JPS62265339A - Vinyl chloride resin composition for coating wire - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat resistance and electrical properties, nonmigrating toward an ABS or PS molding and small in a change after heat aging, by mixing a vinyl chloride resin with a specified epoxidized polyester and at least one higher fatty acid metal salt. CONSTITUTION:A resin composition obtained by mixing 100pts.wt. vinyl chloride resin with, optionally, 0-30pts.wt. filler such as calcium carbonate is mixed with 10-100pts.wt. epoxidized polyester, average MW of 1,000-10,000, obtained by condensing a dibasic acid with a dihydric alcohol, an unsaturated monocarboxylic acid and an unsaturated monohydric alcohol and containing 0.1-20wt% oxirane oxygen and 0.1-5pts.wt. at least one higher fatty acid metal salt selected from among Ca, Ba and Zn salts of 10C or higher fatty acids.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a vinyl chloride resin composition for covering electric wires.

[Prior art and problems to be solved] In recent years, ABS has been used in various electrical appliances, computer equipment, automobile parts, etc.
Resin (styrene-butadiene-acrylonitrile resin)
, As resin (styrene-acrylonitrile resin), polystyrene, and other styrene-based resin molded products are widely used, but such molded products come into contact with electrical cords that are wired for a considerable amount of time and frequency. There is.

On the other hand, vinyl chloride resin compositions used for general electric wire coatings include: ■ vinyl chloride resin ■ filler, ■ plasticizers such as dioctyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dinonyl phthalate, and triisooctyl trimellitate, and ■ Contain lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite sulfite, lead stearate, dibasic lead stearate, and dibasic lead phthalate. obtained by.

However, when such conventional vinyl chloride resin compositions for wire coating come into contact with ABS resin or styrene resin molded products, the plasticizer may migrate to the molded products and attack the molded products. could not. As an improvement, attempts have been made to use saturated polyester plasticizers such as adipic acid-glycol type plasticizers, but when these polyester plasticizers are used in combination with lead-based stabilizers, they undergo hydrolysis and become low molecular weight, resulting in ABS. There were problems such as transfer to resin or styrene resin molded products, poor compatibility with vinyl chloride resin, and bleeding.

As a solution to this problem, attempts were made to use barium stearate and zinc stearate as stabilizers that do not hydrolyze polyester plasticizers, but barium stearate/zinc stearate stabilizers are much more heat-resistant than lead-based stabilizers. Due to its poor properties, it has the disadvantage of causing yellowing of processed products and deterioration of mechanical properties.

As a means to improve this heat resistance, a method is used in which an epoxy plasticizer such as epoxidized soybean oil or epoxidized octyl stearate is used in combination with a polyester plasticizer. Otherwise, there are problems such as transfer to styrene resin molded products.

Therefore, there is a strong demand for the development of a vinyl chloride resin composition for covering electric wires that does not migrate to ABS resin or styrene resin molded products and has excellent heat resistance.

[Means for Solving the Problems] The present inventors have conducted various studies on a vinyl chloride resin composition for covering electric wires that does not transfer to ABS resin and styrene resin molded products and has excellent heat resistance. , by using certain epoxidized polyesters as plasticizers,
We have discovered a composition that does not transfer even when it comes into contact with ABS resin or styrene resin molded products, and has excellent heat resistance, and has led to the present invention.

That is, the present invention uses (A) a vinyl chloride resin and (B) oxirane, an average molecule containing 0.1 to 20% by weight of oxygen! 10
00~toooo epoxidized polyester, and (C
) A vinyl chloride resin for covering electric wires, which is suitable for coming into contact with ABS resin and styrene resin molded products, and is made of at least one higher fatty acid metal salt selected from the group of higher fatty acid calcium, higher fatty acid barium, and higher fatty acid zinc. A composition is provided.

The vinyl chloride resin in the present invention includes, for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride
- Ethylene copolymers, vinyl chloride-propylene copolymers, vinyl chloride-styrene copolymers and the like are already known for use in covering electric wires.

Fillers are usually added to this composition. 'Fillers include, for example, calcium carbonate, clay, and talc. This filler is used in an amount of 0 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin.

An epoxidized polyester having an average molecular weight of 1t1000 to 10000 containing 0.1 to 20% by weight of oxirane oxygen can be produced by, for example, (a) a condensation reaction of a dibasic acid, a dihydric alcohol, an unsaturated monocarboxylic acid, and an unsaturated-hydric alcohol. or (b) epoxidizes a polyester having an unsaturated group obtained by ring-opening polymerization of lactone using an unsaturated monocarboxylic acid as an initiator with formic acid and hydrogen peroxide, then removes the formic acid by washing with water, and then removes water. It is obtained by removing in high vacuum. Dibasic acids, dihydric alcohols, used to prepare the polyester;
The following are typical unsaturated monocarboxylic acids, unsaturated alcohols, and lactones.

Examples of dibasic acids include orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, cepatic acid, and azelaic acid; examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,2-butylene glycol, and 1,3- Butylene glycol, 1,4-butylene glycol, 1,5-bentanediol, neopentyl glycol, l,6-hexanediol, etc., and unsaturated monocarboxylic acids such as linderic acid, tuzuic acid, physetoleic acid, and myristoleic acid. , seamaric acid, petroselic acid, oleic acid, elaidic acid, gadolenic acid,
Gondolaic acid, whale oil acid, erucic acid, branzic acid, ceracoleic acid, linoleic acid, linoleaidic acid, lilunic acid,
Eleostearic acid, moroctic acid, valinaric acid, arachidonic acid, sardine acid, hiraganic acid, nisic acid, etc.
Examples of unsaturated alcohols include oleyl alcohol, and examples of lactones include β-propiolactone, r-butyrolactone, δ-valerolactone,
Examples thereof include ε-caprolactone and methyl-ε-caprolactone.

