JPH08109298A - Vinyl chloride resin composition for covering electric wire - Google Patents

Abstract

PURPOSE: To obtain a vinyl chloride resin composition low in toxicity and excel lent in insulating properties and heat resistance by adding a special hydrotalcite compound and a special alwminosilicate to a vinyl chloride resin. CONSTITUTION: This composition comprises 100 pts.wt. vinyl chloride resin, 0.05 to 10 pts.wt. at least one hydrotalcite compound of the formula I (wherein x1 , x2 , and y are numbers that satisfy 0<=x2 /x1 <10, 2<=x1 +x2 <20, and 0<=y<=2 and m is 0 or an arbitrary positive number) and 0.01 to 3 pts.wt. at least one alwminosilicate having a zeolite skeleton of the formula II (wherein M<1> is an alkaline earth metal, M<2> is an alkali metal, p is 0.3 to 1, q is 0.8 to 10, and r is 0 or a positive number). By the addition of a combination of a compound of the formula I and a compound of the formula II, the composition is less colored, is improved in insulating properties and heat resistance, is low in toxicity, and can be used preferably as a material for covering electric wires.

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 electric wire coating which is stabilized by blending a specific stabilizer system, and more specifically, a hydrotalcite compound and an alkaline earth metal-containing zeolite. TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition for coating electric wires, which has little coloration and is improved in electric insulation and heat resistance by adding a compound together.

[0002]

2. Description of the Related Art Vinyl chloride resins have excellent electrical insulation properties, arc resistance, tracking resistance, and voltage resistance, and are therefore superior to rubber and polyolefin. It is also very important as an insulating material. However, vinyl chloride-based resins suffer from deterioration of their excellent properties due to thermal and oxidative deterioration, making them practically unusable.

In order to make up for the above-mentioned drawbacks, various stabilizers have been conventionally added to vinyl chloride resin insulation materials. Among them, lead stabilizers such as tribasic lead sulfate and lead stearate are particularly prized. Was used. These stabilizers are excellent heat stabilizers and have advantages such as relatively low cost. However, lead-based stabilizers are highly toxic, and their electrical insulating properties are not sufficient, and there is a drawback in that the electrical insulating properties are deteriorated as the temperature of the insulator rises.

Therefore, in JP-A-52-77157 and JP-A-52-77158, a basic inorganic acid salt or a fired product thereof is used as a halogen-containing resin without using a lead-based stabilizer. Attempts have been made to add it, but the effect was still insufficient.

Further, JP-A-63-46248 proposes to use a hydrotalcite compound in combination with magnesium oxide in order to improve foaming property at the time of molding, and JP-A-63-46248 discloses. It has been proposed to use a hydrotalcite compound in combination with nepheline to improve transparency and heat retention of an agricultural film. JP-A-5-156106 discloses a chlorine-containing resin for powder molding. It has been proposed to add hydrotalcite and zeolite together, but it has not even been suggested to improve electric insulation.

Further, in Japanese Patent Laid-Open No. 179090/1993, a hydrotalcite compound and a silicate of aluminum or an alkaline earth metal are added together to a halogen-containing resin to improve electric insulation and heat resistance. Japanese Patent Application Laid-Open No. 4-318047 discloses that
It is described that the organic acid metal salt, hydrotalcite or zeolite and calcium oxide are added to the vinyl chloride resin in combination to improve the electric insulation and heat resistance, and the foaming during processing is improved. When used as an electric wire coating material which is required to have electric insulation and heat resistance, the effect is still insufficient when the compounds described in the above publications are used in combination.

Therefore, an object of the present invention is to provide a vinyl chloride resin composition for electric wire coating, which has low toxicity and is excellent in electric insulation and heat resistance.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies and as a result, chlorinated a vinyl chloride resin by adding a specific hydrotalcite compound and a specific zeolite compound in an amount within a specific range. It has been found that a vinyl resin composition can achieve the above object.

The present invention was made on the basis of the above findings, in which 100 parts by weight of a vinyl chloride resin is added to the following [Chemical formula 3]
At least one kind of the hydrotalcite compound represented by the general formula (I) (same as the above [Chemical formula 1]) 0.05 to 10
An electric wire prepared by blending 1 part by weight and 0.001 to 3 parts by weight of at least one aluminosilicate having a zeolite structure skeleton represented by the general formula (II) of the following [Chemical Formula 4] (the same as [Chemical Formula 2] below) A vinyl chloride resin composition for coating is provided.

