JPS5827734A - Polyvinyl chloride resin composition - Google Patents

Abstract

PURPOSE:The titled composition that contains a plasticizer, a lead stabilizer, an organic acid metal salt, calcium carbonate, clay and organophosphate metal salt, thus showing remarkably improved insulation properties and good processability. CONSTITUTION:(A) 100pts.wt. of polyvinyl cholride resin are combined with (B) 10-100pts. of a plasticizer, (C) 0.01-10pts. of a lead stabilizer, (D) 0.01-10pts. of an organic acid metal salt, (E) 10-40pts. of calcium carbonate and/or 5- 20pts. of clay and (F) 0.01-20pts. of an organophosphate metal salt. As component F, is preferred disodium phenylphosphate or dipotassium octylphosphate. Further, a combination of an organophosphite with an epoxy compound is more preferred.

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 composition containing a plasticizer, a lead-based stabilizer, an organic acid metal salt compound, The present invention relates to a polyvinyl chloride resin composition for electric wires with improved electrical insulation properties, which is made by adding calcium carbonate and/or clay and an organic phosphate metal salt compound.

Generally, polyvinyl chloride resin has excellent electrical insulation properties. However, when this resin is subjected to thermoforming processing, it tends to cause thermal scaling mainly due to dehydrochlorination, which causes a decrease in the electrical insulation properties of processed products, deterioration of mechanical properties, etc.
This results in deterioration of color spacing, resulting in significant disadvantages.

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) organic acid gold. 0.01 to 10 parts by weight of a different compound, (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 an organophosphate metal salt compound. The present invention provides a polyvinyl chloride resin composition with improved electrical insulation properties.

The polyvinyl chloride resin composition of the present invention will be explained in detail below.

Examples of plasticizers used in the composition of the present invention include phthalate-based or other ester-based plasticizers, polyester-based plasticizers, phosphoric ester-based plasticizers, epoxy-based plasticizers, and chlorine-based plasticizers.

Examples of phthalate ester plasticizers include dimethyl phthalate, diethyl phthalate, diallyl phthalate,
Dibutyl phthalate, diisobutyl hepthalate, diallyl phthalate, diallyl phthalate, dimethylisobutylcarbinyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, di-isooctyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diallyl phthalate, Diisodecyl phthalate, ditridecyl phthalate, dilauryl phthalate, cicapril phthalate, dicyclohexyl phthalate, diphenyl phthalate, dibenzyl phthalate, diC 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, inooctyl decyl phthalate, butyl cyclohexyl phthalate, butyl phthalyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate,
There are butyl isohexyl phthalate and di(methylsiftetrahexyl) phthalate.

Examples of other ester plasticizers include di-n-hexyl adipate, dioctyl adipate, dioctyl adipate, di-2-ethylhexyl adipate, diindecyl adipate, cicapryl adipate, dibutyl sebacate, dioctyl sepacate, and di-2-ethylhexyl adipate. -Ethylhexyl sebacate, dioctyl azelate, di-2-ethylhexyl adipate, butyl oleate, dioctyl maleate, dibutyl 7-maleate, methyl acetyl lysyllate, 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 Examples thereof include trimellitate, dibutylbenzyl trimellitate, dioctyl tetrahydrophthalate, diethylene glycol dipenzoate, dipentaerythritol hexaester, polypropylene adipate, and polypropylene sepacate.

Examples of phosphate ester plasticizers include trioctyl phosphate, diphenyl monooxenyl phosphate, triCα-chloroethyl) phosphate, tri(α-momoethyl phosphate), )IJ(α-dichloro Propyl) phosphate, triζα-dibromopropyl) phosphate, triethyl phosphate, tributyl phosphate, tri(α-ethylhexyl) phosphate, tryptoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate,
Tricresyl phosphate, tridimethylphenyl phosphate, 0.0.0-triethyl phosphorothioate, o.

0.0-) butyl phosphorothioate, o, o,.

-triisooctylphosphorothioate, tris(0-
(roethyl) phosphate, diphenyloctyl phosphate, diphenylxylenyl yhx 7-c -)
Also, there are Gi) IJ (t-butyl 7-enyl) phosphate and the like.

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, epoxidized cottonseed oil, epoxidized flower oil, hexyl epoxy nutearate, benzyl epoxy stearate, cyclohexyl epoxy stearate, methoxyebo Φ distearate, phenyl epoxy Stearate, tert-butyl epoxy stearate, octyl epoxy succinate, epoxidized tetrahydrophthalate, epoxidized cyclohexane dicarboxylic acid ester, epoxidized dioctyl hexahydrophthalate or mono-epoxy stearyl), and diacetyl glyceride.

Examples of chlorinated plasticizers include chlorinated paraffin, chlorinated methyl stearate, chlorinated diphenyl, chlorinated dilaurate, and chlorinated diphenylbenzene.

The preferred amount of the plasticizer added is as follows: polyvinyl chloride resin 1i
The amount is 10 to 100 parts by weight per 1100 parts by weight.

