JPH0790135A - Crosslinkable, highly flame-retardant composition - Google Patents

Abstract

PURPOSE:To obtain a crosslinkable composition giving a molding which retains mechanical strength, felxibility, and processability, is excellent in heat resistance and wear resistance, and has high flame retardancy by incorporating a polyolefin resin or rubber having a specific functional group, a flame retardant, and red phosphorus into an ethylene copolymer having an unsaturated bond. CONSTITUTION:The title composition comprises 100 pts.wt. ethylene copolymer having an unsaturated carbon-carbon bond, at least 0.1 pts.wt. polyolefin resin or rubber having at least one functional group (a) selected from a carboxylic acid or acid anhydride group, epoxy, hydroxy, amino, an alkenyl cyclic imino ether group, a silane group, and a titanate group, 5-200 pts.wt. flame retardant, and 0.1-20 pts.wt. red phosphorus, the amount of the functional group (a) being 10<-8> to 10<-3> g equioalent per g of the polymer ingredients.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable highly flame-retardant composition capable of providing a molded article having excellent wear resistance and heat resistance, and more specifically, having a crosslinkable carbon-carbon unsaturated bond. An ethylene copolymer (hereinafter abbreviated as ethylene copolymer), a polyolefin resin or rubber component having a specific functional group introduced therein, a flame retardant, and a crosslinkable highly flame-retardant composition based on red phosphorus, which is flexible. Relating to a cross-linkable highly flame-retardant composition capable of providing a molded article having excellent wear resistance and heat resistance while maintaining high flame resistance, mechanical properties, chemical resistance, processability, and high flame retardancy. Is.

[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, none of them has a high level of flame retardancy and has not been improved in wear resistance and heat resistance.

[0004]

The present invention satisfies the above requirements, retains mechanical strength, flexibility and workability, is excellent in heat resistance and wear resistance, and has high flame retardancy. The present invention provides a crosslinkable highly flame-retardant composition capable of providing a molded article having a composition, which is used for molding films, sheets, containers, electric wires, cables, packings, sealants, hoses, injection products, etc. Is used as.

[0005]

MEANS FOR SOLVING THE PROBLEMS The present invention comprises (A) 100 parts by weight of an ethylene copolymer having a carbon-carbon unsaturated bond, and (B) contains at least one functional group selected from the following a to g. Polyolefin resin or rubber to be used 0.1 part by weight or more (C) Flame retardant 5 to 200 parts by weight (D) Red phosphorus 0.1 to 20 parts by weight, which is a polymer component (A) + In (B), the functional group is added in an amount of 10 ^-8 to 10 per 1 g of all polymer components.
A crosslinkable highly flame-retardant composition characterized by having ^-3 g equivalent. Functional group; a: carboxylic acid group or acid anhydride group, b: epoxy group, c: hydroxyl group, d: amino group, e: alkenyl cyclic iminoether group, f: silane group, g: titanate group

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.

The other unsaturated monomer copolymerizable with the above-mentioned ethylene and a monomer having two or more carbon-carbon unsaturated bonds is an α-olefin such as propylene or 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 means a: carboxylic acid group or acid anhydride group, b: epoxy group, c: hydroxyl group, d: amino group, e: alkenyl cyclic iminoether group, f: silane group. , G: a polyolefin resin or rubber containing a functional group selected from titanate groups, including random copolymers and graft copolymers.

Examples of the compound for introducing the carboxylic acid group of the functional group a or the acid anhydride group include maleic acid, fumaric acid, citraconic acid, itaconic acid and other α, β-unsaturated dicarboxylic acids, acrylic acid, and methacrylic acid. And unsaturated monocarboxylic acids such as furanic acid, crotonic acid, vinylacetic acid and pentenoic acid, and α, β-unsaturated dicarboxylic acids or anhydrides thereof.

B: As a compound for introducing an epoxy group, glycidyl acrylate, glycidyl methacrylate,
Itaconic acid monoglycidyl ester, butene tricarboxylic acid monoglycidyl ester, butene tricarboxylic acid diglycidyl ester, butene tricarboxylic acid triglycidyl ester and α-chloroallyl, maleic acid, crotonic acid, fumaric acid and other glycidyl esters or vinyl glycidyl ether, allyl Examples thereof include glycidyl ethers such as glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, and the like, and glycidyl methacrylate and allyl glycidyl ether are particularly preferable.

C: 1-hydroxypropyl (meth) acrylate as a compound for introducing a hydroxyl group,
2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like can be mentioned.

D: As a compound for introducing an amino group,
Examples thereof include tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate.

