JP3046386B2 - Vinyl chloride resin composition for wire coating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a wire coating vinyl chloride resin composition, particularly, an organic carboxylic acid, metal salts of phenols or organic phosphorus acids, a hydrotalcite compound Mono及 beauty calcium oxide added thermal stability by excellent coloring property and electrically insulating, yet related wire coating for vinyl chloride-based resin composition does not foam during molding.

[0002]

2. Description of the Related Art Vinyl chloride resins are general-purpose resins used for a wide range of applications, and are particularly characterized by excellent transparency and electrical insulation. It is widely used for coating.

However, vinyl chloride resins are inferior in stability to heat and light, and have a drawback that when subjected to heat molding, they tend to undergo thermal decomposition mainly due to dehydrochlorination. In order to avoid such disadvantages, one or several kinds of heat stabilizers have been added to suppress the thermal deterioration in the processing step. Particularly in the case of vinyl chloride resins for covering electric wires, stabilizers such as lead compounds have been used because of their properties such as electrical insulation, coloring, and thermal stability.

However, for example, in applications where transparency is required or in cases where sulfide contamination is a problem, the lead-based stabilizer cannot be used, and metals such as organic acids such as barium, magnesium, calcium, and zinc cannot be used. Used in combination with salt. However, as compared with the case where a lead-based stabilizer is used, the thermal stability is extremely poor, and there is a drawback that the processed product is colored or the mechanical strength is reduced.

In order to improve these drawbacks, various stabilizing aids have been proposed. In particular, by adding an inorganic compound such as a hydrotalcite compound or a zeolite compound, it is possible to improve the heat resistance to some extent. Be looked at. However, these inorganic compounds such as hydrotalcite compounds or zeolite compounds have water of crystallization in the molecule, which causes a problem of foaming during molding. It has been strongly desired to find an additive composition of a vinyl chloride resin for electric wire coating in which foaming is suppressed at times.

[0006]

The present inventors have conducted intensive studies in view of the above-mentioned situation, and as a result, by using a specific additive in combination, the vinyl chloride-based resin has improved heat stability, transparency and The present inventors have found that they are excellent in coloring properties, have less foaming during processing and molding, and have excellent electrical insulation properties, and that they are improved to be practically satisfactory, and have reached the present invention.

That is, the present invention relates to a vinyl chloride resin 10
(A) Metal salts of organic carboxylic acids, phenols or organic phosphoric acids (excluding lead salts) with respect to 0 parts by weight.
05-10 parts by weight, (b) hydrotalcite compound 0.
0.01 to 10 parts by weight and (c) calcium oxide 0.01 to 1
An object of the present invention is to provide a vinyl chloride resin composition for coating electric wires to which 0 part by weight is added.

Hereinafter, the vinyl chloride resin composition of the present invention will be described in more detail.

The metal (but not containing lead) constituting the metal salt of the organic carboxylic acid, phenol or organic phosphoric acid (a) used in the present invention includes lithium, potassium, sodium, calcium and barium. , Magnesium, strontium, zinc, tin, cesium, aluminum or organic tin.

The organic carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid, undecanoic acid, and 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, Salicylic acid, p-tert-octylsalicylic acid, elaidic acid, oleic Acid, linoleic acid, linolenic acid,
Monovalent carboxylic acids such as thioglycolic acid, mercaptopropionic acid and octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and isophthalic acid Acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid,
Maleic acid, fumaric acid, citraconic acid, metaconic acid,
Dihydric carboxylic acids such as itaconic acid, aconitic acid, thiodipropionic acid or monoesters or monoamide compounds thereof; butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, melophanic acid, pyromellitic acid, etc. Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids.

Examples of the above phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isophenol Octyl phenol, 2-ethylhexyl phenol, tertiary nonyl phenol, decyl phenol, tertiary octyl phenol, isohexyl phenol, octadecyl phenol, diisobutyl phenol, methyl propyl phenol, diamyl phenol, methyl isohexyl phenol, methyl tertiary octyl phenol, etc.

The organic phosphoric acids include mono- or di-octyl, -decyl, -dodecyl, -tridecyl, -tetradecyl, -hexadecyl, -octadecyl, -phenyl, -tolyl, -xylyl, -octylphenyl,- Nonylphenylphosphoric acid, pyrophosphoric acid, phosphorous acid and the like can be mentioned.

The amount of the metal salt of these organic carboxylic acids, phenols or organic phosphoric acids is 10
It is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 0 parts by weight.

The above-mentioned hydrotalcite compound of the component (b) has the general formula Mg _1-x Al _x (OH) ₂ A _{x / 2} · mH ₂ O
(I) (where x is a real number in the range of 0 <x ≦ 0.5, A represents CO ₃ or SO ₄ , and m represents a real number.)
Is a hydrated double salt compound composed of magnesium and aluminum.

