JPH0920841A - Flame-retardant polyolefin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising a specific phenolic compound, a thioether compound, a heavy metal deactivator and an epoxy compound, extremely excellent in heavy metal resistance when made into a molding, useful as a polarized yoke, etc. SOLUTION: This flame-retardant polyolefin composition is obtained by blending (A) 100 pts.wt. of a composition comprising (i) 70-30wt.% of a polyolefin and (ii) 30-70wt.% of magnesium hydroxide with (B) 0.01-1 pt.wt. of one or two phenolic compounds of 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) benzene and bis[2-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methyl-6-t- butylphenyl]terephthalate, (C) 0.01-1 pt.wt. of a thioether compound of the formula (R is a 8-28C alkyl), (D) 0.01-1 pt.wt. of a heavy metal deactivator (e.g. benzotriazole, etc.) and (E) 0.01-1 pt.wt. of an epoxy compound (e.g. bisphenol A, etc.).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to flame retardant polyolefin compositions. More specifically, the present invention relates to a flame-retardant polyolefin composition having excellent anti-oxidative deterioration properties of a polyolefin in practical use.

[0002]

2. Description of the Related Art In general, various halogen-based flame retardants have been blended with polyolefins as means for making polyolefins flame-retardant, and are widely used in practice. However, a flame-retardant polyolefin composition containing a halogen-based flame retardant generates a harmful halogen-based gas during combustion. Therefore, a non-halogen-based flame retardant has recently been required as a flame retardant to be used. Among various non-halogen flame retardants, inorganic flame retardants that do not generate harmful combustion gas, especially magnesium hydroxide, are widely used in practice because of their high dehydration decomposition temperature and excellent smoke suppression effect during combustion. . Further, since polyolefins, especially propylene-based polymers, have tertiary carbon which is susceptible to oxidation in the polymer, they have a drawback that they are susceptible to thermal oxidative deterioration during molding and practical use. Therefore, various antioxidants have been widely used for the purpose of preventing thermal oxidation deterioration.

On the other hand, a molded article molded from a flame-retardant polyolefin composition obtained by mixing magnesium hydroxide and various antioxidants into polyolefin is used for contact with heavy metals such as copper, brass, iron and nickel. May be used. However, since the polyolefin is catalytically deteriorated by the heavy metal ions contained in the above-mentioned various heavy metals, a molded article using the flame-retardant polyolefin composition described above is resistant to heat oxidative deterioration (hereinafter There is a drawback that the heavy metal property is significantly reduced. In particular, in recent years, the requirements for flame retardancy have become more and more stringent in applications such as electrical and electronic parts or automobile parts, and with the diversification of the applications of molded articles obtained from flame-retardant polyolefin compositions and the increase in size. The practical use conditions of the molded product (heavy metal resistance and electrical insulation, etc.)
The demand for is becoming severe.

Therefore, for the purpose of improving the heavy metal resistance of a molded article using a flame-retardant polyolefin composition containing magnesium hydroxide, the present inventor has found that the polyolefin contains magnesium hydroxide and a specific phenolic compound. , A thioether-based antioxidant including a specific thioether-based compound, a heavy metal deactivator, an epoxy compound and a fatty acid, respectively, were previously proposed as flame-retardant polyolefin compositions (Patent No. 2-214751). JP-A-2-240148, JP-A-3-81352, and JP-A-4
-36329, JP-A-4-36330 and JP-A-6-
41357).

[0005]

However, by using a cycloaliphatic sulfide as a thioether antioxidant in the above-mentioned JP-A-2-214751, JP-A-3-81352 and JP-A-6-41357, the use of cycloaliphatic sulfides There is no description or suggestion that the heavy metal resistance of the flame-retardant polyolefin composition is further improved.

The inventor of the present invention has found that Japanese Unexamined Patent Publication Nos. 2-214751 and 2-240148, 3-81352, 4-36329, 4-36330 and 4-36330. Further investigations were conducted without being satisfied with the flame-retardant polyolefin composition proposed in JP-A-6-41357. as a result,
The present inventor uses a specific phenolic compound, a specific thioether compound, a heavy metal deactivator and an epoxy compound, or a specific phenolic compound, a specific thioether compound in a flame-retardant composition comprising a polyolefin and magnesium hydroxide. It was found that a flame-retardant polyolefin composition having improved heavy metal resistance can be obtained by blending a heavy metal deactivator, an epoxy compound and a fatty acid in specific amounts, respectively, and based on this finding, the present invention was completed. As is clear from the above description, it is an object of the present invention to provide a flame-retardant polyolefin composition which is excellent in heavy metal resistance of the molded product.

[0007]

The present invention has the following arrangement. (1) One or two phenolic compounds (hereinafter referred to as compound A) selected from the following, per 100 parts by weight of a composition consisting of 70 to 30% by weight of polyolefin and 30 to 70% by weight of magnesium hydroxide. ), A thioether compound represented by the following general formula (1) (hereinafter referred to as compound C), a heavy metal deactivator and an epoxy compound in an amount of 0.01 to 1 part by weight, respectively. 1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate

Embedded image (In the formula, R represents an alkyl group having 8 to 28 carbon atoms.) (2) For 100 parts by weight of a composition comprising 70 to 30% by weight of polyolefin and 30 to 70% by weight of magnesium hydroxide, 0.01 to 1 part by weight of each of one or more phenolic compounds (hereinafter referred to as compound B), compound C, heavy metal deactivator and epoxy compound selected from the above, and 0.5 to 5 parts by weight of fatty acid. Flame-retardant polyolefin composition obtained by. 1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate tris (3,5-di-t -Butyl-4-hydroxybenzyl) isocyanurate

