JPH01163230A - Flame-retardant polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent properties of preventing oxidative deterioration in practical use, by blending a composition consisting of a polyolefin and halogen based flame retardant with a specific phenolic compound, heavy metal deactivator and epoxy compound. CONSTITUTION:The aimed composition obtained by blending 100 pts.wt. flame retardant composition consisting of (A) a polyolefin and (B) a halogen based flame retardant with (C) 0.01-1 pt.wt. phenolic compound expressed by formulas I, II and/or III (R1 is 1-8C alkyl; R2 is H or 1-8C alkyl; R3 and R4 are 1-9C alkyl, cycloalkyl, aryl, etc.; R5 is 1-12C alkyl; R6 is H or 1-12C alkyl; m and n are 1-6; k and y are 0-8; x is 1-12), (D) 0.01-1 pt.wt. heavy metal deactivator and (E) 0.01-1 pt.wt. epoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to flame-retardant polyolefin compositions. More specifically, the present invention relates to a flame-retardant polyolefin composition that is excellent in preventing oxidative deterioration of polyolefin in practical use.

[Prior Art] Generally, various halogen-based flame retardants are blended into polyolefins for the purpose of making them flame retardant, and this is widely used in practice. However, flame-retardant polyolefin compositions containing halogen-based flame retardants,
The halogen-based flame retardant is decomposed by the heat during melt-kneading during molding, and polyolefins undergo oxidative deterioration due to the halogen radicals generated. ) is significantly reduced. In particular, propylene-based polymers have tertiary carbon that is susceptible to oxidation, so the above-mentioned problem of long-term thermal stability becomes significant.

In addition, when the flame-retardant polyolefin composition is molded and the molded products obtained by molding the composition are used for various automotive parts and electrical and electronic parts, the molded products can be made from heavy metals such as steel, brass, iron, and nickel. It may be used in applications where it comes into contact with. However, since polyolefins undergo catalytic oxidative deterioration by heavy metal ions contained in the various heavy metals mentioned above, the thermal oxidative deterioration resistance of flame-retardant polyolefin compositions upon contact with heavy metals (hereinafter referred to as 101 heavy metal properties) is Problems such as a significant decrease occur.

For this reason, for the purpose of improving the long-term thermal stability of flame-retardant polyolefin compositions containing halogen-based flame retardants, metal soap (Japanese Unexamined Patent Application Publication No. 49-31749) ), epoxy compounds (JP-A-52-92258 and JP-A-52-11965)
5), stearic acid metal salts, i.e. metal soaps and epoxy compounds (JP-A-48-60135),
Phenolic antioxidants (JP-A-54-135838, JP-A-55-120644 and JP-A-5
No. 7-145136], a flame-retardant polyolefin composition containing a phenolic antioxidant and a saturated ester of bis-dithiopropionic acid (Japanese Unexamined Patent Publication No. 53-86744) has been proposed. In addition, for the purpose of improving the flame retardancy of a flame-retardant polyolefin composition, a flame-retardant polyolefin composition (JP-A-51-10615
3 and Japanese Unexamined Patent Publication No. 54-73843). On the other hand, polyolefin I! i1 A polyolefin composition prepared by blending the polyolefin with a phenolic compound having a specific spiro ring structure and a metal deactivator for the purpose of improving heavy metal properties (Japanese Patent Application Laid-Open No. 1983-1999).
112643) has been proposed.

