JPH10308122A - Electric wire covering vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent adhesion to a copper wire, improve initial coloring performance, reduce a hue change after a thermal history, and improve copper pollution resistance by blending a benzotrizole compound and a β-diketone compound at a specific rate with a vinyl chloride resin. SOLUTION: This composition is composed of a vinyl chloride resin: 100 pts.wt., a benzotriazole compound of the formula: 0.001 to 10 pts.wt. and a β-diketone compound: 0.001 to 10 pts.wt. In the formula, R1 to R4 are each H, a halogen atom, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group, an alkoxycarbonyl group or an alkanoylamino group. Particularly, diaroyl methane such as dibenzoylmethane, stearoylbenzolymethane and acetylbenzoylmethane or alkanoylaroylmethane or metallic salt is desirable as the β-diketone compound. A metallic stabilizer such as a lead type stabilizer, organic acid metallic salt and an organic tin type stabilizer can be added. They can be suitably used as an electric wire covering material.

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 coating electric wires, and more particularly, to a vinyl chloride resin, which is added with a benzotriazole compound and a .beta.-diketone compound in combination to provide coloring and copper resistance. The present invention relates to a vinyl chloride resin composition for covering electric wires, which has good contamination properties and the like.

[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-based resin deteriorates its excellent properties due to thermal and oxidative deterioration, and becomes practically unusable.

[0003] Further, when used for covering electric wires, there is a problem that the oxidative deterioration of the vinyl chloride resin is accelerated by the catalytic action of copper ions due to contact with the copper wire.

It has been known to use a heavy metal deactivator such as a benzotriazole compound in order to prevent such adverse effects due to copper ions. For example,
JP-A-7-41735 proposes a method for stabilizing the hue of a vinyl chloride resin by heat using a benzotriazole compound having a nitro group, a halogen group or an alkoxyl group. Has proposed a soft polyvinyl chloride resin composition comprising a mixture of dialkyl phthalate, chlorinated paraffin, clay and benzotriazole compound. However, when these benzotriazole compounds are used alone in a vinyl chloride resin, the effect is small, and it is necessary to mix them in a relatively large amount. There were problems such as sticking.

[0005] Further, β-diketone compounds have been used as stabilizers for vinyl chloride resins and have been known to have an effect of improving the initial coloring of products in particular.
However, heretofore, no attempt has been made to use it in combination with a benzotriazole compound.

Accordingly, an object of the present invention is to provide excellent coloring properties,
An object of the present invention is to provide a vinyl chloride-based resin insulating material which is suitable as an electric wire covering material having copper contamination resistance and excellent electric insulation.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object by adding a specific benzotriazole compound and a β-diketone compound to a vinyl chloride resin in combination. I found that.

The present invention has been made on the basis of the above findings, and 100 parts by weight of a vinyl chloride resin is represented by the following general formula (I) of (a) [formula 2] (same as the above [formula 1]). 0.001 of at least one benzotriazole compound used
An object of the present invention is to provide a vinyl chloride resin composition for coating electric wires, comprising 10 to 10 parts by weight and 0.001 to 10 parts by weight of (b) at least one kind of β-diketone compound.

[0009]

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[0010]

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.

In the benzotriazole compound represented by the general formula (I), which is the component (a) used in the present invention, R ₁ , R ₂ , R ₃ and R _{4 in the} general formula (I)
Examples of the halogen atom represented by include fluorine, chlorine, bromine, iodine, and the like, and the alkyl group includes lower alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. And the alkoxycarbonyl group includes groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and butoxycarbonyl, and the alkanoylamino group includes groups such as octyloylamino and decanoylamino.

The benzotriazole compound includes:
For example, 1,2,3-benzotriazole, 4-chloro-1,2,3-benzotriazole, 4-hydroxy-
1,2,3-benzotriazole, 4-nitro-1,
2,3-benzotriazole, 5-carboxy-1,
2,3-benzotriazole, 4-methyl-1,2,3
-Benzotriazole, 6-methylbenzotriazole, 6-butyl-1,2,3-benzotriazole, 6
-Dodecyl-1,2,3-benzotriazole, 5-methoxycarbonyl-1,2,3-benzotriazole,
Examples thereof include 6-octyloylamino-1,2,3-benzotriazole, and in particular, 1,2,3-benzotriazole, 4-methyl-1,2,3-benzotriazole, 6-methylbenzotriazole, and the like. Lower alkyl-substituted-1,2,3-benzotriazole is preferred. These benzotriazole compounds can be used alone or in combination of two or more.