The polyolefin used in the present invention is a crystalline homopolymer of α-olefin such as ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, and the like. Crystalline, low crystalline or amorphous random copolymer or crystalline block copolymer of two or more α-olefins, amorphous ethylene-propylene-nonconjugated diene terpolymer, amorphous ethylene -A polyolefin such as a cyclic alkene copolymer (for example, amorphous ethylene-tetracyclododecene copolymer), a copolymer of the above-mentioned α-olefin and vinyl acetate or an acrylic ester, a ken of the copolymer Compound, these α
-A copolymer of an olefin and an unsaturated silane compound, a copolymer of these α-olefin and an unsaturated carboxylic acid or an anhydride thereof, a reaction product of the copolymer and a metal ion compound, the above-mentioned polyolefin Examples include modified polyolefins modified with unsaturated carboxylic acids or their derivatives, and silane-modified polyolefins modified with the above-mentioned polyolefins with unsaturated silane compounds. These polyolefins can be used alone or in combination of two or more kinds. It is also possible to mix and use.

In addition to the above-mentioned polyolefins, various synthetic rubbers (for example, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene- rubber).
Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-
Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (eg polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, poly polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluorine resin, petroleum resin (e.g. C ₅ petroleum resins, hydrogenated C ₅ system Petroleum resin, C
Softening point of ₉ series petroleum resin, hydrogenated C ₉ series petroleum resin, C ₅ -C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉ copolymerized petroleum resin, acid-modified C ₉ series petroleum resin, etc. Petroleum resin), DCPD resin (for example, cyclopentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene-C ₅ copolymer petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymer petroleum resin, cyclopentadiene-C ₉ Copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-
C ₅ -C ₉ copolymer DCP softening point 80 to 200 ° C., such as petroleum resin
D resin) or the like may be mixed and used. Crystalline propylene homopolymer, crystalline propylene copolymer containing 70% by weight or more of propylene component, crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene- Butene-
1 Random copolymer, crystalline ethylene-propylene-butene-1 terpolymer, crystalline propylene-hexene-butene-1 terpolymer, and mixtures of two or more thereof are particularly preferably used.

As the magnesium hydroxide used in the present invention, plate-like and fibrous ones can be used without any limitation. The average particle size of the plate-shaped magnesium hydroxide is not particularly limited, but usually 0.1 μm to 10 μm, preferably 0.2
μm to 2 μm, most preferably 0.5 μm to 1 μm, and the fiber diameter of fibrous magnesium hydroxide is 0.1 μm to 0.5 μm.
It is preferable that the length is 5 μm and the length is 5 μm to 20 μm. Further, these magnesium hydroxides are surface treatment agents such as metal soap, higher fatty acid ester, higher alcohol, higher fatty acid monoamide, higher fatty acid bisamide, higher aliphatic phosphoric acid, higher aliphatic metal phosphate, higher aliphatic sulfonic acid, higher Known aliphatic sulfonic acid metal salt, polyolefin wax, oxidized polyolefin wax, silane coupling agent, titanate coupling agent, boron coupling agent, aluminate coupling agent, zircoaluminate coupling agent, etc. When surface-treated with a surface-treating agent in advance, compatibility and dispersibility of the magnesium hydroxide and the polyolefin are improved, excellent moldability is obtained, and when the molded product is used, Since the mechanical strength is improved, the hydroxide magnesium surface-treated with a surface treatment agent It is preferable to use Siumu. Not only these magnesium hydroxides can be used alone, but also 2
It is also possible to use one or more kinds of magnesium hydroxide together.
The mixing ratio of the magnesium hydroxide is 30 to 70% by weight, preferably 50 to 65% by weight, based on the composition comprising polyolefin and magnesium hydroxide. If the content is much less than 30% by weight, the flame retardancy of the obtained molded product is insufficient, and if it is much more than 70% by weight, the moldability becomes difficult and the mechanical strength of the obtained molded product also decreases. Not.

The compound A used in the present invention may be used alone or two kinds of compound A may be used in combination. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of a composition in which 30 to 70% by weight of magnesium hydroxide is mixed with polyolefin. If it is less than 0.01 part by weight, the effect of improving heavy metal resistance cannot be sufficiently exerted, and if it is more than 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is also uneconomical.

The compound B used in the present invention may be used alone or in combination of two or more kinds. The compounding ratio of the compound B is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the composition in which 30 to 70% by weight of magnesium hydroxide is mixed with polyolefin. If it is less than 0.01 part by weight, the effect of improving heavy metal resistance cannot be sufficiently exerted, and if it is more than 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is also uneconomical.

The compound C used in the present invention is 1-
[Β- (octylthio) ethyl] -3- (octylthio) cyclohexane, 1- [β- (octylthio) ethyl] -4-
(Octylthio) cyclohexane, 1- [β- (2-ethylhexylthio) ethyl] -3- (2-ethylhexylthio)
Cyclohexane, 1- [β- (2-ethylhexylthio) ethyl] -4- (2-ethylhexylthio) cyclohexane, 1
-[Β- (nonylthio) ethyl] -3- (nonylthio) cyclohexane, 1- [β- (nonylthio) ethyl] -4- (nonylthio) cyclohexane, 1- [β- (dodecylthio) ethyl] -3- (dodecylthio ) Cyclohexane, 1- [β-
(Dodecylthio) ethyl] -4- (dodecylthio) cyclohexane, 1- [β- (tetradecylthio) ethyl] -3-
(Tetradecylthio) cyclohexane, 1- [β- (tetradecylthio) ethyl] -4- (tetradecylthio) cyclohexane, 1- [β- (hexadecylthio) ethyl] -3-
(Hexadecylthio) cyclohexane, 1- [β- (hexadecylthio) ethyl] -4- (hexadecylthio) cyclohexane, 1- [β- (octadecylthio) ethyl] -3-
(Octadecylthio) cyclohexane, 1- [β- (octadecylthio) ethyl] -4- (octadecylthio) cyclohexane, 1- [β- (docosylthio) ethyl] -3- (docosylthio) cyclohexane, 1- [β- ( Docosylthio) ethyl] -4- (docosylthio) cyclohexane, 1-
Examples include [β- (octacosylthio) ethyl] -3- (octacosylthio) cyclohexane and 1- [β- (octacosylthio) ethyl] -4- (octacosylthio) cyclohexane, and especially 1- [ β- (octadecylthio) ethyl] -3- (octadecylthio) cyclohexane and 1-
[Β- (Octadecylthio) ethyl] -4- (octadecylthio) cyclohexane is preferred. These compounds C can be used alone, or two or more compounds C can be used in combination. The compounding ratio of the compound C is 0.01 to 1 part by weight, preferably 0.05 to 100 parts by weight of a composition obtained by mixing 30 to 70% by weight of magnesium hydroxide with polyolefin.
0.5 parts by weight. If it is less than 0.01 part by weight, the effect of improving heavy metal resistance cannot be sufficiently exerted, and if it is more than 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is also uneconomical.

