JPH07173338A - Cross-linkable highly flame retardant composition - Google Patents

Abstract

PURPOSE:To obtain a composition useful as an extrusion molded article such as film or sheet, having excellent flexibility, mechanical characteristics, flame retardancy, etc., by mixing a cross-linkable C-C unsaturated bond-containing ethylene copolymer with an ionomer resin and a flame retardant. CONSTITUTION:This composition comprises (A) 100 pts.wt. of a polymer component containing (i) 95-5wt.% of a C-C unsaturated bond-containing ethylene copolymer [e.g. an ethylene-allyl (meth)acrylate copolymer or an ethylene-vinyl (meth)acrylate copolymer] and (ii) 5-95wt.% of an ionomer resin (preferably an ethylenic ionomer resin), (B) 5-200 pts.wt. of a frame retardant (e.g. and addition type flame retardant such as a halogen-based, a phosphorus-based or an inorganic flame retardant) and preferably (C) 0.1-20 pts.wt. of red phosphorus.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a crosslinkable highly flame-retardant composition, and more particularly to an ethylene copolymer having a crosslinkable carbon-carbon unsaturated bond (hereinafter abbreviated as ethylene copolymer), An ionomer resin and a flame retardant, or a crosslinkable highly flame-retardant composition further containing red phosphorus, which maintains flexibility, mechanical properties, chemical resistance, and processability,
The present invention also relates to a crosslinkable highly flame-retardant composition that retains a high degree of flame retardancy.

[0002]

2. Description of the Related Art Polyethylene resins are excellent in physical and chemical properties, and are therefore formed into films, sheets, pipes, containers, electric wires, cables, etc. by various molding methods such as extrusion molding and injection molding. It is the most popular general-purpose resin used in many applications for household and industrial applications. Since the above-mentioned polyethylene resin is flammable, various methods for making it flame-retardant have been conventionally proposed. The most general method is to add flame retardant to the polyethylene resin by adding an organic flame retardant such as halogen or phosphorus.

As another method, a hydrate of an inorganic metal compound such as aluminum hydroxide or magnesium hydroxide is effective as a non-polluting flame retardant which does not generate a harmful gas during combustion, has a low smoke property and is a pollution-free type. It is well known that they exist (Japanese Unexamined Patent Publication Nos. 2-53845 and 2-145632). However, in a flame-retardant composition using an inorganic flame retardant, it is necessary to highly fill the inorganic flame retardant in order to enhance the flame retardancy. However, increasing the filling amount not only lowers mechanical strength, flexibility, and workability, but also
Since it has the drawback of significantly impairing wear resistance, it is susceptible to external damage due to vibration and friction under high temperature and severe conditions during manufacturing, wiring / assembling, transportation, and normal use, and it also has flame retardancy. It cannot be applied to electrical insulating materials such as electric wires and cables that require abrasion resistance, electrical materials such as protective tubes and joint covers, interior materials such as sheets and floor materials, and molded products such as cabinets and boxes. There is a problem. In order to solve these problems, a technique of cross-linking in the presence of a cross-linking aid (Japanese Patent Application Laid-Open No. 6-58242).
No. 2-252442, JP-A No. 62-275139), a method using an ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid or a derivative thereof (JP-A No. 62-10149), a polyolefin. A method of using as a base polymer a mixture obtained by mixing an ethylene-based resin containing a carboxyl group or a carboxylate salt in the molecule with a thermoplastic elastomer in which maleic acid or maleic anhydride is added in the molecule (JP-A-2-53845).
Gazette) is disclosed. However, all of them still have problems such as insufficient wear resistance, heat resistance and flame retardancy.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a molded article which satisfies the above requirements, maintains flexibility, mechanical properties, chemical resistance, workability, and retains a high degree of flame retardancy. The present invention provides a crosslinkable highly flame-retardant composition, which is used for molding applications such as films, sheets, containers, electric wires, cables, packings, sealants, hoses, and injection products. is there.

