer having a number average molecular weight of 500 to 2,000 comprising a polybasic acid and a polyhydric alcohol and, if necessary, a monohydric alcohol or a monohydric carboxylic acid as a terminal stopper.

Here, when the number average molecular weight is less than 500, there is no flexibility at low temperature and only poor heat aging properties can be obtained.
When it exceeds, it is not preferable because only those having no flexibility at low temperature can be obtained.

The polybasic acids include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid,
Aliphatic dibasic acids such as azelaic acid and dodecanedicarboxylic acid are used alone or in combination. In addition, a small percentage of aromatic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid are used. Polybasic acids or aliphatic polybasic acids such as butanetricarboxylic acid, tricarballylic acid and citric acid can also be used.

The polyhydric alcohol includes, for example, ethylene glycol, diethylene glycol,
2-propanediol, 1,3-propanediol,
2,2-dimethyl-1,3-propanediol, 2,2
-Diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexane Diol, 3-methyl-
Fats such as 1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propylene glycol Aromatic glycols are used alone or as a mixture, in addition to which a small proportion of glycerin,
Polyhydric alcohols such as trimethylolpropane, trimethylolethane, and pentaerythritol can also be used.

Examples of the above monohydric alcohol include methanol, ethanol, propanol, isopropanol, butanol, secondary butanol, isobutanol, hexanol, isohexanol, heptanol, and the like.
Isoheptanol, octanol, isooctanol,
2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol, isodecanol, undecanol, isoundecanol, dodecanol, tridecyl alcohol, isotridecyl alcohol, benzyl alcohol, alcohol constituting 2-alkyl-1-alkanol residue As the (terminal stopper component), for example, 2-butyloctanol, 2-butyldecanol,
2-hexyloctanol, 2-hexyldecanol,
-2-octyldecanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol and the like are used alone or in combination.

The monovalent carboxylic acids include, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexylic acid, octylic acid,
2-Ethylhexylic acid, nonylic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like are used alone or in combination.

The number average molecular weight used in the present invention is 500 to 500.
Among the 2,000 polyester plasticizers, compounds represented by the following general formulas (II) and (III) are particularly preferable.

[0020]

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In the above general formula (II) or (III),
R ₁ and R ₂ are groups derived from the above-mentioned monohydric alcohols or monocarboxylic acids, and examples of the alkyl group having 5 to 13 carbon atoms represented by these include pentyl, hexyl, heptyl, octyl, nonyl, Straight-chain or branched groups such as decyl, undecyl, dodecyl and tridecyl; and A ₁ is a group derived from the above polybasic acid;
₁ is a group derived from the above polyhydric alcohol, and as the alkylene group having 2 to 10 carbon atoms represented by these,
Examples thereof include linear or branched groups such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. Among these polyester plasticizers represented by the general formula (II) or (III), A ₁ is a straight-chain alkylene group having 4 carbon atoms, and G ₁ is a straight-chain alkylene group having 3 to 6 carbon atoms. It is preferable to use a branched alkylene group because a variety of performances can be obtained.

The polyester plasticizer can be produced by a known method. For example, in the presence of a catalyst such as dibutyltin oxide or tetraalkyl titanate,
The polybasic acid described for the general formula (I),
It can be produced using the polyhydric alcohol and the terminal stopper component. The ratio of each of the above components used in the production varies depending on the type of the component used and the properties of the intended polyester plasticizer, molecular weight, etc., but generally 10 to 80% by weight of an aliphatic polybasic acid, It is used in a ratio of 10 to 80% by weight of a polyhydric alcohol and 1 to 50% by weight of a terminal stopper component.

The polyester plasticizer preferably has an acid value of 1 or less and a hydroxyl value of 30 or less.

The amount of the plasticizer comprising the components (a) and (b) in the present invention varies depending on the intended use of the chlorine-containing resin composition. Parts, preferably 25 to 100 parts by weight. If the addition amount is less than 20 parts by weight, the effect of imparting flexibility by using a plasticizer cannot be sufficiently exerted, and if it exceeds 120 parts by weight, no further effect is exhibited, and bleeding occurs. And is economically disadvantageous.