[Problems to be solved by the invention] However, in recent years, flame retardant requirements have become increasingly strict in applications such as electrical and electronic parts or automobile parts, and molded products obtained from flame-retardant polyolefin compositions As the applications of molded products become more diverse and larger, the requirements for the practical use conditions (long-term thermal stability, resistance to heavy metals, electrical insulation, etc.) of the molded products are also becoming stricter. That is, it is necessary to develop a flame-retardant polyolefin composition that has better resistance to thermal oxidative deterioration than ever before. In order to solve these problems, a flame retardant polyolefin composition containing a halogenated flame retardant is blended with one or two selected from metal soaps and epoxy compounds. 31749, JP-A-52-92258, JP-A-52-119655 and JP-A-4
The flame-retardant polyolefin composition proposed in Japanese Patent Publication No. 8-60135 is still not fully satisfactory in terms of long-term thermal stability and hot metal properties.
No. 8, JP-A-55-120644, JP-A-Sho 5
Publication No. 7-145136 and JP-A-53-86744
The flame-retardant polyolefin composition proposed in the publication, in which a phenolic antioxidant is blended alone or a saturated ester of bis-dithiopropionic acid is combined with the phenolic antioxidant, has considerably improved long-term thermal stability. However, it is still not fully satisfactory when used for monthly applications that require a high degree of long-term thermal stability, and its resistance to heavy metals is still not fully satisfactory. Also, JP-A-5
Publication No. 1-106153 and Japanese Unexamined Patent Publication No. 1973-73843
The flame-retardant polyolefin composition containing melamine proposed in the publication is still not fully satisfactory in terms of long-term thermal stability and heavy metal resistance. Also, JP-A-6
Although the long-term thermal stability and heavy metal resistance of the polyolefin composition prepared by blending a phenolic compound having a specific spiro ring structure and a metal deactivator proposed in Japanese Patent No. 2-112643 are quite excellent, The long-term thermal stability and heavy metal resistance of a flame-retardant polyolefin composition prepared by blending a halogenated flame retardant with a polyolefin composition are still not fully satisfactory. This is thought to be due to insufficient scavenging action for halogen radicals generated from halogen-based flame retardants. In addition, the inventor of the present invention
Although the long-term thermal stability of the flame-retardant polyolefin composition prepared by blending a specific phenolic antioxidant, a specific phosphorous antioxidant, and an epoxy compound proposed in Japanese Patent No. 167338 is quite excellent, Heavy metal properties are still not fully satisfactory.

The present inventors have conducted extensive research to solve the above-mentioned problems with flame-retardant polyolefin compositions containing the above-mentioned halogenated flame retardants, that is, long-term thermal stability and heavy metal resistance.

As a result, a phenol compound represented by the following general formula [I] (hereinafter referred to as compound A), a phenol compound represented by the following general formula [■ (Hereinafter, compound B
That's what it means. ) and a phenolic compound (hereinafter referred to as compound C) represented by the following general formula [ml]
It has been discovered that a composition comprising specific amounts of one or more phenolic compounds, a heavy metal deactivator, and an epoxy compound can solve the above-mentioned problems of flame-retardant polyolefin compositions. The present invention was completed based on this knowledge.

(However, in the formula, R5 is an alkyl group having 1 to 8 carbon atoms, R
3 is an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group, a cyclohexylalkyl group, an aryl group, or an arylalkyl group, and R4 is hydrogen or an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group, or a cyclohexylalkyl group. base,
An aryl group or an arylalkyl group, R5 is an alkyl group having 1 to 12 carbon atoms, R6 is hydrogen or an alkyl group having 1 to 12 carbon atoms, m and n are integers of 1 to 6, and k is 0 to 8. , X is an integer from 1 to 12, y is 0
Each represents an integer between 8 and 8. ) As is clear from the above description, an object of the present invention is to provide a flame-retardant polyolefin composition which, when formed into a molded article, has excellent long-term thermal stability and heavy metal resistance.

[Means for solving problems] The present invention has the following configuration.

A phenol compound represented by the phenol formula [II] represented by the following general formula [11] (hereinafter referred to as compound B) is added to a flame retardant composition consisting of a polyolefin and a halogen flame retardant, based on 100 parts by weight of the polyolefin. ) and one or more phenolic compounds selected from the following general formula [I[I] (hereinafter referred to as compound C), a heavy metal deactivator, and an epoxy compound. A flame-retardant polyolefin composition containing .01 to 1 part by weight.