The heavy metal deactivators used in the present invention include benzotriazole, 2,4,6-triamino-1,3,5-triazine and 3,9-bis [2- (3,5-diamino-2 , 4,6-Triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, ethylenediamine-tetraacetic acid, ethylenediamine-tetraacetic acid alkali metal salt (Li, Na, K) salt, N, N'-disalicylidene-ethylenediamine, N, N'-disalicylidene-1,2-propylenediamine, N, N ''-disalicylidene-
N'-methyl-dipropylenetriamine, 3-salicyloylamino-1,2,4-triazole, decamethylene dicarboxylic acid-bis (N'-salicyloyl hydrazide), nickel-bis (1-phenyl- 3-methyl-4-decanoyl-5-pyrazolate), 2-ethoxy-2'-ethyloxanilide, 5-t-butyl-2-ethoxy-2'-ethyloxanilide, N, N-diethyl-N ', N'-diphenyloxamide,
N, N'-diethyl-N, N'-diphenyloxamide, oxalic acid-bis (benzylidene hydrazide),
Thiodipropionic acid-bis (benzylidene hydrazide), isophthalic acid-bis (2-phenoxypropionyl hydrazide), bis (salicyloylhydrazine), N-salicylidene-N'-salicyloylhydrazone, N, N'- Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine,

Tris [2-t-butyl-4-thio (2'-methyl-
4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite, bis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butyl) Phenyl) -5-methylphenyl] -pentaerythritol-diphosphite,
Tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,6-
Hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2-t
-Butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-
Di-carboxylic acid-di-hydroxyethylcarbonyl hydrazide-diphosphite, tetrakis [2
-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-salicylo Ilhydrazide-diphosphite, tetrakis [2-t-butyl-4-
Thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide-diphosphite, tetrakis [2-t
-Butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -N, N'-bis (hydroxyethyl) oxamide-diphosphite and N,
N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide and the like can be exemplified, and particularly oxalic acid-bis (benzylidene hydrazide), N, N'-bis [3- (3,5-di-t-butyl
-4-hydroxyphenyl) propionyl] hydrazine,
Tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy
-5'-t-Butylphenyl) -5-methylphenyl] phosphite and N, N'-bis [2- [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionyloxy] ethyl] oxamide is preferred. These heavy metal deactivators can be used alone, or two or more heavy metal deactivators can be used in combination. The compounding ratio of the heavy metal deactivator is 30 to 70% by weight of magnesium hydroxide in polyolefin.
0.01 to 1 part by weight per 100 parts by weight of the composition containing
Preferably it is 0.05 to 0.5 parts by weight. If it is less than 0.01 part by weight, the effect of improving heavy metal resistance cannot be sufficiently exerted, and if it is more than 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is also uneconomical.

The epoxy compound used in the present invention is not particularly limited as long as it does not significantly volatilize and escape or is decomposed during melt-kneading, and an epoxy equivalent of about 100 to 1,000 is preferable, and epichlorohydrin or Derivatives of epichlorohydrin (eg 2-
Methyl epichlorohydrin, 2-ethyl epichlorohydrin and 2-propyl epichlorohydrin) and bisphenol or a derivative of bisphenol (for example, bisphenol A, bisphenol F, bisphenol S,
Hydrogenated bisphenol A, hydrogenated bisphenol F
And hydrogenated bisphenol S), epoxidized fats and oils (eg epoxidized soybean oil, epoxidized linseed oil and epoxidized castor oil), epoxidized oleic acid, alkyl esters of epoxidized oleic acid (eg epoxidized) Octyl stearate, fatty acid ester of 3,4-epoxycyclohexylmethanol, alkyl ester of 3,4-epoxycyclohexylcarboxylic acid, dialkyl ester of 4,5-epoxycyclohexane-1,2-dicarboxylic acid, 3,4-epoxy- 6-methylcyclohexylmethyl and 3,4-epoxy-6-methylcyclohexanecarboxylate, etc.), tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, novolac glycidyl ether, polyalkylene glycol diglycidyl ether, Glycerin triglycidyl ether, pentaerythritol diglycidyl ether, p-oxybenzoic acid glycidyl ether-ester, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid glycidyl ester, dimer acid dimer Glycidyl ester, glycidyl aniline,
Tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate, epoxidized polybutadiene,
3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate,
3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6)
-Methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether, limonene dioxide, and the like, particularly, a condensate of epichlorohydrin and bisphenol A, 2-methylepichlorohydrin Condensate of bisphenol A with
Triglycidyl isocyanurate and epoxidized soybean oil are preferred. These epoxy compounds may be used alone or in combination of two or more. The compounding ratio of the epoxy compound is a composition in which 30 to 70% by weight of magnesium hydroxide is mixed with polyolefin.
0.01 to 1 part by weight, preferably 0.05 to 1 part by weight per 100 parts by weight
0.5 parts by weight. If it is less than 0.01 part by weight, the effect of improving heavy metal resistance cannot be sufficiently exerted, and if it is more than 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is also uneconomical.

