JPH05179090A - Halogen-containing resin composition - Google Patents

Abstract

PURPOSE:To provide the subject low toxic composition excellent inelectric insulating property, heat resistance and coloring property by adding both a hydrotalcite compound and a specific compound as stabilizers to a chlorine- containing resin. CONSTITUTION:(A) 100 pts.wt. of a halogen-containing resin (e.g. polyvinyl chloride resin) is mixed with both (B) 0.05-10 pts.wt. of a hydrotalcite compound of the formula (x1, x2 are numbers satisfied with 0<=x2/x1>10, 2<=x1+x2<20, and 0<y<=2) and (C) 0.001-3wt.% of an aluminum or alkaline earth metal silicate as stabilizers to provide the objective composition. The component C is preferably aluminum silicate. The further addition of a polyol such as sorbitol in an amount of 0.05-5 pts.wt. is preferable due to the more improvement of the stabilization effect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-containing resin composition stabilized by blending a specific stabilizer system, and more specifically, a hydrotalcite compound and a silicate of a specific metal are used in combination. The present invention relates to a halogen-containing resin composition having improved electrical insulation properties, heat resistance, etc. when added.

[0002]

2. Description of the Related Art Halogen-containing resins have excellent electrical insulation, arc resistance, tracking resistance, and withstand voltage, and therefore, are better than rubber and polyolefin. It is a very important insulating material. However, the halogen-containing resin has a drawback that its excellent various properties are deteriorated due to thermal and oxidative deterioration, and that it cannot be practically used.

In order to make up for the above-mentioned drawbacks, various stabilizers have been conventionally added to halogen-containing resin insulating materials, and among them, lead-based stabilizers such as tribasic lead sulfate and stearic acid are especially preferred. Was there. These stabilizers are excellent heat stabilizers and have advantages such as relatively low cost. However, lead-based stabilizers are highly toxic and are not sufficient in terms of electrical insulation, and also have the drawback that the electrical insulation deteriorates as the temperature of the insulator rises.

Therefore, in JP-A-52-77157 and JP-A-52-77158, a halogen-containing resin containing a basic inorganic acid salt or a fired product thereof is used without using a lead-based stabilizer. However, it was still insufficient.

Further, in JP-A-63-46248, it is proposed to use a hydrotalcite compound and magnesium oxide in combination in order to improve foamability during molding. The publication proposes to use a hydrotalcite compound and nepheline in combination in order to improve transparency and heat retention of the agricultural film, but does not even suggest improvement in electric insulation.

Under the above circumstances, there has been a strong demand for a halogen-containing resin insulating material having low toxicity and excellent electric insulation.

[0007]

In view of the above situation, the inventors of the present invention have made earnest studies to find a halogen-containing resin insulating material having low toxicity and excellent electric insulation, and as a result, a hydrotalcite compound and It has been found that a halogen-containing resin composition for electric wires, which has improved electrical insulation and heat resistance, can be obtained by adding a metal silicate together with the halogen-containing resin.

The present invention has been made on the basis of the above-mentioned findings, and 100 parts by weight of a halogen-containing resin is represented by the following general formula (I) represented by the following [Chemical formula 2] (the same as [Chemical formula 1]). At least one kind of hydrotalcite compound 0.05 to 10
The present invention provides a stabilized halogen-containing resin composition obtained by blending parts by weight and (b) 0.001 to 3 parts by weight of at least one silicate of aluminum or alkaline earth metal.

[0009]

_{Embedded image} Mg _x1 Zn _x2 Al ₂ · (OH) _{2x1 + 2x2 + 4} · (CO ₃ ) _{1-y / 2} (ClO ₄ ) _y · mH ₂ O (I) (wherein x ₁ , x ₂ And y each represent a number satisfying the condition represented by the following formula, and m represents 0 or an arbitrary integer.
0 ≦ x ₂ / x ₁ <10, ₂ ≦ x ₁ + x ₂ <20, 0 <y
≤2)

The halogen-containing resin composition of the present invention will be described in detail below.

The hydrotalcite compound used in the halogen-containing resin composition of the present invention is, as represented by the above-mentioned general formula (I), a double salt compound consisting of magnesium and aluminum, or a zinc, magnesium and aluminum compound. The water of crystallization may be dehydrated.