[0005]

The first invention of the present invention comprises: (I) (A) an ethylene copolymer having a carbon-carbon unsaturated bond: 95 to 5% by weight (B) an ionomer resin: 5 to 95% by weight % Of the polymer component containing 100% by weight of (II) a flame retardant of 5 to 200 parts by weight.

A second invention of the present invention is (I) a polymer containing (A) an ethylene copolymer having a carbon-carbon unsaturated bond in an amount of 95 to 5% by weight, and (B) an ionomer resin in an amount of 5 to 95% by weight. A crosslinkable highly flame-retardant composition comprising (II) 5-200 parts by weight (III) red phosphorus 0.1-20 parts by weight per 100 parts by weight of the component.

The present invention will be described in detail below. The ethylene copolymer having a carbon-carbon unsaturated bond of the component (A) in the present invention means ethylene, a monomer having two or more carbon-carbon unsaturated bonds and, if desired, another unsaturated monomer. Copolymer consisting of polymer, ethylene homopolymer, linear low density polyethylene (LLDPE), ultra low density polyethylene (VLDPE), ethylene-propylene copolymer rubber (EPR), ethylene-propylene-diene copolymer Rubber (EPDM), copolymers of ethylene and other α-olefins, ethylene-vinyl acetate copolymers,
It includes an ethylene polymer such as ethylene- (meth) acrylic acid or an alkyl ester copolymer thereof, which is obtained by addition-polymerizing a monomer having two or more carbon-carbon unsaturated bonds.

The above-mentioned monomer having two or more carbon-carbon unsaturated bonds means allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, divinyltoluene, 1,5-hexadiene-3-yne. , Divinyl compounds such as hexatriene, divinyl ether and divinyl sulfone, polyfunctional methacrylate monomers represented by trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triallyl isocyanurate, diallyl phthalate, vinyl butyrate Polyfunctional vinyl monomers such as phthalates, allyl phthalate, diallyl compounds such as 2,6-diacrylphenol and diallyl carbinol, and other allyl styrene, divinyl styrene, 5
-Vinyl-2-norbornene (VBH), 5-ethylidene-2-norbornene (EBH), vinylcyclohexene (VCH), allyl (meth) acrylate, vinyl (meth) acrylate.

Other unsaturated monomers copolymerizable with the above-mentioned ethylene and monomers having two or more carbon-carbon unsaturated bonds are α-olefins such as propylene and 1-butene,
Styrene or its derivatives, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, and (meth) acrylic acid-
Methyl, -ethyl, -propyl, -isopyropyr, -n
Alkyl esters such as -butyl, -cyclohexyl, -lauryl, -stearyl, maleic acid monomethyl ester, maleic acid dimethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, (meth) acrylic acid glycidyl, etc. Examples thereof include unsaturated carboxylic acid esters, vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluorate, and other vinyl esters. Among these, (meth) acrylic acid alkyl ester and vinyl ester are particularly preferable. More specifically, ethyl acrylate, methyl methacrylate and vinyl acetate can be mentioned.

Specific examples of the ethylene copolymer having a carbon-carbon unsaturated bond as the component (A) include ethylene-
Allyl (meth) acrylate copolymer, ethylene-vinyl (meth) acrylate copolymer, ethylene-allyl (meth) acrylate-vinyl acetate copolymer, ethylene-allyl (meth) acrylate-vinyl acetate copolymer Combined, ethylene-allyl (meth) acrylate- (meth) acrylic acid ester copolymer, ethylene-vinyl vinyl (meth) acrylate-
Examples thereof include vinyl acetate copolymers and ethylene- (meth) acrylic acid vinyl- (meth) acrylic acid ester copolymers. These copolymers are preferably those produced by a high pressure radical polymerization method, but are not particularly limited thereto.

The ethylene copolymer of the present invention includes 70 to 99.99% by weight of ethylene, 0.01 to 30% by weight of a monomer having two or more carbon-carbon unsaturated bonds, and another unsaturated group. Copolymers consisting of 0 to 29.99% by weight of monomers are preferred. When the amount of the monomer having two or more carbon-carbon unsaturated bonds is less than 0.01, the degree of crosslinking due to irradiation with ionizing radiation is low, and when it exceeds 30% by weight, gel is generated due to thermal crosslinking in the processing step. May cause harmful effects. The type and amount of the other unsaturated monomer are appropriately selected so as to impart other properties such as flexibility of the copolymer.