The fatty acid used in the present invention is acetic acid,
Propionic acid, n-butyric acid, i-butyric acid, n-valeric acid, i-valeric acid,
n-hexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid,
Oleic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, 12-hydroxyoctadecanoic acid,
Examples include ricinoleic acid and cerebronic acid, and especially 2-
Ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, montanic acid and 12-hydroxyoctadecanoic acid are preferred. Not to mention the use of these fatty acids alone, 2
It is also possible to use two or more fatty acids in combination. The mixing ratio of the fatty acid is 30 to 70 magnesium hydroxide in the polyolefin.
The amount is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the composition containing 100% by weight. In addition, the method of blending the fatty acid is a method of blending the fatty acid with surface-untreated magnesium hydroxide or magnesium hydroxide surface-treated with a surface-treating agent other than fatty acid, and other compounds, or surface treatment of magnesium hydroxide with fatty acid in advance. Any of the methods of blending as magnesium hydroxide may be used.

In the composition of the present invention, various additives which are usually added to polyolefins such as phenol type (excluding compound A and compound B), thioether type (excluding compound C), phosphorus are used. -Based, hydroxylamine-based antioxidants, light stabilizers, clarifying agents, nucleating agents, lubricants, antistatic agents, antifogging agents, antiblocking agents, non-dripping agents, flame retardants (however, magnesium hydroxide Excluding), flame retardant aids, inorganic or organic antibacterial agents, pigments, radical generators such as peroxides, dispersants or neutralizing agents such as metal soaps, inorganic fillers (eg talc, mica,
Clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, aluminum hydroxide, hydrotalcite, basic aluminum lithium hydroxycarbonate hydrate, silicon dioxide, titanium dioxide, oxide Zinc, calcium oxide, magnesium oxide, zinc sulfide, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal fiber, etc., coupling agents (for example, The inorganic filler or the organic filler (for example, wood flour, pulp, waste paper, synthetic fiber) surface-treated with a surface treating agent such as silane-based, titanate-based, boron-based, aluminate-based, and zircoaluminate-based agents. Natural fibers, etc.) can be used in combination within limits not detrimental to the object of the present invention.

The composition of the present invention comprises a polyolefin containing magnesium hydroxide, compound A, compound C, a heavy metal deactivator and an epoxy compound, or magnesium hydroxide, compound B, compound C, a heavy metal deactivator, an epoxy compound and A predetermined amount of each of the fatty acids and the above-mentioned various additives usually added to the polyolefin is mixed by using an ordinary mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, etc. It can be obtained by melt-kneading pelletizing at a melt-kneading temperature of 150 ° C. to 300 ° C., preferably 200 ° C. to 250 ° C. with an extruder, a twin-screw extruder, a Brabender or a roll. The obtained composition is used for production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method, and a blow molding method.

[0020]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. 1) Heavy metal resistance: evaluated by a copper resistance test. That is, using the pellets obtained, length 50 mm, width 25 mm, thickness 1 mm
The test piece of No. 2 was prepared by the injection molding method, and the test piece was brought into contact with a copper plate having a length of 25 mm, a width of 25 mm and a thickness of 0.3 mm and fixed with a clip, and the circulating hot air was adjusted to a temperature of 150 ° C or 140 ° C. The heavy metal resistance was evaluated by placing in an oven and measuring the time until the copper plate contact portion of the test piece completely deteriorated (time until the deterioration penetrates) (in accordance with JIS K 7212). 2) Flame retardancy: A flame retardancy test was performed according to a combustion test method for a polymer material by an oxygen index method. That is, a test piece for combustion with a length of 150 mm, a width of 6.5 mm and a thickness of 3.0 mm was prepared by using the obtained pellet by an injection molding method, and the oxygen index was measured using the test piece for combustion (in accordance with JIS K 7201). ) And evaluated.

Production Example 1 A Henschel mixer (trade name) in which 100 parts by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of lauric acid as a fatty acid were adjusted to a temperature of 50 ° C. Then, the mixture was stirred and mixed for 5 minutes to obtain surface-treated magnesium hydroxide [1]. Production Example 2 100 parts by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of stearic acid as a fatty acid were placed in a Henschel mixer (trade name) adjusted to a temperature of 80 ° C., and 5 After stirring and mixing for a minute, surface-treated magnesium hydroxide [2] was obtained. Production Example 3 100 parts by weight of surface-untreated magnesium hydroxide having an average particle size of 0.6 to 0.8 μm and 2 parts by weight of oleic acid as a fatty acid were kept at room temperature in a Henschel mixer (trade name; If not mentioned, it means that the temperature is room temperature), and the mixture was stirred and mixed for 5 minutes to obtain surface-treated magnesium hydroxide [3]. Production Example 4 100 parts by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of linoleic acid as a fatty acid were put in a Henschel mixer (trade name), and mixed by stirring for 5 minutes for surface treatment. Magnesium hydroxide [4] was obtained. Production Example 5 100 parts by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of behenic acid as a fatty acid were placed in a Henschel mixer (trade name) adjusted to a temperature of 90 ° C., and 5 After stirring and mixing for a minute, surface-treated magnesium hydroxide [5] was obtained.

