JP2003292711A - Vinyl chloride-based resin composition for electric wire covering use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a low-toxic vinyl chloride-based resin composition for electric wire covering use having high electrical insulation and heat resistance and causing no foaming phenomena in processing. <P>SOLUTION: This vinyl chloride-based resin composition is obtained by compounding 100 pts.wt. of a vinyl chloride-based resin with (a) 0.005-1 pt.wt. of a poly-2-4C alkylene oxide with an average molecular weight of 4,000-400,000, (b) 0.1-5 pt(s).wt. of zinc glycinate, and (c) 0.005-5 pt(s).wt. of an organic acid zinc compound, and optionally (d) 0.01-2 pt(s).wt. of hydrotalcite. <P>COPYRIGHT: (C)2004,JPO

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, which has low toxicity, excellent electric insulation and heat resistance, and has no foaming phenomenon during processing.

[0002]

2. Description of the Related Art Vinyl chloride resin is very important as an insulating material as compared with rubber and polyolefin because it has excellent electric insulation, arc resistance, tracking resistance and voltage resistance. It is something. However, vinyl chloride resins suffer from deterioration of their excellent properties due to thermal and oxidative deterioration, and in practice cannot be used for a long period of time.

Therefore, lead stabilizers such as tribasic lead sulfate and lead stearate have been conventionally used as stabilizers for vinyl chloride resins. These stabilizers have an excellent stabilizing effect on the vinyl chloride resin and are particularly useful as stabilizers against heat deterioration, but on the other hand, they have a serious problem of great toxicity.

Therefore, it has been attempted to blend a zinc salt of an organic acid or an inorganic acid with a vinyl chloride resin as a stabilizer together with hydrotalcite or a calcined product thereof without using a lead stabilizer. (Patent Document 1 and Patent Document 2
reference. ). However, the effect was still insufficient.

A vinyl chloride resin composition containing a hydrotalcite compound in order to improve the thermal stability of a vinyl chloride resin containing a Ca-Zn stabilizer, mainly for application to electric wires. In order to suppress the foaming phenomenon during molding, it has been proposed to incorporate hydrophobic silica (see Patent Document 3). However, particularly when used as an electric wire coating material which is required to have a foaming phenomenon and electric insulation, the effect is still insufficient when the compounds described in the above-mentioned documents are used in combination.

On the other hand, if a large amount of hydrotalcite is blended in order to obtain sufficient heat resistance, foaming will occur when the vinyl chloride resin composition is used for coating the electric wire, and the electric insulation of the covered electric wire and other requirements are required. When using a hydrotalcite compound as a stabilizer, there is a problem that it adversely affects the characteristics, so keep the compounding amount small and
There is also a problem that sufficient heat resistance cannot be obtained to prevent foaming.

[0007]

[Patent Document 1] JP-A-52-077157

[Patent Document 2] Japanese Patent Laid-Open No. 52-077158

[Patent Document 3] Japanese Patent Application Laid-Open No. 06-0880849

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the conventional stabilizers for vinyl chloride resins, and has low toxicity, electrical insulation and heat resistance. It is an object of the present invention to provide a vinyl chloride resin composition for electric wire coating, which is excellent in heat resistance and does not cause a foaming phenomenon during processing.

[0009]

Means for Solving the Problems As a result of intensive studies on these problems, the present inventors have found a new vinyl chloride resin composition for coating electric wires.

The vinyl chloride resin composition for coating an electric wire according to the present invention is (a) based on 100 parts by weight of the vinyl chloride resin.
0.005 to 1 part by weight of a polyalkylene oxide having an average molecular weight of 4,000 to 400,000 and an alkylene group having 2 to 4 carbon atoms, and (b) zinc glycinate.
1 to 5 parts by weight, and (c) other organic acid zinc compound 0.
It is characterized by adding 005 to 5 parts by weight.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin composition for coating electric wires of the present invention will be described in detail below.

The component (a) polyalkylene oxide used in the present invention is obtained by polymerizing polyethylene oxide, polypropylene oxide, polytetramethylene oxide, etc., and has an average molecular weight of 4,000 to 400,
At 000, the electrical insulation of the vinyl chloride resin is remarkably improved and the thermal stability effect is also improved.