The composition of the present invention may further contain various additives usually used as additives for chlorine-containing resins, for example, metal salts of organic acids, organic tin compounds, hydrotalcite compounds, β-diketones. Compounds, lubricants, anti-fog agents,
Antifog, liquid polybutadiene, perchlorates, zeolite compounds, organic phosphite compounds, phenolic or sulfuric antioxidants, epoxy compounds, polyols, ultraviolet absorbers, hindered amine light stabilizers, other inorganic metal compounds Etc. can also be blended.

Examples of the organic acid metal salts include organic acid zinc salts and organic acid alkaline earth salts. The alkaline earth metals constituting the organic acid alkaline earth metal salts include magnesium, calcium, barium and strontium. And the like, as the organic acid, carboxylic acid, phenols or organic phosphoric acid and the like, and the organic acid metal salt is a normal salt,
Acid salts, basic salts or overbased salts may be used.

Examples of the carboxylic acids 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 oil fatty acids, tung oil fatty acids, soybean oil fatty acids, cottonseed oil fatty acids, and other naturally occurring mixtures of the above acids, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid,
Toluic acid, xylic acid, salicylic acid, 5-tert-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid and the like. In addition, as the phenols,
For example, phenol, cresol, ethylphenol,
Cyclohexylphenol, nonylphenol, dodecylphenol and the like are mentioned. Examples of the organic phosphoric acid include 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. .

Examples of the above-mentioned organotin compounds include laurate, malate and dibutyltin or dioctyltin.
Mercapto, malate polymers, 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 (IV), and is obtained by dehydrating water of crystallization. It may be.

[0030]

Embedded image (Where x1 and x2 each represent a condition represented by the following formula, and m represents 0 or a positive number; 0 ≦ x2 / x1 <1
0, 2 ≦ x1 + x2 ≦ 20)

The above 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 hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter, 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. Metal salts (lithium, sodium, potassium, calcium, magnesium, barium, zinc, etc.) and the like.

Examples of the lubricant include hydrocarbon lubricants, fatty acid lubricants, fatty acid amide lubricants, fatty acid ester lubricants, alcohol lubricants, metal soap lubricants and the like.

Examples of the anti-fogging agent include polyoxyethylene lauryl ether, -stearyl ether,-
Nonylphenyl ether, polyethylene glycol monopalmitate, -monostearate, polyoxyethylene sorbitan monolaurate, -monopalmitate, glycerin monolaurate, -monopalmitate, -monostearate, -monooleate, pentaerythritol monolau Rate, sorbitan monopalmitate, -monobehenate, -distearate, diglycerindiolate sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride,
Dodecylamine hydrochloride, lauric lauramide ethyl phosphate, triethylcetyl ammonium iodide, oleylaminodiethylamine hydrochloride, dodecylpyridinium salt and the like can be mentioned.

Examples of the above antifoggant include an anionic fluorinated surfactant, a cationic fluorinated surfactant,
Examples include amphoteric fluorinated surfactants, nonionic fluorinated surfactants, and fluorinated compounds such as fluorinated oligomers.

Examples of the liquid polybutadiene include 1,2-atactic polybutadiene, 1,2-syndiotactic polybutadiene, 1,2-isotactic polybutadiene, and 1,1-atactic polybutadiene obtained by homopolymerization of 1,3-butadiene. 4-cis polybutadiene, 1,
4-transpolybutadiene or block polymers, graft polymers and mixtures thereof, further partially epoxidized, those having terminal hydroxyl and / or carboxyl groups or partially maleated, halogenated, boiled, hydrogenated, acrylic-modified And urethane-modified and ester-modified products. Among these liquid polybutadienes, epoxy-modified ones are particularly preferred since they have the effect of improving weather resistance. The average molecular weight of these liquid polybutadienes is preferably 250
２５25000, more preferably 500〜１０10000.

The above perchlorates include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, barium perchlorate, zinc perchlorate,
Aluminum perchlorate, lead perchlorate, ammonium perchlorate and the like, and these perchlorates may be anhydrous or hydrated salts, and butyl diglycol, alcohols such as butyl diglycol adipate and the like. It may be one dissolved in an ester solvent or the like and a dehydrated product thereof.

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 '- isopropylidene diphenyl phosphite, bis [2,2'-methylenebis
(4,6-Diamylphenyl)] • isopropylidenediphenyl phosphite, hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4′-n-butylidenebis ( 2-
Tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl • 4,4
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 sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionates of polyols.