Examples 1 to 6 and Comparative Examples 1 to 13 Melt flow rate as polyolefin (amount of molten resin discharged for 10 minutes when a load of 21.18 N at 230 ° C. is applied; hereinafter abbreviated as MFR) 20 g / 10 Unstabilized powdery crystalline propylene homopolymer 43% by weight
And 57% by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide in a total amount of 100 parts by weight, 1,3,5-trimethyl-2,4,6-tris (3, 5-the-
t-Butyl-4-hydroxybenzyl) benzene or bis [2
-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4
-Methyl-6-t-butylphenyl] terephthalate, as compound C 1- [β- (octylthio) ethyl] -3- (octylthio) cyclohexane, 1- [β- (octylthio) ethyl] -4- (octylthio) cyclohexane , 1- [β-
(Dodecylthio) ethyl] -3- (dodecylthio) cyclohexane, 1- [β- (dodecylthio) ethyl] -4- (dodecylthio) cyclohexane, 1- [β- (octadecylthio) ethyl] -3- (octadecylthio) cyclohexane , 1- [β- (octadecylthio) ethyl] -4- (octadecylthio) cyclohexane, 1- [β- (octacosylthio) ethyl] -3- (octacosylthio) cyclohexane or 1- [β- (octa Cosylthio) ethyl] -4- (octacosylthio) cyclohexane, N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl as a heavy metal deactivator [Oxy] ethyl] oxamide, tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite, N, N'- Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Yl) propionyl] hydrazine or oxa butyric acid - bis (benzylidene hydrazide),
As an epoxy compound, a condensate of epichlorohydrin and bisphenol A (epoxy equivalent: 700 to 830) or a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent: 180 to 200) and others After adding a predetermined amount of each of the additives described above to a Henschel mixer (trade name) in a mixing ratio described in Table 1 below, stirring and mixing for 3 minutes,
The mixture was melt-kneaded at 250 ° C. with a twin-screw extruder having a diameter of 30 mm and pelletized. In addition, as Comparative Examples 1 to 13, MFR is 20 g / 1
Unstabilized powdery crystalline propylene homopolymer 43% by weight for 0 minutes and average particle size as magnesium hydroxide
Total of 100 consisting of 57% by weight of untreated surface of 0.6 to 0.8 μm
Predetermined amounts of the additives shown in Table 1 below were mixed in parts by weight, and melt-kneaded according to Examples 1 to 6 to obtain pellets. The test pieces used for the copper resistance test and the flammability test were obtained by pelletizing the pellets at a resin temperature of 250 ℃ and a mold temperature of 50 ℃.
Was prepared by injection molding. The obtained test pieces were used to evaluate heavy metal resistance (150 ° C. copper resistance) and flame retardancy by the above-mentioned test method. The results are shown in Table 1.

Examples 7 to 12 and Comparative Examples 14 to 26 50% by weight of powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) which is not stabilized as MFR 30 g / 10 min as polyolefin and water. As a compound A, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-t-butyl-4
-Hydroxybenzyl) benzene or bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-
t-Butylphenyl] terephthalate, 1-as Compound C
[Β- (octylthio) ethyl] -3- (octylthio) cyclohexane, 1- [β- (octylthio) ethyl] -4-
(Octylthio) cyclohexane, 1- [β- (dodecylthio) ethyl] -3- (dodecylthio) cyclohexane, 1
-[Β- (dodecylthio) ethyl] -4- (dodecylthio)
Cyclohexane, 1- [β- (octadecylthio) ethyl] -3- (octadecylthio) cyclohexane, 1- [β-
(Octadecylthio) ethyl] -4- (octadecylthio) cyclohexane, 1- [β- (octacosylthio) ethyl] -3- (octacosylthio) cyclohexane or 1-
[Β- (Otacosylthio) ethyl] -4- (octacosylthio) cyclohexane, N, N ′ as a heavy metal deactivator
-Bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl-4-thio (2'-methyl-4 '] -Hydroxy-5'-t-
Butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide) , Triglycidyl isocyanurate as epoxy compound (epoxy equivalent 100-110) or epoxidized soybean oil (epoxy equivalent)
220-240) and other additives in the prescribed amounts in the blending ratios shown in Table 2 below, Henschel Mixer (trade name)
The mixture was stirred and mixed for 3 minutes, and then melt-kneaded at 250 ° C. in a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 14 to 26, 50% by weight of powdery crystalline ethylene-propylene block copolymer (ethylene content: 8.5% by weight) having an MFR of 30 g / 10 minutes and not stabilized and an average particle size of 0.6 as magnesium hydroxide. ˜0.8 μm surface-untreated 50% by weight, and 100 parts by weight in total, were blended with predetermined amounts of the additives shown in Table 2 below, and melt-kneaded according to Examples 7-12. Pellets were obtained. The test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate heavy metal resistance (150 ° C. copper resistance) and flame retardancy by the above-mentioned test method. Table 2 shows the results.

