JPH07102128A - Cross-linkable and highly flame-retardant composition excellent in heat resistance - Google Patents

Abstract

PURPOSE:To obtain a cross-linkable and highly flame-retardant composition keeping mechanical strength, flexibility, processability, flame retardance, etc., capable of imparting high degree of cross-linking and excellent abrasion and heat resistances to a product and used for films, sheets, containers, electric wire, cables, packing, seals, hoses and injection moldings. CONSTITUTION:This cross-linkable and highly flame-retardant composition excellent in heat resistance contains (I) 100 pts.wt. of a polymer component consisting of (A) 5-95wt.% of a polyolefin resin or rubber, (B) 95-5wt.% of an ethylene copolymer having a carbon-carbon unsaturated bond, (II) >=0.1 pt.wt. of a polymer component containing (C) a polyolefin resin or rubber having a specific functional group, (III) 5-200 pts.wt. of a flame retardant and (IV) 0.1-20 pts.wt. of red phosphorus, and the functional group is contained in a specific amount in the polymer components (I)+(II).

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 excellent in abrasion resistance and heat resistance, and more specifically to a polyolefin resin or rubber, a crosslinkable carbon- An ethylene copolymer having a carbon unsaturated bond (hereinafter abbreviated as an ethylene copolymer), a polymer component having a specific functional group introduced therein, a flame retardant and a crosslinkable highly flame-retardant composition based on red phosphorus, , Flexibility, mechanical properties,
The present invention relates to a crosslinkable highly flame-retardant composition capable of providing a molded article having excellent wear resistance and heat resistance while maintaining chemical resistance.

[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]

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]

The present invention comprises: (I) (A) a polyolefin resin or rubber 5 to 95 wt% (B) an ethylene copolymer having a carbon-carbon unsaturated bond 95 to 5 wt% Polymer component (I) 100 parts by weight, (II) (C) Polymer component (II) 0 containing a polyolefin resin or rubber containing at least one functional group selected from the following a to g 1% by weight or more, (III) flame retardant 5 to 200 parts by weight, (IV) red phosphorus 0.1 to 20 parts by weight, the composition being in polymer component (I) + (II), Functional groups of 10 ^-8 to 10 per 1 g of all polymer components
^A crosslinkable flame-retardant composition having excellent heat resistance, which is 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 polyolefin resin as the component (A) in the present invention is a homopolymer of α / olefin such as ethylene, propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, or an intercopolymer thereof. Specifically, high / medium / low density / ultra low density polyethylene, polypropylene, homopolymers of polybutene-1, etc., copolymers of ethylene and propylene, butene-1, etc., propylene and ethylene, butene-1, etc. And other α-olefin copolymers, ethylene-vinyl ester copolymers, ethylene-α, β-unsaturated carboxylic acids and / or their alkyl ester copolymers.

More specifically, high pressure low density polyethylene (LDPE) and ultra low density polyethylene (VLDP)
E), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HD
PE), polypropylene (PP), poly-1-butene,
Examples thereof include poly-4-methyl-1-pentene, ethylene-vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) ethyl acrylate copolymer, etc., which may be used alone or in combination of two or more. You may use it.

The high-density polyethylene is a low-pressure polyethylene with a density of 0.94 to 0.97 g / cm ³ and an MFR of 0.1 to 20 g / 10 min.
It is preferable to select from the range of 0.5 to 10 g / 10 min. If the MFR is less than 0.1 g / 10 min., The workability deteriorates, and if it is 20 g / 10 min. Or more, the wear resistance becomes insufficient.

As the polypropylene, a known polypropylene (co) polymer such as a homopolymer of propylene, a block copolymer with other α-olefin containing propylene as a main component or a random copolymer is used. You can Melt flow rate of the polypropylene (hereinafter M
Abbreviated as FR) 0.5 to 20 g / 10 min., Preferably 1 to
It is better to select from the range of 18 g / 10 min.

The ethylene-vinyl ester copolymer of the present invention is a vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearic acid containing ethylene as a main component, which is produced by a high pressure radical polymerization method. It is a copolymer with vinyl ester monomers such as vinyl and trifluorovinyl acetate. Among these, ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) is particularly preferable.