The component (B) in the present invention is an olefinic ionomer resin, which uses the olefin / α, β-unsaturated carboxylic acid copolymer (1) as a base resin, and all or part of its carboxyl groups, Usually, it is an ionomer resin in which 5 to 100% is neutralized with metal ions. Among the olefin-based ionomer resins, the ethylene-based ionomer resin is particularly preferable.

The proportion of the olefin units in the copolymer (1) is usually about 75 to 99.5 mol%, preferably 88 to 98 mol%, and the proportion of the α, β-unsaturated carboxylic acid units is , Usually 0.5 to 15 mol%, preferably 1 to 6 mol%.

When the copolymer (1) is neutralized to form the olefinic ionomer resin (B), among the carboxylic acid groups in the copolymer, the carboxylic acid groups which are neutralized by metal ions are The proportion (neutralization degree) is usually 5 to 100%, but in order to obtain a composition having particularly excellent mechanical properties, a neutralization degree of 15 to 100%, particularly 40% or more is used. Is preferred.

Examples of the olefin constituting the above copolymer include α-olefins such as ethylene, propylene, 1-butene, 4-methylpentene-1,1-hexene, 1-octene and 1-dodecene. However, among these, ethylene and propylene are particularly preferable. Examples of the α, β-unsaturated carboxylic acid constituting the above-mentioned copolymer include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, maleic anhydride and the like, which have 3 to 8 carbon atoms and are unsaturated carboxylic acids. Acids are used, of which acrylic acid and methacrylic acid are particularly preferable.

The copolymer is an olefin, α, β-
It may be a terpolymer containing an ester of α, β-unsaturated carboxylic acid or a vinyl ester as the third component in addition to the unsaturated carboxylic acid. Α, β- which is the third component
Examples of the unsaturated carboxylic acid ester include α, β-unsaturated having 4 to 8 carbon atoms such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, butyl methacrylate, and dimethyl fumarate. Carboxylic acid esters are preferably used, and acrylic acid and methacrylic acid esters are particularly preferred. As vinyl ester, vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate,
The vinyl esters such as vinyl stearate and vinyl trifluorate may be mentioned. The proportion of α, β-unsaturated carboxylic acid ester units and vinyl ester units in the copolymer is usually 0 to 10 mol%, preferably 0 to 6 mol%.

The metal ion for neutralizing the carboxylic acid group of the ethylene copolymer is a metal ion having a valence of 1 to 3, particularly I and I in the periodic table of elements.
A metal ion having a valence of 1 to 3 of group I, III, IVA and VIII, specifically Na ⁺ , K
⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , Hg ⁺ , Cu ⁺ , B
e ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Sr ⁺⁺ , Ba ⁺⁺ , Cu ⁺⁺ , Cd
⁺⁺ , Hg ⁺⁺ , Sn ⁺⁺ , Pb ⁺⁺ , Fe ⁺⁺ , Co ⁺⁺ , N
i ⁺⁺ , Zn ⁺⁺ , Al ⁺⁺⁺ , Sc ⁺⁺⁺ , Fe ⁺⁺⁺ , Y ⁺⁺⁺
And so on. These metal ions may be a mixed component of two or more kinds, and may be a mixed component with an ammonium ion. Of these metal ions, Zn ⁺⁺ and Na ⁺ are particularly preferable.

The melt flow rate (190 ° C.) of the olefinic ionomer resin (B) used in the present invention, measured according to ASTM D 1238, is usually 0.1 to 10.
1000 dg / min, preferably 0.1-30 dg / min,
It is particularly preferably in the range of 0.1 to 10 dg / min.

The olefinic ionomer resin (B) used in the present invention may be modified with a diamine, a polyamide oligomer, an epoxy group-containing olefin polymer or the like for the purpose of improving heat resistance and the like.