Examples 13-18, Comparative Examples 27-39 MFR 7.0 g / 10 min as polyolefin Unstabilized powdery crystalline ethylene-propylene-butene-13
Original copolymer (ethylene content 2.5% by weight, butene-1 content
29.59% by weight and magnesium hydroxide [1], magnesium hydroxide [2], magnesium hydroxide [3], magnesium hydroxide [4] or magnesium hydroxide [5] surface-treated with fatty acid as magnesium hydroxide [5] ]
70.41% by weight and a total of 101.4 parts by weight (crystalline ethylene-propylene-butene-1 excluding fatty acids used for surface treatment)
100 parts by weight of the surface-untreated terpolymer and magnesium hydroxide) and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate or tris (3, 5-di-t-butyl-
4-hydroxybenzyl) isocyanurate, 1- [β- (octylthio) ethyl] -3- (octylthio) cyclohexane as compound C, 1- [β- (octylthio) ethyl] -4- (octylthio) cyclohexane, 1- [ β- (dodecylthio) ethyl] -3- (dodecylthio) cyclohexane, 1- [β- (dodecylthio) ethyl] -4- (dodecylthio) cyclohexane, 1- [β- (octadecylthio)
Ethyl] -3- (octadecylthio) cyclohexane, 1-
[Β- (octadecylthio) ethyl] -4- (octadecylthio) cyclohexane, 1- [β- (octacosylthio)
Ethyl] -3- (octacosylthio) cyclohexane or 1
-[Β- (octacosylthio) ethyl] -4- (octacosylthio) cyclohexane, N, as a heavy metal deactivator
N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl-4-thio (2'-methyl- 4'-hydroxy-5'-
t-Butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene) Hydrazide), a condensate of epichlorohydrin and bisphenol A as an epoxy compound (epoxy equivalent 700 to 830) or a mixture of condensate of epichlorohydrin and bisphenol A and condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 180 to 200) ) And other additives in predetermined proportions shown in Table 3 below in a Henschel mixer (trade name), and the mixture is stirred and mixed for 3 minutes, and then the bore diameter is 30 mm.
Was melt-kneaded at 250 ° C. in a twin-screw extruder to form pellets. Further, as Comparative Examples 27 to 39, powdery crystalline ethylene-propylene-butene-1 terpolymer having an MFR of 7.0 g / 10 min and not stabilized (ethylene content 2.5% by weight, butene-1 content 4.5. %) 29.59% by weight and magnesium hydroxide [2] 70.41% by weight surface-treated with fatty acid as magnesium hydroxide, a total of 101.4 parts by weight (crystalline ethylene-propylene-butene-1 excluding the fatty acid used for the surface treatment) 100 parts by weight as a total of terpolymer and untreated magnesium hydroxide) or MFR is 7.0 g
/ 10 min unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymer (ethylene content 2.5
%, Butene-1 content 4.5% by weight) 30% by weight and 70% by weight of magnesium hydroxide as an untreated surface having an average particle size of 0.6 to 0.8 μm. A predetermined amount of each additive was blended and melt-kneaded according to Examples 13 to 18 to obtain pellets. The test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate heavy metal resistance (140 ° C. copper resistance) and flame retardancy by the above-mentioned test method. Table 3 shows the results.

Examples 19-24, Comparative Examples 40-52 MFR 7.0 g / 10 min as a polyolefin Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 55% by weight , Melt index (when a load of 21.18N at 190 ° C is added
Amount of molten resin discharged for 10 minutes; hereinafter abbreviated as MI. ) 20
Unstabilized powdery Ziegler-Natta type high density ethylene homopolymer 10% by weight, Mooney viscosity ML1 + 4 (100 ° C) 25, unstabilized powdery amorphous ethylene-propylene A total of 100 parts by weight of a random copolymer (propylene content 25% by weight) 5% by weight and magnesium hydroxide 30% by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm was added to 1,3 as the compound B. , 5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate or tris (3,5-di-t-butyl) -4-hydroxybenzyl) isocyanurate, as compound C 1- [β-
(Octylthio) ethyl] -3- (octylthio) cyclohexane, 1- [β- (octylthio) ethyl] -4- (octylthio) cyclohexane, 1- [β- (dodecylthio)
Ethyl] -3- (dodecylthio) cyclohexane, 1- [β-
(Dodecylthio) ethyl] -4- (dodecylthio) cyclohexane, 1- [β- (octadecylthio) ethyl] -3-
(Octadecylthio) cyclohexane, 1- [β- (octadecylthio) ethyl] -4- (octadecylthio) cyclohexane, 1- [β- (octacosylthio) ethyl] -3-
(Octacosylthio) cyclohexane or 1- [β- (octacosylthio) ethyl] -4- (octacosylthio) cyclohexane, N, N'-bis [2 as a heavy metal deactivator
-[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5) '-t-Butylphenyl) -5-methylphenyl] phosphite, N, N'-
Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), triglycidyl isocyanurate as an epoxy compound (epoxy equivalent 100-1
10) or epoxidized soybean oil (epoxy equivalent 220-240),
As a fatty acid, acetic acid, 2-ethylhexanoic acid, erucic acid, montanic acid, or 12-hydroxyoctadecanoic acid, and a predetermined amount of each of the other additives were placed in a Henschel mixer (trade name) at a compounding ratio shown in Table 4 below. After stirring and mixing for 3 minutes, the mixture was melt-kneaded at 250 ° C. in a twin-screw extruder having a diameter of 30 mm to form pellets. Also, as Comparative Examples 40 to 52, M
Unstabilized crystalline crystalline ethylene-propylene random copolymer with FR of 7.0 g / 10 min (ethylene content
2.5 wt%) 55 wt%, MI stabilized 20 g / 10 min. Unstabilized powdered Ziegler-Natta high density ethylene homopolymer 10 wt%, Mooney viscosity ML1 + 4 (100 ° C) stabilized at 25 Powdered amorphous ethylene-propylene random copolymer (propylene content 25% by weight) 5% by weight
And a total of 100 parts by weight of magnesium hydroxide as a surface-untreated product having an average particle size of 0.6 to 0.8 μm and 30% by weight, each of which is blended with a predetermined amount of the additive shown in Table 4 below. Melt-kneading treatment was carried out according to to obtain pellets.
The test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate heavy metal resistance (140 ° C. copper resistance) and flame retardancy by the above-mentioned test method. Table 4 shows the results.

