JP2011190320A - Vinyl chloride-based resin composition for electric wire coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl chloride-based resin composition for electric wire coating suitable as an electric wire coating material by improving colorability, heat resistance, and electric insulation of the vinyl chloride-based resin composition using hydrotalcite and a zinc salt of an organic acid as a stabilizer. <P>SOLUTION: The vinyl chloride-based resin composition for electric wire coating contains (a) 0.001-10 pts.mass of a hydrotalcite compound, (b) 0.001-10 pts.mass of a zinc salt of an organic acid, and (c) 5-100 pts.mass of a dialkyl ester compound of terephthalic acid in 100 pts.mass of a vinyl chloride-based resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a vinyl chloride resin composition for covering electric wires, and more particularly to a vinyl chloride resin composition for covering electric wires suitable as an electric wire covering material having excellent colorability, electrical insulation and heat resistance.

  Vinyl chloride resins are inexpensive and are widely used as wire coating materials because they are excellent in heat resistance, weather resistance, and electrical insulation.

  Usually, a stabilizer mainly composed of a metal compound is used for the vinyl chloride resin in order to improve stability to heat and light at the time of thermoforming and use of the product. In recent years, considering the adverse effects on the environment and the human body, etc., it is relatively low in performance, but instead of cadmium-based, lead-based, and organic tin-based stabilizers that are worried about toxicity, it is lower than the former. Stabilizers such as poisonous barium / zinc and calcium / zinc are being developed. For example, Patent Document 1 discloses a vinyl chloride resin composition containing an organic acid zinc salt, and Patent Document 2 discloses a vinyl chloride resin composition containing hydrotalcite.

  Moreover, since the wire covering material usually requires flexibility, a plasticizer component is used. For example, phthalic acid dialkyl ester compounds such as bis (2-ethylhexyl) phthalate and diisononyl phthalate Etc. are mainly used.

JP 2007-204525 A JP 2008-274032 A

  However, low-toxic stabilizers may have insufficient heat resistance compared to cadmium-based, lead-based, organotin-based stabilizers, and various stabilizing aids are available. in use. In addition, when hydrotalcite or an organic acid zinc salt was used as a stabilizer in the vinyl chloride resin composition for covering electric wires, there was sufficient room for improvement in colorability, heat resistance and electrical insulation.

  Accordingly, the object of the present invention is to improve the colorability, heat resistance, and electrical insulation of a vinyl chloride resin composition using hydrotalcite and an organic acid zinc salt as a stabilizer, thereby making it suitable as a wire coating material. An object of the present invention is to provide a vinyl chloride resin composition for covering electric wires.

  As a result of intensive studies, the inventors of the present invention have achieved a vinyl chloride resin composition containing a hydrotalcite compound, an organic acid zinc salt and a terephthalic acid dialkyl ester compound with respect to the vinyl chloride resin. I found out that I could do it.

  That is, the vinyl chloride resin composition of the present invention comprises (a) 0.001 to 10 parts by mass of a hydrotalcite compound and (b) 0.001 to 10 parts by mass of an organic acid zinc salt in 100 parts by mass of a vinyl chloride resin. And (c) 5 to 100 parts by mass of a dialkyl ester compound of terephthalic acid, and a vinyl chloride resin composition for covering electric wires.

  The vinyl chloride resin composition of the present invention preferably further contains 0.001 to 5 parts by mass of (d) a β-diketone compound.

In the vinyl chloride resin composition of the present invention, the (a) hydrotalcite compound is represented by the following formula (I),
Mg _x1 Zn _x2 Al ₂・ (OH) _{2x1 + 2x2 + 4}・ (CO ₃ ) _{1-y1 / 2} (ClO ₄ ) _y1・ mH ₂ O (I)
(In the formula, x1, x2 and y1 each represent a number satisfying the condition represented by the following formula, and m represents 0 or an arbitrary integer.
It is preferable that 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 <20, 0 ≦ y1 ≦ 2).

  In the vinyl chloride resin composition of the present invention, the (b) organic acid zinc salt is preferably a zinc salt of carboxylic acid.

  Furthermore, in the vinyl chloride resin composition of the present invention, it is preferable that the (c) terephthalic acid dialkyl ester compound is bis (2-ethylhexyl) terephthalate.

  INDUSTRIAL APPLICABILITY According to the present invention, a vinyl chloride resin composition for electric wire coating that is excellent in colorability, heat resistance, and electrical insulation can be provided.

  Hereinafter, the vinyl chloride resin composition for electric wire coating of the present invention will be described in detail.