The ethylene-α, β-unsaturated carboxylic acid and / or its alkyl ester copolymer of the present invention includes ethylene-α, β-unsaturated carboxylic acid copolymer,
Ethylene-α, β-unsaturated carboxylic acid ester copolymer, ethylene-α, β-unsaturated carboxylic acid-α, β-unsaturated carboxylic acid ester copolymer, and their amides, imides and the like, but preferably Are ethylene- (meth) acrylate copolymers produced by high-pressure radical polymerization, ethylene- (meth) acrylate copolymers, etc., and particularly ethylene-ethylacrylate copolymers (hereinafter abbreviated as EEA). ) Is mentioned.

As EVA, ethylene 50 to 99.5
A copolymer composed of 1% by weight, 0.5 to 50% by weight of vinyl acetate, and 0 to 49.5% by weight of another copolymerizable monomer is preferable. As EEA, ethylene 50 to 99.5% by weight, acrylic acid ethyl ester 0.5 to 50% by weight,
A copolymer composed of 0 to 49.5% by weight of another copolymerizable monomer is preferable. The EVA and the melt flow rate (MFR) of the EEA are preferably selected from the range of 0.1 to 50 g / 10 min., Preferably 0.5 to 20 g / 10 min. If the MFR is less than 0.1 g / 10 min., The fluidity of the resin composition will be poor, and if it is 50 g / 10 min. Or more, the tensile strength and the like will decrease, which is not desirable. Also, the EVA
And the VA content or EA content of the EEA is 0.5 to 5
0% by weight, preferably 5 to 30% by weight is physical,
Selected for economic reasons.

Examples of the rubber as the component (A) in the present invention include thermoplastic ethylene propylene rubber, thermoplastic butadiene rubber, thermoplastic isoprene rubber, natural rubber, nitrile rubber, isobutylene rubber and the like. However, it may be a mixture.

The thermoplastic ethylene-propylene rubber is a random copolymer (EPM) containing ethylene and propylene as main components, and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as a third component. It refers to a random copolymer (EPDM) containing the main component.

The above-mentioned thermoplastic butadiene rubber means a copolymer having butadiene as a constituent element, and is a styrene-butadiene block copolymer (SBS) and its hydrogenated or partially hydrogenated derivative, styrene-butadiene-ethylene. Examples thereof include a copolymer (SBES), 1,2-polybutadiene (1,2-PB), a maleic anhydride-butadiene-styrene copolymer, and a modified butadiene rubber having a core-shell structure.

The above-mentioned thermoplastic isoprene rubber is a copolymer having isoprene as a constituent element, and is a styrene-isoprene block copolymer (SIS) and its hydrogenated or partially hydrogenated derivative styrene-isoprene-ethylene copolymer. Examples thereof include polymers (SIES) and modified isoprene rubber having a core-shell structure.

The ethylene copolymer having a carbon-carbon unsaturated bond of the component (B) in the present invention means ethylene and
Copolymer consisting of monomers having two or more carbon-carbon unsaturated bonds and, if desired, other unsaturated monomers, ethylene homopolymer, linear low density polyethylene (LLDPE), ultra low density Polyethylene (VLDP
E), ethylene-propylene copolymer rubber (EPR),
Ethylene-propylene-diene copolymer rubber (EPD
M), copolymers of ethylene with other α-olefins, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid or alkyl ester copolymers thereof, and other ethylene polymers having 2 carbon-carbon unsaturated bonds. It includes those obtained by addition-polymerizing monomers having one or more monomers.

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, which is the component (B), 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.

Component (C) 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 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 an alkenyl cyclic iminoether group is represented by the following structural formula (Formula 1).

[0028]

[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.

G: Examples of compounds that introduce a titanate group include tetraisopropyl titanate, tera-n-butyl titanate, tetrakis (2-ethylhexoxy) titanate, and titanium lactate ammonium.

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

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

The blending ratio of the component (A) and the component (B) in the polymer component (I) is in the range of 5 to 95% by weight of the component (A) and 95 to 5% by weight of the component (B). To be selected.
If the blending amount of the component (B) is less than 5% by weight, 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.

