JPH07179675A - Crosslinkable. highly flame-retardant composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. capable of providing a molded product having excellent heat resistance and abrasion resistance while maintaining a flexibility, mechanical properties and a chemical resistance, by blending a polyolefin resin or a rubber with an ionomer resin, an ethylene copolymer, a polymer component and a flame retardant. CONSTITUTION:This compsn. comprises (I) 100 pts.wt. polymer component comprising (A) 5-90wt.% polyolefin resin or rubber, (B) 5-90wt.% ionomer resin and (C) 5-90wt.% ethyulene copolymer having unsatd. carbon-carbon bonds (provided that A+B+C=100wt.%); (II) (D) at least 0.1 pt.wt. polymer component comprising a polyolefin resin or rubber contg. functional groups selected from among (a) to (g) as mentioned below; and (III) 5-200 pts.wt. flame retardant; and, if desired, (IV) 0-20 pts.wt. red phosphorus (provided that the amt. of the functional groups in I+II is 10<-8> to 10<-3> g equivalent per g of all the polymer components). In the functional groups, (a) is a carboxyl group or acid anhydride group; (b) is an epoxy group; (c) is a hydroxyl group; (d) is an amino group; (e) is an alkenyl cyclic imino ether group; (f) is a silane group, and (g) is a titanate group.

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, and more particularly to a polyolefin resin or rubber, an ionomer resin, and an ethylene copolymer having a crosslinkable carbon-carbon unsaturated bond ( Hereinafter, abbreviated as 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, which has flexibility, mechanical properties, and chemical resistance. TECHNICAL FIELD 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 the property.

[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 having maleic acid or maleic anhydride added in the molecule (JP-A-2-5384).
No. 5) is disclosed. However, all of them still have problems such as insufficient wear resistance and heat resistance.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a molded article which satisfies the above requirements and retains mechanical strength, flexibility, processability and flame retardancy, and which is excellent in heat resistance and wear resistance. 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.

[0005]

According to claim 1 of the present invention, (I) A) polyolefin resin or rubber 5 to 90% by weight B) ionomer resin 5 to 90% by weight C) carbon-carbon unsaturated bond is contained. Ethylene copolymer having 5 to 90% by weight However, 100 parts by weight of polymer component (I) consisting of A + B + C = 100% by weight, (II) D) containing at least one functional group selected from the following a to g A composition containing 0.1 part by weight or more of a polymer component (II) containing a polyolefin resin or rubber, (III) 5 to 200 parts by weight of a flame retardant, and (IV) optionally 0 to 20 parts by weight of red phosphorus. The polymer component (I) + (II) has the functional group in an amount of 10 ^-8 to 10 ^-3 g equivalent per 1 g of the total polymer component, which is highly crosslinkable and flame retardant. It is a composition. 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 In the above item 2, the component A is an ethylene (co) polymer produced by high pressure radical polymerization.
It is the crosslinkable highly flame-retardant composition described. Claim 3 of the present invention
Is a crosslinkable highly flame-retardant composition according to claim 1, wherein the component A is a crystalline polyolefin.

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. Yes, 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. Examples thereof include crystalline polyolefins such as copolymers with other α-olefins, ethylene-vinyl ester copolymers, ethylene-α, β-unsaturated carboxylic acids and / or their alkyl ester copolymers.

More specifically, low density polyethylene (L
DPE), ultra low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene (PP), poly-1-butene, poly-4-methyl-1-pentene, high pressure Examples thereof include ethylene vinyl acetate copolymers, ethylene / (meth) acrylic acid copolymers, ethylene / ethyl (meth) acrylate copolymers, and other ethylene copolymers produced by radical polymerization. These may be used alone or in combination. You may mix and use the above.

The high density polyethylene is a medium or low pressure polyethylene having a density of 0.94 to 0.97 g / cm ³ , and an MFR of 0.1 to 20 g / 10 mi.
n. 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.

The rubber as the component A) in the present invention includes thermoplastic ethylene propylene rubber, thermoplastic butadiene rubber, thermoplastic isoprene rubber, natural rubber, nitrile rubber, isobutylene rubber, etc., which may be used alone. 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 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 of the above (1) is neutralized to form the olefinic ionomer resin (B), among the carboxylic acid groups in the copolymer, the 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.