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, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, hexanediol polyglycidyl ether, 2,2-dimethyl-
Examples thereof include 1,3-propanediol polyglycidyl ether, hydrogenated bisphenol polyglycidyl ether, and cyclohexane dimethanol polyglycidyl ether.

Examples of the polyols include 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-C ₇
~ 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)-
1,3,5-triazine, 2- (2-hydroxy-4-
2- (2-hydroxyphenyl) -1,3,5- such as acryloyloxyethoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine
Triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-
3,5-di-tert-butyl-4-hydroxybenzoate,
2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5
Benzoates such as di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano- and cyanoacrylates such as β, β-diphenylacrylate and methyl-2-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, bis (1-octoxy-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-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
Tertiary octylamino-s-triazine polycondensate, 1,
5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1, 5,
8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2
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-triazine-6
-Ylamino] undecane, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) 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-piperidyloxycarbonyloxy)
Butylcarbonyloxydiethyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane and the like.

Examples of the other inorganic compounds include, for example, calcium phosphate, calcium oxide, calcium hydroxide, calcium silicate, calcium carbonate, overbased calcium carbonate, magnesium phosphate, magnesium oxide,
Examples include magnesium hydroxide, aluminum hydroxide, (anhydrous) silicic acid and the like.

The composition of the present invention may further contain other stabilizing aids usually used for chlorine-containing 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 chlorine-containing resin composition of the present invention may contain, if necessary, additives usually used for chlorine-containing resins, for example, fillers, coloring agents, crosslinking agents, antistatic agents, thickeners, Plate-out inhibitor, surface treatment agent, lubricant, gelling agent, thixotropic agent, flame retardant, fluorescent agent, fungicide, bactericide, metal deactivator, release agent, pigment, processing aid, antioxidant , A light stabilizer, a foaming agent, and the like.

The chlorine-containing resin composition of the present invention can be used irrespective of the processing method used for ordinary chlorine-containing resins, for example, calendering, rolling, extrusion molding. It is used for melt casting, pressure molding, paste processing, powder molding and the like.

The chlorine-containing resin composition of the present invention includes building materials such as wall materials, flooring materials, window frames, and wallpaper; electric wire coating materials; interior and exterior materials for automobiles; agricultural materials such as houses and tunnels; Fish food packaging material; can be used as miscellaneous goods such as paints, hoses, pipes, sheets, toys and gloves.

[0052]

EXAMPLES Hereinafter, the chlorine-containing resin composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Using the following formulation, 17
Rolls are kneaded at 0 ° C. to form a 0.5 mm sheet.
The blackening time (min) was measured in a gear oven at 90 ° C. to perform a thermal stability test. Also, roll-up sheets are laminated and pressed at 180 ° C for 5 minutes and 20 minutes, and 1m
m was prepared, and the transparency of the 5-minute press sheet and the coloring properties of the 5-minute and 20-minute sheets were visually evaluated.

The evaluation criteria of transparency are 10 levels, and 1 indicates a state without smudge, and it indicates that as the numerical value increases, the degree of smearing decreases and the transparency decreases. Evaluation criteria for colorability is 10
In the stage, 1 represents a state without coloring, and represents that coloring (yellowing) increases as the numerical value increases.

Further, the sheet obtained by pressing at 180 ° C. for 5 minutes is suspended in a flask filled with a little water without direct contact with water and sealed, put in a gear oven at 70 ° C., and after one day, Three days and one week later, the presence or absence of bleed was confirmed. The evaluation criteria are as follows: ○ indicates a state where no bleed is seen, Δ indicates a state where slight bleed is seen,
X represents a state where bleeding is clearly seen.

Further, a test piece was prepared from a sheet obtained by pressing at 180 ° C. for 5 minutes, and the softening temperature (° C.) was measured according to JIS K 6745.
The hardness, elongation (%), tensile strength (MPa) and 100% modulus (MPa) were measured immediately after the test. Further, a tensile test was also performed on the test specimen which had been heat-aged by placing the test specimen in a gear oven at 100 ° C. for 120 hours, and a residual elongation (%, unaged was 1%).
00%). The results are shown in Tables 1 and 2.