  The vinyl chloride resin used in the present invention is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. For example, polyvinyl chloride, chlorinated polyvinyl chloride, polychlorination Vinylidene, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride- Vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile solution, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride -Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-male Phosphate ester copolymer, vinyl chloride - methacrylic acid ester copolymers, vinyl chloride - acrylonitrile copolymer, vinyl chloride - can be exemplified a chlorine-containing resin such as various vinyl ether copolymers. Further, in addition to the above resins, blends of the above resins, or the above chlorine-containing resins and other synthetic resins not containing chlorine, such as acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene -Ethyl (meth) acrylate copolymers, blends with polyesters, block copolymers, graft copolymers and the like.

  As the hydrotalcite compound which is the component (a) used in the present invention, a double salt compound composed of magnesium and aluminum or zinc, magnesium and aluminum represented by the following general formula (I) is preferably used. Moreover, what dehydrated crystal water may be used.

Mg _x1 Zn _x2 Al ₂・ (OH) _{2x1 + 2x2 + 4}・ (CO ₃ ) _{1-y1 / 2} (ClO ₄ ) _y1・ mH ₂ O (I)
(In the formula, x1, x2 and y1 each represent a number satisfying the condition represented by the following formula, and m represents 0 or an arbitrary integer.
0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 <20, 0 ≦ y1 ≦ 2)

The hydrotalcite compound may be a natural product or a synthetic product. As methods for synthesizing the synthetic product, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, and Japanese Patent Publication No. 61-174270 are disclosed. Examples of known methods described in the above. Further, in the present invention, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter, etc., but preferably the average particle diameter measured by a laser diffraction scattering method Is 5 μm or less, particularly preferably 1 μm or less. Moreover, the BET specific surface area of hydrotalcite is preferably 30 m ² / g or less, more preferably 20 m ² / g or less.

  In addition, the hydrotalcite compound has a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, Those coated with higher fatty acid esters or waxes can also be used.

  The amount of the hydrotalcite compound added is 0.005 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. When the amount is less than 0.005 parts by mass, the heat resistance may be reduced. When the amount exceeds 10 parts by mass, coloring may increase.

  As the organic acid zinc salt which is the component (b) used in the present invention, a carboxylic acid, an organic phosphoric acid or a zinc salt of phenol is used. 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. Acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linolenic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acid, coconut oil fatty acid, Naturally produced mixtures of the above acids, such as tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5- t-octylsalicylic acid, naphthenic acid And cyclohexane carboxylic acid. Examples of the organic phosphoric acid include mono- or dioctyl phosphoric acid, mono- or dododecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, and phosphonic acid stearyl ester. Examples of the phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol, and the like. These are normal salts, acidic salts, basic salts, or overbased complexes. May be. As the organic acid zinc salt, a carboxylic acid zinc salt is preferable, and a zinc stearate salt and a zinc laurate salt are particularly preferable.

  The addition amount of the organic acid zinc salt is 0.005 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. The heat resistance may be lowered, and when it is used in excess of 10 parts by mass, it is not preferable because blackening may occur during use at a high temperature.

  Examples of the (c) component terephthalic acid dialkyl ester compound used in the present invention include dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisopropyl terephthalate, dibutyl terephthalate, diisobutyl terephthalate, diterephthalate diterephthalate. Dibutyl terephthalate, dibutyl terephthalate, diamyl terephthalate, diisoamyl terephthalate, ditertiary amyl terephthalate, dihexyl terephthalate, diheptyl terephthalate, dioctyl terephthalate, bis (2-ethylhexyl) terephthalate, dinonyl terephthalate, Examples thereof include didecyl terephthalate, diundecyl terephthalate, and didodecyl terephthalate. Bis (2-ethylhexyl) terephthalate is preferable because of its excellent plasticization efficiency.

  The addition amount of the terephthalic acid dialkyl ester compound is 5 to 100 parts by mass, preferably 10 to 80 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. If the amount is less than 5 parts by mass, the effect of imparting flexibility may be insufficient. When used in excess of 100 parts by mass, the physical properties may be reduced.

  The terephthalic acid dialkyl ester compound mainly functions as a plasticizer component, but the composition of the present invention can be mixed with other plasticizers usually used for vinyl chloride resins.

  As the plasticizer other than the terephthalic acid dialkyl ester compound, a plasticizer usually used in vinyl chloride resins can be arbitrarily used. For example, dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl Phthalate plasticizer (ortho) such as phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; adipate plasticizer such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate; triphenyl Phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, triethyl phosphate Phosphate plasticizers such as til phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene Glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentylglycol and the like, and dibasic acids such as oxalic acid, malonic acid, succinic acid, Polyester based on glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. Others: Tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenylene Examples thereof include polycarboxylic acid plasticizers.

