JP2002020567A - Vinyl chloride-based resin composition for wire coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride-based resin composition for wire coating excellent in heat resistance and coloring prevention. SOLUTION: This vinyl chloride-based resin composition for wire coating is obtained by adding (a) 0.1-20 mass parts of a polyglycidyl ether compound, (b) 0.05-10 mass parts of a hydrotalcite compound represented by general formula (I) MgX1ZnX2Al2 (OH)2X1+2X2+4CO3.mH2O (1) (X1 and X2 are each a number for satisfying a condition represented by the formulas 0<=X1/X1<10, 2<=X1+X2<20) and (c) 0.05-5 mass parts of a phosphoric ester zinc salt to 100 pts.wt. of a vinyl chloride-based resin.

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 covering electric wires, which is stabilized by compounding a specific stabilizer. By adding a site compound and a phosphate ester zinc salt, heat resistance,
The present invention relates to a vinyl chloride resin composition for covering electric wires with improved anti-coloring properties.

[0002]

2. Description of the Related Art Vinyl chloride resins have excellent electrical insulation, arc resistance, tracking resistance, and voltage resistance. Therefore, it is very important as an insulating material. However, the vinyl chloride resin deteriorates in various excellent properties due to thermal and oxidative deterioration, and is practically unusable.

In order to make up for the above-mentioned disadvantages, various stabilizers have been conventionally added to vinyl chloride resin insulating materials, and among them, lead stabilizers such as tribasic lead sulfate and lead stearate have been used. However, zinc-based stabilizers have been proposed because they are highly toxic and do not have sufficient electric insulation properties. In particular, the increase in the temperature of the insulator causes a decrease in electric insulation properties.

[0004] For example, JP-A-57-77157,
JP-A-57-77158 reports a vinyl chloride resin composition using hydrotalcite and an organic zinc acid as a stabilizer. A zinc-based stabilizer generates zinc dichloride, which promotes the decomposition of vinyl chloride. Therefore, it has been proposed to use a zinc-based stabilizer in combination with an organic acid metal salt or an epoxy-terminated compound which has an effect of reducing this. For example, Japanese Patent Application Laid-Open
JP-A-240992 and JP-A-7-11084 report a vinyl chloride-based resin composition in which an organic acid zinc is used in combination with these stabilizers, but those still having satisfactory heat resistance and anti-coloring properties. Was not.

Japanese Patent Application Laid-Open No. 10-212386 describes an organic zinc phosphate such as zinc stearyl phosphate and various epoxy compounds as a stabilizer for the vinyl chloride composition. However, there is no description about the optimal combination, and no effect is mentioned at all.

Accordingly, an object of the present invention is to provide a vinyl chloride resin composition for covering electric wires having excellent heat resistance and anti-coloring properties.

[0007]

As a result of repeated studies, the present inventors have solved the above-mentioned problems by using a specific stabilizer, a zinc phosphate ester and a polyglycidyl ether compound having a specific structure. The inventors have found that the present invention can be performed, and have reached the present invention.

[0008] The present invention has been made based on the above findings, and 100 parts by mass of a vinyl chloride resin, 0.1 to 20 parts by mass of a polyglycidyl ether compound (a),
(B) Vinyl chloride for electric wire coating comprising 0.05 to 10 parts by mass of a hydrotalcite compound represented by the following general formula (I) and (c) 0.05 to 5 parts by mass of a zinc phosphate ester The present invention provides a resin composition. Mg _X1 Zn _X2 Al ₂ (OH) _{2X1 + 2X2 + 4} CO ₃ .mH ₂ O (I) (wherein, X1 and X2 each represent a number satisfying a condition represented by the following formula, and m is 0 or Indicates any positive number: 0 ≦
X2 / X1 <10, 2 ≦ X1 + X2 <20)

[0009]

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

The vinyl chloride resin used in the present invention is not particularly limited in its composition and its polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, as long as it is generally used for wire coating. There is no limitation, and well-known general ones can be used. Examples of the vinyl chloride resin include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and vinyl chloride-propylene copolymer. Polymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile ternary Copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleate Copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride-acrylo Chlorine-containing resins such as tolyl copolymers, vinyl chloride-various vinyl ether copolymers, and their mutual blends, and further, those chlorine-containing resins and other chlorine-free synthetic resins, for example, acrylonitrile-styrene copolymers Polymers, acrylonitrile-styrene-butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blends with polyester, etc., block copolymers, graft copolymers, etc. Is mentioned.

