JP2019114511A - Chlorine-containing resin composition for wire coating material - Google Patents

Abstract

To provide a chlorine-containing resin composition for wire coating material in which heat resistance in wire formation and reduction in a strength of a wire coating material by addition of an EVA resin are suppressed.SOLUTION: A composition is used as a material of a wire coating material, in which the composition contains a chlorine-containing resin, an ethylene-vinyl acetate copolymer, a hydrotalcite type powder and a plasticizer, and the hydrotalcite type powder contains a magnesium element (Mg) and/or zinc element (Zn) and an aluminum element (Al) and has an oil absorption amount of 30 ml/100 g or less.SELECTED DRAWING: None

Description

The present invention relates to a chlorine-containing resin composition for a wire covering material.

Chlorine-containing resins represented by polyvinyl chloride are developed in various applications because of their high flexibility and ease of processing. On the other hand, chlorine-containing resins have a problem in thermal stability, and conventionally, lead-based stabilizers and powdery Ca / Zn-based stabilizers are mainly used in chlorine-containing resin compositions used for wire coating materials. It is prescribed. However, when such a stabilizer is added, there is a problem that flexibility and trauma resistance are reduced. It is known that this problem can be improved by adding an EVA resin (ethylene-vinyl acetate copolymer) to soften the resin (see, for example, Patent Documents 1 and 2).

JP, 2016-095995, A Unexamined-Japanese-Patent No. 2017-111920

As mentioned above, flexibility and trauma resistance are improved by adding EVA resin to chlorine containing resin for wire covering material mainly formulated with lead based stabilizer and powdery Ca / Zn based stabilizer. There is a problem that the heat resistance at the time of wire forming and the strength of the wire covering material decrease. For this reason, development of the chlorine containing resin composition for wire covering materials in which the heat resistance at the time of wire forming and the fall of the intensity of a wire covering material was controlled even if it added EVA resin was called for.

An object of the present invention is to provide a chlorine-containing resin composition for electric wire covering material in which the heat resistance at the time of electric wire molding and the decrease in strength of the electric wire covering material are suppressed.

This inventor suppresses the heat resistant fall of the chlorine containing resin composition for electric wire covering materials to which EVA resin was added by adding the hydrotalcite known as a component which suppresses the heat resistant fall of chlorine containing resin. Tried to do. Although such a decrease in heat resistance was suppressed, a further decrease in the strength of the wire covering material was observed, and a new problem was found that hydrotalcite causes the strength of the wire covering material to further decrease. The inventors of the present invention have repeatedly studied the new problem and found that there is a causal relationship between the oil absorption of hydrotalcite and the processability when forming a wire with a resin composition using the hydrotalcite. The More specifically, it is assumed that there is a negative correlation between the oil absorption of the hydrotalcite and the kneading strength or kneading state at the time of wire molding, and the hydrotalcite with an oil absorption below a predetermined value is added to the resin composition Then, it is found that the heat resistance can be suppressed without causing a further decrease in the strength of the wire covering material, and it is conceived to be able to solve the above-mentioned problems clearly, and the present invention has been completed.

That is, the present invention is a composition used as a material of a wire covering material, wherein the composition contains a chlorine-containing resin, an ethylene-vinyl acetate copolymer, a hydrotalcite-type powder and a plasticizer. Talcite-type powder contains magnesium element (Mg) and / or zinc element (Zn) and aluminum element (Al) and has an oil absorption of 30 ml / 100 g or less. It is a chlorine containing resin composition.

The chlorine-containing resin composition for a wire covering material preferably contains 0.05 to 5 parts by mass of the hydrotalcite-type powder with respect to 100 parts by mass of the chlorine-containing resin.

The chlorine-containing resin composition for a wire covering material preferably contains 1 to 20 parts by mass of the ethylene-vinyl acetate copolymer with respect to 100 parts by mass of the chlorine-containing resin.