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 from the standpoint of producing the modified polymer, 10 ^-7 to 10 ^-7 . 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 can be produced by addition-modifying at least one compound having a 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 (I) + (II) of the present invention is adjusted to be in the range of 10 ^-8 to 10 ^-3 g equivalent. When a modified polymer is used, the functional group is 10
If less than ^-8 g equivalent, or in the case of using a random copolymer of ethylene and a functional group-containing compound compound, if the functional group is less than 10 ^-6 g equivalent, the polymer component and the flame retardant of the component (III) are used. The coupling effect of is insufficient and the mechanical strength is poor. 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 (III) 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-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 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 flame retardant or a phosphorus flame retardant is selected as the flame retardant, 100 parts by weight of the polymer component (I),
The amount of these flame retardants is 5 to 50 parts by weight, preferably 6 to 40 parts by weight, based on 0.1 part by weight or more of the polymer component (II). 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,
100 parts by weight of polymer component (I), polymer component (II)
The inorganic flame retardant is 30 to 20 with respect to 0.1 parts by weight or more.
It is 0 part 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, red phosphorus (IV) is further added.
By blending, it is possible to provide a highly flame-retardant composition having higher flame retardancy. (IV) of the present invention
As the red phosphorus component, 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 the 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 can be almost completely suppressed. Does not occur. The blending amount of the above red phosphorus is 100 parts by weight of the polymer component (I), the polymer component (II)
0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, relative to 5 to 200 parts by weight of the component (III).
The range is parts by weight. If the amount of red phosphorus is less than 0.1 parts by weight, the effect of addition is small, and if the amount of red phosphorus is more than 20 parts by weight, the flame retardant effect is not further improved, and the physical properties and the economy are not preferable. .

In the present invention, the amount of the flame retardant compounded can be reduced and other characteristics 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 treated with 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, within the range not impairing the physical properties of the composition of the present invention. Scratch-whitening inhibitors such as fatty acid amides, alkylphenols or alkylnaphthol alkylene oxide adducts may be added.

The method for 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 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 (I) comprising a polyolefin resin or rubber as the component (A) and an ethylene copolymer having a carbon-carbon unsaturated bond as the component (B), and a polymer component containing the functional group ( II),
A flame retardant as the component (III), red phosphorus as the component (IV) and, if necessary, a cross-linking agent, a cross-linking auxiliary agent, an inorganic filler, an additive and the like are blended, and these are dry blended with an ordinary tumbler, Alternatively, a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, a roll, etc. are melt-kneaded and uniformly dispersed by a usual kneading machine to produce a mixture of resin compositions or a molded product made of them, Then, it may be crosslinked by heating, water crosslinking in warm water, or irradiation with electron beam or high energy radiation 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. When a peroxide-decomposable polymer such as polypropylene is used as the polymer component (I) or (II), 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.

[0056]

The composition of the present invention comprises the polymer component (I), the polymer component (II), the flame retardant as the component (III), the red phosphorus as the component (IV), and an additive to be added if necessary. Which is a cross-linkable flame-retardant composition having excellent heat resistance, wherein the polyolefin resin or rubber of the component (A) has processability, flexibility,
It has the role of enhancing wear resistance, heat resistance, and mechanical strength. The ethylene copolymer having a carbon-carbon unsaturated bond of the component (B) increases the acceptance of the flame retardant, and
Crosslinking efficiency is good, and it has a role of enhancing the flame retardant effect without lowering the mechanical strength. The polymer component (II) containing the polyolefin resin or rubber having a functional group of the component (C) is the resin of the above components (A) and (B) and (III).
It has a coupling effect with the flame retardant of the components, enhances mutual compatibility of resins, improves mechanical strength, wear resistance, heat resistance and workability, and char (carbonized layer) during combustion.
It has a role of improving drip resistance due to formation.
The flame retardant as the component (III) 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. (IV)
The component red phosphorus has a role of achieving a 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.