The blending ratio of the component (A) and the component (B) in the polymer component (I) is 95 to 5% by weight of the component (A),
The component (B) is selected in the range of 5 to 95% by weight. (A)
If the blending ratio of the components is less than 5% by weight, the crosslinkability, abrasion resistance and heat resistance will be insufficient. On the other hand, when it exceeds 95% by weight, gelation proceeds, resulting in a fear that mechanical strength and the like decrease.

As the flame retardant which is the component (II) of the present invention, addition type flame retardants such as halogen flame retardants, phosphorus flame retardants, inorganic flame retardants and the like can be used. As a halogen-based flame retardant, tetrabromobisphenol A (TB
A), hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TBE), tetrabromobutane (TBB), hexabromocyclodecane (HBC
D) and other bromine and chlorinated paraffin, chlorinated polyphenyl, chlorinated diphenyl, perchloropentacyclodecane, chlorinated naphthalene and other chlorinated compounds are listed, and more effective when used in combination with antimony trioxide. To do.

Further, as the phosphorus-based flame retardant, tricresyl phosphate, tri (β-chloroethyl) phosphate, tri (dichloropropyl) phosphate, tri (dibromopropyl) phosphate, 2,3-dibromopropyl-2,3 A phosphoric acid ester such as chloropropyl phosphate or a halogenated phosphoric acid ester is mainly mentioned.

As the inorganic flame retardant, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite,
Calcium hydroxide, barium hydroxide, tin oxide hydrate, hydrates of inorganic metal compounds such as borax, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate-calcium carbonate, calcium carbonate, barium carbonate ,
Examples thereof include magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide and red phosphorus. These may be used alone or in combination of two or more. Among these, hydrates of at least one metal compound selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, and hydrotalcite, especially aluminum hydroxide and water. Magnesium oxide has a good flame retardant effect and is economically advantageous. The particle size of these inorganic flame retardants varies depending on the type, but in the above aluminum hydroxide, magnesium hydroxide, etc., the average particle size is preferably 20 μm or less, more preferably 10 μm or less.

When a halogen type flame retardant or a phosphorus type flame retardant is selected as the flame retardant, 5 to 50 parts by weight, preferably 100 parts by weight of the polymer component (I) of these flame retardants (II) are used. 6 to 40 parts by weight. If the blending amount of these flame retardants is less than 5 parts by weight, it is difficult to make the flame retardant to a high degree. On the other hand, if the blending amount exceeds 50 parts by weight, the flame retarding is not improved so much and it becomes uneconomical. On the other hand, when an inorganic flame retardant is selected as the flame retardant, the inorganic flame retardant is 30 to 200 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the polymer component (I). If the blending amount of the inorganic flame retardant is less than 30 parts by weight, it is difficult to make the flame retardant sufficient with the inorganic flame retardant alone, and therefore it is necessary to use the organic flame retardant together.
On the other hand, when the amount is more than 200 parts by weight, the abrasion resistance is poor, the mechanical strength is lowered such as the impact strength is lowered, the flexibility is lost, and the low temperature characteristics are poor. When an inorganic flame retardant is selected as the flame retardant, there is an advantage that no toxic gas such as halogen gas is generated when burning.

In the present invention, red phosphorus (II
By blending I), it is possible to provide a highly flame-retardant composition having higher flame retardancy. (I of the present invention
As the red phosphorus as the component II), it is desirable to use red phosphorus coated with an organic and / or inorganic compound.

Red phosphorus coated with an organic and / or inorganic compound means that the surface of red phosphorus particles is coated with a thermosetting resin such as epoxy resin, phenol resin, polyester resin, silicone resin, polyamide resin or acrylic resin. Those coated with aluminum hydroxide, zinc, magnesium, etc., and further coated with the thermosetting resin, metal phosphide and then coated with a thermosetting resin, titanium,
Examples include modified red phosphorus such as those coated with a metal complex hydrated oxide such as cobalt or zirconium.

The red phosphorus preferably has an average particle size of 5 to 30 μm, and the content of particles having a particle size of 1 μm or less and 100 μm or more is 5% by weight or less. In the case of complex hydrated oxides such as titanium-cobalt type, Ti + C per total weight of red phosphorus particles
The metal component such as o is preferably 0.5 to 15% by weight, and the organic resin is preferably 0.1 to 20% by weight based on the total weight.