The hydrotalcite-type powder has the following general formula (1):
_{{(Mg) x (Zn)} y} (Al) z (OH) 2 (A n-) z / n · mH 2 O (1)
(In the formula, A ^{n −} represents an n-valent interlayer anion. X, y and z represent 0 <x <1, 0 ≦ y <1, 0.2 ≦ z ≦ 0.4, x + y + z = 1 And the ratio of x + y to z {(x + y) / z} is 2.20 or less, and n and m are numbers satisfying 1 ≦ n ≦ 4 and 0 ≦ m, respectively. It is preferable that it is represented by.

The chlorine-containing resin composition for a wire covering material preferably contains a trimellitic acid ester compound as the plasticizer.

The present invention is also a wire covering material using the chlorine-containing resin composition for a wire covering material of the present invention.

The chlorine-containing resin composition for a wire covering material of the present invention is a resin composition in which the heat resistance deterioration due to the inclusion of the EVA resin is suppressed without causing a further decrease in strength, and is suitable as a material such as a wire covering material It can be used for

Hereinafter, although an example of the present invention is explained concretely, the present invention is not limited only to the following descriptions, and can be suitably changed and applied in the range which does not change the gist of the present invention.

The chlorine-containing resin composition (also referred to simply as a "resin composition") for a wire covering material of the present invention comprises a chlorine-containing resin, an ethylene-vinyl acetate copolymer, a hydrotalcite-type powder, and a plasticizer. Including. As necessary, it may further contain one or more other components, and each component may be used alone or in combination. Each component will be described below.

<Chlorine-containing resin>
The chlorine-containing resin is not particularly limited as long as it is a resin (polymer) containing a chlorine atom, but a vinyl chloride resin is preferable. Thereby, the molded object which is excellent in a softness | flexibility or a flame retardance is obtained.

Examples of vinyl chloride resins include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, etc .; vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer Combination, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer , Vinyl chloride-acrylic acid ester copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, chloride Vinyl-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate Polymers, vinyl chloride - maleic acid ester copolymer, vinyl chloride - methacrylic acid ester copolymers, vinyl chloride - acrylonitrile copolymer, vinyl chloride - copolymers such as maleimide copolymer; and the like. A blend of a chlorine-containing resin and a non-chlorine-containing resin may be used, and the polymerization method for obtaining a vinyl chloride resin is not particularly limited.

<Ethylene-vinyl acetate copolymer>
The ethylene-vinyl acetate copolymer is not particularly limited as long as it is a copolymer obtained by copolymerizing a monomer component containing ethylene and vinyl acetate, and a component other than ethylene and vinyl acetate is a copolymer It may be one obtained by copolymerizing ethylene and vinyl acetate alone.

When the ethylene-vinyl acetate copolymer has a structural unit derived from ethylene and a structural unit other than a structural unit derived from vinyl acetate, carbon monoxide has flexibility or resistance as a monomer for forming another structural body. It is preferable at the point which improves the effect of improving trauma nature. That is, it is preferable that it is an ethylene-vinyl acetate-carbon monoxide copolymer.

The ethylene-vinyl acetate copolymer preferably has a melt mass flow rate (MFR) of 5 to 50 g / 10 min. More preferably, it is 30 to 50 g / 10 min. By using such a MFR one, the effect of improving the flexibility and trauma resistance of a molded article using the resin composition is more fully exhibited.
MFR of an ethylene-vinyl acetate copolymer can be measured by JIS K 7210-1 (2014).

In the resin composition of the present invention, the content of the ethylene-vinyl acetate copolymer is preferably, for example, 0.1 to 20 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. As a result, the effect of improving flexibility and trauma resistance in a winter or a cold region of a molded article using the resin composition is exhibited. More preferably, it is 1-10 mass parts, More preferably, it is 1-5 mass parts.