The compounds and additives relating to the present invention shown in Tables 1 to 4 are as follows. Magnesium hydroxide [0]: Surface-untreated product having an average particle size of 0.6 to 0.8 μm Magnesium hydroxide [1]: Surface-untreated product having an average particle size of 0.6 to 0.8 μm 100 parts by weight of lauric acid (fatty acid [3]) Two
Surface-treated product surface-treated with parts by weight Magnesium hydroxide [2]: 100 parts by weight of surface-untreated product having an average particle size of 0.6 to 0.8 μm and stearic acid (fatty acid [4])
Surface-treated product surface-treated with 2 parts by weight Magnesium hydroxide [3]: 100 parts by weight of surface-untreated product having an average particle size of 0.6 to 0.8 μm and oleic acid (fatty acid [5]) 2
Surface-treated product surface-treated with parts by weight Magnesium hydroxide [4]: Linoleic acid (fatty acid [6]) 2 in 100 parts by weight of surface-untreated product having an average particle size of 0.6 to 0.8 μm
Surface-treated product surface-treated with 1 part by weight Magnesium hydroxide [5]: Surface-treated product with 100 parts by weight of surface-untreated product having an average particle size of 0.6 to 0.8 μm and 2 parts by weight of behenic acid (fatty acid [7]) Compound A [1]: 1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene compound A [2]: bis [2- (3'-t-butyl-5'-methyl-2 '
-Hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate Compound B [1]: 1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene compound B [2]: bis [2- (3'-t-butyl-5'-methyl-2 '
-Hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate compound B [3]: tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate compound C [1]: 1- [Β- (octylthio) ethyl] -3-
(Octylthio) cyclohexane compound C [2]: 1- [β- (octylthio) ethyl] -4-
(Octylthio) cyclohexane compound C [3]: 1- [β- (dodecylthio) ethyl] -3-
(Dodecylthio) cyclohexane compound C [4]: 1- [β- (dodecylthio) ethyl] -4-
(Dodecylthio) cyclohexane compound C [5]: 1- [β- (octadecylthio) ethyl] -3- (octadecylthio) cyclohexane compound C [6]: 1- [β- (octadecylthio) ethyl] -4- ( Octadecylthio) cyclohexane compound C [7]: 1- [β- (octacosylthio) ethyl] -3- (octacosylthio) cyclohexane compound C [8]: 1- [β- (octacosylthio) ethyl]- 4- (octacosylthio) cyclohexane

Heavy metal deactivator [1]: N, N'-bis [2]
-[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide heavy metal deactivator [2]: tris [2-t-butyl-4-thio (2'- Methyl-4'-hydroxy-5'-t-butylphenyl) -5-
Methylphenyl] phosphite Heavy metal deactivator [3]: N, N'-bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyl] hydrazine Heavy metal deactivator [4]: Oxalic acid-bis (benzylidene hydrazide) Epoxy compound [1]: Condensate of epichlorohydrin and bisphenol A (epoxy equivalent 700-830; CIBA
-ARALDITE GT7004 manufactured by GEIGY AG) Epoxy compound [2]: a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 18
0-200; ADK CIZER E manufactured by Asahi Denka Co., Ltd.
P-17) Epoxy compound [3]: triglycidyl isocyanurate (epoxy equivalent 100 to 110; CIBA-GEIGY A)
G ALALDITE PT 810) Epoxy compound [4]: Epoxidized soybean oil (epoxy equivalent 220-240; Asahi Denka Kogyo ADK CIZER)
O-130P) fatty acid [1]: acetic acid fatty acid [2]: 2-ethylhexanoic acid fatty acid [3]: lauric acid fatty acid [4]: stearic acid fatty acid [5]: oleic acid fatty acid [6]: linoleic acid fatty acid [ 7]: behenic acid fatty acid [8]: erucic acid fatty acid [9]: montanic acid fatty acid [10]: 12-hydroxyoctadecanoic acid

Phosphorus antioxidant 1: bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite Phosphorus antioxidant 2: bis (2,6-di-t-butyl-4) -Methylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 3: tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite phenolic antioxidant 1 : 2,6-di-t-butyl-p-cresol Phenolic antioxidant 2: Tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 3: 2,2-bis [4- [2- (3,5-di
-t-butyl-4-hydroxyphenylpropionyloxy)
Ethoxy] phenyl] propane phenolic antioxidant 4: tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate phenolic antioxidant 5: tris [3- (3,5-di -t-Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate Phenolic antioxidant 6: 1,1,3-tris (5-t-butyl)
-4-Hydroxy-2-methylphenyl) -butane phenolic antioxidant 7: Bis [3,3-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] ethylene glycol ester phenolic oxidation Inhibitor 8: 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Thioether antioxidant 1: Dimyristyl thiodipropionate Thioether antioxidant Agent 2: Pentaerythritol-
Tetrakis (3-lauryl thiopropionate) Higher fatty acid ester: Butyl stearate Higher alcohol: Stearyl alcohol Higher fatty acid monoamide: Stearic acid amide Carbon black: Carbon # 45 Mitsubishi Chemical Corporation Ca-St: Calcium stearate

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

The examples and comparative examples shown in Table 1 are cases where a crystalline propylene homopolymer was used as the polyolefin and a surface-untreated product was used as the magnesium hydroxide. As can be seen from Table 1, Examples 1 to 6 are obtained by blending crystalline propylene homopolymer with magnesium hydroxide (untreated surface), compound A, compound C, heavy metal deactivator and epoxy compound. Examples 1 to 6 and Comparative Examples 1 to 4
(In Examples 1 to 6, thioether-based antioxidants 1 and 2 other than compound C were blended in place of compound C; the present inventor previously disclosed JP-A-2-214751 and JP-A-2-240148. Compared with the composition proposed as the publication), Examples 1 to 6 are excellent in heavy metal resistance,
It can be seen that in the presence of magnesium hydroxide, the thioether antioxidants 1 and 2 other than the compound C do not sufficiently exhibit the peroxide decomposing effect, that is, the antioxidant effect. Example 1
Comparative Examples 5 to 6 in which phenolic antioxidants 2 to 8 other than Compound A are blended instead of Compound A respectively
Comparing No. 11 with Examples 1 to 6, Examples 1 to 6 are excellent in heavy metal resistance, and the phenolic antioxidants 2 to 8 other than the compound A in the presence of magnesium hydroxide are radical chain-inhibited. It is understood that the action, that is, the antioxidant effect is not sufficiently exhibited. Further, comparing Comparative Examples 12 to 13 and Examples 1 to 6 in which the epoxy compound is not blended in Examples 1 to 6, the heavy metal resistance of Comparative Examples 12 to 13 is still insufficient. Therefore, it is apparent that the comparative examples that do not simultaneously satisfy the formulation of the four components of the compound A, the compound C, the heavy metal deactivator and the epoxy compound according to the present invention do not exhibit the effects of the present invention. That is, the heavy metal resistance obtained in the present invention is observed only when compound A, compound C, a heavy metal deactivator and an epoxy compound are used in combination with a flame-retardant polyolefin composition containing magnesium hydroxide. It can be said that this is a unique effect. The flame-retardant composition according to the present invention containing compound A, compound C, a heavy metal deactivator, and an epoxy compound is comparable in flame retardancy to conventionally known flame-retardant compositions. It was confirmed to be a thing.