The benzotriazole compound is used in an amount of 0.001 to 100 parts by weight of the vinyl chloride resin.
10 to 10 parts by weight, preferably 0.01 to 5 parts by weight.
When the amount is less than 0.001 part by weight, the effect is not sufficiently exhibited, and when the amount is more than 10 parts by weight, defects such as lowering of insulation properties and blooming occur.

The component (b) used in the present invention, β-
Examples of the diketone compound include dehydroacetic acid, acetyltetralone, benzoyltetralone, 2-benzoylcyclohexanone, dibenzoylmethane, benzoyl-4-chlorobenzoylmethane, bis (4-methylbenzoyl) methane, and 4-tert-butylbenzoyl. -4-methoxybenzoylmethane, benzoyl-4-isopropylbenzoylmethane, bis (4-methoxybenzoyl) methane, acetylbenzoylmethane, acetylbenzoylallylmethane, propionyl-3-methoxycarbonylbenzoylmethane, isovaleroylbenzoylmethane, octa Noylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, dipivaloylmethane, distearoylmethane, tribenzoylmethane, 1,3-bi (Benzoyl acetyl) benzene or their metal salts (lithium, sodium, potassium, calcium, magnesium, barium, zinc, nickel, cobalt, manganese, copper, iron, salts, such as titanium)
Among them, diaroylmethane such as dibenzoylmethane, stearoylbenzoylmethane, and acetylbenzoylmethane, or alkanoylaroylmethane is preferable because of excellent performance. These β-diketone compounds can be used alone or in combination of two or more.

The amount of the β-diketone compound used is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. When the amount is less than 0.001 part by weight, the effect is not sufficiently exhibited, and when the amount is more than 10 parts by weight, not only the effect of increasing the amount is not observed but also the heat resistance is lowered.

The vinyl chloride resin used in the present invention is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Examples thereof include polyvinyl chloride and chlorinated polyvinyl chloride. , Polyvinyl chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer , Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Chlorine-containing resins such as nil-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their blends, or Chlorine-containing resin and other synthetic resin containing no chlorine, for example, acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer,
Examples include ethylene-ethyl (meth) acrylate copolymers, blends with polyesters and the like, block copolymers, graft copolymers, and the like.

The composition of the present invention may contain commonly used metal stabilizers, such as lead stabilizers, organic acid metal salts, and organotin stabilizers. And their composite stabilizers.

Examples of the lead-based stabilizer include, for example, lead white,
Basic lead silicate, basic lead sulfate, dibasic lead sulfate, tribasic lead sulfate, basic lead sulfite, dibasic lead phosphite, silica gel coprecipitated lead silicate, dibasic lead phthalate, tribasic Lead maleate, lead salicylate, lead stearate, basic lead stearate, dibasic lead stearate, lead laurate,
Examples include lead octylate, lead 12-hydroxystearate, lead behenate, and lead naphthenate.

The metal salts of organic acids include metals such as carboxylic acids, organic phosphoric acids and phenols (Li,
Na, K, Ca, Ba, Mg, Sr, Zn, Cd, S
n, Cs, Al, organic Sn) salts and the like. Examples of the carboxylic acid include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, and myristin. 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, arachiic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acids, coconut oil fatty acids, tung oil fatty acids,
Mixtures of the above naturally occurring acids such as soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5-t-octylsalicylic acid, Naphthenic acid, cyclohexanecarboxylic acid and the like, and
Examples of the organic phosphoric acids include mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (nonylphenyl) phosphoric acid, nonyl phenyl phosphonate, stearyl phosphonate and the like. And the phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol, and the like. These may be normal salts, acidic salts, basic salts or overbased complexes. Good.