<Hydrotalcite-type powder>
The hydrotalcite-type powder contained in the chlorine-containing resin composition for wire covering material of the present invention contains magnesium element (Mg) and / or zinc element (Zn) and aluminum element (Al), and the oil absorption amount is It is 30 ml / 100 g or less.
By using the hydrotalcite-type powder having such an oil absorption amount, it is possible to suppress the heat resistance deterioration without causing the reduction of the strength of the resin composition caused by the hydrotalcite.
The oil absorption of the hydrotalcite-type powder is preferably 28 ml / 100 g or less, more preferably 25 ml / 100 g or less. The oil absorption of the hydrotalcite-type powder is usually 30 to 100 ml / 100 g.
In the present specification, the oil absorption of the hydrotalcite-type powder is measured in accordance with JIS K 5101-13-1 (2004: refined linseed oil method).

The hydrotalcite-type powder has the following general formula (1):
_{{(Mg) x (Zn)} y} (Al) z (OH) 2 (A n-) z / n · mH 2 O (1)
(In the formula, A ^{n −} represents an n-valent interlayer anion. X, y and z represent 0 <x <1, 0 ≦ y <1, 0.2 ≦ z ≦ 0.4, x + y + z = 1 And the ratio of x + y to z {(x + y) / z} is 2.20 or less, and n and m are numbers satisfying 1 ≦ n ≦ 4 and 0 ≦ m, respectively. It is preferable that it is represented by.). The use of such a hydrotalcite-type powder makes the cured product of the resin composition of the present invention more excellent in heat resistance and thermal stability.
In the general formula (1) it is not particularly restricted but includes n-valent interlayer anion, in view of reactivity and environmental load reduction, the hydroxide ion (OH ^-), carbonate ions (CO 3 ^_2-) and sulfate ions At least one selected from the group consisting of (SO ₄ ^2- ) is preferred. Among them, carbonate ion is preferable.

x, y and z are numbers satisfying 0 <x <1, 0 ≦ y <1, 0.2 ≦ z ≦ 0.4, x + y + z = 1, and the ratio of x + y to z {(x + y) / Z} is 2.20 or less.
Here, what is y = 0 is called Mg / Al type hydrotalcite, and what is 0 <y is called zinc modified hydrotalcite. In the present invention, any of these can be suitably used. In the case of using zinc-modified hydrotalcite, it is preferable that 0.01 ≦ y <1.

The ratio {(x + y) / z} of x + y to z is preferably 2.15 or less, more preferably 2.10 or less, and still more preferably 2.05 or less. The lower limit is not particularly limited, but is preferably 1.9 or more, more preferably 2.0 or more.

n is a number satisfying 1 ≦ n ≦ 4, and may be appropriately adjusted according to the valence of the interlayer anion. Preferably it is an integer of 1-3, More preferably, it is 2.

The shape of the particles in the hydrotalcite-type powder is not particularly limited, and examples thereof include plate-like, spherical and disc-like. Among them, a plate or a disc is preferable.
The particle shape can be observed by a scanning electron microscope or the like.

The average particle diameter of the hydrotalcite-type powder is preferably, for example, 0.1 μm or more and 2.0 μm or less. Thereby, the dispersibility to chlorine containing resin is improved, and the effect of the present invention is further improved. More preferably, it is 0.3 μm or more, and more preferably, 1.5 μm or less.

In the present specification, the average particle size can be measured as D50 using, for example, a laser diffraction particle size distribution measuring apparatus (LA950 manufactured by HORIBA).
D50 means the 50% integrated particle size on a volume basis, and when the powder is divided into two from a certain particle size, the larger side and the smaller side are equal. Specifically, it is determined according to the following method.

