JP2006241405A - Flame-retardant ethylene copolymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene copolymer composition which has excellent mechanical properties, heat resistance, flame retardance, etc., and also can be suitably used as a covering material for a cable which is used for a camera or in medical treatment and thus required to be highly flexible. <P>SOLUTION: The flame-retardant ethylene copolymer composition contains a polymer composition (D) and a specified amount of ammonium polyphosphate (E). The polymer composition (D) is prepared by melt kneading 99.9-50 wt% of at least one ethylene copolymer (A) selected from among an ethylene-vinyl ester copolymer (A1), an ethylene-unsaturated carboxylic ester copolymer (A2), and an ethylene-unsaturated carboxylic acid copolymer (A3) with 0.1-50 wt% of a resin (B) in the presence of an organic peroxide (C). The resin (B) is a multi-component propylene copolymer prepared by copolymerizing 0.1-20 mol% of a component other than propylene or is a blend of the multi-component propylene copolymer and a propylene homopolymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant ethylene copolymer composition, and more particularly, has a flame retardant property excellent in flame retardancy, for example, a flame retardant ethylene copolymer composition suitable as a coating material for electric / communication cables. Product (resin composition).

  Among ethylene copolymers, especially ethylene-vinyl ester copolymers and ethylene-unsaturated carboxylic acid copolymers are fillers to ethylene copolymers since they have good filler filling properties. Addition of an inorganic flame retardant, particularly magnesium hydroxide or aluminum hydroxide, is widely used as a flame retardant coating material for electric wires and communication lines, or a flame retardant building material.

  However, since it is necessary to add 50% or more of an inorganic flame retardant in order to obtain a flame retardant effect, the flexibility and mechanical properties are inevitably deteriorated. Among electrical and communication cables, camera cables and medical cables require high flexibility and heat resistance, so a flame-retardant resin composition with an excellent balance of flexibility, mechanical properties, heat resistance, and flame resistance Was demanded.

  In view of the present situation, the present inventors have provided excellent flame retardancy without substantially impairing the inherently preferable physical properties of the ethylene copolymer, for example, a camera cable or a medical cable. In order to obtain an ethylene copolymer composition that can be suitably used as a coating material, a specific ratio of a specific ethylene copolymer, a specific resin, a specific flame retardant, and an organic peroxide is studied. It was found that the polymer composition obtained by mixing and melt-kneading in order to satisfy the above-mentioned requirements, and has completed the present invention.

In Patent Document 1, halogen is added by adding 10 to 200 parts by weight of metal hydroxide and 1 to 30 parts by weight of zinc stannate and / or zinc hydroxystannate to 100 parts by weight of polyolefin resin. A method for improving flame retardancy and mechanical properties without inclusion is disclosed.
JP 2001-348466 A

  The present invention is intended to solve the problems associated with the prior art as described above, and retains preferable physical properties inherently possessed by an ethylene copolymer and has excellent heat resistance and flame retardancy. And it aims at providing the flame-retardant ethylene-type copolymer composition (resin composition) which can be used conveniently especially as an electric wire coating | covering material.

The flame retardant ethylene copolymer composition according to the present invention has an ethylene-vinyl ester copolymer (A1) having a melt flow rate (JIS K7210, 190 ° C., 2160 g load) of 0.1 to 300 g / 10 min. An ethylene-unsaturated carboxylic acid ester copolymer (A2) having a melt flow rate (JIS K7210, 190 ° C., 2160 g load) of 0.1 to 300 g / 10 minutes, and a melt flow rate (JIS K7210, 190 ° C., At least one ethylene copolymer (A) selected from ethylene-unsaturated carboxylic acid copolymer (A3) having a load of 2160 g) of 0.1 to 300 g / 10 min; ,
Resin (B) 0.1 to 50% by weight (provided that component (A) and component (B ) Is 100% by weight)
Polymer composition (D) obtained by melt-kneading in the presence of 0.005 to 3 parts by weight of organic peroxide (C) with respect to 100 parts by weight of the total of component (A) and component (B) )When,
It contains ammonium polyphosphate (E), and the content of the ammonium polyphosphate (E) is 5 to 100 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B). It is characterized by being.

  The flame-retardant ethylene copolymer composition according to the present invention is a polymer obtained by melt-kneading an ethylene copolymer (A) and a resin (B) in the presence of an organic peroxide (C). The composition obtained by adding the said ammonium polyphosphate (E) to a composition (D), and melt-kneading may be sufficient. Moreover, the composition obtained by melt-kneading ethylene copolymer (A), resin (B), organic peroxide (C), and ammonium polyphosphate (E) simultaneously may be sufficient. .

In the present invention, the ethylene-vinyl ester copolymer (A1) is preferably an ethylene-vinyl acetate copolymer containing 5 to 50% by weight of vinyl acetate units.
In the present invention, the multi-component propylene copolymer as the resin (B) is a binary copolymer composed of propylene and ethylene, or a ternary copolymer composed of propylene, ethylene and 1-butene. It is also preferred that the multicomponent propylene copolymer as the resin (B) has an initial flexural modulus (ASTM D790) of 1,400 MPa or less.

The flame retardant ethylene copolymer composition according to the present invention may further contain at least one resin selected from the following (F1) to (F3) and / or an elastomer (F). The content of the resin and / or elastomer (F) is 1 to 20 parts by weight (provided that the component (A), with respect to the total 99 to 80 parts by weight of the ethylene copolymer (A) and the resin (B)). The total of component (B) and component (F) is preferably 100 parts by weight), and the content of the resin and / or elastomer (F) is that of the ethylene copolymer (A) and the resin (B). It is also preferable that it is 1-25 weight part with respect to a total of 100 weight part.
(F1) Olefin-based thermoplastic elastomer and graft modified product thereof (F2) Styrenic thermoplastic elastomer and graft-modified product thereof (F3) Graft-modified polyolefin resin.