[0010]

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[0011]

[Chemical 4]

The vinyl chloride resin composition for coating electric wires according to the present invention will be described in detail below.

The hydrotalcite compound represented by the above general formula (I) used in the present invention improves the electrical insulating property and heat stability effect of the vinyl chloride resin. The hydrotalcite compound is, as represented by the general formula (I), magnesium and aluminum,
Alternatively, it may be a double salt compound composed of zinc, magnesium and aluminum, and may be one obtained by dehydrating water of crystallization. Moreover, the said hydrotalcite compound can be used by 1 type (s) or 2 or more types.

The hydrotalcite compound may be a natural product or a synthetic product. As a method for synthesizing the above-mentioned synthetic product, Japanese Patent Publication No. 46-2280,
Japanese Examined Patent Publication No. 50-30039, Japanese Examined Patent Publication No. 51-2912
No. 9, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-
Known methods described in Japanese Patent No. 174270 can be exemplified. In addition, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle size and the like.

The surface of the hydrotalcite compound is higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali oleic acid salt, organic sulfonic acid metal salt such as dodecylbenzene sulfonic acid alkali metal salt, Those coated with higher fatty acid amide, higher fatty acid ester or wax can also be used.

The amount of the above-mentioned hydrotalcite compound added is 0.05 based on 100 parts by weight of the vinyl chloride resin.
-10 parts by weight, preferably 0.1-5 parts by weight. When the amount is less than 0.05 parts by weight, almost no effect is observed, and when it exceeds 10 parts by weight, not only the effect of increasing the amount is not obtained, but also large coloring or foaming may occur. There is

The aluminosilicate having a zeolite structural skeleton represented by the general formula (II) used in the present invention (hereinafter referred to as "zeolite compound") is an electrical insulating and thermal stability of vinyl chloride resin. It is to improve the effect. In the general formula (II), examples of the alkaline earth metal represented by M ¹ include calcium, magnesium, barium, and strontium. Particularly preferred is calcium or magnesium, and the alkaline metal represented by M ² is lithium. , Potassium, sodium, etc., p represents a number of 0.3 to 1, and preferably 0.5.
If it is less than 0.3, the effect of improving the insulating property is small. Moreover, q shows 0.8-10, r shows 0 or a positive number. The above-mentioned zeolite compound is one kind or two
It can be used in more than one species.

The amount of the above zeolite compound is 0.001 to 3 parts by weight, preferably 0.05 to 2 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, almost no effect is observed, and when the amount is more than 3 parts by weight, not only the effect of increasing the amount is not obtained, but also the heat resistance is deteriorated and large coloring is caused. There is a fear of giving.

The vinyl chloride resin used in the present invention is a vinyl chloride homopolymer produced by a known method such as a suspension polymerization method, a bulk polymerization method or an emulsion polymerization method, or vinyl chloride and ethylene, propylene or acetic acid. Vinyl, (meth) acrylic acid ester, maleic anhydride, phenylmaleimide,
Copolymers with cyclohexylmaleimide, etc., polyvinylidene chloride, polyvinyl bromide, chlorinated polyethylene, ethylene / vinyl acetate copolymers and vinyl chloride graft polymers, urethane resins with unsaturated groups and vinyl chloride Graft polymers and the like are included, and a mixture of these with other thermoplastic resins is also included.

The composition of the present invention also includes a carboxylic acid,
Metals of organic phosphoric acids or phenols (Li, Na,
K, Ca, Ba, Mg, Sr, Zn, Cd, Sn, C
s, Al, organic Sn) salt may be added, and examples of the carboxylic acid include caproic acid, caprylic acid,
Pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid,
12-hydroxystearic acid, chlorostearic acid,
12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linolenic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids, and tallow fatty acid, coconut oil fatty acid, tung oil fatty acid,
Naturally occurring mixtures of the above acids such as soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5-t-octylsalicylic acid, Examples thereof include naphthenic acid and cyclohexanecarboxylic acid, and examples of the above-mentioned organic phosphoric acids include mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (nonylphenyl).
Examples thereof include phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, and the above-mentioned phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol, and the like.