[D50 measurement method]
Add 60 mL of 0.025 wt% sodium hexametaphosphate aqueous solution to 0.1 g of a sample (sample powder), set the strength to V-LEVEL 3 using an ultrasonic homogenizer (US-600, manufactured by Nippon Seiki Seisakusho Co., Ltd.) 2 Prepare a suspension of the sample by performing a dispersion treatment for 1 minute. After that, a 0.025 wt% sodium hexametaphosphate aqueous solution is circulated to the sample circulator, the above suspension is dropped so that the permeability becomes 80 to 95%, and the circulation speed is 5, and the stirring speed is 60. Ultrasonication is performed for a second and then measurement is performed.

In the hydrotalcite-type powder, particles in the powder may have a coating layer. In this case, it is preferable that the physical properties of the hydrotalcite-type powder including the particles having the coating layer satisfy the above physical properties (particle shape, average particle size, specific surface area, etc.). Although it does not specifically limit as a coating layer, It is preferable that it surface-treats and coats using a surface treating agent.

The surface treatment agent is not particularly limited, and, for example, higher fatty acids, higher fatty acid metal salts (metal soaps), anionic surfactants, phosphoric esters, silane coupling agents, titanium coupling agents, aluminum coupling agents, etc. Coupling agents are mentioned. In addition, 1 type or 2 types or more can be used.

More specific surface treatment agents are, for example, higher fatty acids such as stearic acid, oleic acid, erucic acid, palmitic acid and lauric acid, metal salts such as lithium salts, sodium salts and potassium salts of these higher fatty acids; stearyl alcohol , Sulfuric acid ester salts of higher alcohols such as oleyl alcohol, sulfuric acid ester salts of polyethylene glycol ether, amide bond sulfuric acid ester salts, ether bond sulfonates; ester bond sulfonates, amide bond alkyl aryl sulfonates, ether bond alkyl aryl sulfonic acid Anionic surfactants such as salts; mono- or diesters of orthophosphoric acid with oleyl alcohol, stearyl alcohol etc. or mixtures thereof, phosphates such as acids or alkali metal salts or amine salts thereof; Silane coupling agents such as silane, γ-methacryloxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, etc .; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl Examples include titanium coupling agents such as tridecyl benzene sulfonyl titanate; and alkaline coupling agents such as acetoalkoxyaluminum diisopropylate.

The amount of the surface treatment agent to be used is not particularly limited. For example, the amount of the surface treatment agent coated is 0.1 to 100% by mass of the hydrotalcite-type powder containing particles having a finally obtained coating layer. It is preferable to adjust the amount of the surface treatment agent to be in the range of 30% by mass. More preferably, it is in the range of 0.1 to 20% by mass.

In the said resin composition, it is preferable that content of hydrotalcite type powder is 0.05-5 mass parts with respect to 100 mass parts of chlorine containing resin, for example. This further improves the heat resistance and the heat stability. More preferably, it is 0.1 to 3 parts by mass.

<Plasticizer>
Examples of the plasticizer contained in the resin composition of the present invention include phthalic acid ester compounds, adipic acid ester compounds, phosphoric acid ester compounds, trimellitic acid ester compounds, etc. More specifically, as phthalic acid ester compounds, Examples include dioctyl phthalate (DOP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP), and examples of adipic acid ester compounds include dioctyl adipate (DOA) and trimellitic acid ester compounds such as trioctyl trimellitate (TOTM). . Of these, trimellitic acid ester compounds are particularly preferred.

In the said resin composition, it is preferable that content of a plasticizer is 30-100 mass parts with respect to 100 mass parts of chlorine containing resin, for example. This becomes a wire covering material that is flexible and easy to handle at the time of wiring. More preferably, it is 40-80 mass parts, More preferably, it is 45-60 mass parts.

<Organic acid metal salt>
The resin composition of the present invention preferably also contains an organic acid metal salt. By containing an organic acid metal salt, the chlorine of the chlorine-containing resin can be stabilized, and the effect of suppressing discoloration during processing and use can be exhibited, so that a molded body can be obtained without reducing the appearance. become.

