JPH0128774B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a polyvinyl chloride resin composition with significantly improved electrical insulation properties, specifically, a polyvinyl chloride resin containing a plasticizer, a lead-based stabilizer, an organic acid metal salt compound, calcium carbonate and/or clay, The present invention also relates to a polyvinyl chloride resin composition for electric wires with improved electrical insulation properties, which is obtained by adding an organic phosphate metal salt compound. Generally, polyvinyl chloride resin has excellent electrical insulation properties. However, this resin tends to undergo thermal decomposition mainly due to dehydrochlorination during thermoforming, resulting in a decrease in electrical insulation, deterioration of mechanical properties, and deterioration of color tone of the processed product.
This will cause significant disadvantage. Conventionally, in order to avoid such disadvantages, one or more types of thermal stabilizers have been added to the resin to suppress thermal deterioration during this processing step. Stabilizers such as lead compounds have been used for this purpose. However, it did not have sufficient performance to satisfy the industry, and in particular, improvements in electrical insulation and workability were desired. In view of the above-mentioned current situation, the present inventors have conducted extensive research over many years, and as a result, have succeeded in developing a polyvinyl chloride resin with significantly improved electrical insulation properties. That is, in the present invention, based on 100 parts by weight of polyvinyl chloride resin, (1) 10 to 100 parts by weight of a plasticizer, (2) 0.01 to 10 parts by weight of a lead-based stabilizer, and (3) 0.01 parts by weight of an organic acid metal salt compound.
-10 parts by weight, (4) 10 to 40 parts by weight of calcium carbonate and/or 5 to 20 parts by weight of clay, and (5) 0.01 to 20 parts by weight of a specific organophosphate metal salt compound. The present invention provides an improved polyvinyl chloride resin composition. The polyvinyl chloride resin composition of the present invention will be explained in detail below. Plasticizers used in the composition of the present invention include phthalate esters or other esters,
Examples include polyester type, phosphate ester type, epoxy type, and chlorine type. Examples of phthalate ester plasticizers include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dihexyl phthalate, dimethylisobutylcarbinyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, and dipropyl phthalate. -isooctyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diallyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dilauryl phthalate, dicapryl phthalate, dicyclohexyl phthalate, diphenyl phthalate, dibenzyl phthalate, di(mixed alcohol) phthalate , dimethyl glycol phthalate, dibutoxyethyl phthalate, butyl lauryl phthalate, butyl benzyl phthalate, octyl capryl phthalate, butyl octyl phthalate, butyl isodecyl phthalate, octyl decyl phthalate, butyl coconut alkyl phthalate, isooctyl decyl phthalate, butyl cyclohexyl phthalate, Butylphthalyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate,
Examples include butyl isohexyl phthalate and di(methylcyclohexyl) phthalate. Examples of other ester plasticizers include di-n-hexyl adipate, dioctyl adipate, dioctyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dicapryl adipate, dibutyl sebacate, dioctyl sebacate, and di-2-ethylhexyl sebacate. cate, dioctyl azelate, di-2-ethylhexyl azelate, butyl oleate, dioctyl maleate, dibutyl fumarate, methyl acetyl ricinolate, triethylene glycol di-
2-ethylhexoate, tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate, tridecyl trimellitate, triethyl citrate, acetyl triethyl citrate,
Tributyl citrate, acetyl tributyl citrate, acetyl tri-2-ethylhexyl citrate, tributyl trimellitate, dibutylbenzyl trimellitate, dioctyl tetrahydrophthalate, diethylene glycol dibenzoate, dipentaerythritol hexaester, polypropylene adipate or polypropylene sebacate, etc. There is. Examples of phosphoric acid ester plasticizers include trioctyl phosphate, diphenyl monooxenyl phosphate, and tri(α-chloroethyl).
phosphate, tri(α-bromoethyl) phosphate, tri(α-dichloropropyl) phosphate, tri(α-dibromopropyl) phosphate, triethyl phosphate, tributyl phosphate, tri(α-ethylhexyl) phosphate, tributoxyethyl phosphate, Triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, tridimethyl phenyl phosphate, o, o, o-triethyl phosphorothioate, o, o, o-tributyl phosphorothioate, o, o, o-tri Examples include isooctyl phosphorothioate, tris(o-chloroethyl) phosphate, diphenyl octyl phosphate, diphenyl xylenyl phosphate, and tri(t-butylphenyl) phosphate. Examples of epoxy plasticizers include butyl epoxy stearate, octyl epoxy stearate, octyl epoxy benzoate, butyl epoxy oleate, 2-ethylhexyl epoxidized tall oil fatty acid ester, epoxidized soybean oil, epoxidized linseed oil, and epoxidized cottonseed oil. , epoxidized