Examples of the organotin-based stabilizer include methyl stanoic acid, butyl stanoic acid, octyl stanoic acid, dimethyl tin oxide, dibutyl tin oxide, dioctyl tin oxide, dimethyl tin sulfide, Dibutyltin sulfide, dioctyltin sulfide, monobutyltin oxide sulfide, methylthiostannoic acid, butylthiostannoic acid, octylthiostannoic acid, dibutyltin dilaurate, dibutyltin distearate, dioctyltindiolate, dibutyltin basic Laurate, dibutyltin dicrotonate, dibutyltin bis (butoxydiethylene glycol malate), dibutyltin methyl octyl neopentyl glycol malate, dibutyltin isooctyl 1,4-butanedi Olemalate, dibutyltin dimethacrylate, dibutyltin dicinnamate, dioctyltin bis (oleylmalate), dibutyltinbis (stearylmalate), dibutyltinitaconate, dioctyltinmalate, dimethyltin dicrotonate, dioctyltinbis (butylmalate), dibutyltin Dimethoxide, dibutyltin dilauroxide, dioctyltin ethyleneglycoxide, pentaerythritol dibutyltin oxide condensate, dibutyltin bis (lauryl mercaptide), dimethyl tin bis (stearyl mercaptide), monobutyltin tris (lauryl mercaptide) , Dibutyltin-β
-Mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, monobutyltin tris (isooctylmercaptoacetate), monooctyltin tris (2-ethylhexyl mercaptoacetate), dibutyltin bis (isooctylmercaptoacetate) Acetate), dioctyltin bis (isooctylmercaptoacetate), dioctyltin bis (2
-Ethylhexylmercaptoacetate), dimethyltinbis (isooctylmercaptoacetate), dimethyltinbis (isooctylmercaptopropionate), monobutyltin tris (isooctylmercaptopropionate), bis [monobutyldi (isooctoxycarbonylmethylenethio) ) Tin] sulfide, bis [dibutylmono (isooctoxycarbonylmethylenethio) tin] sulfide, monobutylmonochlorotinbis (isooctylmercaptopropionate), monobutylmonochlorotinbis (isooctylmercaptoacetate), monobutylmonochlorotin Bis (lauryl mercaptide), butyltin bis (ethylcellulobmalate), bis (dioctyltin butylmalate) malate, bis (methyltin diisooctyltilgyl) (Colate) disulfide, bis (methyl / dimethyltin mono / diisooctylthioglycolate) disulfide, bis (methyltin diisooctylthioglycolate) trisulfide, bis (butyltin diisooctylthioglycolate) trisulfide And 2-butoxycarbonylethyltin tris (butylthioglycolate).

The amount of the metal stabilizer is preferably 0.05 to 1 with respect to 100 parts by weight of the vinyl chloride resin.
0 parts by weight.

The composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, for example, plasticizers, polyols, epoxy compounds, phosphorus compounds, phenol compounds or sulfur compounds. An antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, a hydrotalcite compound, other inorganic stabilizers, a filler, and the like can also be blended.

Examples of the plasticizer include phthalate plasticizers such as diheptyl phthalate, dioctyl phthalate and diisononyl phthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate and di (butyl diglycol) adipate; and trimellitate plasticizers. Agents, pyromellitate plasticizers, biphenyltetracarboxylate plasticizers, phosphate plasticizers, polyester plasticizers, chlorinated paraffin plasticizers, and the like.

Examples of the polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentarisritol, polypentaerythritol, pentaerythritol or half-stearic acid ester of dipentarisritol, bis (dipentaerythritol) Adipate, glycerin, tris (2-hydroxyethyl) isocyanurate and the like can be mentioned.

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, and epoxidized safflower oil. 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 diepoxide, dicyclohexene diepoxide, 3 And epoxy compounds such as 1,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate.