  The amount of the plasticizer other than the component (c) is within a range that does not inhibit the function of the terephthalic acid dialkyl ester compound as the component (c) of the present invention, that is, the use of the terephthalic acid dialkyl ester compound as the component (c). Although any amount can be used within the range not exceeding the amount, it is preferably used in a range of less than 50 parts by mass, particularly less than 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  In addition, the vinyl chloride resin composition for electric wire coating of the present invention can use a low-toxic organic acid metal salt other than the organic acid zinc salt. Examples of the organic acid metal salt include carboxylic acid, organic phosphorus Examples thereof include metal (Li, Na, K, Ca, Ba, Mg, Sr, Al) salts of acids or phenols. 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, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids, and Naturally occurring mixtures of the above acids such as fatty fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, pt-butyl benzoic acid, ethyl benzoic acid, isopropyl benzoic acid, toluic acid, Examples include xylic acid, salicylic acid, 5-t-octylsalicylic acid, naphthenic acid, and cyclohexanecarboxylic acid. Examples of the organic phosphoric acid include mono- or dioctyl phosphoric acid, mono- or dododecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, and phosphonic acid stearyl ester. Etc. Examples of the phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol, and the like, which may be a normal salt, an acid salt, a basic salt, or an overbased complex.

  The amount of the organic acid metal salt other than zinc is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Moreover, it is preferable to use the (d) β-diketone compound in the composition of the present invention because an effect of improving the colorability is expected. Examples of the β-diketone compound include acetylacetone, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, Octylbenzoylmethane, bis (4-octylbenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-carboxymethylbenzoyl) methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, cyclohexane-1,3-dione, Methyl 3,6-dimethyl-2,4-dioxycyclohexane-1carboxylate, 2-acetylcyclohexanone, dimedone, 2- Such as emissions benzoyl cyclohexane, and the like. Also, metal salts of these β-diketone compounds can be used. Examples of metal species that can provide the β-diketone metal salt include alkali metals such as lithium, sodium and potassium; magnesium, calcium, strontium and Alkaline earth metals such as barium; zinc, aluminum, tin, alkyl tin and the like can be mentioned.

  The addition amount of the β-diketone compound is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Further, the composition of the present invention further includes various additives usually used as additives for vinyl chloride resins, such as organic phosphite compounds, phenolic antioxidants, sulfur-based antioxidants, epoxy Compounds, polyols, ultraviolet absorbers, hindered amine light stabilizers, fillers and the like can also be blended.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono , Dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditert-butylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol), 1, 4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol-pentaerythritol diphosphite, tetra _(C 12 _{~ 15} mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, 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'-butylidenebi (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphite, 9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite and the like. The content of the organic phosphite compound is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylenebis [(3,5-ditert-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] glyco Ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-ditert-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-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl- 4-hydro Ciphenyl) bropionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2 -Acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-hydroxyethyl] -2,4,8,10-tetraoxaspiro [5,5 ] Undecane-bis [β- (3-tert-butyl-4-hydroxy-5-butylphenyl) propionate], triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 3- (3,5-ditert-butyl-4-hydroxyphenyl) -N-octadecylpropionamide and the like. The content of the phenolic antioxidant is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic acid esters. The content of the sulfur-based antioxidant is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, and epoxidized animal and vegetable oils, 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, bisphenol A diglycidyl ether, vinylcyclohexene Examples include epoxy compounds such as diepoxide, dicyclohexylene epoxide, and 3,4-epoxycyclohexylmethyl epoxycyclohexanecarboxylate. The content of the epoxy compound is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Examples of the polyol compound include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol stearic acid half ester, bis (dipentaerythritol) adipate, glycerin, and tris. (2-hydroxyethyl) isocyanurate and the like. The content of the polyol compound is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4- 2- (2-hydroxyphenyl) benzotriazoles such as trioctyl-6-benzotriazolyl) phenol, polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; Benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate Substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3 -Methyl-3- (p-methoxyphenyl) acrylate What cyanoacrylates and the like. The content of the ultraviolet absorber is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  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, 2,2, 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) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis ( , 2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2, 2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetraethyl-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- -(2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12- Tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino ] Undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino And hindered amine compounds such as undecane. The content of the hindered amine light stabilizer is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Specific examples of the filler include calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, and alumina silicic acid. Examples thereof include sodium, hydrotalcite, hydrocalumite, aluminum silicate, magnesium silicate, calcium silicate, metal silicates such as zeolite, activated clay, talc, clay, bengara, asbestos, and antimony trioxide.

  Moreover, the stabilization aid normally used for a vinyl chloride resin can be added to the composition of this invention. Examples of such stabilizing aids include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, zeolite, and perchlorate.