The content of oxirane oxygen in the epoxidized polyester of the present invention is 0.1 to 20% by weight, preferably 1%.

The molecular weight of epoxidized polyester is 1000-100
00, preferably 1500-8000. 100
If it is less than 0, it is easy to migrate, and if it is more than 10000, the viscosity becomes high and workability may deteriorate. The amount of epoxidized polyester is 1 part per 100 ffi of vinyl chloride resin.
The amount is 0 to 100 parts by weight, preferably 40 to 80 parts by weight, and those within this range provide physical properties suitable for covering electric wires.

The higher fatty acid metal salt used in the present invention is at least one selected from the group of higher fatty acid calcium, higher fatty acid barium, and higher fatty acid zinc.

Here, higher fatty acids refer to saturated fatty acids having 10 or more carbon atoms, such as lauric acid, tridecylic acid, myristic acid, stearic acid, araxic acid, behenic acid, cerotic acid, montanic acid, nonacosanoic acid, melisic acid, etc. show.

The amount of higher fatty acid metal salt is 0.1 to 5 parts by weight, preferably 1 to 3 parts by weight per 100 parts by weight of vinyl chloride.

If it is less than 0.1 part by weight, heat resistance is insufficient, and if it is more than 5 parts by weight, blooming may occur. There are two methods for producing these higher fatty acid metal salts: a direct method and a double decomposition method (indirect method).

The direct method is a method in which higher fatty acids are obtained by dehydration from total oxides or metal hydroxides, and the double decomposition method is a method in which a higher fatty acid sodium or potassium salt aqueous solution is reacted with a metal chloride aqueous solution to obtain by-produced NaCl or KCj! This is a method of removing it by washing with water, dehydrating it, and drying it.

The higher fatty acid metal salt used in the composition of the present invention is preferably one produced by a direct method. The reason for this is that higher fatty acid metal salts obtained by the metathesis method contain a small amount of NaC.
This is because 1 or KCl is present, and this deteriorates the electrical resistance. Furthermore, if necessary, pentaerythritol, dipentaerytol, esters thereof, dibenzoylmethane, magnesium oxide, and bisphenol may be mixed with the higher fatty acid metal salt for the purpose of further increasing the heat resistance of the composition of the present invention. You can also do that.

Also included in the composition of the present invention are the following, for example, an average molecular weight of 1
Saturated polyester with t1500 or more; Other polymers other than vinyl chloride resin such as ethylene-vinyl acetate coweight and MBS resin; Reinforcing agents such as glass fiber, polyester fiber, and nylon fiber; Processing aids; Pigments and organic phosphorus Other additives such as acid esters can also be contained.

Hereinafter, the present invention will be explained by giving examples.

In the examples, parts mean parts by weight.

Examples 1 to 7, Ratio Examples 1 to 3 The formulations shown in Table 1 were rolled on an 8-inch roll at 165°C
After kneading for a minute, a 0.7 m sheet was taken out. The heat resistance of this sheet was measured.

■Fit to heat-resistant Congo Red method JIS K-6723! . In addition, two of these sheets were stacked in a 1 m 1 I thick mold at 170°C.
A press sheet with a thickness of 1 dragon was obtained by pressing at 170°C for 5 minutes. The following physical properties were measured for this sheet.

■Normal tensile test (23°C, lmm-thickness No. 3 tongue water) Based on JIS K-6723 ■120
℃ Tensile test after heat aging for 120 hours JIS K-672
Compliant with 3 ■Volume resistivity (lmm thick sheet) Compliant with JIS K-6723 Molded products of each resin (thickness l mm, 5x5cffl)
Place a press sheet (thickness 1 dragon, 4 x 4 cm) on the
This was wrapped in aluminum foil, then sandwiched between 6 x 6 cnl glass plates, and a 4.8 kg weight was placed on top of it. After leaving this in a dryer at 70°C for a week, I took it out and observed the appearance of each resin molded product, and gave the following rating: F+! fi
Evaluation was made based on the basics.

(Migration evaluation criteria) ◎: No traces are observed on the surface of the resin molded product where the press sheet of the initial vinyl chloride resin composition is placed.

○: Very few traces are observed.

△: Traces are observed.

×: Strong traces.

XX: Traces are extremely strong.

(2) Bleeding After the pressed sheet was left in a constant temperature bath at 70° C. and 90% humidity for 30 days, its stickiness was observed and evaluated using the following evaluation criteria.

○: Stickiness (burrito) is not observed.

△: Slightly observed.

×；〃　　　　　　Accepted.

The results are summarized in Table-1.

〔effect〕

The vinyl chloride resin composition for electric wire coating of the present invention has excellent heat resistance, has no migration to ABS resin, As resin, or polystyrene molded products, and has a change rate after heat aging (physical properties after heat aging/normal state). physical properties) and electrical properties.
C can also satisfy the quality required as a wire coating.

Claims (1)

[Claims] (A) Vinyl chloride resin, (B) Oxirane oxygen 0.1~
Average molecular weight 1000-10000 containing 20% by weight
and (C) at least one higher fatty acid metal salt selected from the group of higher fatty acid calcium, higher fatty acid barium, and higher fatty acid zinc salt.