The (a) polyglycidyl ether compound according to the present invention is an organic compound having two or more glycidyl ether groups in a molecule, and the compound is represented by (b)
The combined use of the hydrotalcite compound and the zinc phosphate (c) has an effect of imparting remarkable heat resistance to the vinyl chloride resin composition.

The above-mentioned polyglycidyl ether compound is
A compound having two or more glycidyl ethers in a molecule obtained by a reaction between a polyhydroxy compound and epichlorohydrin or a reaction between a polyhalogen compound and glycidyl alcohol.

The polyhydroxy compound used for the reaction of the polyhydroxy compound with epichlorohydrin includes, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,
3-propanediol, 2-butyl-2-ethyl-1,
3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentane Diol, 2
-Methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol , 2-methyl-1,
8-octanediol, 1,9-nonanediol, 1,
Aliphatic diols such as 10-decanediol, diethylene glycol and triethylene glycol; cyclohexanedimethanol, cyclohexanediol, bis (4-
Alicyclic diols such as hydroxycyclohexyl) methane (hydrogenated bisphenol F) and 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A); trimethylolethane, trimethylolpropane, 1-ethyl-1 Trihydric or higher alcohols such as 1,1,1-trimethylolheptane, hexitol, pentitol, glycerin, pentaerythritol, tetramethylolethane, and tetramethylolpropane; ethylene oxide and / or propylene oxide adducts of the above low-molecular polyols , Polyether polyols such as polytetramethylene glycol; polyols having an ester bond such as polyester polyol, polyester polycarbonate polyol, and polycarbonate polyol; resorcinol; Tekoru, hydroquinone, 3
-Methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-tert-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propyl Hydroquinone, 3-butylhydroquinone, 3-tert-butylhydroquinone, 3-
Phenylhydroquinone, 3-cumylhydroquinone-
Dihydroxyaryls such as 4,4'-dihydroxydiphenyl; bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenoxy) Ethane, 1,3-bis (4-hydroxyphenyl)
Propane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-) Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-
3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-cyclohexylphenyl) propane, 2,2-bis (4-
(Hydroxy-3-tert-butylphenyl) propane, 2,
2-bis (4-hydroxyphenyl-3-methoxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)
Isobutane, 2,2-bis (4-hydroxy) butane,
Bis (hydroxyaryl) alkanes such as 2,4-bis (4-hydroxyphenyl-2-methyl) butane and the like can be mentioned. Examples of polyglycidyl ether compounds obtained therefrom include diglycidyl ether of bisphenol A type, Aromatic polyglycidyl ethers such as bisphenol F-type diglycidyl ether; hydrogenated bisphenol A-type diglycidyl ether, hydrogenated bisphenol F-type diglycidyl ether, alkane or polyether polyglycidyl having cycloalkanediyl in the chain Alicyclic polyglycidyl ethers such as ethers; aliphatic polyglycidyl ethers such as alkane polyglycidyl ethers and polyether polyglycidyl ethers;

Representative examples of these polyglycidyl ether compounds are shown below.

[0015]

Embedded image

Of these, aliphatic polyglycidyl ethers are preferred because they impart particularly excellent anti-coloring properties and heat resistance. 12, No. The triglycidyl ether of trimethylolalkane represented by 13 is preferred.

If the amount of the polyglycidyl ether compound used is less than 0.1 part by mass with respect to 100 parts by mass of the vinyl chloride resin, a sufficient effect cannot be obtained. Not only is the addition effect not improved, but bleeding is likely to occur.
0 parts by mass, preferably 0.5 to 10 parts by mass.

The hydrotalcite compound (b) according to the present invention is a double salt compound comprising magnesium and aluminum, or zinc, magnesium and aluminum, as represented by the above general formula (I). It may be dehydrated.

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.
JP, JP-B-3-36839, JP-A-61-1
A known method described in, for example, Japanese Patent No. 74270 can be exemplified. Further, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter, and the like.