  The flame-retardant ethylene-based copolymer composition according to the present invention desirably has a tensile strength at break (JIS K6760) of 2 MPa or more and an elongation at break (JIS K6760) of 100% or more. .

In addition, the flame-retardant ethylene copolymer composition according to the present invention preferably has a flexural modulus (JIS K7106) of 100 MPa or less.
In the present specification, the term “elastomer” of “resin and / or elastomer (F)” includes a rubber composed only of a soft segment such as an olefin rubber, a styrene block polymer, and a hydrogenated product thereof. .

  According to the present invention, there is provided an ethylene copolymer composition that retains preferable properties inherently possessed by an ethylene copolymer such as an ethylene-vinyl ester copolymer and has excellent flame retardancy. Can do.

The ethylene copolymer composition according to the present invention can be particularly preferably used for coating materials for camera cables and medical cables that require high flexibility among electric and communication cables.

  The flame-retardant ethylene-based copolymer composition according to the present invention includes an industrial packing, an architectural packing, an industrial sealing material, an architectural sealing material, a vehicle interior material, hoses, in addition to the wire coating material. It can also be widely used for applications that require flame retardancy, such as films, tapes, sheets, and injection molded articles. Moreover, you may use the flame-retardant ethylene-type copolymer composition which concerns on this invention for lamination | stacking with other resin, or lamination | stacking with other raw materials other than resin. The flame-retardant ethylene-based copolymer composition according to the present invention can be coated with a pressure-sensitive adhesive on the surface of the molded product, if necessary.

Hereinafter, the flame retardant ethylene copolymer composition according to the present invention will be described in detail.
The flame-retardant ethylene copolymer composition according to the present invention comprises a specific ethylene copolymer (A), a specific resin (B), an organic peroxide (C), and ammonium polyphosphate (E). And may contain the resin and / or elastomer (F) in a specific ratio.

[Ethylene copolymer (A)]
The ethylene-based copolymer (A) used in the present invention is an ethylene-vinyl ester copolymer (A1), an ethylene-unsaturated carboxylic acid ester copolymer (A2) or an ethylene-unsaturated carboxylic acid copolymer ( A3). These copolymers can be used alone or in combination of two or more. Examples of such combinations include a blend of copolymer (A1) and copolymer (A2), a blend of copolymer (A1) and copolymer (A3), and copolymer (A2). And copolymer (A3) blend, copolymer (A1), copolymer (A2) and copolymer (A3) blend, two or more copolymers (A1) blend Examples thereof include a blend of two or more types of copolymers (A2), a blend of two or more types of copolymers (A3), and the like.

The ethylene-vinyl ester copolymer (A1) is melt flow rate (MFR; JIS).
K7210, 190 ° C., 2160 g load) is 0.1 to 300 g / 10 minutes, preferably 0.2 to 200 g / 10 minutes, more preferably 0.2 to 100 g / 10 minutes. When the MFR of the ethylene-vinyl ester copolymer (A1) is in the above range, the flame retardancy is excellent in workability and excellent in basic physical properties such as tensile strength at break and elongation at break and excellent in heat resistance. An ethylene-based copolymer composition is obtained.

  Specific examples of the vinyl ester component copolymerizable with ethylene in the ethylene-vinyl ester copolymer (A1) include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl persamic acid, vinyl laurate, stearin. Examples include vinyl acid vinyl, vinyl benzoate, vinyl salicylate, and vinyl cyclohexanecarboxylate.

  Specific examples of the ethylene-vinyl ester copolymer (A1) include ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl propionate copolymer, ethylene-n-vinyl butyrate copolymer, ethylene- Persic acid vinyl copolymer, ethylene-vinyl laurate copolymer, ethylene-vinyl stearate copolymer, ethylene-vinyl benzoate copolymer, ethylene-vinyl salicylate copolymer, ethylene-vinyl cyclohexanecarboxylate copolymer A polymer etc. are mentioned.

The ethylene-vinyl ester copolymer (A1) has a constituent unit content derived from ethylene (ethylene unit content) of 95 to 50% by weight, preferably 90 to 54% by weight, more preferably 85 to 60% by weight. In addition, it is desirable that the constituent unit content (vinyl ester component unit content) derived from the vinyl ester component is 5 to 50% by weight, preferably 10 to 46% by weight, and more preferably 15 to 40% by weight. When the ethylene unit content of the ethylene-vinyl ester copolymer (A1) is within the above range, the resulting composition retains preferable physical properties inherently possessed by the ethylene copolymer.

  The ethylene-unsaturated carboxylic acid ester copolymer (A2) has a melt flow rate (MFR; JIS K7210, 190 ° C., 2160 g load) of 0.1 to 300 g / 10 minutes, preferably 0.2 to 250 g / 10 minutes. More preferably, it is 0.5 to 200 g / 10 minutes. When the MFR of the ethylene-unsaturated carboxylic acid ester copolymer (A2) is within the above range, the flame retardancy is excellent in workability and basic physical properties such as tensile strength at break and elongation at break. An ethylene copolymer composition is obtained.

  Specific examples of the unsaturated carboxylic acid ester component copolymerizable with ethylene in the ethylene-unsaturated carboxylic acid ester copolymer (A2) include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, Examples include n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, dimethyl maleate, and diethyl maleate.

  Specific examples of the ethylene-unsaturated carboxylic acid ester copolymer (A2) include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer (EEA), and ethylene-isopropyl acrylate copolymer. , Ethylene-isobutyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-isooctyl acrylate copolymer, ethylene-acrylic acid-2-ethylhexyl copolymer, ethylene-methyl methacrylate copolymer , Ethylene-ethyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, ethylene-dimethyl maleate copolymer, ethylene-diethyl maleate copolymer, and the like.