Examples of the phosphorus antioxidants include trisnonylphenyl phosphite, tris (2,4-ditertbutylphenyl) phosphite, and tris [2-tertbutyl-4- (3-tert-butyl). Butyl-4-hydroxy-5-
Methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite,
Monodecyldiphenyl phosphite, mono (dinonylphenyl) bis (nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite,
Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-
4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-triphenylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl-4-methylphenyl) pentaerythritol diphosphite, tetra (Tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (C
_12-15 mixed alkyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2
-Methyl-4-hydroxy-5-tert-butylphenyl)
Butanetriphosphite, tetrakis (2,4-ditertbutylphenyl) biphenylenediphosphonite, 2,
2'-methylenebis (4,6-di-tert-butylphenyl)
(Octyl) phosphite 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, thiodiethylenebis [ (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5- Di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric acid] glycol ester, 4,
4′-butylidenebis (6-tert-butyl-m-cresol), 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-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] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the above sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionate esters of polyols.

Examples of the ultraviolet absorber include, for example, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2- such as hydroxy-4-methoxybenzophenone)
Hydroxybenzophenones; 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-3,5-dicumylphenyl) benzotriazole,
2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-
2- (3-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-hydroxyphenyl) benzotriazoles; 2
-(2-hydroxy-4-hexyloxyphenyl)-
4,6-diphenyl-1,3,5-triazine, 2-
(2-hydroxy-4-octoxyphenyl) -4,6
2- (2-hydroxyphenyl) -1, such as -bis (2,4-dimethylphenyl) -1,3,5-triazine,
3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4 Benzoates such as -hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-
Substituted oxanilides such as dodecyl oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; Metal salts or metal chelates, especially salts or chelates of nickel or chromium, are mentioned.

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, 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 (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-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
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
And hindered amine compounds such as -bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane.

The above hydrotalcite compound is represented by the following general formula (II): magnesium, an alkali metal and / or carbonic acid and / or zinc / aluminum.
Alternatively, it may be a perchloric acid double salt compound obtained by dehydrating water of crystallization.

Ia _x1 Mg _x2 Zn _x3 Al _y (OH) _{x1 + 2 (X2 + X3) + 3y-2} · (CO ₃ ) _{1-z / 2} (ClO ₄ ) _Z · mH ₂ O (II) In the formula, Ia represents an alkali metal atom, x1, x2,
x3, y and z each represent a condition represented by the following formula,
m indicates a real number. 0 ≦ x1 ≦ 10, 0 ≦ x2 ≦ 10,0
≤ x3 ≤ 10, 1 ≤ y ≤ 10, 0 ≤ z ≤ 1, provided that x1 and x2 never become 0 at the same time. )

The hydrotalcite compound may be a natural product or a synthetic product. Examples of the method for synthesizing the synthetic product include JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, and JP-A-61-17.
A known method described in, for example, Japanese Patent No. 4270 can be exemplified. Further, the above hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter and the like.

As the hydrotalcite compound, the surface thereof 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 the like. Those coated with higher fatty acid amides, higher fatty acid esters or waxes can also be used.

Examples of the above-mentioned other inorganic stabilizers include calcium oxide, calcium hydroxide, calcium silicate, amorphous aluminosilicate, alkali and / or alkaline earth aluminosilicate having a zeolite crystal structure, and powdered silicon. Acids (silica), 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, M
OS, 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,
A light stabilizer and the like can be blended.

The composition of the composition of the present invention is as described above. In particular, 100 parts by weight of a vinyl chloride resin is
The above benzotriazole compound (component (a)) 0.01
To 5 parts by weight and a β-diketone compound [component (b)]
A composition comprising 0.01 to 5 parts by weight is preferred.

The composition of the present invention is prepared by a usual method, and is applied to a use as an electric wire coating material by a usual method.

The composition of the present invention has excellent initial coloring properties, little change in hue after heat history, and excellent copper stain resistance without sticking between the copper wire and the coating material.

[0041]

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

Example 1 The following components were kneaded on a roll at 160 ° C. and 20 rpm for 6 minutes, and then pressed at 180 ° C. for 5 minutes to form a 1 mm thick sheet, and the yellowness of the sheet was measured. The yellowness of the sheet pressed under the same conditions for 30 minutes was also measured. A test piece was prepared from this sheet, heated in a gear oven at 210 ° C., and the time until blackening was measured to evaluate the thermal stability.