A specific example of the synthetic product is Mg _4.5 Al
₂ (OH) ₁₃ CO ₃ .3.5H ₂ O (manufactured by Kyowa Chemical; DH
T-4), Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O
(Manufactured by Kyowa Chemical; DHT-6), Mg ₄ Al ₂ (OH) ₁₂
CO ₃ · 3H ₂ O (manufactured by Wako; Alkamizer 1), M
g ₄ Al ₂ (OH) ₁₂ CO ₃ (manufactured by Kyowa Chemical; Alkamizer 2), Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ .3H ₂
O (manufactured by Kyowa Chemical; Alkamizer 4), Mg _3.5 Zn
_0.5 Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O (manufactured by Kyowa Chemical;
Alkamizer 7) 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, or an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate. It may be coated with higher fatty acid amide, higher fatty acid ester, wax or the like.

When the amount of the hydrotalcite compound used is less than 0.05 part by mass with respect to 100 parts by mass of the vinyl chloride resin, a sufficient effect cannot be obtained. In addition to not being able to improve the effect of addition, it may cause coloring or foaming, so it is 0.05 to 10 parts by mass, preferably 0.1 to 10 parts by mass.
5 parts by mass.

The phosphoric acid ester zinc salt (c) according to the present invention is a compound represented by the following general formula (II) or (II ') or a mixture thereof.

[0024]

Embedded image

The alkyl group having 6 to 18 carbon atoms represented by R in the above general formulas (II) and (II ') includes n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl and isononyl. , Decyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, peptadecyl, stearyl, and the like. Examples of the aryl group having 6 to 18 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl. , 4-
Vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2- Ethylhexyl) phenyl, 2,3
-Dimethylphenyl, 2,4-dimethylphenyl, 2,
5-dimethylphenyl, 2,6-dimethylphenyl,
3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-ditert-butylphenyl and the like can be mentioned.

Among these phosphoric acid ester zinc salts,
Those in which R is an alkyl group are preferable because they have no coloring and have good compatibility with the vinyl chloride resin composition,
In particular, those in which R is stearyl are preferred.

If the amount of the zinc phosphate ester used is less than 0.05 part by mass relative to 100 parts by mass of the vinyl chloride resin, a sufficient effect of addition cannot be obtained and 5 parts by mass If the amount exceeds the above range, not only the addition effect cannot be improved, but also the physical properties of the vinyl chloride resin composition are affected. Therefore, the amount is 0.05 to 5 parts by mass, preferably 0.1
３3 parts by mass.

The composition of the present invention contains various additives which are usually used as additives for vinyl chloride resins,
For example, β-diketone compounds, various metal salts, insulation improvers, polyols, organic phosphite compounds, phenolic or sulfuric antioxidants, ultraviolet absorbers, hindered amine light stabilizers, plasticizers, inorganic stabilizers , A filler and the like can also be blended.

In particular, a β-diketone compound is preferably used when used in combination with a zinc-based stabilizer, because it gives an excellent coloring prevention effect. Examples of the β-diketone compound include dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene, and the like, and metal salts thereof. (Lithium, sodium, potassium, calcium, magnesium, barium, zinc, etc.) and the like,
The amount used per 100 parts by mass of the vinyl chloride resin is 0.1%.
When the amount is less than 01 parts by mass, the effect of addition cannot be obtained.
If the amount is more than 10 parts by mass, not only the addition effect cannot be improved but also the heat resistance may be deteriorated.

Examples of the insulating improver include JP-A-57-177040, JP-A-5-262943, JP-A-5-179090, and JP-A-9-324089.
Amorphous calcium silicate (hydrate), a composition composed of α-dicalcium silicate hydrate and calcium hydroxide, a silicate of aluminum or alkaline earth metal, and the like, described in Japanese Patent Application Laid-Open Publication No. H10-163, etc. are exemplified. Among them, amorphous calcium silicate (hydrate) is preferable because of its excellent insulation and heat resistance.

Examples of the above-mentioned amorphous calcium silicate include tobermorite gel, CSH (I) and CSH (II). When the amount of the amorphous calcium silicate used is less than 0.001 with respect to 100 parts by mass of the vinyl chloride resin, little effect is obtained, and when the amount is more than 3 parts by mass, heat resistance may be reduced and coloring may occur. Therefore, 0.001 to 3 parts by mass is preferable, and 0.01 to 1 part by mass is more preferable.