  The ethylene-unsaturated carboxylic acid ester copolymer (A2) preferably has an ethylene unit content of 99.5 to 40% by weight, more preferably 95 to 50% by weight, more preferably 90 to 60% by weight, The constituent unit content derived from the unsaturated carboxylic acid ester component (unsaturated carboxylic acid ester component unit content) is preferably 0.5 to 60% by weight, more preferably 5 to 50% by weight, more preferably 10 to 40%. % By weight. When the ethylene unit content of the ethylene-unsaturated carboxylic acid ester copolymer (A2) is within the above range, the obtained flame retardant ethylene copolymer composition inherently has the ethylene copolymer. It has desirable physical properties.

  The ethylene-unsaturated carboxylic acid copolymer (A3) has a melt flow rate (MFR; JIS K7210, 190 ° C., 2160 g load) of 0.1 to 300 g / 10 min, preferably 0.2 to 250 g / 10 min. More preferably, it is 0.5-200 g / 10min. When the MFR of the ethylene-unsaturated carboxylic acid copolymer (A3) is within the above range, it is excellent in workability and has excellent basic properties such as tensile strength such as tensile strength at break and elongation at break. A copolymer composition is obtained.

  Specific examples of the unsaturated carboxylic acid copolymerizable with ethylene in the ethylene-unsaturated carboxylic acid copolymer (A3) include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, and anhydrous. Maleic acid, itaconic anhydride, monomethyl maleate, monoethyl maleate and the like can be mentioned.

Specific examples of the ethylene-unsaturated carboxylic acid copolymer (A3) include an ethylene-acrylic acid copolymer (EAA), an ethylene-methacrylic acid copolymer, an ethylene-ethacrylic acid copolymer, and an ethylene-maleic acid. Acid copolymer, ethylene-fumaric acid copolymer, ethylene-itaconic acid copolymer, ethylene-maleic anhydride copolymer, ethylene-itaconic anhydride copolymer, ethylene-monomethyl monomethyl copolymer, ethylene- Mention may be made, for example, of a monoethyl maleate copolymer.

  The ethylene-unsaturated carboxylic acid copolymer (A3) preferably has an ethylene unit content of 99.5 to 40% by weight, more preferably 99 to 50% by weight, more preferably 99 to 60% by weight. The constituent unit content derived from the saturated carboxylic acid component (unsaturated carboxylic acid component unit content) is preferably 0.5 to 60% by weight, more preferably 1 to 50% by weight, more preferably 1 to 40% by weight. is there. When the ethylene unit content of the ethylene-unsaturated carboxylic acid copolymer (A3) is within the above range, the resulting flame-retardant ethylene copolymer composition is preferably inherently possessed by the ethylene copolymer. Has various physical properties.

  These copolymers (A1), (A2), and (A3) may be ternary or higher multi-component ethylene copolymers. In addition to the above-mentioned components capable of copolymerization with ethylene, propylene, butene Unsaturated hydrocarbons such as 1,3-butadiene, pentene, 1,3-pentadiene, 1-hexene, 3-hexene, 1-octene and 4-octene; acid compounds such as vinyl sulfuric acid and vinyl nitric acid; vinyl chloride, Halogen compounds such as vinyl fluoride and vinyl iodide; vinyl group-containing primary and secondary amine compounds and amide compounds; carbon monoxide, sulfur dioxide and the like may be copolymerized with ethylene as a third component.

  Examples of the multi-component ethylene copolymer include ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-vinyl propionate-carbon monoxide copolymer, ethylene-methyl acrylate-carbon monoxide copolymer, ethylene -Ethyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate-carbon monoxide copolymer, ethylene-ethyl methacrylate-carbon monoxide copolymer, ethylene-acrylic acid-carbon monoxide copolymer, Examples thereof include ternary ethylene copolymers such as ethylene-methacrylic acid-carbon monoxide copolymer, ethylene-vinyl acetate-methacrylic acid copolymer, and ethylene-methacrylic acid-isobutyl acrylate copolymer.

  The constituent unit content (third component unit content) derived from the third component in these copolymers is preferably 0.01 to 40% by weight, particularly preferably 0.1 to 30% by weight, and ethylene. The unit content is preferably 95 to 40% by weight, particularly preferably 90 to 50% by weight.

  Preferred ethylene-based copolymers include ethylene-vinyl acetate copolymers (EVA), ethylene-vinyl acetate-carbon monoxide copolymers, ethylene-vinyl acetate copolymers such as ethylene-vinyl acetate-methacrylic acid copolymers, and the like. Polymer (A1); ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-acrylic Ethylene-unsaturated carboxylic acid ester copolymer (A2) such as acid isobutyl copolymer; ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer (EAA), ethylene-isobutyl methacrylate acrylic acid copolymer And an ethylene-unsaturated carboxylic acid copolymer (A3). Among the specific examples of the ethylene-vinyl ester copolymer (A1), an ethylene-vinyl acetate copolymer is particularly preferable.

  The ethylene-based copolymer (A) such as the ethylene-vinyl ester copolymer (A1) is usually 99.9-50 with respect to a total of 100% by weight of the copolymer (A) and the resin (B). % By weight, preferably 95-70% by weight.

[Resin (B)]
The resin (B) used in the present invention is a multi-component propylene copolymer which is a binary or ternary or higher copolymer.

  Specific examples of components other than propylene copolymerizable with propylene in the multi-component propylene copolymer include ethylene, α-olefins having 4 to 12 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-octene and the like can be mentioned. These components can be used alone or in combination of two or more.

  As the multi-component propylene copolymer, specifically, a propylene binary copolymer such as propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / 4-methyl-1-pentene copolymer, Examples thereof include propylene terpolymers such as propylene / 1-butene / ethylene copolymer and propylene / ethylene / styrene copolymer. Among these, a propylene / ethylene copolymer having an ethylene unit content of 1 to 10 mol% in the copolymer, an 1-butene unit content of 1 to 10 mol% in the copolymer, Most preferred is a propylene / 1-butene / ethylene copolymer having an ethylene unit content of 1 to 10 mol%. These copolymers may be random copolymers or block copolymers.