The organic acid in the organic acid metal salt is not particularly limited, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthate, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid and undecane Acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-t-butylbenzoic acid, dimethylhydroxybenzoic acid Acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid Acetoxybenzoic acid, salicylic acid, p-t-octylsalicylic acid, A monovalent organic carboxylic acid such as identic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid Etc., monoesters or monoamide compounds of divalent organic carboxylic acids, butane tricarboxylic acid, butane tetracarboxylic acid, hemimellitic acid, trimellitic acid, merophonic acid, pyromellitic acid, etc. 3 Di- or tetravalent organic carboxylic acid or Riesuteru; and the like. In addition, part of hydrogen atoms constituting these organic acids may be substituted by hydroxyl group or the like.
Among them, higher fatty acids having 12 to 20 carbon atoms are preferable. Specifically, myristic acid, palmitic acid, isostearic acid, metal salts of stearic acid, etc. which have appropriate lubricity and compatibility with chlorine-containing resins are preferable. Among them, metal salts of palmitic acid, metal salts of stearic acid and the like are preferably used because they are inexpensive and easily available.
In addition, a compound applicable to an organic acid metal salt or a β-diketone compound, such as zinc dehydroacetate described later, is classified as a β-diketone compound in the present invention. That is, the metal salt of an organic acid is a metal salt of an organic acid and is other than the compound corresponding to the β-diketone compound.

The metal forming the organic acid metal salt is not particularly limited, and examples thereof include alkaline earth metals such as Ca, Sr, and Ba, Zn, Pb, and Sn.
Among the organic acid metal salts, those containing Pb are referred to as lead-based stabilizers, those containing Sn are referred to as Sn-based stabilizers, and those which do not contain Pb and which are not classified as Sn-based stabilizers are generally Ca. It is called a / Zn-based stabilizer. The Ca / Zn-based stabilizer does not mean only those containing both Ca and Zn, and also includes a stabilizer containing only Zn and a stabilizer containing neither Ca nor Zn, and no Sn. In addition to Ca and Zn, a stabilizer containing a metal element other than Pb such as Sn as an auxiliary may be included in the Ca / Zn-based stabilizer.
In the present invention, even if Sn is contained, a Ca / Zn-based stabilizer containing 0.5 wt parts or less of Sn and a Sn-based stabilizer containing Sn more than 0.5 wt parts Classify as

The content of the organic acid metal salt is not particularly limited. For example, the content is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the chlorine-containing resin. Thereby, discoloration can be suppressed. More preferably, it is 0.1 parts by mass or more. Moreover, it is preferable that it is 5 mass parts or less, and, thereby, heat resistance can be improved more, the external appearance of a molded object will not fall more, and a color tone will become more favorable. More preferably, it is 2 parts by mass or less.

<Β-diketone compound>
The resin composition of the present invention may also contain a β-diketone compound. The coloring property at the time of shaping | molding can be aimed at by containing a (beta) -diketone compound.

The β-diketone compound is not particularly limited, and examples thereof include stearoylacetylmethane, benzoylacetylmethane, dibenzoylmethane, stearoylbenzoylmethane, octylbenzoylmethane, bis (4-octylbenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis Alkanoylaroylmethanes such as (4-carboxymethylbenzoyl) methane, 2-carboxymethylbenzoylacetyloctylmethane, 2-benzoylcyclohexane and the like, and diaroylmethane; dehydroacetic acid; and metal salts thereof are suitable.
Moreover, when using a chlorine containing resin composition as a wire coating material, it is suitable to contain a dehydro acetate zinc. In the resin additive industry, zinc dehydroacetate is regarded as a metal salt of a β-diketone compound, and is treated in the same manner in the present application.

When the said resin composition contains a (beta) -diketone compound, the content is not specifically limited, For example, it is preferable that it is 2 mass parts or less with respect to 100 mass parts of chlorine containing resin. More preferably, it is 0.1 to 1 part by mass.

<Filler>
The resin composition of the present invention preferably also contains a filler. As a result, the dimensional stability of the molded product and the strength of the molded product are improved, so that the resin composition is preferable for molded product applications. The filler also functions as a neutralizing agent.