These modified red phosphorus are excellent in heat resistance stability and hydrolysis resistance, and the hydrolysis reaction in the presence of water or at high temperature is almost completely suppressed. Does not occur. Red phosphorus (III) above
The compounding amount is 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight based on 100 parts by weight of the polymer component (I) and 5 to 200 parts by weight of the component (II). If the compounding amount of the red phosphorus is less than 0.1 part by weight, the effect of addition is small, and
Addition of an amount in excess of parts by weight does not further improve the flame retardant effect, and is not preferable in terms of physical properties and economy.

In the present invention, the amount of the flame retardant compounded can be reduced and other properties can be imparted by using the composition and the inorganic filler in combination. Examples of the inorganic filler include calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black. , Mica, glass plate, sericite, pyrophyllite, aluminum flakes, graphite, silas paloon, metal paloon, glass paloon, pumice stone, glass fiber, carbon fiber, whiskers, metal fiber, graphite fiber, silicon carbide fiber, asbestos, Wollastonite and the like can be mentioned. These compounding agents are applied up to about 100 parts by weight per 100 parts by weight of the composition of the present invention. If the blending amount exceeds 100 parts by weight, mechanical properties such as impact strength of the molded product deteriorate, which is not preferable.

In the present invention, when a flame retardant or an inorganic filler is used, the surface of the flame retardant or the filler is a fatty acid such as stearic acid, oleic acid or palmitic acid or a metal salt thereof, paraffin, It is preferable to apply a surface treatment such as coating with wax, polyethylene wax or a modified product thereof, organic silane, organic borane, organic titanate and the like.

Mineral oils, waxes, paraffins, higher fatty acids and their esters, amides or metal salts, silicones, partial fatty acid esters of polyhydric alcohols or fatty acid alcohols, fatty acids, to the extent that the physical properties of the composition of the present invention are not impaired. Scratch-whitening inhibitors such as fatty acid amides, alkylphenols or alkylnaphthol alkylene oxide adducts may be added.

The method of crosslinking the composition of the present invention is not particularly limited, and a crosslinking method using an organic peroxide, a method of irradiating with high-energy radiation such as electron beam, β ray, γ ray and the like. Any method such as a water crosslinking method using a silane compound may be used. The gel fraction of the flame-retardant composition after crosslinking is preferably 50% or more. If it is 50% or less, the effect of improving heat resistance and flame retardancy becomes insufficient. The larger the gel fraction, the larger the effect of improving wear resistance, heat resistance, flame retardancy, etc., and therefore it is preferable. As the cross-linking agent used in the present invention, a cross-linking agent by a free radical mechanism such as organic peroxide, a dicumyl compound, a cross-linking agent of natural or synthetic rubber such as sulfur or a sulfur compound, a silane compound, a dihydro compound, etc. may be used. it can.

Examples of the organic peroxide include hydroperoxide, dicumyl peroxide, t-butylcumyl peroxide, dialkyl (allyl) peroxide, diisopropylbenzene hydroperoxide, dipropionyl peroxide, dioctanoyl. Peroxide, benzoyl peroxide, peroxysuccinic acid, peroxyketal, 2,5-dimethyl-2,
5 Di (t-butylperoxy) hexane, t-butyloxyacetate, t-butylperoxyisobutyrate and the like are preferably used.

As the dihydroaromatic compound, dihydroquinoline or its derivative, dihydrofuran, 1,2-
Dihydrobenzene, 1,2-dihydronaphthalene, 9,
10-dihydrophenanthrene and the like can be mentioned.

Specific examples of the dicumyl compound include 2,
3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-di (p-methylphenyl) butane, 2,3-diethyl-2,3-di (p-bromo Examples thereof include phenyl) butane, and particularly 2,3-diethyl-2,3-diphenylbutane is preferably used.

The amount of these crosslinking agents added is such that the gel fraction is 50.
% Or more. Generally, composition 1
It is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 00 parts by weight.