The various metal salts include, for example, metals of organic acids or phenols (Li, Na, K, Ca,
Ba, Mg, Sr, Zn, Cd, Sn, Cs, Al, organic Sn) salts and metals of organic phosphoric acids (Li, Na, K, C
a, Ba, Mg, Sr, Cd, Sn, Cs, Al, an organic Sn) salt, and the like, and the amount thereof is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. is there.

Examples of the above organic acids include caproic acid, caprylic acid, perargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like.
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, and the phenols include, for example, phenol, Cresol, ethyl phenol, cyclohexyl phenol, nonyl phenol, lauryl phenol and the like can be mentioned. Examples of the organic phosphoric acid include mono- or dioctyl phosphoric acid, mono- or dilauryl phosphoric acid, mono- or distearyl phosphoric acid, mono- or di (nonylphenyl) Examples include phosphoric acid, nonylphenyl phosphonate, stearyl phosphonate, and the like.

Among the above-mentioned various metal salts, a zinc salt of an organic acid and / or an alkaline earth metal salt of an organic acid have a coloring prevention property.
It is preferable because it is advantageous in terms of heat resistance and cost.

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

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,5-
Di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl)
Phosphite, tris (nonylphenyl mono- and di-mixed)
Phosphite, diphenyl acid phosphite, 2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Octyl phosphite, diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyldiisodecyl phosphite, tributyl phosphite,
Tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexanedimethyldi Phosphite, bis (2,4-di-tert-butylphenyl)
Pentaerythritol diphosphite, bis (2,5-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C ₁₂ - ₁₅ mixed alkyl) -4,
4'-isopropylidenediphenyl phosphite, bis [2,2'-methylenebis (4,6-diamylphenyl)]. Isopropylidenediphenylphosphite, tetratridecyl / 4,4'-butylidenebis (2-tert-butyl -5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-
5-tert-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, tris (2-
[(2,4,7,9-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-
Yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide and 2-butyl-2-ethylpropanediol.2,4,6-tritert-butylphenol monophosphite.

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 (2,
6-di-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 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-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-acryloyl-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, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

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 mercaptopropionic esters of polyols.

Examples of the ultraviolet absorber include, for example, 2,
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, for example, 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,
2,2,6,6-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-triazine-6-
Ilamino] 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-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) butylcarbonyloxy {ethyl] -2,4
8,10-tetraoxaspiro [5.5] undecane and the like.

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 inorganic stabilizers include calcium oxide, calcium hydroxide, amorphous aluminosilicate, alkali and / or alkaline earth aluminosilicate having a zeolite crystal structure, powdered silica (silica), Examples include sodium perchlorate, magnesium perchlorate, barium perchlorate, and the like.

Examples of the filler include calcium carbonate, silica, clay, glass beads, mica, sericite, glass flake, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite,
MOS, phosphate fiber, glass fiber, carbonate fiber, aramid fiber, and the like.

In addition, the composition of the present invention may further contain, if necessary, additives usually used for vinyl chloride resins, for example,
Cross-linking agent, antistatic agent, anti-fog agent, plate-out inhibitor,
Surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides, fungicides,
Metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents, and the like can be added.

[0045]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the present invention is not limited at all by the following Examples and Comparative Examples.

[Examples 1 to 12 and Comparative Examples 1 to 15] The composition according to the following formulation 1 was kneaded on a roll at 170 ° C. and 30 rpm for 7 minutes, and then pressed at 180 ° C. for 5 minutes to form a 1 mm thick film. Created a sheet.

With respect to this sheet, the yellowness Y after pressing is
1. The anti-coloring property due to yellowness Y2 when pressed for 30 minutes and the heat resistance due to the blackening time at 190 ° C. were evaluated. The results are shown in Tables 1 to 4.

(Blend 1) Parts by mass Polyvinyl chloride resin (degree of polymerization 1050) 100 dioctyl phthalate 17 zinc stearate 0.3 barium stearate 0.8 stearoyl benzoyl methane 0.2 CSH (manufactured by Kawai Lime Industry Co., Ltd.) (Crystalline calcium silicate) 0.3 Hydrotalcite (Tables 1 to 4) Stabilizer A (Tables 1 to 4) Stabilizer B (Tables 1 to 4)

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[Examples 13 to 15 and Comparative Examples 16 to 1]
8] A composition having the following composition 2 was heated at 170 ° C. and 30 rpm.
And kneaded on a roll for 7 minutes, and then pressed at 180 ° C. for 5 minutes to form a sheet having a thickness of 1 mm.