Further, this 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. Examples of the vinyl ester serving as the third component include vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. The proportion of α, β-unsaturated carboxylic acid ester units or vinyl ester units in the copolymer is usually 0 to
It is 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 ethylene copolymer having a carbon-carbon unsaturated bond of the component C) in the present invention means ethylene, a monomer having two or more carbon-carbon unsaturated bonds and, if desired, other unsaturated compounds. A copolymer consisting of monomers, or
Ethylene homopolymer, linear low density polyethylene (LL
DPE), ultra low density polyethylene (VLDPE), ethylene-propylene copolymer rubber (EPR), ethylene-propylene-diene copolymer rubber (EPDM), copolymer of ethylene and other α-olefin, ethylene-acetic acid It includes an ethylene polymer such as a vinyl copolymer, 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 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 C), 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.

As the ethylene copolymer of the component C) of the present invention, 70 to 99.99% by weight of ethylene and 0.01 to 30% by weight of a monomer having two or more carbon-carbon unsaturated bonds, A copolymer composed of 0 to 29.99% by weight of another unsaturated monomer is preferable. 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 D) 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: 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 or the acid anhydride group of the functional group a are α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid and itaconic acid, acrylic acid, 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 the alkenyl cyclic iminoether group is represented by the following structural formula (Formula 1).

[0036]

[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 as a random copolymer of ethylene and the functional group-containing compound, the above A) component, B) component,
Examples thereof include a method of introducing the component (C), the component (D) and the functional group-containing compound by addition reaction with an extruder in the presence of an organic peroxide and the like.

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 the components A), B),
A polymer component containing 100 parts by weight of a polymer component (I) containing the component C) as an essential component and a polyolefin resin or rubber containing as a component D) at least one functional group selected from the above a to g. (II) 0.1 parts by weight or more, 5 to 200 parts by weight of the flame retardant as the component (III), and optionally 0 to 20 parts by weight of red phosphorus as the component (IV), and the polymer component (I). It is essential that the functional group in + (II) is in the range of 10 ⁻⁸ to 10 ⁻³ g equivalent per 1 g of the total polymer component.

Component A) and B) in the polymer component (I).
The ratio of the components, C) is 5 to 90% by weight for A), 5 to 90% by weight for B), and 5 to 90% by weight for C) (provided that A + B + C = 100% by weight). Selected in. Among the above components A), ethylene (co) polymers obtained by high pressure radical polymerization can be preferably used. E among ethylene (co) polymers produced by high-pressure radical polymerization
EA and EVA are preferred. Because EEA and E
Since VA and the like are highly flexible, even if the inorganic flame retardant of component (III) is selected, it can be filled in a high compounding amount and the flexibility of electric wires and cables can be maintained, thus further improving flame retardancy. . When the component (A) is an ethylene (co) polymer such as EEA or EVA, when the content of the component (A) is less than 5% by weight,
Mechanical strength is not improved and elongation is insufficient. Also, 9
If the amount exceeds 0% by weight, the cross-linking property, wear resistance, and heat deformation rate are lowered.

A crystalline polyolefin can also be preferably used in the above component A). HDP as component A)
Choosing a crystalline polyolefin such as E or PP is
For example, it is a case where the purpose is to improve the performance such as heat resistance (heat deformation rate) and abrasion resistance required when the crosslinkable highly flame-retardant composition of the present invention is used for an automobile harness cable or the like. In this case, when the amount of the crystalline polyolefin as the component A) is less than 5% by weight, heat resistance (heat deformation rate) and abrasion resistance are not improved. On the other hand, if it exceeds 90% by weight, the crosslinkability is poor and the gel fraction is lowered. If the component B) is less than 5% by weight, high flame retardancy cannot be achieved. On the other hand, when it exceeds 90% by weight, the mechanical strength is not improved, the elongation is insufficient, and the cross-linking property and the heat deformation ratio are lowered. When the content of the component C) is less than 5% by weight, the improvement of the crosslinkability cannot be achieved and the heat deformation rate decreases. On the other hand, if it exceeds 90% by weight, it becomes too rigid and inflexible.