Examples of lead-based stabilizers used in the present invention include white lead,
Inorganic acid salts such as basic lead silicate, tribasic lead sulfate, dibasic lead phosphite, silica gel co-precipitated lead silicate, basic lead silicate, basic lead carbonate, lead stearate, dibasic Organic acid salts include lead stearate, tribasic lead maleate, lead phthalate, dibasic lead phthalate, tribasic lead heptalate, 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 the metal of the skeleton metal salt includes Group I metals such as Li, Na, and K, Mg, and Oa.
, 8r, Ba, Zn, O (1st grade group II metal, fin.

Mention may be made of Zr, 8b, Bi and organic 8nf.

Examples of carboxylic acids include acetic acid, pionic 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, iristic acid, hal(5-nic acid, isostearic acid, stearin) acid, 12-hydroxystearic acid, hehenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-ta
rt-butylbenzoic acid, dimethylhydroxybenzoic acid,
5,5-di-t-rt-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, finic acid, n-propylbenzoic acid, ami]benzoic acid, N,
N-dimethylinobenzoic acid, acetoxybenzoic acid, salicylic acid, P-tart-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linoleic acid, thioglycolic acid, mercapdobutopionic acid, monovalent carboxylic acid octylmercaptopropionate Acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sepatic acid, phthalic acid,
Isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid,
Monoesters or monoamide compounds of dicarboxylic acids such as citraconic acid, methaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid; trivalent compounds such as hemimellitic acid, trimellitic acid, mephanic acid, and pyromellitic acid. Or di- or triester compounds of tetravalent carboxylic acids can be mentioned.

Examples of phenols include tθrt-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoaglephenol, ethylphenol, isopropylphenol, inoctylphenol, 2- ethylhexylphenol, tart
-nonylphenol, tesylphenol, t@rt-
Examples include octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, siaylphenol, methylisohexylphenol, and methyl-t-octylphenol.

The preferred amount of the organic acid metal salt compound added is 0.01 to 10 parts by weight per 100 parts by weight of the polyvinyl chloride resin 1ii.

Examples of calcium carbonate used in the present invention include heavy calcium carbonate, light coal 51 lucium, precipitated calcium carbonate, slight calcium carbonate, ultrafine precipitated calcium carbonate, colloidal calcium carbonate or activated calcium carbonate. Those coated with organic substances such as resins, metal soaps, organic acids, and surfactants 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.

(9) In the present invention, clay is added to the resin together with the above-mentioned calcium carbonate or in place of the above-mentioned calcium carbonate, and the clay includes kaolin clay (hard clay, soft clay), waxite clay, calcined clay. , Kurji, sericite, mica, asbestos, bentonite, or those whose surfaces are coated with organic substances such as resins, metal soaps, organic acids, and surfactants can be used.

The preferable addition amount of the above clay is 1 part of polyvinyl chloride resin.
00 parts by weight, it is 5 to 20 parts by weight.

Further, as the organic phosphate metal salt compound used in the present invention, a compound represented by the following general formula [1), 1 or (1) is preferable.

1 (Roip→OMt) sn [l) 10 RO-P<>M2 CM) (in the above formula, R
are each independently alkyl, aryl, arylalkyl,
It represents alkylaryl or an ether-containing alkyl group, Ml represents a Group I metal, and M2 represents a Group I metal or dialkyltin. n represents 1 or 2. ) More specifically, examples of the alkyl group constituting the metal salt represented by the above general formula (1), [seal] or (1) are:
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, 5-butyl, decyl, neopentyl, isoaru, hexyl, inohexyl, heptyl, octyl, inoctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl , 012-15
Mixed alkyl, stearyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl and the like can be mentioned.

Examples of the aryl group include phenyl, naphthyl, and the like. Arylalkyl group (7)N is benzyl, β-7aleethyl, r-phenylpropyl,
Examples include β-phenylpropyl.

Examples of alkylaryl groups include tolyl, xylyl, ethylphenyl, butylphenyl, 4-tert-butylphenyl, octylphenol, inoctylphenyl, tertiary
Examples include octylphenyl, nonylphenyl, 2,4-di-5-butylphenyl, and the like.

Examples of the ether-bonded alkyl group include furfuryl, tetrahydrofurfuryl, 5-methylfurfuryl, and α-furfuryl.
Methylfurfuryl group or methyl-, ethyl-, impropyl-, butyl-, isobutyl-, hexyl-, cyclohexyl-, phenyl cellosol residue; methyl-, ethyl-, isopropyl-, butyl-, isobutylcarpitol Residues: triethylene glycol monomethyl ether, -monoethyl ether, -monobutyl ether Residues: glycerin 1,2-dimethyl ether, -1,5-dimethyl ether, -1,3-diethyl ether, -1-
Ethyl-2-propyl ether residue; examples include nonylphenoxypolyethoxyethyl and lauroxypolyethoxyethyl groups.

In addition, the Group I metals are preferably Li, Ha, and K, and the Group I metals are Ba, Mg, Oa,
Sr, Ba.