(However, in the formula, R4 is an alkyl group having 1 to 8 carbon atoms,
2 is hydrogen or an alkyl group having 1 to 8 carbon atoms, R3 is an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group, a cyclohexylalkyl group, an aryl group, or an arylalkyl group, and R4 is hydrogen or an alkyl group having 1 to 9 carbon atoms. -9 alkyl group, cycloalkyl group, cyclohexylalkyl group, aryl group or arylalkyl group, R6 has 1 carbon number
~12 alkyl group, R6 is hydrogen or carbon number 1~
12 alkyl groups, m and n are integers of 1 to 6, k
is an integer from 0 to 8, X is an integer from 1 to 12, and y is an integer from 0 to 8.
Indicate each integer. ) 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-11 octene-1, or two or more of these. Crystalline, low-crystalline or non-crystalline random copolymers or crystalline block copolymers of α-olefins, amorphous ethylene-propylene-nonconjugated diene ternary copolymers, the above-mentioned α-olefins and acetic acid Copolymers with vinyl or acrylic acid esters, saponified products of these copolymers, copolymers of these α-olefins with unsaturated silane compounds, copolymers of these α-olefins with unsaturated carboxylic acids or their anhydrides. Examples include polymers, reaction products of copolymers and metal ion compounds, modified polyolefins obtained by modifying polyolefins with unsaturated carboxylic acids or derivatives thereof, and silane-modified polyolefins obtained by modifying polyolefins with unsaturated silane compounds. It is possible to use these polyolefins alone, but it is also possible to use a mixture of two or more polyolefins. In addition, the above-mentioned polyolefins and various synthetic rubbers (for example, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-styrene block copolymer) , styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-
propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resins (e.g., polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate,
(polycarbonate, polyvinyl chloride, fluororesin, etc.)
It is also possible to use a mixture of the following. Crystalline propylene homopolymer, propylene copolymer containing 70% by weight or more of propylene component, including crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene- 1 random copolymer, crystalline ethylene-propylene-butene-1
Tertiary copolymer, crystalline propylene-hexene-butene-
13-component copolymers and mixtures of two or more thereof are particularly preferably used.