The filler is not particularly limited, and examples thereof include inorganic powders such as inorganic salts, inorganic oxides and inorganic hydroxides, and examples thereof include zinc, titanium, iron, cerium, barium, calcium, silicon, aluminum, magnesium, strontium And salts such as boron and zirconium, oxides, hydroxides and complex oxides. The salts are not particularly limited, and examples thereof include sulfates, carbonates, hydrochlorides, acetates and nitrates. Specifically, for example, calcium carbonate, zinc carbonate, magnesium carbonate, silica, zinc oxide, titanium oxide, cerium oxide, cerium oxide, iron oxide, barium sulfate, strontium sulfate, magnesium sulfate, silicon oxide, aluminum oxide, magnesium oxide, silicic acid Zinc, zinc titanate, barium titanate, clay, talc and the like can be mentioned, among which calcium carbonate is preferred.

<Wax>
The resin composition of the present invention may also be used, if necessary, for hydrocarbon wax such as polyethylene wax and paraffin wax and / or fatty acid ester wax for adjustment of resin kneading state during molding, appearance adjustment of molded articles such as gloss etc. May be included. Specifically, as the polyethylene wax, for example, high wax series made by Mitsui Chemicals, Sanwax series made by Sanyo Chemical Industries, Viscor series made by Sanyo Chemical Industries, Ruvacs series made by Nippon Seiwa Co., Ltd., etc. may be mentioned. . As ester wax, Riken vitamin company make RIKESTA series, Emery company make Roxyol series etc. are mentioned, for example.

When the resin composition of this invention contains a wax, the content is not specifically limited, For example, it is preferable that it is 0.01-1 mass part with respect to 100 mass parts of chlorine containing resin. More preferably, it is 0.05-0.5 mass parts.

<Other ingredients>
The resin composition of the present invention may further contain other components as needed. For example, various additives such as a heat resistance aid, an ultraviolet light absorber, an antioxidant, a crosslinking aid and the like can be mentioned. The additives are not particularly limited, but examples thereof include polyhydric alcohol compounds such as dipentalithitol and epoxy compounds such as epoxy resin as a heat-resistant assistant, and monoglycerides of stearic acid, monoglycerides of palmitic acid and stearin as lubricants. Examples include acids and palmitic acid.

<Chlorine-containing resin composition for wire covering material>
The method for obtaining the chlorine-containing resin composition for a wire covering material of the present invention is not particularly limited, and a chlorine-containing resin, a hydrotalcite-type powder, a plasticizer and optional components used as needed may be mixed. The mixing method is also not particularly limited. For example, it is preferable to mix the mixture obtained by a Henschel mixer or a super mixer, and uniformly knead the obtained mixture using a roll, a Banbury mixer, an extruder or the like.

The chlorine-containing resin composition of the present invention uses a specific hydrotalcite-type powder to reduce heat resistance due to the inclusion of an ethylene-vinyl acetate copolymer to improve flexibility and trauma resistance. It is a resin composition suppressed without reducing the strength, and can be suitably used as a material of a wire covering material.
Such a wire covering material using the chlorine-containing resin composition for wire covering material of the present invention is also one of the present invention, and a coated wire having a structure in which the wire is covered with the wire covering material is also used. , Is one of the present invention.

Although the manufacturing method of a coated wire is not limited, the method etc. which are manufactured by putting an electric wire and the chlorine-containing resin composition for wire covering materials of this invention in an extrusion molding machine, and extrusion-forming it can be used. As for extrusion formation, when the rated value of the motor capacity of the extrusion screw becomes a large one of 11 Kw or more, the kneading becomes effective, and the resistance to the traumatic property of the molded article tends to be improved.