The amount of the metal salt added is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

In the composition of the present invention, various additives which are usually used as additives for vinyl chloride resins, such as polyols, organic phosphite compounds and / or epoxy compounds, plasticizers, Inorganic stabilizers, fillers and the like can also be added.

Examples of the above-mentioned polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or stearic acid half ester of dipentaerythritol, and bis (dipentaerythritol). Examples include adipate, glycerin, 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 (nonylphenyl) phosphite, tris (mono and di mixed nonylphenyl) phosphite, diphenyldecyl phosphite, diphenyl (tridecyl) phosphite. Fight, phenyl dioctyl phosphite, 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, phenyl- 4,4'-isopropylidene diphenol pentaerythritol diphosphite, tetra (C
12-15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite and the like can be mentioned.

The amount of the above 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 compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, and other epoxidized animal and vegetable oils. , Epoxidized methyl stearate, -butyl, -2
-Ethylhexyl, -Stearyl ester, epoxidized polyptadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide, 3 Examples include epoxy compounds such as 1,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate.

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 (butyldiglycol) adipate, and phosphate plasticizers. Agents, polyester plasticizers, chlorinated paraffin plasticizers, trimellitate plasticizers, pyromellitate plasticizers and the like.

Examples of the inorganic stabilizers include calcium oxide, calcium hydroxide, powdered silicic acid (silica).
Examples thereof include aluminosilicate, sodium perchlorate, magnesium perchlorate and barium perchlorate.

Examples of the filler include calcium carbonate, silica, clay, glass beads, mica, sericite, glass flakes, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite, M.
Examples thereof include OS, phosphate fiber, glass fiber, carbonic acid fiber, aramid fiber and the like.

In addition to the above, the composition of the present invention may optionally contain additives commonly used in vinyl chloride resins, such as
Cross-linking agent, foaming agent, antistatic agent, anti-fog agent, anti-plateout agent, surface treatment agent, lubricant, flame retardant, fluorescent agent, antifungal agent,
A bactericide, a metal deactivator, a release agent, a pigment, a processing aid, an antioxidant, a light stabilizer and the like can be added.

The composition of the present invention has excellent effects on electric insulation and heat resistance, and is therefore used as a wire coating material.

[0033]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 The following formulation was kneaded on a roll at 160 ° C. and 30 rpm for 5 minutes and then pressed at 190 ° C. for 5 minutes to prepare a sheet having a thickness of 1 mm, and the yellowness of the sheet was measured. . Also,
The color difference from the sheet pressed for 20 minutes under the same conditions was determined. In addition, a test piece was prepared from the above sheet, heated in a gear oven at 210 ° C., and the time until blackening was measured to evaluate thermal stability. In addition, JIS. K 6723
From the above, a volume resistivity test (VR) and a thermal stability test (CR) using Congo red test paper at 180 ° C. were performed. The results are shown in [Table 1] below.

(Composition) Parts by weight Polyvinyl chloride resin (manufactured by Shin-Etsu Chemical: TK-1300) 100 Diisononyl phthalate 50 Zinc stearate 0.7 Dibenzoylmethane 0.05 Sorbitol 0.02 Alkamizer 1 (HT) ^{* 1} 2.5 Test compound (see [Chemical formula 1] below) [Table 1] * 1: Hydrotalcite manufactured by Kyowa Chemical Co., Ltd. Compositional formula: Mg ₄ Al ₂ (OH) ₁₂ CO ₃ / 3H ₂ O

[0036]

[Table 1]

* 2 to * 5 and # in the above [Table 1] are
It is as follows (hereinafter the same). * 2: Na-A type zeolite: Na ₂ O ・ Al ₂ O ₃・ 2SiO ₂・ 4.5H ₂ O * 3: Ca-A type zeolite: (CaO) _0.67・ (Na ₂ O) _0.33・ Al ₂
O ₃・ 2SiO ₂・ 4.5H ₂ O * 4: Ca-X type zeolite: (CaO) _0.67・ (Na ₂ O) _0.33・ Al ₂
O ₃・ 2.5SiO ₂・ 6H ₂ O * 5: Mg-A type zeolite: (MgO) _0.67・ (Na ₂ O) _0.33・ Al ₂
O ₃・ 2SiO ₂・ 4.5H ₂ O #: Convert Alcamizer 1 to calcium stearate