safflower oil, hexyl epoxy stearate, benzyl epoxy stearate, cyclohexyl epoxy stearate, methoxy epoxy stearate, phenyl epoxy stearate, tert-butyl epoxy stearate, octyl epoxy succinate, epoxidized tetrahydrophthalate, Examples include epoxidized cyclohexanedicarboxylic acid ester, epoxidized dioctyl hexahydrophthalate or mono(epoxystearyl), diacetylglyceride, and the like. Examples of chlorinated plasticizers include chlorinated paraffin, chlorinated methyl stearate, chlorinated diphenyl, chlorinated benzyl laurate, and chlorinated diphenylbenzene. The preferred amount of the plasticizer added is 10 to 100 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Examples of lead-based stabilizers used in the present invention include white lead, basic lead silicate, tribasic lead sulfate, dibasic lead phosphite, silica gel co-precipitated lead silicate, basic lead silicate, and base Inorganic acid salts such as lead carbonate, stearic acid, dibasic lead stearate, tribasic lead maleate, lead phthalate, dibasic lead phthalate,
There are organic acid salts such as tribasic lead phthalate, lead octylate, basic lead octylate, and lead lanophosphate. The preferred amount of the lead-based stabilizer added is 0.01 to 10 parts by weight per 100 parts by weight of the polyvinyl chloride resin. The organic acid metal salt compound used in the present invention is a metal salt of carboxylic acid or phenol, and metals of the metal salt include group metals such as Li, Na, and K, Mg,
Group metals such as Ca, Sr, Ba, Zn, Cd, Sn, Zr,
Mention may be made of Sb, Bi and organic Sn. Examples of carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid,
Lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12
-Hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-tert-
Butylbenzoic acid, dimethylhydroxybenzoic acid,
3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid Acids, monohydric carboxylic acids such as salicylic acid, P-tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, oxalic acid, malonic acid, succinic acid , glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
Monoesters of dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, etc. Examples include monoamide compounds, di- or triester compounds of trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophanoic acid, and pyromellitic acid. Examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol,
Isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol,
Examples include methylisohexylphenol and methyl-t-octylphenol. The preferable amount of the organic acid metal salt compound added is as follows:
0.01 to 10 per 100 parts by weight of polyvinyl chloride resin
Parts by weight. Calcium carbonate used in the present invention includes:
Heavy calcium carbonate, soft calcium carbonate, precipitated calcium carbonate, slight calcium carbonate, ultrafine precipitated calcium carbonate, colloidal calcium carbonate or activated calcium carbonate, or their use as resins, metal soaps, organic acids, surfactants, etc. A material coated with an organic substance can be used. The preferred amount of calcium carbonate added is 10 to 40 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Further, in the present invention, clay is added to the resin together with the above calcium carbonate or in place of the above calcium carbonate, and the clay includes kaolin clay (hard clay, soft clay),
It is possible to use waxite clay, calcined clay, kurta, sericite, mica, asbestos, bentonite, or those whose surfaces are coated with organic substances such as resins, metal soaps, organic acids, and surfactants. The preferred amount of the clay added is 5 to 20 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Further, the organic phosphate metal salt compound used in the present invention is a compound represented by the following general formula [], [] or []. (In the above formula, each R is independently alkyl, aryl,
It represents an arylalkyl, alkylaryl or ether-containing alkyl group, M ₁ represents a group metal, and M ₂ represents a group metal or dialkyltin. n
indicates 1 or 2. ) More specifically, examples of the alkyl group constituting the metal salt represented by the above general formula [], [] or [] include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary-butyl. , amyl, neopentyl, isoamyl,
hexyl, isohexyl, heptyl, octyl,
isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl, _C12-15 mixed alkyl, stearyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-
Examples include methylcyclooctyl. Examples of aryl groups include phenyl, naphthyl, and the like. Examples of arylalkyl groups include benzyl, β-phenylethyl, γ-phenylpropyl, β-phenylpropyl, and the like. Examples of alkylaryl groups include tolyl, xylyl, ethyl phenyl, butylphenyl, 4-tert-butylphenyl, octylphenyl, isooctyl phenyl, tert-octyl phenyl, nonylphenyl, 2,4-di-tert-butylphenyl, and the like. . Ether-containing alkyl groups include furfuryl, tetrahydrofurfuryl, 5-methylfurfuryl, and α-methylfurfuryl groups, or methyl, ethyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, and methylfurfuryl. enyl cellosolve residue; methyl-, ethyl-, isopropyl-, butyl-, isobutyl carbitol residue; triethylene glycol monomethyl ether, -monoethyl ether, -monobutyl ether residue; glycerin 1,2-dimethyl ether, -