The hydrotalcite compound may be a natural product or a synthetic product. As a synthesis method, Japanese Patent Publication No. 46-2280 and Japanese Patent Publication No. 50-
No. 30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, and Japanese Patent Publication No. 61-174270.
Known methods described in, for example, Japanese Patent Publication can be exemplified. Further, the hydrotalcite compound in the present invention can be used without being limited by its crystal structure, crystal particle size and the like.

As the hydrotalcite compound used in the halogen-containing resin composition of the present invention, the surface of the hydrotalcite compound may be a higher fatty acid such as stearic acid or a higher fatty acid metal such as an alkali metal oleate salt. Salts, organic sulfonic acid metal salts such as dodecylbenzene sulfonic acid alkali metal salts, higher fatty acid amides,
Those coated with higher fatty acid ester or wax can also be used.

The amount of the hydrotalcite compound added is 0.05 to 100 parts by weight of the halogen-containing resin.
10 parts by weight, more preferably 0.1 to 5 parts by weight.

Examples of the metal species constituting the metal silicate used in the halogen-containing resin composition of the present invention include aluminum and alkaline earth metals such as calcium, magnesium, barium and strontium. Aluminum is preferred. Examples of the acid radicals forming the metal silicates include orthosilicic acid, metasilicic acid, mesodisilicic acid, mesotrisilicic acid, and mesotetrasilicic acid.

The amount of the metal silicate added is 0.001 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the halogen-containing resin.

In the halogen-containing resin composition of the present invention, the stabilizing effect is further improved by adding the polyols together.

Examples of the polyols include sorbitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentalithritol, polypentaerythritol, pentaerythritol, or stearic acid half ester of dipentalithritol.
Examples thereof include bis (dipentaerythritol) adipate, glycerin, and tris (2-hydroxyethyl) isocyanurate.

The amount of the above polyols added is preferably 0.01 to 10 relative to 100 parts by weight of the halogen-containing resin.
Parts by weight, more preferably 0.05 to 5 parts by weight.

The halogen-containing resin in the present invention includes
Vinyl chloride homopolymer or vinyl chloride and ethylene, propylene, vinyl acetate, (meth) acrylic acid ester, maleic anhydride, phenylmaleimide produced by well-known methods such as suspension polymerization method, bulk polymerization method and emulsion polymerization method. , Copolymers with cyclohexylmaleimide, polyvinylidene chloride, polyvinyl bromide, chlorinated polyethylene, ethylene / vinyl acetate copolymer and vinyl chloride graft polymers, urethane resins having unsaturated groups and vinyl chloride And the like, and also includes a mixture of these with other thermoplastic resins.

The halogen-containing resin composition of the present invention contains a metal (L) of carboxylic acid, organic phosphoric acid or phenol.
i, Na, K, Ca, Ba, Mg, Sr, Zn, Cd,
Naturally, Sn, Cs, Al, organic Sn) salts can also be added. Examples of the carboxylic acid forming the metal salt 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, linoleic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acids , Coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, such as naturally occurring mixtures of the above acids,
Benzoic acid, pt-butyl benzoic acid, ethyl benzoic acid, isopropyl benzoic acid, toluic acid, xylyl acid, salicylic acid, 5-t-octyl salicylic acid, naphthenic acid, cyclohexanecarboxylic acid, etc. Examples of phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, and the like. Examples of the phenols constituting the above metal salt include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like.

The amount of the above metal salt added is such that the halogen-containing resin 1
It is preferably 0.05 to 10 parts by weight with respect to 00 parts by weight.

Further, the halogen-containing resin composition of the present invention further contains various additives which are usually used as additives for halogen-containing resins, for example, organic phosphite compounds and / or epoxy compounds, plasticizers and the like. It can also be blended.

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 (C
_12-15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite and the like can be mentioned.

The amount of the above organic phosphite compound added is
With respect to 100 parts by weight of the halogen-containing resin, preferably 0.
01 to 5 parts by weight.

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 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.

In addition, if necessary, additives usually used in vinyl chloride resins such as cross-linking agents, fillers, foaming agents, antistatic agents, antifogging agents, antiplateout agents, surface treatment agents, and lubricants. , Flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, zeolites, silicic acid powder (silica), perchlorine Sodium acid salt, magnesium perchlorate, barium perchlorate and the like can be added.

Further, the halogen-containing resin composition of the present invention is
It can be used regardless of the processing method of halogen-containing resin, and is suitable for calendar processing, roll processing, extrusion molding processing, injection molding processing, pressure molding processing, paste processing, powder molding, etc. can do.

[0030]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples. In addition, in Example 4, the combined effect of polyols was confirmed.