E: The compound introducing the alkenyl cyclic iminoether group is represented by the following structural formula (Formula 1).

[0017]

[Chemical 1]

Here, n is 1, 2 and 3, preferably 2 and 3, and more preferably 2. Also R ¹ , R
² , R ³ and R each represent a C1 to C12 inactive alkyl group and / or hydrogen, and the alkyl group may have an inactive substituent. The term "inert" as used herein means that the graft reaction and the function of the product are not adversely affected. Also, all R need not be the same.
Preferably R ¹ = R ² = H, R ³ = H or Me,
R = H, that is, 2-vinyl and / or 2-isopropenyl-2-oxazoline, 2-vinyl and / or 2
-Isopropenyl-5,6-dihydro-4H-1,3-
It is oxazine. These may be used alone or as a mixture.
Among these, 2-vinyl and / or 2-isopropenyl-2-oxazoline are particularly preferable.

F: As a compound for introducing a silane group,
Vinyltrimethoxysilane, vinyltriethoxysilane,
Examples thereof include vinyltriacetylsilane and vinyltrichlorosilane.

Functional group g: Tetraisopropyl titanate, tera-n-butyl titanate, tetrakis (2-ethylhexoxy) as a compound for introducing a titanate group.
Examples include titanate and titanium lactate ammonium.

A specific method for introducing the functional group selected from the above a to g into the polymer component of the present invention is as a modified polyolefin resin or rubber obtained by grafting the functional group onto a polyolefin resin or rubber. Introduction method, introduction method as a random copolymer of ethylene and the functional group-containing compound, the above components A), B) and the functional group-containing compound in an extruder in the presence of an organic peroxide and the like. Examples thereof include a method of introducing by addition reaction.

The polyolefin resin or rubber used for addition modification is not particularly limited,
High, medium and low density polyethylene, linear low density polyethylene, ultra low density polyethylene, EPR, EPDM, EV
Ethylene homopolymers and copolymers such as A and EEA;
Alternatively, propylene homopolymers, copolymers with other α-olefins and the like can be mentioned, with a density of particularly 0.91 to 0.9.
An ethylene-α-olefin copolymer of 7 g / cm ³ is preferably used. Among the polyolefin resins having these functional groups, maleic anhydride-modified polyethylene is most preferable.

The crosslinkable highly flame-retardant composition of the present invention comprises (A)
100 parts by weight of the component, 0.1 part by weight or more of the polyolefin resin or rubber containing at least one functional group selected from the above a to g as the (B) component, and the flame retardant of the (C) component is 5 parts by weight. 200 parts by weight and 0.1 to 20 parts by weight of red phosphorus as the component (D), and a polymer component (A)
In (B), the amount of the functional group is 1 per 1 g of all polymer components.
It is important to be in the range of 0 ^-8 to 10 ^-3 g equivalent.

If the amount of component (A) is less than 100 parts by weight, the abrasion resistance and heat resistance will be insufficient. On the other hand, when the amount exceeds 100 parts by weight, gelation proceeds, resulting in a fear that mechanical strength and the like decrease.

The addition amount of the functional group of the addition-modified modified polymer is 10 ^-8 to 10 ^-4 g equivalent to 1 g of the modified polymer, and 10 ^-7 to 10 ^-7 from the standpoint of producing the modified polymer. 10
A range of ^-4 g equivalent is preferred. In the case of a random copolymer with ethylene or an olefin, 10 ^{-6 to} 3 × 10 ^-3 g equivalent, preferably 10 ^-5 to 10 ^-4 g equivalent, per 1 g of the random copolymer is used in production. It is a range. In the present invention, 1 g equivalent of the functional group contained per 1 g of the total polymer means 1 mol of the compound introducing the functional group.

The addition-modified modified polymer of the present invention may be produced by addition-modifying at least one compound having the functional group in the presence or absence of a radical initiator by a melting method or a solution method. Can be obtained.
Of these, the melting method is preferred. Examples of the radical initiator include cross-linking agents such as organic peroxides, dihydroaromatic compounds and dicumyl compounds. Further, in the case of a peroxide decomposable polymer such as polypropylene or the like, since the polymer chain is cleaved by the peroxide, a relatively gentle dicumyl compound, dihydro aromatic compound or the like is used as the radical initiator. Is desirable.