The blending amount of polyalkylene oxide is
0.005 to 1 part by weight, preferably 0.05 to
0.5 parts by weight. If the compounding amount is less than 0.005 parts by weight, almost no effect is observed, and if it exceeds 1 part by weight, there is no effect of increasing the amount and it is not economical.

The average molecular weight of the polyalkylene oxide is 4,000 to 400,000, preferably 6,000 to 200,000. When the above-mentioned average molecular weight is 4,000 or less, it is difficult to obtain a preferable electric insulation effect, and when it is 400,000 or more, it is difficult to obtain it practically, which is not preferable.

The component (b), zinc glycinate, used in the present invention may be a basic salt obtained by the reaction of glycine and zinc white, in which glycine is 2 mol or less per 1 mol of zinc white. It may be an acid salt consisting of 2 mol or more of excess glycine. The finer the particle system of these glycines is, the more preferable is 10 μm or less. As a method for synthesizing the zinc glycinate, known methods described in JP-A-64-087646 and the like can be exemplified. Zinc glycinate is an amino acid zinc compound also called zinc glycine or zinc aminoacetate.

The amount of the zinc glycinate compounded is 0.1 to 0.1%.
It is 5 parts by weight, preferably 0.2 to 3. If the amount is 0.1 part by weight or less, the heat resistance improving effect is not sufficient, and if it is 5 parts by weight or more, the heat resistance improving effect is good, but it is not economical.

The other organic acid zinc compound as the component (c) used in the present invention is a zinc salt of a saturated or non-corrosive fatty acid having 8 to 24 carbon atoms such as zinc stearate, zinc laurate, zinc oleate and the like. Examples thereof include zinc benzoate, zinc p-toluate, zinc pt-butyl benzoate, and other aromatic carboxylic acid zinc salts having an alkyl substituent having 1 to 5 carbon atoms. In addition, a normal salt composed of 1 mol of zinc per 2 mol of these acids or a basic salt composed of 1 mol or more of zinc per 2 mol of acid may be used.

That is, here, the other organic acid zinc compound as the component (c) is a normal salt or a basic salt, such as zinc stearate, zinc laurate, zinc oleate, and the like.
Zinc of saturated fatty acid of 8 to 24 or zinc salt of innocuous fatty acid,
And an organic acid zinc selected from the group consisting of zinc salts of aromatic carboxylic acids having an alkyl substituent having 1 to 5 carbon atoms, such as zinc benzoate, zinc p-toluate, and zinc pt-butylbenzoate. Compounds are preferred.

In the present invention, the amount of the other organic acid zinc compound is 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Used.

The component (d) hydrotalcite used in the present invention is, as already known, a water-containing basic carbonate mineral (double salt compound) of magnesium and aluminum. , Usually the general formula Mg
_x Al ₂ (OH) _{2x + 4} · C0 ₃ · mH ₂₀ (wherein
X is a number of 2 to 6, and m is a positive number. ) And hydrotalcite represented by the formula (1), or those in which a part of magnesium is replaced by zinc in the above general formula are also used.

Such hydrotalcite may be produced naturally, and higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali oleic acid salts, organic metals such as dodecylbenzene sulfonic acid alkali metal salts and the like. It may be a synthetic product whose surface is coated with a sulfonic acid metal salt, higher fatty acid amide, higher fatty acid ester, wax or the like.

The hydrotalcite may be a perchlorate ion type hydrotalcite in which a part of carbonate ion is replaced by perchlorate ion in the above general formula,
As a method for producing a synthetic product, JP-A-60-203657 is used.
The method described in the publication can be exemplified.

In the present invention, hydrotalcite is
0.01-2 with respect to 100 parts by weight of vinyl chloride resin
It is used in parts by weight, preferably 0.05 to 1 part by weight.

The vinyl chloride resin used in the present invention includes 1) vinyl chloride homopolymer and 2) vinyl chloride produced by known methods such as suspension polymerization, bulk polymerization and emulsion polymerization. , Copolymers with monomers selected from the group consisting of ethylene, propylene, vinyl acetate, (meth) acrylic acid esters, maleic anhydride, phenylmaleimide and cyclohexylmaleimide, 3) polyvinylidene chloride, polyvinyl bromide, chlorinated Polyethylene, ethylene /
Graft polymer of pinyl acetate copolymer and vinyl chloride,
4) A graft polymer of a urethane resin having an unsaturated group and vinyl chloride, etc. may be mentioned, and a mixture of these and another thermoplastic resin may be used.