Example 1 The following (composition) composition was added at 170 ° C. and 30 rpm for 5 minutes.
After kneading on a roll for 5 minutes, it was pressed at 180 ° C. for 5 minutes to form a sheet having a thickness of 1 mm, and the yellowness of the sheet was measured. Further, the color difference from the sheet pressed for 30 minutes under the same conditions was obtained. In addition, a test piece was prepared from this sheet and 2
The heat stability was evaluated by heating in a gear oven at 10 ° C. and measuring the time until blackening. In addition, JIS. K
According to 6723, volume resistivity test (VR) was performed.

The results are shown in Table 1 below.

(Combined) parts by weight polyvinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd .: TK-1300) 100 diisononyl phthalate 50 calcium carbonate 15 zinc stearate 0.5 dibenzoylmethane 0.1 tris (2-hydroxyethyl) isocyanate Nurate 0.2 Alkamizer 1 ^{* 1} 4.0 Test compound (see [Table 1]) * 1: Hydrotalcite manufactured by Kyowa Chemical Co., Ltd.

[0034]

[Table 1]

Example 2 The following composition (composition) was kneaded on a roll at 170 ° C. for 5 minutes and then pressed at 80 ° C. for 5 minutes to prepare a sheet having a thickness of 1 mm. A test piece was prepared from the prepared sheet, heated in a gear oven at 210 ° C., and the time until blackening was measured. In addition, JIS. According to K-6723, a volume resistivity test (VR) and a thermal stability test (CR) using Congo red test paper were performed.

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 Aluminum silicate 0.5 Sorbitol 0.05 Test compound (see [Table 2])

[0038]

[Table 2]

Example 3 The same test as in Example 1 was conducted using the composition (composition) described below. However, the thermal stability was evaluated by setting the temperature of the 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-8) 100 Dioctyl phthalate 30 Epoxidized soybean oil 5 Zinc laurate 0.5 DHT-4A ^{* 5} 2.0 Dibenzoylmethane 0.1 Bisphenol A 0.3 Test compound (See [Table 3]) * 5: Hydrotalcite manufactured by Kyowa Chemical Co., Ltd.

[0042]

[Table 3] Example 4 The following (composition) composition was kneaded on a roll at 170 ° 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 and subjected to a volume resistivity test (VR) and a thermal stability test (CR) using Congo red test paper.

The results are shown in Table 4 below.

(Distribution) Parts by Weight Polyvinyl Chloride Resin (S-1003 manufactured by Nippon PVC Co., Ltd.) 100 Tris (2-ethylhexyl) trimellitate 50 Calcium carbonate 30 Clay 5 Epoxidized soybean oil 2 Zinc stearate 0.5 Alkamizer 1 2.0 Dibenzoylmethane 0.1 Calcium silicate 0.2 Test compound (see [Table 4])

[0045]

[Table 4]

As is clear from the results of Examples 1 to 3, when the metal silicate is not used, the electric insulation is insufficient, and when the hydrotalcite compound is not used or the metal silicate is not used. When a large amount of silicate is used, it has a drawback that the coloring property is significantly lowered. On the other hand, by adding the hydrotalcite compound and an appropriate amount of metal silicate together, not only the volume resistivity and thermal stability are significantly improved, but also the coloring property is excellent, and the present invention It is clear that the present invention provides a wire material having excellent insulation and heat resistance. It is also apparent from the results of Example 4 above that the effects of the present invention as described above are further improved by the combined addition of polyols.

[0047]

The halogen-containing resin composition of the present invention has low toxicity and excellent electric insulation.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaru Nagahama 5-2-13 Shirahata, Urawa City, Saitama Prefecture Asahi Denka Kogyo Co., Ltd.

Claims (1)

[Claims] 1. 100 parts by weight of a halogen-containing resin, (a)
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 (b) at least one 0.001 of an aluminum or alkaline earth metal silicate. A stabilized halogen-containing resin composition containing 3 to 3 parts by weight. _{Embedded image} Mg _x1 Zn _x2 Al ₂ · (OH) _{2x1 + 2x2 + 4} · (CO ₃ ) _{1-y / 2} (ClO ₄ ) _y · mH ₂ O (I) (wherein x ₁ , x ₂ And y each represent a number satisfying the condition represented by the following formula, and m represents 0 or an arbitrary integer.
0 ≦ x ₂ / x ₁ <10, ₂ ≦ x ₁ + x ₂ <20, 0 <y
≤2)