  In addition, in the composition of the present invention, additives that are usually used for vinyl chloride resins as necessary, for example, crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents, surface treatment agents, lubricants, Flame retardants, antifogging agents, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, and the like can be blended.

  The production method of the vinyl chloride resin composition for covering electric wires of the present invention is not particularly limited. For example, a vinyl chloride resin and an additive may be mixed by dry blending, and a part of the additive is preblended. Thereafter, it may be dry blended with the remaining components. After dry blending, for example, mixing may be performed using a mill roll, a Banbury mixer, a super mixer, or the like, and kneading may be performed using a single screw or twin screw extruder.

  The composition of the present invention can be used regardless of the processing method of the vinyl chloride resin, and is suitable for, for example, roll processing, extrusion molding processing, melt casting, pressure molding processing, and the like. Can be used.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by the following Example.

Example 1
The following blend was pre-kneaded, kneaded on a roll at 170 ° C. and 30 rpm for 7 minutes, and then pressed at 190 ° C. for 30 minutes or 60 minutes for a 1 mm thick sheet General-purpose color difference meter Color Ace TC-8600A ( Yellowness was measured using Tokyo Denshoku Co., Ltd.
Moreover, the time (min, heat stability) until it puts into a 200 degreeC gear oven and becomes black was measured. Further, according to JIS K 6723, a thermal stability test (Congo Red test) using Congo red paper was performed at 200 ° C.
Furthermore, the volume resistivity (VR value) was measured under the conditions of an applied voltage of 500 V, a temperature of 30 ° C., and a humidity of 42%.

Further, in accordance with JIS K 7113, a prescribed test piece was prepared, a tensile test was performed, and elongation (%) and tensile strength (MPa) were measured. Furthermore, after the test piece was promoted to deteriorate for 168 hours in a gear oven at 100 ° C., a tensile test was performed to measure elongation (%) and tensile strength (MPa). The residual elongation rate (%) was determined from the elongation before and after the deterioration test.
The results are shown in [Table 1].

(Formulation) Mass parts vinyl chloride resin (degree of polymerization 1000) 100
Calcium carbonate 20
Silicic anhydride 0.2
Zinc stearate 0.5
Hydrotalcite 2.7
(Compositional formula: Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O,
(BET specific surface area: 9 m ² / g, average particle size: 0.48 μm)
Dibenzoylmethane 0.15
Tetrakis [methylene-3- (3,5-ditert-butyl-0.3
4-hydroxyphenyl) propionate] methane
Sorbitol 0.05
Magnesium hydroxide 0.1
Test compounds (Table 1) Table 1

＊１：テレフタル酸ビス（２−エチルヘキシル）
＊２：フタル酸ビス（２−エチルヘキシル）
＊３：フタル酸ジイソノニル
＊４：トリメリット酸トリス（２−エチルヘキシル）

* 1: Bis (2-ethylhexyl) terephthalate
* 2: Bis (2-ethylhexyl) phthalate
* 3: Diisononyl phthalate * 4: Tris-trimellitic acid tris (2-ethylhexyl)

  As is apparent from the above examples, the composition of the present invention has little colorability when left at high temperature, exhibits high heat resistance in the Congo Red test, and also exhibits high insulation in the VR test.

Claims (5)

  To 100 parts by weight of vinyl chloride resin, (a) 0.001 to 10 parts by weight of a hydrotalcite compound, (b) 0.001 to 10 parts by weight of an organic acid zinc salt, and (c) 5 to 100 dialkyl ester compounds of terephthalic acid. A vinyl chloride resin composition for covering electric wires, characterized by containing a mass part.   Furthermore, the vinyl chloride resin composition for electric wire coating | cover of Claim 1 containing 0.001-5 mass parts of (d) (beta) -diketone compound. The (a) hydrotalcite compound is represented by the following formula (I),
Mg _x1 Zn _x2 Al ₂・ (OH) _{2x1 + 2x2 + 4}・ (CO ₃ ) _{1-y1 / 2} (ClO ₄ ) _y1・ mH ₂ O (I)
(In the formula, x1, x2 and y1 each represent a number satisfying the condition represented by the following formula, and m represents 0 or an arbitrary integer.
The vinyl chloride resin composition for covering electric wires according to claim 1 or 2, represented by 0≤x2 / x1 <10, 2≤x1 + x2 <20, 0≤y1≤2.   The vinyl chloride resin composition for electric wire coating according to any one of claims 1 to 3, wherein the (b) organic acid zinc salt is a zinc salt of a carboxylic acid.   The vinyl chloride resin composition for electric wire coating according to any one of claims 1 to 4, wherein the (c) dialkyl terephthalate compound is bis (2-ethylhexyl) terephthalate.