Compound A used in the present invention includes tetrakis[methylene-3-(3'-methyl-4'-hydroxy-5'-
t-butylphenyl>acetate comethane, tetrakis[methylene-3-(3',5'-di-t-butyl-4'
-hydroxyphenyl)acetate comethane, tetrakis[methylene-3-(3'-t-butyl-4'-hydroxyphenyl)propionate comethane, tetrakis[
Methylene-3-(3'-t-amyl-4'-hydroxyphenyl)propionate comethane, tetrakis [Methylene-3-(3'-t-octyl-4'-hydroxyphenyl)propionate comethane, tetrakis [ Methylene-3-(3'-methyl-42-hydroxy-5'-1
-butylphenyl)propionate comethane, tetrakis[methylene-3-(3'-methyl-4'-hydroxy-5'-t-amylphenyl)propionate comethane, tetrakis[methylene-3-('3'- Methyl-4'
-Hydroxy-51-t-octylphenyl)propionate comethane, tetrakis[methylene-3-(3'-
Ethyl-4'-hydroxy-5'-t-butylphenyl)propionate comethane, tetrakis[methylene-3
-(3'-i-propyl-4'-hydroxy-5'-t
-butylphenyl)propionate comethane, tetrakis[methylene-3-(3'-1-butyl-4'-hydroxy-5'-t-butylphenyl)propionate comethane, tetrakis[methylene-3-(3'-s-Butyl-4'-hydroxy-5'-t-butylphenyl)propionate comethane, tetrakis[methylene-3.(3
',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane, tetrakis[methylene-3
-(3'-t-butyl-4'-hydroxy-5'-t-
amyl phenyl)propione-tocomethane, tetrakis[methylene-3-(3'-t-butyl-4'.hydroxy-5'-t-octylphenyl)propionate comethane, tetrakis[methylene-3-(3', 5'-di-t-amyl-4'-hydroxyphenyl)propionate comethane, tetrakis[methylene-3-(3',5
'-di-t-octyl-4'-hydroxyphenyl)propionate comethane, tetrakis[methylene-3-(
2'-Methyl-4'-hydroxy-52/t-butylphenyl)propionate comethane, tetrakis[methylene-3-(2',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane Methane, tetrakis [
Methylene-3-(2'-methyl-4'-hydroxy-5
'-t-octylphenyl)propionate comethane,
Tetrakis[methylene-3-(2'-t-butyl-4'
-hydroxy-5'-methylphenyl)propionate comethane, tetrakis[methylene-3-(3'-methyl-41-hydroxy-5'-t-butylphenyl)butyrate comethane, tetrakis[methylene-3-( 3',
5'-di-t-butyl-4'-hydroxyphenyl)butyrate comethane, tetrakis[methylene-3-(3'
-Methyl-4'-hydroxy-5'-t-butylphenyl)hexoate comethane, tetrakis[methylene-3
-(3',5'-di-t-butyl-4'-hydroxyphenyl)hexoate comethane, tetrakis[ethylene-3-(3'-methyl-4'-hydroxy-5'-t-
butylphenyl)acetate comethane, tetrakis[ethylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)acetatecomethane, tetrakis[
Ethylene-3-(3'-methyl-4'-hydroxy-5
'-t-butylphenyl)propionate comethane, tetrakis[ethylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane, tetrakis[ethylene-3-(3 '-methyl-4'
-Hydroxy-5'-t-butylphenyl)butyratecomethane, tetrakis[ethylene-3-(3',5'-
di-t-butyl-4'-hydroxyphenyl)butyrate comethane, tetrakis[ethylene-3-(3'-methyl-4'-hydroxy-5'-t-butylphenyl)hexoate comethane, tetrakis[ Ethylene-3-(3
', 5'-di-t-butyl-4'-hydroxyphenyl)hexoate comethane, tetrakis[hexamethylene-3-(3'-methyl-4'-hydroxy-5'-t-
butylphenyl) acetate comethane, tetrakis[hexamethylene-3-(3',5'-di-t-butyl-4
'-hydroxyphenyl)acetate comethane, tetrakis[hexamethylene-3-(3'-methyl-4'-hydroxy-5'-t-butylphenyl)propionate comethane, tetrakis[hexamethylene-3-(3' ,
5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane, tetrakis[hexamethylene-
3-(3'-Methyl-4'-hydroxy-5'-t-butylphenyl)butyratecomethane, tetrakis[hexamethylene-3-(3',5'-di-t-butyl-4')
-hydroxyphenyl)butyrate comethane, tetrakis[hexamethylene-3-(3'-methyl-4'-hydroxy-5'-t-butylphenyl)hexoate comethane and tetrakis[hexamethylene-3-(3 ',
Examples include 5'-di-t-butyl-hydroxyphenyl)hexoate comethane, particularly tetrakis[methylene-3-(3'-methyl-4'-hydroxy-5')
-t-butylphenyl)propionate comethane and tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane are preferred. These phenolic compounds can be used alone, but two or more phenolic compounds can also be used in combination.