Zn, OL, 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 2-salt, tridecyl phosphate 2NajJL
Nonylphenyl phosphate fistzcjl 4-t-Butylphenyl phosphate 2M salt, diphenyl phosphate salt, bis(a-t-butylphenyl) phosphate Na salt, dinonyl phosphate L1 salt, bis(nonylphenyl) phosphate Na salt, di- Benzyl phosphate X salt, bis(methylphenyl)phosphate Ba
salt, bis(2-ethylhexyl)phosphate-)Na salt,
octylphosphate) Zn salt, tridecylphosphate)
Zn salt, decylphosphate-)OL salt, tridecylphosphate-)Ba salt, 2-ethylhexylphosphate-)Mg[
BatJ
salt, t-butylphenyl phosphate) 8rtJE% phenyl phosphate dibutyltin salt, dinonyl phosphate) ZntJ [, bis(2-ethylhexyl) phosphate Zn salt, bis(2-ethylhexyl) phosphate)
OL salt, siazurphosphate) BajJ[, dioctyl phosphate Br salt, diphenyl phosphate) Zn salt,
Diphenyl phosphate Mg salt, bis(nonylphenyl) phosphite) ZntJi, bis(nonylphenyl)
Phosphate○ajL His(2-t-butylphenyl)phosphate Ba salt, bis(4-t-methylphenyl)phosphate-)ca salt, ') Phenylphosphate.
These include dibutyltin salt, ditridecylphosphate-dioctyltin salt, and the like.

The preferred amount of the organic phosphate metal salt compound added is 0.01 to 20 parts by weight per 100 parts by weight of the polyvinyl chloride resin.

It is also possible to use other organotin stabilizers in combination with the composition of the present invention.

The composition of the present invention may further contain an organic phosphite compound and /l
Thermal stability can be increased by using an epoxy compound or an epoxy compound in combination, so it can be used as appropriate depending on the purpose of use.

Adding an antioxidant to the composition of the present invention can increase the anti-oxidative deterioration properties of the composition, so 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*a 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 benzophenone, benzotriazole, salicylate, substituted acrylonitrile, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine, piperidine, 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, repellents, reinforcing agents, pesticides, rodent repellents, and the like can be included.

Examples of the -.logen-containing polymers used in the present invention include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinyl chloride/
, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-boupylene copolymer, bis-styrene chloride copolymer, chloride Vinyl-isobutylene copolymer, 1''=-''c''l; Vinyl-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-imprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Halogen-containing synthetic resins such as vinyl-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, The above halogen-containing resin and α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-5-methylbutene, or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers, and copolymers thereof, polystyrene,
Acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic esters Examples include blended products with -butadiene-styrene copolymer.

The following examples illustrate the effects of the halogen-containing polymer composition according to the present invention, but the present invention is not limited by these examples.

Example 1 In order to demonstrate the excellent thermal stability of the polyvinyl chloride resin composition according to the present invention, the following formulation was used, and a thickness of 1
A sheet (2) was prepared and subjected to a heat deterioration test at 200°C and an initial colorability test at 180°C. The results are shown in Table 1 below.

<Composition> PVO (Goon 1033CP) 1
00 parts by weight polyester plasticizer 6
゜ (PS-350 manufactured by Adeka Argus) Evo Φ Soybean oil Calcium pentapodate
1゜ Clay [Sakuzan Crane 33
) 10 dibasic lead stearate
5 Barium stearate
0.3 stearin fIl zinc
0.2 Organophosphate metal salt compound C Table 1) 0.3 Table 1 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.

<Formulation> PVO (Gson 1031P) 100 parts by weight trimellitic acid ester 30 (ADEKA Sizer C-8) P from D
50 Calcium carbonate 2
0 Southern Cres = φ53 10 Tribase 7 Barium Stearate 0.5 Stearic Acid fI? 0.2 Organophosphate metal salt compounds (Table 2) 0.1
2 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 result is the next 31st! ! Shown below.

<Composition> PVO (Geon1031P) I DO
Weight part DOP
40x-soO (chlorinated paraffin) 2
0 Calcium Carbonate 20 Southern Clay ◆33 10 Tribase
5.0 Barium Stearate 0.3 Stearin 1 Ilt Lead
0.3 Organic phosphate gold maple salt compound (@Table 5) 5.0 Table S 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 volume resistivity were measured. The results are shown in Table 4 below.

<Composition> PVO (G@on 1051P) 10
0 parts by weight DOP 50 Epoxidized soybean oil 2 Dibasic lead phosphite 5 Calcium carbonate
10 Southern clay φ33
10 Zinc stearate
0.5 Calcium stearate 0
．． 5 Dibutyltin dilaurate 0.2 Organophosphate metal salt compound C Table 4) 0.05
Table 4

Claims (1)

[Claims] For 100 parts by weight of polyvinyl chloride resin 1i, (1) 10 to 100 parts by weight of plasticizer, (2) 0°01 to 100 parts by weight of lead-based stabilizer.
10 parts by weight, (3) organic acid metal salt compound 0.01-10
parts by weight, (4) 10 to 40 parts by weight of calcium carbonate and/or
Or a polychlorinated or vinyl resin composition with improved electrical insulation properties, which is prepared by adding 5 to 20 parts by weight of clay and (5) 0.01 to 20 parts by weight of an organic phosphate metal salt compound.