The hydrotalcite compound may be a natural product or a synthetic product. As the synthesis method, JP-B-46-2280, JP-B-50-3
Known methods described in JP-A-0039, JP-B-51-29129 and the like can be exemplified. Further, in the present invention, it can be used without being limited by its crystal structure, crystal particle diameter and the like.

Further, the surface of the hydrotalcite compound may be made of 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, a higher fatty acid amide, or the like. Those coated with higher fatty acid esters or waxes can also be used.

Further, a compound in which a part of the metal of the hydrotalcite compound is substituted with another metal such as zinc can also be used.

[0018]

The addition amount of these hydrotalcite compounds is 0.0 to 100 parts by weight of the vinyl chloride resin.
It is 1 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

As the calcium oxide of the component (c), a white powder obtained by igniting limestone, calcium carbonate, hydroxide, nitrate, etc. can be used as it is. For example, it is desirable to add a fatty acid, a plasticizer, a process oil, or the like, and to use it in the form of a paste or wet powder.

The amount of the calcium oxide to be added depends on the water content of the vinyl chloride resin composition containing other additives, but is usually 0.01 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. Parts by weight, preferably 0.05-5
Parts by weight.

The components (a) to (c) used as stabilizers in the composition of the present invention can be separately added to a vinyl chloride resin when they are added. In this case, it can be used as a so-called composite stabilizer containing other stabilizers or auxiliary components as necessary.

The vinyl chloride resin used in the present invention includes, for example, polyvinyl chloride, pentachlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, chloride Vinyl-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl , Cycloalkyl or arylmaleimide copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene polymer, vinyl chloride-isoprene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Vinyl-acrylate copolymer, vinyl chloride-
Maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-based resin such as vinyl chloride-urethane copolymer and the above vinyl chloride-based resin and polyethylene,
Polypropylene, polybutene, α-olefin polymer such as poly-3-methylbutene or ethylene-vinyl acetate copolymer, polyolefin such as ethylene-propylene copolymer and their copolymers, polystyrene, acrylic resin, styrene and other Copolymers with monomers (e.g., maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, methacrylate-butadiene-styrene copolymers, blends with polyurethane, and the like can be given. it can.

In the composition of the present invention, other stabilizers, plasticizers and other additives usually used in vinyl chloride resin compositions for coating electric wires can be used in combination.

Other stabilizers that can be used in combination with the composition of the present invention include inorganic metal compounds, epoxy compounds, organic phosphite compounds, and pure organic stabilizing aids.

Examples of the inorganic metal compound include oxides, hydroxides, carbonates, phosphates, pyrophosphates, chlorates, perchlorates, hypochlorites and the like of various metals.

The amount of the inorganic metal compound is 0.01 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.
Preferably it is 0.1 to 5 parts by weight.

Examples of the epoxy compound include bisphenol-type and novolak-type epoxy resins, epoxidized natural oils such as epoxidized soybean oil and epoxidized linseed oil, and epoxidized unsaturated fatty acid alkyl esters such as epoxidized tall oil fatty acid octyl. And alicyclic epoxy compounds such as vinylcyclohexene diepoxy.

The amount of the epoxy compound is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, and tris (nonylphenyl)
Phosphite, tris (mono and dinonylphenyl) phosphite, diphenyldecyl phosphite, trioctyl phosphite, phenyl dioctyl phosphite,
Trioctyl phosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol diphosphite, tetra (tridecyl)
Bisphenol A diphosphite, tetra (C ₁₂ -C ₁₅
Mixed alkyl) bisphenol A diphosphite, hexa (tridecyl) -1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butanetriphosphite, diphenylacid phosphite, bis (nonylphenyl) acid Phosphite and the like.

The amount of the organic phosphite compound is 0.01 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 0.1 to 5 parts by weight.

Examples of the pure organic stabilizing aid include phenols such as bisphenol A and hydrogenated bisphenol A; pentaerythritol, dipentaerythritol,
Polyhydric alcohols such as dipentaerythritol adipate, mannitol, sorbitol and their ester compounds or partial ester compounds; β-diketone compounds such as dibenzoylmethane, benzoylacetone, stearyl benzoylmethane, dehydroacetic acid, and metal salts thereof 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid didodecyl ester;
Organic nitrogen-containing compounds such as 2-phenylindole and melamine are exemplified.

The addition amount of these pure organic stabilizing aids is 0.001 to 5 per 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 0.005 to 3 parts by weight.

These other stabilizers can be used in combination of two or more depending on the purpose. In general, it is preferable to use a metal salt of an organic acid / organic phosphite compound in combination with the composition of the present invention.