(Blending) Parts by weight Vinyl chloride resin (degree of polymerization: 1000) 100 Epoxidized soybean oil 2 Zinc stearate 0.5 Hydrotalcite [Composition formula: Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O] 0.8 dibenzoylmethane 0.1 stearyl (3,5-di-tert-butyl-4-hydroxy 0.1 phenyl) propionate plasticizer composition (Tables 1 and 2) 50

[0058]

[Table 1]

[0059]

[Table 2]

As is clear from the examples, when the glycol dibenzoic acid diester as the component (a) is used alone (Comparative Example 1-1), there is no flexibility at low temperature,
When the polyester plasticizer such as the component (b) is used alone (Comparative Example 1-4), it has a drawback of causing bleeding.

Even when a glycol dibenzoic acid diester such as the component (a) is combined with a polyester plasticizer such as the component (ii), the specific ratio [(a)
[Comparative Examples 1-2 and 1-3] when combined outside the ranges of 5 to 95% by weight of the component and (95 to 5% by weight of the component (b)), change in comparison with the case of using each alone. Absent.

Further, when a glycol dibenzoic acid diester such as the component (a) is combined with a diester compound having a number average molecular weight of less than 500 [Comparative Example 1-5], there is no flexibility at low temperature and heat aging When a polyester-based plasticizer having a number average molecular weight of 3000 (more than 2000) is combined [Comparative Example 1-6], there is no flexibility at low temperatures.

On the other hand, the glycol dibenzoic acid diester of the component (A) of the present invention and the polyester plasticizer having a number average molecular weight of 500 to 2,000 of the component (B) are added in a specific ratio [the component (A) is 5 to 95% by weight. %, (B) 5 to 95% by weight of the component], and using the plasticizer component [Examples 1-1 to 1-7], without causing bleeding.
It is excellent in flexibility at low temperature and heat aging as compared with di (2-ethylhexyl) phthalate. Further, among them, a specific ratio [(a) component 10 to 50% by weight, (b)
Component 50-90% by weight] [Example 1
-3 to 1-7] are obtained, which have particularly excellent flexibility at low temperatures.

[0064]

According to the present invention, bleeding does not occur.
An object of the present invention is to provide a chlorine-containing resin composition having excellent low-temperature properties and heat aging properties.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Teruo Arai 5-2-13-Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. F-term (reference) 4J002 BB24W BD03W BD05W BD06W BD07W BD08W BD10W BD18W CF03X EH046 FD010 FD030 FD050 FD070 FD200

Claims (5)

[Claims] 1. A chlorine-containing resin composition comprising a chlorine-containing resin, a plasticizer, and other additives, wherein the plasticizer is (a) glycol dibenzoate diester 5 represented by the following general formula (I): ~ 95% by weight and (b) number average molecular weight 5
95 to 5% by weight of a polyester-based plasticizer of 100 to 2000%
A chlorine-containing resin composition comprising: Embedded image (Wherein, G represents an alkylene group having 2 to 10 carbon atoms, and p represents 1 to 10) 2. The chlorine-containing resin composition according to claim 1, wherein the polyester plasticizer is represented by the following general formula (II) or (III). Embedded image (Wherein R ₁ and R ₂ are each independently 5 carbon atoms)
Represents an alkyl group having from 13 to 13, and A ₁ has 2 to 10 carbon atoms.
G ₁ represents an alkylene group having 2 to 10 carbon atoms, and n represents a positive number) 3. The polyester-based plasticizer is represented by the general formula (II) or (III), wherein A ₁
Is a linear alkylene group having 4 carbon atoms, and G ₁ is a linear or branched alkylene group having 3 to 6 carbon atoms. The chlorine-containing resin composition according to claim 2, wherein 4. The polyester plasticizer having a plasticizer having (a) 10 to 50% by weight of a glycol dibenzoic diester represented by the general formula (I) and (b) a polyester plasticizer having a number average molecular weight of 500 to 2,000. The chlorine-containing resin composition according to claim 1, wherein the composition comprises 0.1% by weight. 5. The chlorine-containing resin composition according to claim 1, wherein 20 to 120 parts by weight of the plasticizer is blended with respect to 100 parts by weight of the chlorine-containing resin. .