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 functional group in the polymer component (A) + (B) of the present invention is adjusted so as to be in the range of 10 ⁻⁸ to 10 ⁻³ g equivalent. When a modified polymer is used, the functional group is 10 ^-8.
When it is less than g equivalent, or when a random copolymer of ethylene and a compound containing a functional group is used, the functional group is 1
If it is less than 0 ^-6 g equivalent, the coupling effect between the polymer component and the flame retardant as the component (C) becomes insufficient, resulting in poor mechanical strength. Further, if the content of the functional group is 10 ⁻³ g equivalent or more, the mechanical strength and abrasion resistance of the resin composition may decrease. Further, when the composition burns, the formation of char (carbonized layer) may be impaired, and the drip resistance may decrease.

As the flame retardant which is the component (C) of the present invention, an addition type flame retardant such as a halogen flame retardant, a phosphorus flame retardant, and an inorganic flame retardant 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.

As the phosphorus 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 and tin oxide. These are 1 or 2
You may use together 1 or more types. Among these, especially aluminum hydroxide, magnesium hydroxide, zirconium hydroxide,
A hydrate of at least one metal compound selected from the group consisting of basic magnesium carbonate, dolomite, and hydrotalcite, particularly aluminum hydroxide and magnesium hydroxide, has a good flame retarding effect and is economically advantageous. . The particle size of these inorganic flame retardants varies depending on the type, but in the above aluminum hydroxide and magnesium hydroxide, the average particle size is 20 μm or less, preferably 10 μm.
The following are preferred.

When a halogen-based flame retardant or a phosphorus-based flame retardant is selected as the flame retardant, 100 parts by weight of the ethylene copolymer (A) and 0.1 part by weight of the polyolefin resin or rubber (B) containing the functional group are used. The amount of these flame retardants (C) is 5 to 50 parts by weight, preferably 6 to 40 parts by weight, based on the above parts. If the blending amount of these flame retardants is less than 5 parts by weight,
It is difficult to achieve a high degree of flame retardation, and even if the amount exceeds 50 parts by weight, flame retardancy is not improved so much and it becomes uneconomical. On the other hand, when an inorganic flame retardant is selected as the flame retardant, 100 parts by weight of the ethylene copolymer (A), 0.1 part by weight or more of the polyolefin resin or rubber (B) containing the functional group, The amount of the inorganic flame retardant is 30 to 200 parts by weight, preferably 40 to 150 parts by weight. 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, by further adding red phosphorus (D), a highly flame-retardant composition having a higher flame retardancy can be provided. As the red phosphorus which is the component (D) of the present invention, it is preferable to use red phosphorus coated with an organic and / or inorganic compound.

Red phosphorus coated with an organic and / or inorganic compound means the surface of red phosphorus particles coated with a thermosetting resin such as an epoxy resin, a phenol resin, a polyester resin, a silicone resin, a polyamide resin or an 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. The amount of the above-mentioned red phosphorus is 0.1-2 with respect to 100 parts by weight of the component (A), 0.1 parts by weight or more of the component (B), and 5 to 200 parts by weight of the component (C).
The amount is 0 parts by weight, preferably 0.2 to 15 parts by weight. If the amount of red phosphorus is less than 0.1 parts by weight, the effect of addition is small, and even if the amount of red phosphorus is more than 20 parts by weight, the flame retardant effect is not further improved, and it is preferable in terms of physical properties and economically. Absent.

In the present invention, by using the above composition and the inorganic filler in combination, the blending amount of the flame retardant can be reduced and other characteristics can be imparted. 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 cross-linking the composition of the present invention is not particularly limited, and a method of cross-linking using an organic peroxide, or a method of irradiating with high-energy radiation such as electron beam, β-ray or γ-ray. 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 the above 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. are used. be able to.

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 can be produced by a known method. For example, a polymer component composed of the component (A) and the component (B), a flame retardant as the component (C), red phosphorus as the component (D) and optionally a crosslinking agent or a crosslinking aid, an inorganic filler, Additives and the like, and dry blend these with a normal tumbler, or Banbury mixer, pressure kneader, kneading extruder, twin-screw extruder, roll,
Melt kneading with a usual kneading machine such as to produce a mixture of resin compositions or a molded product composed of them by uniformly dispersing,
Then, it may be crosslinked by heating, water crosslinking in warm water, or irradiation with electron beam or high energy radiation to crosslink. It is also possible to melt-knead with an ordinary kneading machine and uniformly disperse the mixture to produce a mixture of resin compositions or a molded product made of them, and simultaneously obtain a crosslinked product. When a peroxide decomposable polymer such as polypropylene is used as the polymer component (A) or (B), the polymer chain is cleaved by the peroxide as described above, and therefore a dicumyl compound or a radical initiator is used. It is desirable to use a dihydro aromatic compound or the like.