As the plasticizer used in the present invention, any plasticizer usually used for vinyl chloride resins can be used. For example, phthalate plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; Adipate plasticizers such as butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate octyl Phosphate plasticizers such as diphenyl phosphate; As the alcohol, 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 -Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. Use, if necessary, monovalent alcohol, polyester plasticizer using monocarboxylic acid as a stopper, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized safflower oil, Epoxidized stearic acid Epoxy plasticizers such as butyl, -butyl, 2-ethylhexyl, -stearyl ester, epoxidized polybutadiene, epoxidized tall oil fatty acid ester, and epoxidized linseed oil fatty acid ester; other, tetrahydrophthalic acid plasticizer, azelaic acid Plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer and the like.

If necessary, the composition of the present invention may contain, for example, an ultraviolet absorber, a light stabilizer, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, a plateout inhibitor, a surface treatment agent, and a lubricant. , A flame retardant, a fluorescent agent, a light degrading agent, a fungicide, a bactericide, a non-metal stabilizer, a processing aid, a mold release agent, and the like.

[0037]

EXAMPLES Next, the stabilizing effect of the composition of the present invention will be specifically shown by examples. However, the invention is not limited by the following examples.

Example 1 [combination] parts by weight vinyl chloride resin (degree of polymerization: 1450) 100 phthalic acid, adipic acid / 1,4-butylene glycol polyester 50 epoxidized soybean oil 5 calcium carbonate 10 clay # 33 10 magnesium oxide 0 1.3 Barium stearate 1.8 Zinc stearate 0.7 Inorganic compounds (Table 1) 1.5 Calcium oxide * 1.0 Tetra (C _2-15 mixed alkyl) bisphenol A diphosphite 1.0 *: Omi Chemical Company “CMS # 242”

The above composition was kneaded with a roll at 175 ° C. to form a 0.7 mm thick sheet.
The thermal stability at 180 ° C. by the Congo Red method was measured according to 6723. In addition, this sheet
A sheet having a thickness of 1 mm was prepared by pressing at 70 ° C. × 5 minutes and at 180 ° C. × 15 minutes, and each color difference (coloring property) was visually determined. Further, the state of generation of bubbles in the press sheet was observed, and the volume resistivity (VR) at 30 ° C. was measured. Table 1 shows the results. In addition, in the table, each test result was relatively represented by ○, Δ, ×, XX in the order of goodness.

[0040]

[Table 1]

Example 2 [combination] parts by weight vinyl chloride resin (degree of polymerization: 1300) 100 di-2-ethylhexyl phthalate 45 epoxidized soybean oil 5 bisphenol A diglycidyl ether 3 calcium stearate 1.5 basic zinc octylate 1 0.0 Dibenzoylmethane 0.05 Inorganic compound (Table 2) 0.5 Calcium oxide * 1.5 Diphenyl isodecyl phosphite 0.8 *: "CML # 31" manufactured by Omi Chemical Industry Co., Ltd.

A test similar to that of Example 1 was conducted using the above-mentioned composition. The haze was measured at 170 ° C. for 5 minutes to form a 1 mm-thick press sheet, and the sheet was measured with a haze meter. Table 2 shows the results. still,
In the table, each test result was relatively represented by △, Δ, ×, XX in the order of goodness.

[0043]

[Table 2]

From the above results, it can be seen that the vinyl chloride resin composition of the present invention has excellent thermal stability, thermal coloring properties and transparency, prevents bubbles from being generated in a press sheet, and has good electrical insulation properties. It is clear that is also excellent.

[0045] In contrast, when not using calcium oxide, or do not use a hydrotalcite site, either bubbles press sheet is produced, poor thermal stability,
It is a vinyl chloride resin composition that is not suitable for covering electric wires.

From the above results, the effect of the present invention is as follows.
It can be seen that a highly specific effect of combining a metal salt and a hydrotalcite compound Mono及 beauty calcium oxide.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08K 5/49 C08K 5/49 H01B 3/44 H01B 3/44 B (72) Inventor Hidehiro Ishizuka 5-chome, Shirahata, Urawa City, Saitama Prefecture No. 13 Asahi Denka Kogyo Co., Ltd. (56) References JP-A-57-80444 (JP, A) JP-A-1-275642 (JP, A) JP-A-63-132953 (JP, A) 577-177033 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/06 C08K 3/18 C08K 3/20

Claims (1)

(57) [Claims] (1) 0.05 to 10 parts by weight of a metal salt of an organic carboxylic acid, a phenol or an organic phosphoric acid (not including a lead salt), based on 100 parts by weight of a vinyl chloride resin, b) hydrotalcite compound 0. A vinyl chloride resin composition for coating electric wires, comprising 0.01 to 10 parts by weight of (c) 0.01 to 10 parts by weight of calcium oxide.