  The structural unit content derived from components other than propylene in the propylene copolymer (the total amount thereof when two or more types are included) is 0.1 to 20 mol%, preferably 0.2 to 18 mol%, More preferably, it is 0.5-15 mol%.

  The resin (B) used in the present invention has a melt flow rate (MFR; ASTM D1238, 230 ° C., 2160 g load) of 0.5 to 50 g / 10 minutes, preferably 1 to 45 g / 10 minutes, more preferably 2 It is desirable that it is ˜40 g / 10 minutes. When the MFR of the resin (B) is within the above range, a flame-retardant ethylene copolymer composition having excellent workability and excellent basic properties such as tensile strength at break and elongation at break can be obtained. .

In addition, although the said multi-component propylene copolymer itself is excellent in heat resistance and a tensile characteristic, it is inferior to a softness | flexibility. Moreover, the composition (uncrosslinked composition) consisting only of the ethylene copolymer (A) such as the ethylene-vinyl ester copolymer (A1) and the resin (B) is inferior in heat resistance and tensile properties.
Moreover, it is preferable that the bending initial elastic modulus (ASTM D790) of the multi-component propylene copolymer which is resin (B) is 1,400 Mpa or less.

  The resin (B) is used in a proportion of 0.1 to 50% by weight, preferably 5 to 30% by weight, based on 100% by weight of the total of the ethylene copolymer (A) and the resin (B). When the resin (B) is used in a proportion within the above range, the ethylene copolymer having excellent heat resistance and flame retardancy as well as maintaining preferable physical properties inherently possessed by the ethylene copolymer (A). A composition (resin composition) is obtained.

[Organic peroxide (C)]
Specific examples of the organic peroxide (C) used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane. 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3 , 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert- Examples include butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, tert-butylperoxy-2-ethylhexanoate, etc. It is.

Among these, in terms of odor and scorch stability, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert- Butylperoxy) hexyne-3
1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) ) Valerate, tert-butylperoxy-2-ethylhexanoate, etc. are preferred, among which 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, tert-butylperoxy-2- Ethyl hexanoate is most preferred.

  The organic peroxide (C) is 0.005 to 3 parts by weight, preferably 0.01 to 2.5 parts by weight based on 100 parts by weight of the total of the ethylene copolymer (A) and the resin (B). It is used in an amount of parts by weight, more preferably 0.01 to 2.0 parts by weight. When the organic peroxide (C) is used in an amount within the above range, a flame retardant ethylene copolymer composition having excellent fluidity and excellent moldability can be obtained.

[Ammonium polyphosphate (E)]
The ammonium polyphosphate (E) used in the present invention is, for example, the following formula (NH) _{n + 2} P _n O _{3n + 1}
(In formula, n is an integer greater than or equal to 2, Preferably it is 20-100.)
It is a compound represented by these.

  Such an ammonium polyphosphate (E) includes, for example, Exolit 422, Exolit 700 (manufactured by Clariant), Sumisafe P (Sumitomo Chemical), Phos-chek P / 30, Phoscheck P / 40 (manufactured by ASTARIS) is commercially available, and microcapsules with melamine resin include, for example, Exolit 462 (manufactured by Clariant), coated with a thermoplastic resin, and a nitrogen-containing compound. Examples of the polymerized products are commercially available under trade names such as Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.), TERAJU C60, TERRAGE C40 (manufactured by Chisso).

  Ammonium polyphosphate (E) is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, and more preferably 25 parts per 100 parts by weight in total of the ethylene copolymer (A) and the resin (B). Used in an amount of ~ 70 parts by weight. When ammonium polyphosphate (E) is used in an amount within the above range, a flame retardant ethylene copolymer composition excellent in flame retardancy can be obtained.

[Inorganic compounds]
In the present invention, an inorganic compound may be added as necessary. Examples of such an inorganic compound include hydroxide, carbonate, silicate, sulfate, and nitride), carbon black, and graphite. .

Specific examples of the hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate.
Specific examples of the carbonate include calcium carbonate, magnesium carbonate, aluminum carbonate, zinc carbonate, barium carbonate, dosonite, and hydrotalcite.

  Specific examples of silicates include magnesium silicate, aluminum silicate, calcium silicate (wollastonite, zonotlite), talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, cerosalite, glass Examples include fibers, glass beads, and silica-based baluns.

Specific examples of the sulfate include calcium sulfate, barium sulfate, and gypsum fiber.
Specific examples of the nitride include aluminum nitride, boron nitride, and silicon nitride.

  As the carbon black, conventionally known carbon black can be used. Specifically, carbon black such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, MT, etc., these carbon blacks as silane coupling agents, etc. And the like that have been surface-treated.

  The surface of the inorganic compound may be coated with higher fatty acids, phosphate esters, various silane coupling agents, metal salts, silicone polymers, etc. in consideration of dispersibility improvement and safety. Two or more kinds of inorganic compounds having different values may be blended.

In the present invention, an inorganic compound imparting flame retardancy may be used as the inorganic compound. As the inorganic compound imparting flame retardancy, conventionally known inorganic flame retardants can be used, specifically,
Magnesium hydroxide, aluminum hydroxide, hydrotalcite, basic magnesium carbonate, calcium carbonate metal silicate;
Examples include boric acid metal salts, silica, alumina, talc, clay, zeolite, and carbon black. The surface of the flame retardant may be coated with higher fatty acids, phosphate esters, various silane coupling agents, metal salts, silicone polymers, etc. in consideration of dispersibility improvement and safety. Two or more types of flame retardants having different values may be blended. Further, brominated flame retardants such as tetrabromobisphenol A and decabromodiphenyl ether and chlorinated flame retardants such as chlorinated paraffin may be used in combination.