[0058]

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] (I) Polymer component (A) component A-1: HDPE [Nisseki Staflen E-807 (F), trade name, manufactured by Nippon Petrochemical Co., Ltd., MFR = 0.6 g / 10 min .
Density = 0.950 g / cm ³ ] A-2: PP [Nisseki Polypro J620G, trade name, manufactured by Nippon Petrochemical Co., Ltd., MFR = 1.5 g / 10 min. Density = 0.
900 g / cm ³ ] A-3: Ethylene-ethyl acrylate copolymer (hereinafter EE
A)) [EA content = 10 wt%, MFR = 0.4 g /
10 min.] A-4: Ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) [VA content = 10 wt%, MFR = 1.0 g / 10 mi
n.] A-5: VLDPE [Nisseki Softlex D9010, trade name; manufactured by Nippon Petrochemical Co., Ltd., MFR = 1.0 g / 10 min.
Density = 0.900 g / cm ³ ] A-6: LLDPE [Nisseki Linirex AF2380, trade name, manufactured by Nippon Petrochemical Co., Ltd., MFR = 1.0 g / 10 mi
n. Density = 0.921g / cm ^3]

Component (B) B-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.] B-2: Ethylene-vinyl methacrylate copolymer (hereinafter referred to as E-VMA) [VMA content = 1.0 wt%, MF
R = 1.0 g / 10 min.] B-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.] B-4: Ethylene-vinyl methacrylate-ethyl acrylate copolymer (hereinafter referred to as E-EA-VMA) [VM
A content = 1.0 wt%, EA content = 10 wt%, MFR =
0.4g / 10min.]

(II) Polymer Component (C) Component C-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%] C-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%] C-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%]

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

(IV) Component 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)
Knead component (C) with a roll at 120 ° C,
The sample which was thermally crosslinked for 30 minutes with the press molding machine of
The residual rate after pulverizing within the mesh and extracting with xylene at 120 ° C. for 10 hours was obtained. (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 9) 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.

(Examples 10 to 20) The compositions having the formulations shown in Table 2 were molded in the same manner as in Example 1 to prepare samples, which were then subjected to the test. The test results obtained in the same manner as in Example 1 are shown in Table 2.
It is shown together with.

(Examples 21 to 30) The compositions having the formulations shown in Table 3 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 shown in Table 3.
It is shown together with.

(Comparative Example 1) A sample piece was prepared in the same manner as in Example except that HDPE was used as the component (A) and the component (B) was not used. The results are shown in Table 4.

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

(Comparative Example 3) A sample piece was prepared in the same manner as in Example except that the component (C) was not used. The results are shown in Table 4.
Shown in.

(Comparative Example 4) A sample piece was prepared in the same manner as in Example except that the blending amount of the component (III) was out of the range and red phosphorus was not used. The results are shown in Table 4.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

As described above, according to the present invention, the component (A) polyolefin resin or rubber and the component (B) carbon-
Polymer components (I) and (C) consisting of an ethylene copolymer having a carbon unsaturated bond, and polymer components (I) consisting of a polyolefin resin or rubber having a specific amount of functional groups of the components (I).
A flame-retardant composition having excellent heat resistance and crosslinkability, which is obtained by blending I), a flame retardant as a component (III), red phosphorus as a component (IV) or various additives as required. And has a high degree of flame retardancy, and (II
When an inorganic flame retardant is used as the flame retardant of component (I), no toxic gas such as halogen gas is generated during combustion, it has excellent wear resistance and heat resistance, and it is safe, flexible, processable, and mechanical. It is also used for molding applications such as extrusion molded products such as films, sheets and pipes, injection molded products, for electric wires, cables, etc. It is used in various fields such as electricity, electronics, automobiles, ships, aircraft, construction, and civil engineering, and has a high industrial utility value.

Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area // (C08L 23/08 23:26)

Claims (1)

[Claims] 1. A polymer component (I) 100 comprising (I) (A) a polyolefin resin or rubber 5 to 95% by weight (B) an ethylene copolymer having a carbon-carbon unsaturated bond (95 to 5% by weight). (II) (C) 0.1 parts by weight or more of a polymer component (II) containing a polyolefin resin or rubber containing at least one functional group selected from the following a to g, (III) ) 5 to 200 parts by weight of flame retardant, (IV) 0.1 to 20 parts by weight of red phosphorus, wherein the functional groups in the polymer component (I) + (II) are all polymers. 10 ^-8 to 10 per 1 g of ingredient
^A crosslinkable flame-retardant composition having excellent heat resistance, which is 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