Examples include 1,3-dimethyl ether, -1,3-diethyl ether, -1-ethyl-2-propyl ether residues; nonylphenoxypolyethoxyethyl, lauroxypolyethoxyethyl groups, and the like. In addition, the group metals are preferably Li, Na, and K, and the group metals are Be, Mg, Ca, Sr, Ba,
Zn, Cd, etc. are preferred. Further, as the dialkyltin, dibutyltin, dioctyltin, etc. can be suitably used. Next, specific examples of preferred organic phosphate metal salt compounds will be shown. Phenyl phosphate, 2Na salt, octyl phosphate, 2K salt, tridecyl phosphate, 2Na salt, nonylphenyl phosphate,
2K salt, 4-t-butylphenyl phosphate
2Na salt, diphenyl phosphate K salt, bis(4
-t-butylphenyl) phosphate Na salt, dinonyl phosphate Li salt, bis(nonylphenyl) phosphate Na salt, dibenzyl phosphate K salt, bis(methylphenyl) phosphate
Na salt, bis(2-ethylhexyl) phosphate Na salt, octyl phosphate Zn salt, tridecyl phosphate Zn salt, decyl phosphate Ca salt,
Tridecyl phosphate Ba salt, 2-ethylhexyl phosphate Mg salt, phenyl phosphate
Ba salt, nonylphenyl phosphate Zn salt, nonylphenyl phosphate Ca salt, 2,6-di-t
-Butylphenyl phosphate Zn salt, t-butylphenyl phosphate Sr salt, phenyl phosphate dibutyltin salt, dinonyl phosphate
Zn salt, bis(2-ethylhexyl) phosphate Zn salt, bis(2-ethylhexyl) phosphate Ca salt, diamyl phosphate Ba salt, dioctyl phosphate Sr salt, diphenyl phosphate Zn salt, diphenyl phosphate Mg salt, Bis(nonylphenyl) phosphate Zn salt, bis(nonylphenyl) phosphate Ca salt, bis(2-
t-butylphenyl) phosphate Ba salt, bis(4-t-butylphenyl) phosphate Ca salt,
These include diphenyl phosphate/dibutyl tin salt, ditridecyl phosphate/dioctyl tin salt, etc. The preferable amount of the organic phosphate metal salt compound added is 0.01 parts by weight per 100 parts by weight of the polyvinyl chloride resin.
~20 parts by weight. It is also possible to use other organotin stabilizers in combination with the composition of the present invention. Thermal stability can be increased by further adding an organic phosphite compound and/or an epoxy compound to the composition of the present invention, so it can be used as appropriate depending on the purpose of use. Since adding an antioxidant to the composition of the present invention can increase the anti-oxidative deterioration properties of the composition,
It can be used as appropriate depending on the purpose of use. These antioxidants include phenolic antioxidants, sulfur-containing compounds, and the like. If an ultraviolet absorber is added to the composition of the present invention, the photostability can be improved, so it is possible to select and use these as appropriate depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazines, piperidines, and the like. Others may be added as necessary, such as crosslinking agents, pigments, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, bactericidal agents, and metal-free agents. Activators, photodegradants, processing aids, mold release agents, reinforcing agents, rodenticides, rodent repellents, and the like can be included. Examples of the halogen-containing polymer used in the present invention include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer Coalescence, 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, vinyl chloride-acrylic acid ester copolymer, vinyl chloride- Halogen-containing synthetic resins such as maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and the above halogen-containing resins and polyethylene, polypropylene, polybutene, polyester, etc. -α-olefin polymers such as 3-methylbutene or ethylene-
Polyolefins and their copolymers such as vinyl acetate copolymers, ethylene-propylene copolymers, polystyrene, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene,
Examples include copolymers with acrylonitrile (such as acrylonitrile), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and blends with methacrylic ester-butadiene-styrene copolymers. The following examples illustrate the effects of the halogen-containing polymer composition according to the present invention, but the present invention is not limited to these examples. Example 1 In order to demonstrate the excellent thermal stability of the polyvinyl chloride resin composition according to the present invention, a sheet with a thickness of 1 mm was prepared using a kneading roll according to the following formulation, and a thermal deterioration test at 200°C and a sheet at 180°C were carried out. An initial coloring test was conducted. The results are shown in Table 1 below. <Composition> PVC (Geon103EP) 100 parts by weight Polyester plasticizer (PN manufactured by Adeka Argus)
-350) 60 Epoxidized soybean oil 5 Calcium carbonate 10 Clay (Southern Clay #33) 10 Dibasic lead stearate 3 Barium stearate 0.3 Zinc stearate 0.2 Organophosphate metal salt compounds (Table 1) 0.3