  The inorganic compound is 0 to 100 parts by weight, preferably 0 to 80 parts by weight, more preferably 0 to 70 parts by weight, based on 100 parts by weight of the total of the ethylene copolymer (A) and the resin (B). It is used in the ratio. When an inorganic compound is used in the above ratio, a flame-retardant ethylene copolymer composition excellent in heat resistance and flame retardancy can be obtained.

[Resin and / or Elastomer (F)]
Examples of the resin and / or elastomer (F) used as necessary in the present invention include (F1) an olefinic thermoplastic elastomer and a graft modified product thereof, (F2) a styrene thermoplastic elastomer and a graft modified product thereof, (F3) ) Graft-modified polyolefin resin.

  Of the olefinic thermoplastic elastomer and the graft modified product (F1), examples of the olefinic thermoplastic elastomer include ethylene / α-olefin copolymer rubber, propylene / α-olefin copolymer rubber, ethylene / propylene / Diene copolymer rubber, block copolymer obtained by copolymerizing ethylene / propylene copolymer with polypropylene with controlled regularity, vulcanization site monomer in ethylene / methyl acrylate copolymer, ethylene / methyl acrylate copolymer Examples include added terpolymers. The α-olefin is preferably an α-olefin having 3 to 12 carbon atoms.

The graft modified product of an olefinic thermoplastic elastomer is a modified product obtained by modifying the above olefinic thermoplastic elastomer with a graft monomer. Specifically, an unsaturated carboxylic acid or acid anhydride thereof as a graft monomer is an acrylic resin. Examples include acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride and the like. The content of the graft monomer unit in the graft-modified olefinic thermoplastic elastomer is preferably 0.01 to 20% by weight with respect to the graft-modified olefinic thermoplastic elastomer.

  Of the styrenic thermoplastic elastomer and its graft modified product (F2), examples of the styrenic thermoplastic elastomer include styrenic block copolymers and hydrogenated products thereof, specifically, styrene-butadiene-styrene block. Copolymer (SBS), its hydrogenated styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and its hydrogenated styrene-ethylene -A propylene-styrene block copolymer (SEPS), a styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), etc. are mentioned.

  The styrenic thermoplastic elastomer and the graft modified product thereof are modified products obtained by modifying the styrenic thermoplastic elastomer with the above-described graft monomer. The content of the graft monomer unit in the graft-modified styrene thermoplastic elastomer is preferably 0.01 to 20% by weight with respect to the graft-modified styrene thermoplastic elastomer.

  Specific examples of the graft-modified polyolefin resin (F3) include unsaturated carboxylic acid graft-modified polyolefins such as maleic acid graft-modified polyethylene and itaconic acid graft-modified polyethylene; maleic anhydride graft-modified polyethylene and itaconic anhydride graft-modified polyethylene. And silane graft modified polyolefin such as unsaturated carboxylic anhydride graft modified polyolefin such as silane graft modified polyethylene.

  Examples of the graft monomer include those described above. The content of the graft monomer unit in the graft-modified polyolefin is preferably 0.01 to 20% by weight with respect to the graft-modified polyolefin.

  The melt flow rate (MFR; ASTM D1238, 190 ° C., 2160 g load) of the resin and / or elastomer (F) is 0.1 to 300 g / 10 minutes, preferably 0.2 to 250 g / 10 minutes, more preferably 0. It is desirable to be 5 to 200 g / 10 minutes.

The resin and / or elastomer (F) is 1 to 20% by weight, particularly 5 to 15% by weight, with respect to the total 99 to 80% by weight of the ethylene copolymer (A) and the resin (B). It is preferable to use it. The resin and / or elastomer (F) is 1 to 25% by weight, particularly 5 to 20% by weight, based on 100% by weight of the total amount of the ethylene copolymer (A) and the resin (B). It is also preferable to use it.
When the resin and / or elastomer (F) is used in the above ratio, a thermoplastic resin composition having an excellent balance between flexibility and heat resistance can be obtained.

In the present invention, resins or elastomers other than the component (A), the component (B), and the component (F) can be used at the time of preparing the composition as long as the object of the invention is not impaired.
[Other ingredients]
When preparing the flame retardant ethylene copolymer composition according to the present invention, an antioxidant, a light stabilizer, an ultraviolet absorber, a processing aid, a crosslinking aid, a flame retardant aid, if necessary. Additives such as heat stabilizers, silicone oils, copper damage inhibitors, and colorants can be added as long as the object of the present invention is not impaired.

As the antioxidant, any conventionally known phenol-based, sulfur-based or phosphorus-based antioxidant can be blended.
Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl- 4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-isobutyl-4-n-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (Α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-t-butyl-4- Methoxymethylphenol, n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-t-butylphenol) propionate, 2,6-diphenyl-4-octadecyloxyphenol, 2,4-bis- ( n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4,6-tris (3 ', 5'-di-t-butyl -4'-hydroxybenzylthio) -1,3,5-tri Gin, 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,2'-thio-bis- (6 -t-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 2,2'-thio-bis- (6-t-butyl-3-methylphenol), 4,4 '-Thio-bis (6-t-butyl-2-methylphenol), 2,2'-methylene-
Bis- (6-t-butyl-4-methylphenol), 2,2'-methylene-bis- (6-t-butyl-4-ethylphenol), 2,2'-methylene-bis- {4-methyl -6- (α-methylcyclohexyl) -phenol}, 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis (6-nonyl-4-methylphenol) ), 2,2'-methylene-bis- {6- (α-methylbenzyl) -4-nonylphenol}, 2,2'-methylene-bis- {6- (α, α-dimethylbenzyl) -4-nonylphenol }, 2,2'-methylene-bis- (4,6-di-t-butylphenol), 2,2'-ethylidene-bis- (4,6-di-t-butylphenol), 2,2'-ethylidene -Bis- (6-t-butyl-4-isobutylphenol), 4,4'-methylene-bis- (2,6-di-t-butylphenol), 4,4'-methylene-bis- (6-t -Butyl-2-methylphenol), 4,4'-butylidene-bis- (6-t-butyl-2-methyl) Tilphenol), 4,4'-butylidene-bis- (6-t-butyl-3-methylphenol), 4,4'-butylidene-bis- (2,6-di-t-butylphenol), 4,4 '-Butylidene-bis- (3,6-di-t-butylphenol), 1,1-bis- (5-t-butyl-4-hydroxy-2-methylphenyl) -butane, 2,6-di- ( 3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5-t-butyl-4-hydroxy-2-methylphenyl) -butane, bis { 3,3-bis (4′-hydroxy-3′-t-butylphenyl) butyric acid} ethylene glycol ester, di- (3-t-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene, Di- {2- (3′-t-butyl-2′-hydroxy-5′-methylbenzyl) -6-t-butyl-4-methylphenyl} terephthalate, 1,3,5-trimethyl-2,4, 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene 1,3,5-tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (4-t-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris-{(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl} isocyanurate, tetrakis {methylene-3- (3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate} methane and the like.
These phenolic antioxidants can be used alone or in combination of two or more.

