JPH08109297A - Vinyl chloride resin composition for covering electric wire - Google Patents

Abstract

PURPOSE: To obtain a vinyl chloride resin composition low in toxicity and excellent in insulating properties and heat resistance, by adding a combination of a special hydrotalcite compound and a special alkali earth metal silicate 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 a positive number of 1 or more) and 0.001 to 3 pts.wt. at least one alkaline earth metal silicate of the formula II (wherein M is an alkaline earth metal, p is 2.2 to 8, and q 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 coating electric wires, which is stabilized by blending a specific stabilizer system, and more specifically, to a specific hydrotalcite compound and a specific composition. The present invention relates to a vinyl chloride-based resin composition for electric wire coating, which is less colored and has improved electric insulation and heat resistance when an alkaline earth metal silicate is added in combination.

[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 resins suffer from deterioration of their excellent properties due to thermal and oxidative deterioration, and are 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 and nepheline in combination to improve the transparency and heat retention of an agricultural film, but no suggestion has been made regarding the improvement of electrical 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. However, the effect is still insufficient when used in combination with the compounds described here, especially when used as a wire coating material that requires electrical insulation and heat resistance. Met.

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 As a result of extensive studies, the inventors of the present invention have used a vinyl chloride resin in combination with a specific hydrotalcite compound and a metal silicate having a specific composition in an amount within a specific range. It was found that the vinyl chloride resin composition obtained by addition 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 silicate of an alkaline earth metal represented by the general formula (II) of the following [Chemical formula 4] (the same as the above [Chemical formula 2]). A vinyl chloride resin composition for coating is provided.

[0010]

Embedded image

[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 insulation and thermal stability of the vinyl chloride resin.
The hydrotalcite compound is a double salt compound composed of magnesium and aluminum, or zinc, magnesium and aluminum, as represented by the general formula (I), and may be dehydrated water of crystallization. Also,
The hydrotalcite compound may be used alone or in combination of two or more.

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 above-mentioned hydrotalcite compound is
The surface is coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an oleic acid alkali metal salt, an organic sulfonic acid metal salt such as a dodecylbenzenesulfonic acid alkali metal salt, a higher fatty acid amide, a higher fatty acid ester or wax. Things 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 alkaline earth metal silicate represented by the above general formula (II) used in the present invention (hereinafter sometimes simply referred to as “metal silicate”) is an electrically insulating material of vinyl chloride resin. And to improve thermal stability. In the above general formula (II), examples of the alkaline earth metal represented by M include calcium, magnesium, barium, strontium, and the like. Particularly, calcium is preferable, n is 2.2 to 8, and n is 2 When it is less than 0.2, the effect of improving heat resistance and electric insulation is small, which is not preferable. The metal silicates may be used alone or in combination of two or more.

The amount of the metal silicate compounded 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. The above blending amount is 0.
If the amount is less than 001 parts by weight, almost no effect is observed, and if the amount exceeds 3 parts by weight, not only the effect of increasing the amount is not exhibited, but also the heat resistance is deteriorated and there is a fear of giving large coloring.

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, (meta)
Acrylic ester, maleic anhydride, phenylmaleimide, copolymer with cyclohexylmaleimide, polyvinylidene chloride, polyvinyl bromide, chlorinated polyethylene, ethylene / vinyl acetate copolymer and vinyl chloride graft polymer, A graft polymer of a urethane resin having a saturated group and vinyl chloride is included, and a mixture of these and another thermoplastic resin 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, myristin. 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 stabilizer,
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 blended 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, diphenyldecylphosphite, diphenyl (tridecyl) phosphite, 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 (C12-
15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, hydrogenated -4,4'-isopropylidene diphenol polyphosphite and the like.

The blending amount of the above organic phosphite compound is
0.01-5 with respect to 100 parts by weight of vinyl chloride resin
It is preferable to use parts by weight.

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, non-crystalline aluminosilicate, alkali having a zeolite crystal structure, and / or
Alternatively, alkaline earth aluminosilicates, powdered silicic acids (silicas), sodium perchlorate, magnesium perchlorate, barium perchlorate and the like can be mentioned.

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. Further, a test piece was prepared from this sheet, heated in a gear oven at 210 ° C., and the time until blackening was measured to evaluate the thermal stability. Furthermore, 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.

(Distribution) 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 compounds (see [Table 1] below) [Table 1] * 1: Hydrotalcite manufactured by Kyowa Chemical Co., Ltd. (hereinafter the same) Composition formula: Mg ₄ Al ₂ (OH) ₁₂ CO ₃ / 3H ₂ O

[0036]

[Table 1]

Example 2 The following composition 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.

(Combined) 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 CaO · 2.5SiO ₂ · 0.9H ₂ O 0.5 sorbitol 0.05 Test compound (see [Table 2] below) [Table 2]

[0039]

[Table 2]

* 2 and * 3 in the above [Table 2] are as follows. * 2: manufactured by Kyowa Chemical Co., Ltd. hydrotalcite composition _{formula: Mg 4 Al 2 (OH)} 12 CO 3 * 3: manufactured by 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 was performed 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 ^{* 4} 2.0 dibenzoylmethane 0.1 Bisphenol A 0.3 Test compound (See [Table 3] below) [Table 3] * 4: Hydrotalcite manufactured by Kyowa Chemical Co., Ltd. Compositional formula: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O

[0043]

[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 metal silicate of the general formula (II) is added to the vinyl chloride resin (Comparative Example 1-
2) Alternatively, when only the above metal silicate is added (Comparative Examples 1-5, 2-1 to 2-3), it is difficult to use in electric wire applications because of extremely low heat resistance. 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 electrical insulation is insufficient. Furthermore, when the above hydrotalcite compound and a metal silicate other than the above general formula (II) are used in combination (Comparative Examples 1-3,1-4,3-2,3-3), heat resistance, electrical insulation Although the sex is improved to some extent, the improvement effect is still insufficient.

On the other hand, when the above-mentioned hydrotalcite compound and the above-mentioned metal silicate are added to the vinyl chloride resin in combination (Examples 1-1 to 1-4, 2-1 to 2-5, 3-1 to 3) -4) has little coloring, and has excellent heat resistance and electrical insulation.

[0046]

The vinyl chloride resin composition for coating electric wires of the present invention has low toxicity, and is excellent in 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] A vinyl chloride resin composition for coating an electric wire, which comprises 0.001 to 3 parts by weight of at least one silicate of an alkaline earth metal represented by the general formula (II). Embedded image Embedded image