[Table] Example 2 A test sheet was prepared in the same manner as in Example 1 using the following formulation. Then, the thermal stability at 180°C and the volume resistivity (VR) at 30°C were measured. The results are shown in Table 2 below. <Composition> PVC (Geon103EP) 100 parts by weight trimellitic acid ester (ADEKA Sizer C-
8) 30 DIDP 30 Calcium carbonate 20 Southern clay #33 10 Tribase 7 Barium stearate 0.5 Zinc stearate 0.2 Organophosphate metal salt compounds (Table 2) 0.1

【table】

[Table] Example 3 A test sheet was prepared in the same manner as in Example 1 using the following formulation. Then, the thermal stability at 180°C and the volume resistivity were measured. The results are shown in Table 3 below. <Composition> PVC (Geon103EP) 100 parts by weight DOP 40 E-500 (chlorinated paraffin) 20 Calcium carbonate 20 Southern Clay #33 10 Tribase 5.0 Barium stearate 0.3 Zinc stearate 0.3 Organophosphate metal salt compound (Table 3) 3.0

【table】

[Table] Example 4 A test sheet was prepared in the same manner as in Example 1 using the following formulation. Then, the thermal stability at 200°C and the volume resistivity were measured. The results are shown in Table 4 below. <Composition> PVC (Geon103EP) 100 parts by weight DOP 50 Epoxidized soybean oil 2 Dibasic lead phosphite 5 Calcium carbonate 10 Southern clay #33 10 Zinc stearate 0.3 Calcium stearate 0.5 Dibutyltin dilaurate 0.2 Organophosphate metal salt compound (Table 4) 0.05

【table】

Claims (1)

[Claims] 1. For 100 parts by weight of polyvinyl chloride resin, (1)
10 to 100 parts by weight of plasticizer (2) 0.01 to 10 parts by weight of lead stabilizer, (3) 0.01 to 10 parts by weight of organic acid metal salt compound, (4) 10 to 40 parts by weight of calcium carbonate and/or 5 to 10 parts by weight of clay.
20 parts by weight and (5) 0.01 to 0.01 parts by weight of an organic phosphate metal salt compound represented by the following general formula [], [] or []
20 parts by weight of a polyvinyl chloride resin composition with improved electrical insulation properties. (In the above formula, each R is independently alkyl, aryl,
It represents an arylalkyl, alkylaryl or ether-containing alkyl group, M ₁ represents a group metal, and M ₂ represents a group metal or dialkyltin. n
indicates 1 or 2. )