The sheet was evaluated for anti-coloring properties, heat resistance and insulation properties by a volume resistance test according to JIS K-6723 in the same manner as in Example 1. Table 5 shows the results.

(Blending 2) Parts by mass Polyvinyl chloride resin (degree of polymerization 1050) 100 Tri-2-ethylhexyl trimellitate 50 Zinc stearate 0.4 Barium stearate 0.6 Calcium carbonate 20 Dibenzoylmethane 0.1 CSH (Amorphous calcium silicate manufactured by Kawai Lime Industry Co., Ltd.) 0.4 Clay # 33 10 Alkamizer 11 Stabilizer A (described in Table 5) Stearyl phosphate zinc salt 0.5

[0056]

[Table 5]

[Examples 16 to 17 and Comparative Examples 19 to 2]
1] A composition according to the following formulation 3 was mixed at 170 ° C. and 30 rpm
And kneaded on a roll for 7 minutes, and then pressed at 180 ° C. for 5 minutes to form a sheet having a thickness of 1 mm.

This sheet was evaluated for anti-coloring properties, heat resistance and insulation properties by a volume resistance test according to JIS K-6723, as in Example 1. Table 5 shows the results.

(Blend 3) parts by mass Polyvinyl chloride resin (degree of polymerization 1300) 100 Adecaizer PN1030 60 (polyester plasticizer manufactured by Asahi Denka Kogyo KK) Epoxidized soybean oil 5 Zinc stearate 0.3 Stearic acid Barium 0.8 Calcium carbonate 15 Stearoylbenzoylmethane 0.1 CSH (Amorphous calcium silicate manufactured by Kawai Lime Industry Co., Ltd.) 0.4 Clay # 33 15 Alkamizer 1 0.7 Stabilizer A (Table 6) Stearyl Zinc phosphate 0.5

[0060]

[Table 6]

[0061]

The vinyl chloride resin composition for covering electric wires of the present invention is excellent in heat resistance and anti-coloring properties.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01B 7/29 H01B 7/34 A (72) Inventor Osamu Yoshiguchi 5-2-13, Shirahata, Urawa-shi, Saitama Asahi Denka Within Industrial Co., Ltd. (72) Inventor Megumi Ogawa 5-2-1-3 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. F-term (reference) 4J002 BB241 BD041 BD051 BD061 BD071 BD081 BD101 BD181 CD012 CD022 CD052 CD072 CD122 DE286 DJ009 EE048 EW047 FD010 FD020 FD040 FD050 FD070 FD129 GQ01 5G315 CA02 CB02 CC08 CD05 CD17

Claims (5)

[Claims] 1. A 100 parts by mass of a vinyl chloride resin,
(A) 0.1 to 20 parts by mass of a polyglycidyl ether compound; (b) 0.05 to 10 parts by mass of a hydrotalcite compound represented by the following general formula (I); A vinyl chloride resin composition for covering electric wires, comprising 0.5 to 5 parts by mass. Mg _X1 Zn _X2 Al ₂ (OH) _{2X1 + 2X2 + 4} CO ₃ .mH ₂ O (I) (where X1 and X2 each represent a number satisfying a condition represented by the following formula, and m is 0 or Indicates any positive number: 0 ≦ X
2 / X1 <10, 2 ≦ X1 + X2 <20) 2. The vinyl chloride resin composition according to claim 1, wherein the (a) polyglycidyl ether compound is an aliphatic polyglycidyl ether. 3. The vinyl chloride resin composition according to claim 2, wherein the aliphatic polyglycidyl ether is a triglycidyl ether compound of trimethylolalkane. 4. The vinyl chloride resin for wire coating according to claim 1, further comprising 0.01 to 10 parts by mass of a β-diketone compound per 100 parts by mass of the vinyl chloride resin. Resin composition. 5. The vinyl chloride for wire coating according to claim 1, wherein 0.001 to 3 parts by mass of an insulation improver is further added to 100 parts by mass of the vinyl chloride resin. -Based resin composition.