The composition of the present invention also includes a carboxylic acid,
Metals other than zinc, such as organic phosphoric acids or phenols (L
i, Na, K, Ca, Ba, Mg, Sr, Cd, Sn,
Cs, Al, organic Sn) salt can be added, and as the carboxylic acid, for example, caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, cabrinic acid, neodecanoic acid, undecylic acid, lauric acid, myristin Acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, behenic acid, erucic acid and similar acids and tallow fatty acid, coconut oil fatty acid, tung oil fatty acid, soybean oil Naturally occurring mixtures of the above acids such as fatty acids and cottonseed oil fatty acids, benzoic acid, p-t-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, salicylic acid, 5-t-octylsalicylic acid, naphthenic acid, etc. Examples of the above-mentioned organic phosphates include mono- or dioctyl groups. Phosphoric acid, mono- or didodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, and the like, and as the phenols, phenol, Examples include cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like.

The addition amount of the metal salt of carboxylic acid, organic phosphoric acid or phenol is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of vinyl chloride thread resin.

Further, in the composition of the present invention, various additives which are usually used as additives for vinyl chloride resins, such as polyols other than the polyalkylene oxide of the present invention, organic phosphite compounds and It is also possible to add an epoxy compound, a plasticizer, an inorganic stabilizer, a filler and the like.

Examples of the above-mentioned polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or stearic acid half ester of dipentaerythritol, bis (dipentaerythritol) adipate, Glycerin,
Examples include tris (2-hydroxyethyl) isocyanurate.

The amount of the above polyols added is preferably 0.01 to 1 with respect to 100 parts by weight of the vinyl chloride resin.
It is 0 part by weight, more preferably 0.05 to 5 parts by weight.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,
4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (mono and di mixed nonylphenyl) phosphite, diphenyldecylphosphite, diphenyl (tridecyl) phosphite, phenyldioctylphosphite, Phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, tridecyl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, diphenyl acid phosphite, di (nonylphenyl) acid phosphite, distearyl pentaerythritol diphosphite, Di (tridecyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl) 4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6
Tri-t-butylphenyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite , Hydrogenation-4,4 '
-Isopropylidenediphenol polyphosphite,
2,2'-methylenebis (4,6-di-t-butylphenyl) (octyl) phosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) (fluoro)
Examples include phosphite.

The amount of the organic phosphite compound added is
It is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight 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 the like. Animal and vegetable oils, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate, 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, 3,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate, etc. Epoxy compounds, and the like.

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 phosphate. -Based plasticizers, polyester-based plasticizers, chlorinated paraffin-based plasticizers, trioctyl trimellitate, tri (C7-
9 mixed alkyl) trimellitate plasticizers such as trimellitate, pyromellitate plasticizers such as tetraoctylpyromellitate, and biphenyltetracarboxylate plasticizers.

Examples of the above-mentioned inorganic stabilizer include magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, calcium silicate, amorphous aluminosilicate, alkali and / or alkaline earth having a zeolite crystal structure. Aluminosilicate, sodium perchlorate, magnesium perchlorate, barium perchlorate and the like.

Examples of the above-mentioned filler include calcium carbonate, clay, glass beads, mica, glass flakes, wollastonite, potassium titanate and the like.

In addition, if necessary, the composition of the present invention may contain additives usually used for vinyl chloride resins, such as a cross-linking agent, a foaming agent, an antistatic agent, an antifogging agent and a plate-out prevention agent. , Surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides, bactericides, metal deactivators, release agents, pigments, processing aids,
Antioxidants, light stabilizers and the like can be added. INDUSTRIAL APPLICABILITY The composition of the present invention has low toxicity, is excellent in electric insulation and heat resistance, and has no foaming phenomenon during processing, and thus is used as a wire coating material.