Specific examples of phosphorus antioxidants include distearyl-pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,6-diphosphite) -t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) pentaerythritol-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di) -t-butylphenyl) octyl phosphite.
These phosphorus antioxidants can be used alone or in combination of two or more.

Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate,
4,4'-thiobis- (6-tert-butyl-3-methylphenol), dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis ( 3-lauryl thiopropionate).
These sulfur antioxidants can be used alone or in combination of two or more.
Moreover, a phenol type, phosphorus type, or sulfur type antioxidant can be used individually by 1 type or in combination of 2 or more types.
Furthermore, examples of the antioxidant other than the above include 4,6-bis (octylthiomethyl) -o-cresol [trademark IRGSTAB CABLE KV10, manufactured by Ciba Specialty Chemicals Co., Ltd.].

Examples of the light resistant stabilizer include conventionally known light resistant stabilizers such as hindered amine light stabilizers (HALS).
Specifically, as a hindered amine light stabilizer,
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidine) -1,2,3,4-butanetetracarboxylate,
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidine) -1,2,3,4-butanetetracarboxylate,
CHIMASSORB 944 [Trademark; Ciba Specialty Chemicals Co., Ltd.]
FLAMESTAB NOR 116 [Trademark; manufactured by Ciba Specialty Chemicals Co., Ltd., NOR-type hindered amine]
And so on.

  As the ultraviolet absorber, a conventionally known ultraviolet absorber can be used. Specifically, Tinuvin 326 [trademark; manufactured by Ciba Specialty Chemicals Co., Ltd.], Tinuvin 327 [trademark; Ciba Specialty Chemicals] Co., Ltd.], Tinuvin 120 [trademark; Ciba Specialty Chemicals Co., Ltd.], and the like.

  As the processing aid, conventionally known processing aids can be used. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid; barium stearate, zinc stearate, calcium stearate, etc. And salts of higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid.

  As the crosslinking aid, conventionally known crosslinking aids can be used. Specifically, quinone oximes such as p-quinonedioxime and p, p-dibenzoylquinoneoxime; lauryl (meth) acrylate, ethylene (Meth) acrylates such as glycol acrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triethylene glycol dimethacrylate; allyls such as diallyl fumarate, triallyl cyanurate, triallyl isocyanurate (TAIC), diallyl phthalate Maleimides such as maleimide and phenylmaleimide; sulfur, maleic anhydride, itaconic acid, divinylbenzene, vinyltoluene, 1,2-polybutadiene and the like.

As the flame retardant aid, a conventionally known flame retardant aid can be used. Specifically, antimony trioxide, red phosphorus, fatty acid metal salt, zinc borate, triazine compound, expanded graphite, phosphate ester, phosphorus Examples thereof include acid salts and isobutylene-maleic anhydride copolymers.
A conventionally well-known silicone can be used as a silicone oil.
A conventionally known copper damage inhibitor can be used as the copper damage inhibitor.

As the colorant, conventionally known colorants such as inorganic pigments, organic pigments, and dyes can be widely used. Specifically, azo pigments, nitroso pigments, basic dyes, acid dyes, mordant dyes and other lakes, phthalocyanine pigments, organic fluorescent pigments and other organic pigments, aluminum powder, titanium oxide, zinc white, precipitated silica, carbon black , Inorganic pigments such as cadmium red, ultramarine, and red bean. These may be used alone or in combination of two or more.

[Flame-retardant ethylene copolymer composition]
The flame retardant ethylene copolymer composition according to the present invention includes, for example, an ethylene copolymer (A), a resin (B), an organic peroxide (C), and optionally a resin and / or elastomer. (F) is melt-kneaded to prepare a polymer composition (D), and then ammonium polyphosphate (E) and the above-mentioned additives are added to the polymer composition (D) and melt-kneaded. The ethylene copolymer (A), the resin (B), the organic peroxide (C), the ammonium polyphosphate (E), the resin and / or the elastomer (F), the additives described above It is also possible to produce in one step by melt kneading.

  Specifically, two components of ethylene copolymer (A) and resin (B), or three components of ethylene copolymer (A), resin (B), resin and / or elastomer (F) or The polymer composition (D) is prepared by melt-kneading (dynamic heat treatment) under temperature conditions where the four components are melted and the organic peroxide (C) is sufficiently decomposed. The polymer composition (D) can be produced by adding ammonium polyphosphate (E) and the above-mentioned additives and melt-kneading them. Further, the ethylene copolymer (A), the resin (B), the organic peroxide (C), the ammonium polyphosphate (E), the resin and / or the elastomer (F), and the above-described additives are added to the resin component. It can be produced by melting and kneading (dynamic heat treatment) under a temperature condition that melts and the organic peroxide (C) is sufficiently decomposed. In the flame-retardant ethylene polymer composition thus obtained, at least one of the ethylene copolymer (A) and the resin (B) is partially or completely crosslinked.