[0045]

The composition of the present invention comprises an ethylene copolymer having a carbon-carbon unsaturated bond as the component (A), a polyolefin resin or rubber containing the functional group as the component (B),
A crosslinkable highly flame-retardant composition having excellent heat resistance and wear resistance, which comprises a flame retardant as a component (C), red phosphorus as a component (D), and an additive to be added as necessary. The ethylene copolymer having a carbon-carbon unsaturated bond has a role of increasing the amount of the flame retardant to be received, having a good crosslinking efficiency, and enhancing the flame retardant effect without lowering the mechanical strength. The polyolefin-based resin or rubber having a functional group of the component (B) has a coupling effect between the polymer component of the component (A) + the component (B) and the flame retardant of the component (C), so It has a role of improving compatibility, improving mechanical strength, wear resistance, heat resistance and workability, and improving drip resistance due to char (carbonized layer) formation during combustion. The flame retardant as the component (C) 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 a toxic gas such as a halogen gas when burned is obtained. Can be provided. (D)
The component red phosphorus plays a role in achieving higher flame retardancy.

Within the scope of the present invention, organic fillers, antioxidants, lubricants, organic or inorganic pigments, UV inhibitors, dispersants, copper damage inhibitors, neutralizing agents, plasticizers, nucleating agents. Etc. may be added.

[0047]

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] (A) component 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) B-1: Maleic anhydride-modified ethylene-butene-1 copolymer (hereinafter referred to as MAn LLDPE) MFR = 1.2 g / 10
min. Density = 0.92 g / cm ³ , maleic anhydride = 0.
17 wt%] B-2: ethylene-glycidyl methacrylate copolymer (abbreviated as E-GMA) [MFR = 4.0 g / 10 min. Density = 0.935 g / cm ³ , glycidyl methacrylate = 1
0 wt%] B-3: Oxazoline-modified ethylene-butene-1 copolymer (referred to as oxazoline LL) [MFR = 3.0 g / 10mi
n. Density = 0.930 g / cm ³ , oxazoline = 0.2.
wt%]

Component (C) 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 (D) Red phosphorus [trade name: manufactured by HISHIGARD Nippon Chemical Industry 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 of 120 ° C. and thermally crosslinked with a press molding machine of 160 ° C. for 30 minutes, and the sample was pulverized 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 compositions shown in Table 1 were dry blended, and then melt-kneaded at a resin temperature of 200 ° C. using a 50 mmφ extruder 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 7) The 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 test. The results of the tests conducted in the same manner as in Example 1 are also shown in Table 1.

Comparative Example 1 A sample piece was prepared in the same manner as in Example 1 except that the component (D) was not used. The results are shown in Table 2.
Shown in.

(Comparative Example 2) A sample piece was prepared in the same manner as in Example 4 except that the component (B) was not used. The results are shown in Table 2.
Shown in.

(Comparative Example 3) A sample piece was prepared in the same manner as in Example 3 except that the blending amount of the component (C) was out of the range. The results are shown in Table 2.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

As described above, the present invention provides an ethylene copolymer having a carbon-carbon unsaturated bond as the component (A),
Crosslinking obtained by compounding a polyolefin resin or rubber having a specific amount of a functional group of the component (B), a flame retardant of the component (C), red phosphorus of the component (D) or various additives if necessary. It provides a highly flame-retardant composition having excellent flame retardancy, and has a high degree of flame retardancy, and when an inorganic flame retardant is used as the flame retardant of the component (C), it does not emit toxic gas such as halogen gas during combustion. Since it does not occur, it has excellent wear resistance and heat resistance, and also has excellent safety, flexibility, processability, mechanical properties, chemical resistance, electrical properties, etc.
It is used for molding applications such as extrusion molded products such as films, sheets, and pipes, injection molded products, and for electric wires, cables, etc., in various fields such as textiles, electricity, electronics, automobiles, ships, aircraft, construction, civil engineering, etc. It is used and has a high industrial utility value.

Claims (1)

[Claims] 1. (A) 100 parts by weight of ethylene copolymer having a carbon-carbon unsaturated bond (B) Polyolefin resin or rubber containing at least one functional group selected from the following a to g: 1 part by weight or more (C) 5 to 200 parts by weight of flame retardant (D) 0.1 to 20 parts by weight of red phosphorus, wherein the functional group is contained in the polymer component (A) + (B). 10 ^-8 to 10 groups per 1 g of all polymer components
A crosslinkable highly flame-retardant composition having an equivalent weight of ^-3 g. Functional group; a: carboxylic acid group or acid anhydride group, b: epoxy group, c: hydroxyl group, d: amino group, e: alkenyl cyclic iminoether group, f: silane group, g: titanate group