The addition amount of the functional group of the above-mentioned addition-modified modified polymer (D) is 10 ^-8 to 10 ^{-4 with} respect to 1 g of the modified polymer.
g equivalent, which is 10 ^-7 from the standpoint of producing a modified polymer.
The range of 10 ^-4 g equivalent is preferable. In the case of the random copolymer (D) with ethylene or olefin, 10 ^{-6 to} 3 per 1 g of the random copolymer in production.
× 10 ⁻³ g equivalent, preferably 10 ⁻⁵ to 10 ⁻⁴ g equivalent. 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.

As the method for producing the addition-modified modified polymer (D) of the present invention, at least one compound having the above-mentioned functional group is melted or solution-processed in the presence or absence of a radical initiator. It can be obtained by addition modification. Of these, the melting method is preferred. Examples of the radical initiator include organic peroxides, dihydroaromatic compounds,
Examples of the crosslinking agent include 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 a derivative thereof, 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 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
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, 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-based flame retardant or a phosphorus-based flame retardant is selected as the flame retardant, 100 parts by weight of the polymer component (I) and 0.1 part by weight or more of the polymer component (II) are used. The flame retardant is 5 to 50 parts by weight, preferably 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, 100 parts by weight of the polymer component (I) and the polymer component (I
I) 30 parts by weight of the inorganic flame retardant with respect to 0.1 parts by weight or more.
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 toxic gas such as halogen gas is not generated when burned.

In the present invention, a highly flame-retardant composition having a higher flame retardancy can be provided by further adding red phosphorus (IV), if desired. As the red phosphorus which is the component (IV) 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 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 is almost completely suppressed, so that odorous and toxic phosphine gas is generated. Does not occur. The blending amount of the above red phosphorus (IV) is 100 parts by weight of the polymer component (I), 0.1 part by weight or more of the polymer component (II), and the flame retardant 5 of the component (III).
It is in the range of 0 to 20 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 0.2 to 15 parts by weight with respect to ˜200 parts by weight. If the red phosphorus is not blended, a higher flame retardancy cannot be obtained, and if the blending amount is less than 0.1 parts by weight, the addition effect is small, and if the blending amount exceeds 20 parts by weight, the flame retardant effect is further improved. Is not improved and is not preferable in terms of physical properties and economically.

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 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 and 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 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 of component A), an ionomer resin of component B), and an ethylene copolymer having a carbon-carbon unsaturated bond of component C), containing the functional group. The polymer component (II) to be mixed, a flame retardant as the component (III), and optionally red phosphorus as the component (IV), and if necessary, a crosslinking agent, a crosslinking aid, an inorganic filler, an additive, and the like, These are dry blended with an ordinary tumbler, or melt-kneaded with an ordinary kneading machine such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll to uniformly disperse the resin composition. It is also possible to produce a mixture of the above or a molded product thereof and then crosslink by heating, crosslink with water in warm water, or irradiate 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 thereof, and at the same time obtain a crosslinked product. 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.

[0065]

The composition of the present invention comprises a polyolefin resin or rubber as component A), an ionomer resin as component B), and C).
Component (I), which is a component comprising an ethylene copolymer having a carbon-carbon unsaturated bond, and component (II), (III) containing a polyolefin resin or rubber containing the functional group of component D). ) Component flame retardant, optionally (I
A crosslinkable highly flame-retardant composition having excellent heat resistance, which is composed of V) component red phosphorus and an additive compounded as necessary. The polyolefin resin or rubber as the A component has processability and flexibility. Has the role of enhancing the heat resistance, wear resistance, heat resistance, and mechanical strength. The ionomer resin as the component B) has a role of enhancing flame retardancy, flexibility, and mechanical strength. The ethylene copolymer having a carbon-carbon unsaturated bond, which is the component C), 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 polymer component (II) containing a polyolefin resin or rubber having a functional group of the component D) has a coupling effect between the resin of the components A), B) and C) and the flame retardant of the component (III). However, it has the role of improving the mutual compatibility of the resins, improving the mechanical strength, wear resistance, heat resistance and workability, and improving the drip resistance due to the formation of char (carbonized layer) during combustion. 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. The component (IV), red phosphorus, plays a role in achieving a higher flame retardancy.