<Material used in Example>
(Chlorine-containing resin)
Vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd .: TK-1000)
(Ethylene-vinyl acetate-carbon monoxide copolymer)
EVA resin (Mitsui Dupont Polychemicals: Elvaloy 742, MFR 35 g / min)
(Organic acid metal salt (stabilizer))
Zinc stearate (manufactured by Sakai Chemical Industry Co., Ltd .: SZ-P)
Calcium stearate (manufactured by Sakai Chemical Industry Co., Ltd .: SC-P)
(Hydrotalcite-type powder)
In the hydrotalcite production operation described in Example 4 of Japanese Patent No. 5056014, each molar ratio of magnesium sulfate, aluminum sulfate and zinc sulfate, and production conditions are changed variously, synthesis is carried out, and each production is described later. The oil absorption and the specific surface area were measured by the following method, and hydrotalcite-type powders listed in Tables 1 and 2 were selected.
(Plasticizer)
Trimellitic acid tris (2-ethylhexyl) (made by Mitsubishi Chemical Corporation)
(Color inhibitor)
Dibenzoylmethane (manufactured by RHODIA: RHODIASTAB 83P)

<Examples 1 to 3 and Comparative Examples 1 to 3>
1. Preparation of resin composition The temperature of the mixture was measured with a 20 L Henschel mixer (manufactured by Nippon Coke Co., Ltd.) with a material weighed at a weight ratio described in Table 1 to 3 kg of a chlorine containing resin (TK-1000 manufactured by Shin-Etsu Chemical Co., Ltd.) It mixed until it became 100 degreeC, and the resin composition was produced.

2. A laboratory extruder (made by Toyo Seiki Co., Ltd., conical 2D20C type, motor capacity rating value) using suction molding (apparatus for smoothing the surface properties of molded products) having a cooling function using the resin composition obtained by molding processing The pipe was formed according to 5.5 Kw).
The extrusion conditions were set as follows. The cylinder temperature is from the position close to the raw material inlet, cylinder temperature 1: 175 ° C, cylinder temperature 2: 180 ° C, cylinder temperature 3: 185 ° C, adapter mold temperature 185 ° C, mold 1 180 ° C, gold The mold 2 was at 205 ° C. The mold used was for pipes.
In Examples 1 to 3 and Comparative Examples 1 to 3, using a small-sized extruder, the amount of the plasticizer contained in the composition is made small to increase the viscosity of the resin composition for molding. When molding with a small extruder, the larger the amount of plasticizer contained, the less effective the kneading and the less the difference in physical properties. Therefore, molding a composition with a large amount of plasticizer contained in this way with a large extruder The state of kneading in the case of mixing is simulated in a pseudo manner.

3. Evaluation test Physical properties were evaluated by the following test.
Using a pipe obtained by the above molding, a 3 kg weight was dropped from a position of 1.5 m, and the strength of the molded product was measured based on the following criteria (the number of test pieces: 10). The results are shown in Table 1.
:: All pipe surfaces are cracked, no cracks, no change with the pipe before falling.
Δ: Cracked on the surface of one or more pipes, and a crack was found but did not lead to destruction.
X: Cracks were observed on the surface of five or more pipes, cracks were observed, and were broken.

Example 4
1. Preparation of resin composition The temperature of the mixture was measured with a 20 L Henschel mixer (manufactured by Nippon Coke Co., Ltd.) with the material weighed in the weight ratio described in Table 2 to 3 kg of chlorine-containing resin (TK-1000 manufactured by Shin-Etsu Chemical Co., Ltd.) It mixed until it became 100 degreeC, and the resin composition was produced.

2. The resulting vinyl chloride resin composition was kneaded for 5 minutes with an 8-inch roll machine (KANSAI ROLL) adjusted to a roll surface temperature of 160 ° C. to form a roll sheet having a thickness of 0.6 mm.