  Examples of the melt kneading apparatus used at this time include a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader, and a roll. Among these, it is particularly preferable to use a single screw or twin screw extruder. The melt-kneading is usually performed at a temperature of 130 to 250 ° C. for 30 seconds to 15 minutes.

  The melt flow rate (JIS K7210, 190 ° C., 2160 g load) of the flame retardant ethylene copolymer composition according to the present invention obtained as described above is usually 0.01 to 30 g / 10 min, preferably 0.01 to 15 g / 10 min, more preferably 0.01 to 5 g / 10 min.

The flame-retardant ethylene copolymer composition according to the present invention preferably has a UL flame resistance test result of a level of V-2 (thickness 3 mm) or more, that is, V-2 to V-0.
The flame-retardant ethylene-based copolymer composition according to the present invention has a tensile strength at break (JIS K6760) of 2 MPa or more, preferably 5 MPa or more, and an elongation at break (JIS K6760) of 100% or more. Preferably, it is desirable that it is 300% or more.

Further, it is desirable that the flexural rigidity (JIS K7106) is 100 MPa or less, preferably 80 MPa or less.
Furthermore, in the flame-retardant ethylene copolymer composition according to the present invention, in the heat resistance test (JIS K7121, JIS K6301 No. 3 dumbbell, 1 mm thickness) 120 ° C. × 96 hours, the test piece does not deform at all by visual observation. Alternatively, it is preferable that a slight deformation is observed. Note that the slight deformation means that the test piece does not expand or contract and that the surface of the test piece has some unevenness.

The flame retardant ethylene-based copolymer composition according to the present invention is excellent in heat resistance, flame retardancy, etc., and is a coating material for electric wires and communication cables, particularly for camera cables and medical cables that require high flexibility. Suitable as a coating material. A covered electric wire can be formed by the conventionally well-known extrusion coating molding method, for example using the flame-retardant ethylene-type copolymer composition which concerns on this invention.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.

The tests, evaluations, and measurements of heat resistance, flame retardancy, tensile properties, flexural rigidity, and workability performed in Examples and Comparative Examples were performed according to the following methods.
(1) Tensile test A tensile test was conducted according to JIS K6301 (No. 3 dumbbell, 1 mm thickness, tensile speed 200 mm / min) to determine the tensile strength at break and the elongation at break.

(2) Flexural rigidity Measured according to JIS K7106.
(3) Heat resistance test According to JIS K7212 (JIS K6301 No. 3 dumbbell, 1 mm thickness), the test piece was set in an oven, heated at 120 ° C. for 96 hours and allowed to cool naturally, and its shape retention state was visually observed. Then, the presence or absence of powdering, cracks, cracks, and deformation was confirmed, and the heat resistance was evaluated according to the following three-stage evaluation criteria.
<Evaluation criteria for heat resistance>
○: No deformation at all Δ: Some deformation was observed ×: The original was not retained, or dropped in the oven.

(4) Evaluation of flame retardancy The evaluation method described in the UL94 flame resistance test standard was followed (manufactured by Suga Test Instruments Co., Ltd.). The thickness of the test piece was 1 mm.
The evaluation of flame retardancy was judged in light of the following required levels. In the present invention, V-2 was also evaluated as rejected.
V-0: A: The flammable combustion time of each test is 10 seconds or less. B: The total flammable combustion time of 5 specimens is 50 seconds or less. C: Do not burn flame or flamelessly until the clamp. Do not ignite E ... Second flameless combustion time is 30 seconds or less V-1: A ... Each flame combustion time is 30 seconds or less B ... Total flame combustion time of 5 test pieces is 250 seconds or less C, D ... Same as V-0 E ... Second flameless combustion time is 60 seconds or less V-2: A, B, C, E ... Same as V-1 D ... Lower cotton ignition OK
V-2 out: those which did not correspond to any of the above The components used in Examples and Comparative Examples are as follows.

[Ethylene copolymer (A)]
Ethylene / vinyl acetate copolymer (EVA)
Vinyl acetate unit content = 33% by weight
MFR (JIS K7210-1999, 190 ° C, 2160 g load) = 14 g / 10 min [Resin (B)]
Ternary propylene random copolymer Propylene unit content = 93.5 mol%
Ethylene unit content = 3.0 mol%
Butene unit content = 3.5 mol%
MFR (ASTM D1238, 230 ° C., 2160 g load) = 7.2 g / 10 min. Initial flexural modulus (ASTM D790) = 720 MPa
[Organic peroxide (C)]
t-Butylperoxy-2-ethylhexanoate (manufactured by Atofina Yoshitomi)
[Ammonium polyphosphate (E)]
Exolit AP-750 (manufactured by Clariant)
(G): Ethylene / vinyl acetate copolymer, vinyl acetate unit content = 28 wt%, MFR = 1 g / 10 min (H): Magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., trade name: Kisuma 5A).
(I): A maleic anhydride-modified ethylene / vinyl acetate copolymer having a vinyl acetate concentration of 33% by weight, MFR = 6.0 g / 10 min, and a maleic anhydride concentration of 1% by weight was prepared and used.

  80 parts by weight of an ethylene copolymer (A), 20 parts by weight of a resin (B), 0.2 parts by weight of an organic peroxide (C), an antioxidant (tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane, trade name: Irganox 1010, manufactured by Ciba Specialties Co., Ltd.) 0.2 part by weight, Using a single screw extruder having an L / D of 28, a polymer composition (D) in which at least one of the component (A) and the component (B) is at least partially crosslinked is melt-kneaded at a resin temperature of 200 ° C. Obtained.