Table 2 shows a crystalline ethylene-propylene block copolymer used as the polyolefin and a surface-untreated product as the magnesium hydroxide, and the same effects as above were confirmed for these.

In the examples and comparative examples shown in Table 3, crystalline ethylene-propylene-butene-1 was used as the polyolefin.
This is the case of using a terpolymer and a surface-treated product obtained by surface-treating a fatty acid as magnesium hydroxide. As can be seen from Table 3, Examples 13-18 are crystalline ethylene-propylene-
This is a mixture of butene-1 terpolymer with magnesium hydroxide (surface treated product), compound B, compound C, a heavy metal deactivator and an epoxy compound. Examples 13-18 and Comparative Examples 27-29 (In Examples 13 to 18, thioether-based antioxidants 1 and 2 other than compound C were blended in place of compound C; the present inventor previously disclosed JP-A-3-81352 and JP-A-6-41357. In comparison with the composition proposed as the publication), Examples 13 to 18 have excellent heavy metal resistance, and thioether antioxidants 1 and 2 other than compound C in the presence of magnesium hydroxide are peroxides. It can be seen that the decomposition action, that is, the antioxidant effect is not sufficiently exhibited. Instead of compound B in Examples 13-18, compound B
Comparing Comparative Examples 30 to 36 and Examples 13 to 18 in which the other phenolic antioxidants 2 to 8 were blended, Examples 13 to 18 were excellent in heavy metal resistance and coexisted with magnesium hydroxide. Below, phenolic antioxidants other than compound B 2
It can be seen that a radical chain inhibition effect of 8 to 8, that is, an antioxidant effect is not sufficiently exhibited. Further, in Examples 13 to 18, magnesium hydroxide (surface-treated product) was replaced with magnesium hydroxide (surface-untreated product) and a surface-treating agent other than fatty acid, that is, higher fatty acid ester, higher alcohol or higher fatty acid monoamide, respectively. Comparing Comparative Examples 37 to 39 and Examples 13 to 18, Comparative Example 37
Heavy metal resistance of ~ 39 is not yet sufficient. Therefore, the compound B, the compound C, the heavy metal deactivator according to the present invention,
It is apparent that the comparative examples that do not simultaneously satisfy the combination of the five components of the epoxy compound and the fatty acid do not exhibit the effects of the present invention. That is, the heavy metal resistance obtained in the present invention is
Compound B, Compound C, a heavy metal deactivator, in a flame-retardant polyolefin composition containing magnesium hydroxide.
It can be said that this is a unique effect that can be seen only when the epoxy compound and the fatty acid are used in combination. In addition, the flame-retardant composition according to the present invention, which comprises compound B, compound C, a heavy metal deactivator, an epoxy compound and a fatty acid, has no flame-retardant property as compared with conventionally known flame-retardant compositions. It was confirmed to be comparable.

Table 4 shows a crystalline ethylene-propylene random copolymer as a polyolefin, a mixture of a Ziegler-Natta high-density ethylene homopolymer and an amorphous ethylene-propylene random copolymer, and a surface-untreated magnesium hydroxide. The same effects as those described above were confirmed for these products.

[0037]

EFFECTS OF THE INVENTION The composition of the present invention is (1) superior to a conventional flame-retardant polyolefin composition having improved resistance to heavy metals prepared by incorporating magnesium hydroxide. The heavy metal resistance of the molded product is remarkably excellent. (2) Since the heavy metal resistance is remarkably excellent, there is no deterioration in electrical insulation due to the oxidative deterioration of the polyolefin, and therefore, applications in which flame resistance and heavy metal resistance in various molding fields are required (for example, a deflection yoke, It can be preferably used for electric and electronic functional parts such as CRT sockets and connectors, automotive parts such as distributor caps, car heater cases and car air conditioner cases, and insulating materials such as wire coating materials.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08K 5/15 KET C08K 5/15 KET 5/3492 KFB 5/3492 KFB 5/375 KFE 5/375 KFE

Claims (2)

[Claims] 1. One or two phenolic compounds selected from the following, based on 100 parts by weight of a composition consisting of 70 to 30% by weight of polyolefin and 30 to 70% by weight of magnesium hydroxide, the following general formula: A flame-retardant polyolefin composition comprising 0.01 to 1 part by weight of each of a thioether compound (1), a heavy metal deactivator and an epoxy compound. 1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate (However, in the formula, R represents an alkyl group having 8 to 28 carbon atoms.) 2. Based on 100 parts by weight of a composition comprising 70 to 30% by weight of polyolefin and 30 to 70% by weight of magnesium hydroxide, one or more phenolic compounds selected from the following, compound C 0.01 to 1 part by weight of heavy metal deactivator and epoxy compound, respectively, and 0.5 of fatty acid.
A flame-retardant polyolefin composition containing up to 5 parts by weight. 1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate tris (3,5-di-t -Butyl-4-hydroxybenzyl) isocyanurate