Example 2 The following formulation was kneaded on a roll at 160 ° C. for 5 minutes and then pressed at 180 ° C. for 5 minutes to prepare a sheet having a thickness of 1 mm. A test piece was prepared from this sheet, heated in a gear oven at 210 ° C., and the time until blackening was measured.
In addition, JIS. From K-6723, volume resistivity test (V
R) and a thermal stability test (CR) using Congo red test paper at 180 ° C. The results are shown in [Table 2] below.

(Distribution) parts by weight polyvinyl chloride resin (manufactured by Shin-Etsu Chemical: TK-1300) 100 diisononyl phthalate 50 calcium carbonate 15 zinc stearate 0.5 dibenzoylmethane 0.1 tris (2-hydroxyethyl) isocyanate Nurate 0.2 CA Zeolite 0.5 Sorbitol 0.05 Test compound (see [Table 2] below) [Table 2]

[0040]

[Table 2]

* 6 and * 7 in the above [Table 2] are as follows. * 6: manufactured by Kyowa Chemical Co., Ltd. hydrotalcite composition _{formula: Mg 4 Al 2 (OH)} 12 CO 3 * 7: Kyowa Chemical Co., Ltd. hydrotalcite composition _{formula: Mg 3 ZnAl 2 (OH)} 12 CO 3 · 3H ₂ O

Example 3 The same test as in Example 1 was conducted using the following formulation. However, thermal stability (measurement of blackening time) was carried out in a gear oven at 200 ° C. The results are shown in [Table 3] below.

(Distribution) Parts by weight Polyvinyl chloride resin (Neon Zeon: Geon 103 EP) 100 Dioctyl phthalate 30 Clay 5 Epoxidized soybean oil 5 Zinc laurate 0.5 DHT-4A ^{* 8} 2.0 Dibenzoylmethane 0.1 Bisphenol A 0.3 Test compound (see [Table 3] below) [Table 3] * 8: Hydrotalcite manufactured by Kyowa Chemical Co., Ltd. Compositional formula: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O

[0044]

[Table 3]

From the results of the above [Table 1] to [Table 3], the following is clear. When neither the hydrotalcite compound of the general formula (I) nor the alkaline earth-containing zeolite of the general formula (II) is added to the vinyl chloride resin (Comparative Example 1-2) or only the alkaline earth-containing zeolite described above. When added (Comparative Examples 1-4,2-1 to 2-3), the heat resistance is extremely low, and it is difficult to use it for electric wire applications. Further, when only the hydrotalcite compound is added (Comparative Examples 1-1 and 3-1), the heat resistance is improved to some extent, but the electric insulation is insufficient. Furthermore, when the above-mentioned hydrotalcite compound and alkali metal type zeolite are used together (Comparative Examples 1-3 and 3-2), both heat resistance and electric insulation are improved to some extent, but the improvement effect is still insufficient. Is.

On the other hand, the hydrotalcite compound and the alkaline earth metal-containing zeolite were added to a vinyl chloride resin in combination (Examples 1-1 to 1-5, 2-1 to 2-).
In the case of 4, 3-1 to 3-5), the coloring is small and the heat resistance and the electric insulation are excellent.

[0047]

Industrial Applicability The vinyl chloride resin composition for coating electric wires of the present invention has low toxicity and excellent electric insulation and heat resistance. Therefore, the vinyl chloride resin composition for electric wire coating of the present invention can be suitably used as an electric wire coating material.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Osamu Yoshiguchi 5-2-13 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd.

Claims (1)

[Claims] 1. To 100 parts by weight of a vinyl chloride resin, 0.05 to 10 parts by weight of at least one hydrotalcite compound represented by the general formula (I) of the following [Chemical formula 1] and the following [Chemical formula 2] At least one aluminosilicate having a zeolite structural skeleton represented by the general formula (II) 0.0
A vinyl chloride resin composition for electric wire coating, which comprises 0.1 to 3 parts by weight. Embedded image Embedded image