The method for producing the crosslinkable highly flame-retardant composition of the present invention is not particularly limited, and it can be produced by a known method. For example, a polymer component (I) composed of the component (A) and the component (B), a flame retardant as the component (II), or red phosphorus as the component (III) may be added, and a crosslinking agent or Crosslinking aids, inorganic fillers, additives and the like are blended, and these are dry blended with an ordinary tumbler or the like, or ordinary Banbury mixer, pressure kneader, kneading extruder, twin-screw extruder, roll, etc. It is melt-kneaded by a kneader and uniformly dispersed to produce a mixture of resin compositions or a molded product made of them, and then crosslinked by heating, water-crosslinking in warm water, or electron beam or high energy radiation. May be irradiated to crosslink. The crosslinked product may be obtained at the same time as producing a mixture of resin compositions or a molded product made of them by melt-kneading and uniformly dispersing with a usual kneader.

[0038]

The composition of the present invention comprises polymer components (I) and (II) consisting of an ethylene copolymer having a carbon-carbon unsaturated bond as the component (A) and an ionomer resin as the component (B). A crosslinkable highly flame-retardant composition comprising a flame retardant, or (III) component red phosphorus, and an additive compounded as necessary, wherein (A) an ethylene copolymer having a carbon-carbon unsaturated bond. The polymer has a role of increasing the amount of the flame retardant to be accepted, having good crosslinking efficiency, and enhancing the flame retardant effect without lowering the mechanical strength. The ionomer resin as the component (B) has a role of enhancing processability, flexibility, and mechanical strength. The flame retardant as the component (II) imparts flame retardancy. When an inorganic flame retardant is used as the flame retardant, a non-halogen flame retardant crosslinked product that does not generate toxic gas such as halogen gas when burned is obtained. Can be provided. The red phosphorus as the component (III) plays a role of achieving higher flame retardancy.

In addition, organic fillers, antioxidants, lubricants, organic or inorganic pigments, UV inhibitors, dispersants, copper damage inhibitors, neutralizing agents, plasticizers, nucleating agents, without departing from the scope of the present invention. Etc. may be added.

[0040]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. [Resin and materials used] Component (A) A-1: Ethylene-allyl methacrylate copolymer (hereinafter referred to as E)
-Referred to as AMA) [AMA content = 1.0 wt%, MFR
= 1.0 g / 10 min.] A-2: Ethylene-vinyl methacrylate copolymer (hereinafter referred to as E
-Referred to as VMA) [VMA content = 1.0 wt%, MFR
= 1.0 g / 10 min.] A-3: Ethylene-allyl methacrylate-ethyl acrylate copolymer (hereinafter referred to as E-EA-AMA) [AMA content = 1.0 wt%, EA content = 10 wt%, MFR = 0.4
g / 10 min.] A-4: Ethylene-vinyl methacrylate-ethyl acrylate copolymer (hereinafter referred to as E-EA-VMA) [VMA
Content = 1.0 wt%, EA content = 10 wt%, MFR = 0.
4g / 10min.]

Component (B) B1: Ionomer [ethylene content 90 wt%, methacrylic acid content 10 wt%, metal ion Zn, neutralization degree 7
2%, MFR = 1.0 g / 10 min.] B2: Ionomer [ethylene content 85 wt%, methacrylic acid content 15 wt%, metal ion Mg, neutralization degree 5
0%, MFR = 1.0 g / 10 min.]

Component (II) C-1: Magnesium hydroxide [Product name: Kisuma 5J Kyowa Chemical Co., Ltd.] C-2: Aluminum hydroxide [Product name: Hydilite 42M]
Made by Nippon Light Metal Co., Ltd.]

Component (III) Red phosphorus [trade name: manufactured by Hishiguard Nippon Kagaku Kogyo Co., Ltd.]