Further, a copper foil is sandwiched on a roll sheet for
A laminated film having a thickness of 1 mm was prepared by pressing at 80 ° C. for 5 minutes and placed in a thermostatic chamber at 60 ° C. and a humidity of 80%, and after one and three months, coloring of the vinyl chloride film The property was visually determined, and the copper contamination was evaluated. The evaluation criterion is a 10-level scale of 1 to 10, where 1 represents almost no coloration, indicating that the coloration increases as the numerical value increases.

Further, the interface between one of the coating materials of the laminated film and the copper foil is partially peeled off, the copper foil surface is fixed, a spring gauge is attached to the coating material, and the coating is slowly peeled off. The highest value indicated by the scale was read to evaluate the peel strength.

The results are shown in the following [Table 1].

(Combination) parts by weight polyvinyl chloride resin (degree of polymerization 1050) 100 diisononyl phthalate 50 calcium carbonate 30 clay # 33 5 tribasic lead sulfate 4 dibasic lead stearate 0.5 n-lead lead stearate 0.5 Dibenzoylmethane 0.05 Test compound (see [Table 1] below) 0.05

[0047]

[Table 1]

Example 2 The same test (excluding peel strength) as in Example 1 was performed with the following formulation. The results are shown in Table 2 below.

(Combination) parts by weight polyvinyl chloride resin (degree of polymerization 1050) 100 diisodecyl phthalate 50 calcium carbonate 30 clay # 335 5 zinc stearate 0.7 sorbitol 0.02 Alkamizer 1 (HT) ^{* 2} 0 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy 0.2 phenyl) isocyanurate tris (nonylphenyl) phosphite 0.1 stearoylbenzoylmethane 0.05 Test compound (see the following [Table 2)) 0.05 * 2: Hydrotalcite manufactured by Kyowa Chemical Co., Ltd. Composition: Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O

[0050]

[Table 2]

Example 3 The same test as in Example 2 was conducted with the following formulation.
The results are shown in Table 3 below.

(Combination) parts by weight polyvinyl chloride resin (degree of polymerization 1050) 100 triisononyl trimellitate 50 calcium carbonate 20 clay # 33 10 zinc stearate 0.7 calcium stearate 1.0 dibenzoylmethane 0.15 sorbitol 0 .02 Stearyl (3,5-di-tert-butyl-4-hydroxy 0.2 phenyl) propionate Calcium silicate 0.3 1,2,3-benzotriazole 0.05 Test compound (see Table 3 below) 05

[0053]

[Table 3]

As is apparent from the results of Tables 1 to 3, when the benzotriazole compound is used alone in the vinyl chloride resin, the effect of improving the copper contamination is small with a small amount. Examples 1-3 and 3-1) When the amount is increased, the effect is increased to some extent, but disadvantages such as coloring and adhesion of the coating material-copper interface occur (Comparative Examples 1-4 and 2-3). . Further, when the β-diketone compound was used alone, the effect of improving copper contamination was hardly observed (Comparative Examples 1-1, 2-1 and 3-
2).

On the other hand, when the benzotriazole compound represented by the above general formula (I) and the β-diketone compound are added to the vinyl chloride resin in combination, the copper contamination is remarkably improved due to the synergistic effect. And the thermal coloring property is not reduced, and the coating material-copper interface is not adhered (Examples 1-1 to 1-3, 2-1 to 2-1).
2-3, 3-1 to 3-3).

[0056]

The vinyl chloride resin composition for covering electric wires according to the present invention has excellent coloring properties, copper contamination and the like, and can be suitably used as a covering material for electric wires.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Osamu Yoshiguchi 5-2-13-Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd.

Claims (1)

[Claims] 1. 100 parts by weight of a vinyl chloride resin,
(A) 0.001 to 10 parts by weight of at least one kind of a benzotriazole compound represented by the following general formula (I) and (b) 0.001 to 10 parts by weight of at least one kind of a β-diketone compound A vinyl chloride resin composition for covering electric wires, which is blended. Embedded image