  Next, 100 parts by weight of the polymer composition (D) obtained as described above (that is, 99.6 parts by weight of the total amount of (A) and (B)) and ammonium polyphosphate (E) 45 After blending with parts by weight with a Henschel mixer, using a pressure kneader, melt-kneaded at a resin temperature of 160 ° C., sheeted with a roll, and pelletized to obtain flame retardant ethylene copolymer composition pellets. .

Next, the pellet of the composition obtained as described above was press-molded for 10 minutes under the condition of a pressure of 100 kg / cm ² (gauge pressure) in a press molding machine in which the hot plate temperature was set to 160 ° C. A predetermined press sheet was produced.

Flame retardant ethylene in the same manner as in Example 1 except that 100 parts by weight of the polymer composition (D) was blended with 45 parts by weight of ammonium polyphosphate (E) and 10 parts by weight of maleic anhydride-modified EVA (I). Pellets and press sheets of the system copolymer composition were obtained.
[Comparative Example 1]
Flame retardant ethylene-based polymer as in Example 1, except that 100 parts by weight of the polymer composition (D) was not blended with ammonium polyphosphate (E) and 200 parts by weight of magnesium hydroxide (H) was blended. A pellet and a press sheet of the copolymer composition were obtained.
[Comparative Example 2]
After blending 100 parts by weight of ethylene / vinyl acetate copolymer (G) and 45 parts by weight of ammonium polyphosphate (E) with a Henschel mixer, it was melt-kneaded at a resin temperature of 160 ° C. using a pressure kneader, After the sheeting, pelletizing was performed to obtain pellets of the flame retardant ethylene copolymer composition.

Next, using the pellets of the composition obtained as described above, a press sheet was produced in the same manner as in Example 1.
The heat resistance of each press sheet obtained as described above was evaluated according to the above method. Moreover, the tensile strength at break, tensile elongation at break, and bending rigidity were determined according to the above methods as basic physical properties. These results are shown in Table 1.

Claims (11)

An ethylene-vinyl ester copolymer (a1) having a melt flow rate (JIS K7210, 190 ° C., 2160 g load) of 0.1 to 300 g / 10 min, and a melt flow rate (JIS K 7210, 190 ° C., 2160 g load) of 0 An ethylene-unsaturated carboxylic acid ester copolymer (a2) having a viscosity of 1 to 300 g / 10 min, and an ethylene having a melt flow rate (JIS K7210, 190 ° C., 2160 g load) of 0.1 to 300 g / 10 min. 99.9 to 50% by weight of at least one ethylene copolymer (A) selected from unsaturated carboxylic acid copolymer (a3);
Resin (B) 0.1 to 50% by weight (provided that component (A) and component (B ) Is 100% by weight)
Polymer composition (D) obtained by melt-kneading in the presence of 0.005 to 3 parts by weight of organic peroxide (C) with respect to 100 parts by weight of the total of component (A) and component (B) )When,
It contains ammonium polyphosphate (E), and the content of the ammonium polyphosphate (E) is 5 to 100 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B). A flame retardant ethylene copolymer composition, wherein   To the polymer composition obtained by melt-kneading the ethylene copolymer (A) and the resin (B) in the presence of the organic peroxide (C), the ammonium polyphosphate (E) is added and melted. The flame-retardant ethylene copolymer composition according to claim 1, wherein the flame-retardant ethylene copolymer composition is obtained by kneading.   It is obtained by melt-kneading ethylene copolymer (A), resin (B), organic peroxide (C), and ammonium polyphosphate (E) simultaneously. The flame retardant ethylene copolymer composition described.   The ethylene-vinyl ester copolymer (A1) is an ethylene-vinyl acetate copolymer containing a vinyl acetate unit in a proportion of 5 to 50% by weight. The flame retardant ethylene copolymer composition described.   The multi-component propylene copolymer as the resin (B) is a binary copolymer composed of propylene and ethylene, or a ternary copolymer composed of propylene, ethylene and 1-butene. Item 5. The flame retardant ethylene copolymer composition according to any one of Items 1 to 4. The flame-retardant ethylene-based system according to any one of claims 1 to 5, wherein the multicomponent propylene copolymer as the resin (B) has an initial flexural modulus (ASTM D790) of 1,400 MPa or less. Copolymer composition. Furthermore, it contains at least one resin selected from the following (F1) to (F3) and / or an elastomer (F), and the content of the resin and / or elastomer (F) is an ethylene copolymer (A). And 1 to 20 parts by weight (provided that the total of the ethylene copolymer (A), resin (B) and component (F) is 100 parts by weight) with respect to 99 to 80 parts by weight in total of the resin (B) The flame-retardant ethylene copolymer composition according to any one of claims 1 to 6, wherein
(F1) Olefin-based thermoplastic elastomer and graft modified product thereof (F2) Styrenic thermoplastic elastomer and graft-modified product thereof (F3) Graft-modified polyolefin resin. Furthermore, it contains at least one resin selected from the following (F1) to (F3) and / or an elastomer (F), and the content of the resin and / or elastomer (F) is an ethylene copolymer (A). The flame retardant ethylene copolymer composition according to any one of claims 1 to 6, wherein the content is 1 to 25 parts by weight with respect to 100 parts by weight of the total of the resin (B); ) Olefin-based thermoplastic elastomer and its graft modified product (F2) Styrenic thermoplastic elastomer and its graft-modified product (F3) Graft-modified polyolefin resin.   The flame retardancy according to any one of claims 1 to 8, wherein the tensile strength at break (JIS K6760) is 2 MPa or more and the elongation at break (JIS K6760) is 100% or more. Ethylene copolymer composition.   The flame-retardant ethylene-based copolymer composition according to any one of claims 1 to 9, wherein a flexural rigidity (JIS K7106) is 100 MPa or less.   Heat resistance test (JIS K7121, JIS K6301 No. 3 dumbbell, 1 mm thickness) At 120 ° C. × 96 hours, the test piece is in a state in which the test piece is not deformed at all or is slightly deformed. The flame-retardant ethylene copolymer composition according to any one of 1 to 10.