(Test method) (1) Tensile test (YTS), (UTS) and elongation (UE
L) (%) A test piece punched with a No. 3 dumbbell from a sheet having a thickness of 1 mm was measured with a Tensilon at a tensile speed of 200 mm / min. (2) Oxygen index (OI) The oxygen index was measured according to JIS K7201. (3) Wear resistance test Using a Taber type wear tester, wear wheels H-22, load 1
Weight loss was measured after testing at Kg, 1000 revolutions. (4) Gel Fraction Dicumyl peroxide [trade name: Park Mill D, manufactured by NOF CORPORATION] 2.0w%, Thiobis [trade name: Nocrac 300, manufactured by Ouchi Shinko Co., Ltd.] 0.2w% A) B) C)
The components were kneaded with a roll at 120 ° C., and thermally crosslinked for 30 minutes by a press molding machine at 160 ° C., and the sample was crushed to within 35 to 20 mesh and extracted with xylene at 120 ° C. for 10 hours to obtain a residual rate. (5) Heat resistance (heat deformation rate) The heat resistance was measured according to JIS C3005. Temperature 120 ℃,
It was measured with a load of 1 kg.

Example 1 The compositions having the formulations shown in Table 1 were dry blended, and then melt-kneaded at a resin temperature of 200 ° C. using an extruder of 50 mmφ and pelletized. 180 more
A sample was prepared by press molding at a temperature of 100 ° C., a pressure of 100 kg / cm ² , and a time of 5 minutes, and used for the test. The test results are shown in Table 1. The test items were MFR, tensile strength, elongation, oxygen index, wear resistance, gel fraction, heat resistance (heat deformation rate), etc. (however, the gel fraction was measured without adding a flame retardant).

(Examples 2 to 19) Compositions having the formulations shown in Table 1 were molded in the same manner as in Example 1 to prepare samples, which were then subjected to the tests. The results of the tests conducted in the same manner as in Example 1 are also shown in Table 1.

(Comparative Example 1) As the component (A) of the polymer component (I), high-pressure radical polymerization low density polyethylene [LD]
Abbreviated as PE. Product name: Nisseki Lexron W2000, MF
R1.0 g / 10 min., Density 0.920 g / cm ³ , manufactured by Nippon Petrochemical Co., Ltd.], and the composition having the composition shown in Table 2 was molded in the same manner as in Example 1 to prepare a sample, It was submitted to the test. The results of the tests conducted in the same manner as in Example 1 are shown in Table 2.

(Comparative Examples 2 to 5) A composition having a composition outside the scope of the present invention shown in Table 2 was molded in the same manner as in Example 1 to prepare a sample, which was subjected to the test. The results of the tests conducted in the same manner as in Example 1 are also shown in Table 2.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a polymer component (I) comprising an ethylene copolymer having a carbon-carbon unsaturated bond of the component (A) and an ionomer resin (B),
A highly flame-retardant composition having excellent crosslinkability, which comprises the flame retardant of component (II) or red phosphorus of component (III) as an essential component, and is blended with various additives as necessary. And has a high degree of flame retardancy,
When an inorganic flame retardant is used as the component (II) flame retardant, no toxic gas such as halogen gas is generated during combustion,
And safety, flexibility, processability, mechanical properties, chemical resistance,
It has excellent electrical properties, so it is used for molding applications such as extrusion molded products such as films, sheets, pipes, injection molded products, and for electric wires and cables. It is used in various fields such as aircraft, construction, and civil engineering, and has a high industrial utility value.

Claims (2)

[Claims] 1. 100 parts by weight of a polymer component (I) containing (I) (A) an ethylene copolymer having a carbon-carbon unsaturated bond in an amount of 95 to 5% by weight (B) an ionomer resin in an amount of 5 to 95% by weight. On the other hand, a crosslinkable highly flame-retardant composition comprising (II) a flame retardant in an amount of 5 to 200 parts by weight. 2. A polymer component (I) containing 100 parts by weight of (I) (A) an ethylene copolymer having a carbon-carbon unsaturated bond in an amount of 95 to 5% by weight (B) an ionomer resin in an amount of 5 to 95% by weight. On the other hand, (II) flame retardant 5 to 200 parts by weight (III) red phosphorus 0.1 to 20 parts by weight, a crosslinkable highly flame retardant composition.