3. Evaluation test (press heat resistance)
Seven sheets of the sheet prepared above are stacked and preheated for 5 minutes and pressurized for 5 minutes with a press at 180 ° C. using a press with a press surface temperature of 180 ° C. (TOYOSEIKI MINI TEST PRESS-10 manufactured by Toyo Seiki Co., Ltd.) 50 kgf / cm ² ) to make a 5 mm thick press sheet. Further, a 5 mm thick press sheet is prepared by preheating for 5 minutes and pressurization for 30 minutes (50 kgf / cm ² ), and the color difference (ΔE) from the sheet for 30 minutes of pressurization based on the sheet for 5 minutes of pressurization Was measured with a color difference meter (Nippon Denshoku Kogyo Co., Ltd., simultaneous photometric method spectral color difference meter SQ-2000), and used as an index of heat resistance. If ΔE is less than 5 under the above-described press sheet forming conditions, it can be said that there is no problem in manufacturing the wire covering material.
[Oven heat resistance]
The roll sheet prepared by the above formulation was placed in an ESPEC gear oven heated to 185 ° C. and held for 40 minutes. Based on the sheet before holding in the gear oven, the color difference (ΔE) with the sheet after holding for 40 minutes is measured with a color difference meter (Nippon Denshoku Kogyo Co., Ltd., simultaneous photometric spectral color difference meter SQ-2000) It was used as a sex indicator. If ΔE is less than 10 under the above-mentioned holding condition in the gear oven, it can be said that there is no problem in manufacturing the wire covering material.

As shown in Table 1, the pipe obtained by molding the resin composition of Examples 1 to 3 using a hydrotalcite having an oil absorption of 30 ml / 100 g or less has cracks on the surface even in the falling ball test. Pipes obtained by molding the resin compositions of Comparative Examples 1 to 3 using hydrotalcite having an oil absorption of more than 30 ml / 100 g while having no generation of cracks and sufficient strength In the falling ball test, more than half of the pipes were destroyed. From these results, it was confirmed that the wire covering material using the chlorine-containing resin composition for wire covering material of the present invention has sufficient strength.
Further, as shown in Table 2, the wire covering material using the chlorine-containing resin composition for wire covering material of the present invention containing EVA resin has sufficient heat resistance both in press heat resistance and oven heat resistance. It was confirmed to have.
From these, it was confirmed that the chlorine-containing resin composition for wire covering material of the present invention is excellent in both the heat resistance at the time of wire molding by the addition of EVA resin and the strength of the wire covering material.

Claims (6)

A composition used as a material of a wire covering material,
The composition comprises a chlorine-containing resin, an ethylene-vinyl acetate copolymer, a hydrotalcite-type powder and a plasticizer.
The hydrotalcite-type powder includes a magnesium element (Mg) and / or a zinc element (Zn) and an aluminum element (Al), and has an oil absorption of 30 ml / 100 g or less. Chlorine-containing resin composition for materials. The chlorine-containing resin composition for a wire covering material according to claim 1, wherein the hydrotalcite-type powder is contained in an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. The chlorine-containing resin composition for a wire covering material according to claim 1, wherein the ethylene-vinyl acetate copolymer is contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. The hydrotalcite-type powder has the following general formula (1):
_{{(Mg) x (Zn)} y} (Al) z (OH) 2 (A n-) z / n · mH 2 O (1)
(In the formula, A ^{n −} represents an n-valent interlayer anion. X, y and z represent 0 <x <1, 0 ≦ y <1, 0.2 ≦ z ≦ 0.4, x + y + z = 1 And the ratio of x + y to z {(x + y) / z} is 2.20 or less, and n and m are numbers satisfying 1 ≦ n ≦ 4 and 0 ≦ m, respectively. The chlorine-containing resin composition for a wire covering material according to any one of claims 1 to 3, characterized in that The chlorine-containing resin composition for a wire covering material according to any one of claims 1 to 4, wherein a trimellitic acid ester compound is contained as the plasticizer. A wire covering material comprising the chlorine-containing resin composition for wire covering material according to any one of claims 1 to 5.