Further, 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.

[0067]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. [Resin and Material 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 min.
Density = 0.921 g / cm ³ ]

B) Component B-1: Ionomer [ethylene content 90 wt%, methacrylic acid content 10 wt%, metal ion Zn, neutralization degree 72%, MFR = 1.0 g / 10 min.] B-2: ionomer [ Ethylene content 85wt%, Methacrylic acid content 15wt%, Metal ion Mg, Neutralization degree 50%, MFR = 1.0g / 10min.]

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

(II) Polymer Component D) Component D-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%] D-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%] D-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 (III) E-1: Magnesium hydroxide [Product name: Kisuma 5J Kyowa Chemical Co., Ltd.] [abbreviated as Mg (OH) ₂ ] E-2: Aluminum hydroxide [Product name: Hydilite 42]
M Nippon Light Metal Co., Ltd.] [abbreviated as Al (OH) ₃ ]

Component (IV) Red phosphorus [Product name: 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 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 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 15) 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 Examples 1 to 4) 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.

[0077]

[Table 1]

(Examples 16 to 30) 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 tests. The test results obtained in the same manner as in Example 1 are shown in Table 2.
Shown in.

(Comparative Examples 5 to 7) 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 results of the tests conducted in the same manner as in Example 1 are also shown in Table 2.

[0080]

[Table 2]

(Examples 31 to 45) Compositions having the formulations shown in Table 3 were molded in the same manner as in Example 1 to prepare samples, which were subjected to the test. The results of the tests conducted in the same manner as in Example 1 are shown in Table 3.
Shown in.

(Comparative Examples 8 to 10) 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 test. The results of the tests conducted in the same manner as in Example 1 are also shown in Table 3.

[0083]

[Table 3]

[0084]

Industrial Applicability As described above, the present invention provides a polymer comprising a polyolefin resin or rubber as component A, an ionomer resin as component B), and an ethylene copolymer having a carbon-carbon unsaturated bond as component C). In the case of imparting a high flame retardancy to the polymer components (II) and (III) composed of a polyolefin resin or rubber having a specific amount of functional groups of the combination components (I) and D), a flame retardant. (IV) To provide a highly flame-retardant composition having excellent heat resistance and cross-linking property, which is obtained by blending red phosphorus or, if necessary, various additives, while having a high degree of flame retardancy,
When an inorganic flame retardant is used as the flame retardant of the component (III), no toxic gas such as halogen gas is generated during combustion, it is excellent in wear resistance and heat resistance, and safety, flexibility, processability, It has excellent mechanical properties, chemical resistance, electrical properties, etc., so it can be used for molding applications such as extrusion molded products such as films, sheets, pipes, injection molded products, electric wires, etc.
It is used for cables, etc., and is used in various fields such as textiles, electricity, electronics, automobiles, ships, aircraft, construction, and civil engineering, and has a high industrial utility value.

Claims (3)

[Claims] 1. I) A) polyolefin resin or rubber 5 to 90% by weight B) ionomer resin 5 to 90% by weight C) ethylene copolymer having carbon-carbon unsaturated bond 5 to 90% by weight, Polymer component (I) consisting of A + B + C = 100% by weight 100 parts by weight, (II) D) Polymer component containing a polyolefin resin or rubber containing at least one functional group selected from the following a to g ( II) 0.1 part by weight or more, (III) flame retardant 5 to 200 parts by weight, (IV) a composition containing 0 to 20 parts by weight of red phosphorus, which is a polymer component (I) + (II). A crosslinkable highly flame-retardant composition, characterized in that the functional group is contained therein in an amount of 10 ^-8 to 10 ^-3 g equivalent per 1 g of all polymer components. 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 2. The crosslinkable highly flame-retardant composition according to claim 1, wherein the component A is an ethylene (co) polymer produced by high-pressure radical polymerization. 3. The crosslinkable highly flame-retardant composition according to claim 1, wherein the component A is a crystalline polyolefin.