[0037]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1

[0039]

[Table 1]

The substances shown in Table 1 were further added to the formulations shown in the above-mentioned common formulation table 1 and mixed well. Further, the obtained mixture was kneaded on a roll at 160 ° C.-6 inch roll, 25 rpm for 5 minutes, and then pressed at 190 ° C. for 5 minutes to prepare a sheet having a thickness of 1 mm, and a test piece was prepared from this sheet. Heat in a gear aging tester at 190 ℃ and
It was taken out every 0 minutes and the state of discoloration and the foaming phenomenon were observed to evaluate the thermal stability and foamability. In addition, JIS. K 672
From 3, the volume resistivity value (VR) was measured and the electrical insulation was evaluated. The evaluation results are also shown in Table 1.

[0041]

[Table 2]

* 1 to * 4 in Table 1 indicate the following.

* 1: Zinc glycinate having an average particle size of 5 μm produced by reaction from 1 mol of zinc white and 2 mol of glycine * 2: PEG-10000 manufactured by NOF CORPORATION * 3: Kyowa Chemical Industry DHT-4A * 4 : 1.0 mol hydrotalcite, 1.0 perchloric acid
The perchlorate ion-type hydrotalcite produced by the reaction from the mole was measured for the degree of discoloration by the following scale. As a measure of thermal stability, the test piece was placed in a gear oven at a predetermined temperature, and the degree of discoloration after a lapse of a predetermined time was visually determined according to the following criteria.

[0044]

[Table 3]

Example 2

[0046]

[Table 4]

The same procedure as in Example 1 was carried out by adding the substances shown in Table 2 to the formulations shown in the common formulation table 2 above.

[0048]

[Table 5]

* 5 to * 8 in Table 2 indicate the following.

* 5 to * 7: Polyethylene glycol manufactured by NOF CORPORATION * 8: Polypropylene glycol manufactured by Sanyo Kasei Kogyo Co., Ltd. Comparative Example 2-1 is a comparative example of the formulation itself shown in Common Formulation Table 2. .

From the results shown in Tables 1 and 2 above, the following is clear. When the component (a) polyalkylene oxide according to the present invention is not used in combination with the vinyl chloride resin (Comparative Examples 1-2, 1-4, 2-1 to 2-4), the volume resistivity value is remarkably inferior.

When the components (b) and (c) are not used together (Comparative Example 1-3), the heat resistance is poor. Further, when a large amount of component (d) is used together (Comparative Example 1-5), a foaming phenomenon is observed, but within the scope of the claims of the present invention, the foaming phenomenon does not occur. As shown in the results of Table 2, the polyalkylene oxides other than the present invention and the polyalkylene oxides of the present invention outside the range of the average molecular weight do not raise the volume specific resistance value, which causes a problem in electrical insulation. On the other hand, it can be seen that the examples have excellent heat resistance, no foaming phenomenon, a large volume resistivity value, and excellent electrical insulating properties.

[0053]

EFFECT OF THE INVENTION The vinyl chloride resin composition for coating electric wires according to the present invention has excellent heat resistance and electrical insulation, and has a composition capable of high-speed processing without foaming during processing. It can be used suitably as a wire coating material.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshinori Sato             1-11-3 Minami Shinozaki, Kazo City, Saitama Prefecture Nissan             Chemical industry Co., Ltd. Saitama factory Kazo factory F term (reference) 4J002 BD031 CH012 CH022 DE218                       DE268 EG036 EG037 EL02                       EN116 EW06 FD01 FD02                       FD03 GQ01                 5G305 AA02 AB35 BA12 CA03

Claims (4)

[Claims] 1. A polyalkylene oxide having an average molecular weight of 4,000 to 400,000 and an alkylene group having 2 to 4 carbon atoms in an amount of 0.005 to 100 parts by weight of a vinyl chloride resin. 1 part by weight, (b) 0.1 to 5 parts by weight of zinc glycinate, and (c) 0.005 to 5 parts by weight of other organic acid zinc compound are blended, and a vinyl chloride system for electric wire coating. Resin composition. 2. The vinyl chloride resin composition for electric wire coating according to claim 1, which further comprises 0.01 to 2 parts by weight of (d) hydrotalcite with respect to 100 parts by weight of the vinyl chloride resin. object. 3. The vinyl chloride resin composition for coating electric wires according to claim 1, wherein the polyalkylene oxide is polyethylene oxide. 4. The vinyl chloride resin composition for coating electric wires according to claim 1, wherein the polyalkylene oxide is polypropylene oxide.