Compound B used in the present invention is 3,9-bis[l
, 1-dimethyl-2-((3-t-butyl-4-hydroxy-5-methylphenyl)carbonyloxy)ethyl-2.4,8.10-tetraoxaspiro[5,5-oundecane, 3.9-bis [1,1-dimethyl-2・(
(3,5-di-t-butyl-4-hydroxyphenyl)
carbonyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[
l, 1-dimethyl-2-((3,5-diphenyl-4-
hydroxyphenyl)carbonyloxy)ditylco2
．． 4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,l-dimethyl-2-{β-(
3゜5-dicyclohexyl-4-hydroxyphenyl)
carbonyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[
1,1-dimethyl-2-{β-(3-t-butyl-4-
hydroxy-5-methylphenyl)acetyloxy)ethyl]-2,4,8,lo-tetraoxaspiro[5
,5] undecane, 3,9-bis[1,1-dimethyl-
2-{β-(3,5-di-t-butyl-4-hydroxyphenyl)acetyloxy)ethyl]-2,4,8,1
0-tetraoxaspiro[5,5-oundecane, 3.9
-bis[1,1-dimethyl-2-{β-(3,5-diphenyl-4-hydroxyphenyl)acetyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,
51 undecane, 3,9-bisEl, l-dimethyl 2
-{β-3,5-dicyclohexyl-4-hydroxyphenyl)acetyloxy)ethyl] -2,4,8,
10-tetraoxaspiro[5,5]undecane, 3,
9-bis[l,1-dimethyl-2-{β-(3-1-butyl-4-hydroxyphenyl)propionyloxy)
ethyl]-2.4,8.10-tetraoxaspiro[5
, 5-oundecane, 3,9-bis[1,l-dimethyl-
2.{β-(3-t-amyl-4-hydroxyphenyl)propionyloxy)ethyl] -2,4,8,10
-tetraoxaspiro[5,5-oundecane, 3,9-
Bis[1,l-dimethyl-2-{β-(3-t-octyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5
,5] undecane, 3,9-bis[1,1-dimethyl-
2-{β-(3-methyl-4-hydroxy-5-t-amylphenyl)propionyloxy)ethylco2.4
, 8.10-Tetraoxaspiro[5,5]undecane, 3,9-bis[l,1-dimethyl-2-{β-(3-
methyl-4-hydroxy-5-t-octylphenyl)
propionyloxy)ethyl] -2,4,8,10-
Tetraoxaspiro[5,51 undecane, 3,9-bis[1,1-dimethyl-2-{β-(3-ethyl tovidroxy-5-t-butylphenyl)propionyloxy)ethyl]-2,4, 8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{β-(3-1-propyl-4-hydroxy-
5-tert-butylphenyl)propionyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5-oundecane, 3,9-bis[l,1-dimethyl-2-{
β-(3-1-butyl-4-hydroxy-5-t-butylphenyl)propionyloxy)ethyl] -2,4
,8゜10-tetraoxaspiro[5,5]undecane, 3,9-bis[! , l-dimethyl-2-{β-(3-
3-Butyl-4-hydroxy-5-4-butylphenyl)propionyloxy)dityl]-2.4,8.10-
Tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{β-(3-1-butyl-
4-hydroxy-5-methylphenyl)propionyloxy)dityl]-2.4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,l-dimethyl-2-{β -(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl] -2
,4,8゜10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{β-(
3-t-butyl-4-hydroxy-5-t-amylphenyl)propionyloxy)ethyl]-2.4,8.1
0-tetraoxaspiro[5,5]undecane, 3,9
-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-t-octylphenyl)propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro[ 5,5] undecane, 3,9-bis[1
,1-dimethyl-2-{β-(3,5-di-t-amyl-4-hydroxydiphenyl)propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5,
5] Undecane, 3.9-bis[l, ■-dimethyl-2
-{β-(3,5-di-t-octyl-4-hydroxyphenyl)propionyloxy)ethyl2.4,8
．． 10-tetraoxaspiro[5,5]undecane, 3
．．゛9-bis[1,l-dimethyl-2-{β・(2-methyl-4-hydroxy-5-t-butylphenyl)propionyloxy)ethyl] -2,L8,10-tetraoxaspiro[5, 5] undecane, 3,9-bis[1
,1-dimethyl-2-{β-(2,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl] -2,4,8°10-tetraoxaspiro[5,
5] Undecane, 3,9-bis[1,1-dimethyl-2
-{β-(2-methyl-4-hydroxy-5-t-octylphenyl)propionyloxy)ethyl] -2,
4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{β-(2
-t-butyl-4-hydroxy-5-methylphenyl)
propionyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{β-(3,5-dicyclohexyl- 4-Hydroxyphenyl)propionyloxy)ethyl] -2,4,8,10-tetraoxasbid
[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{β-(3,5-di(1-methylcyclohexyl)-4-hydroxyphenyl)propionyloxy)ethyl]-2. 4,8.10-tetraoxaspiro[
5,5-oundecane, 3,9-bis[1,l-dimethyl-2-{β-(3,5-diphenyl-4-hydroxyphenyl)propionyloxy)ethyl2.4,8.
10-tetraoxaspiro[5,5]undecane, 3,
9-bis[1,l-dimethyl-2-{β-(3,5-dibenzyl-4-hydroxyphenyl)propionyloxy)ethylco2.4,8.10-tetraoxaspiro[5,5oundecane, 3. 9-bis[1,1-dimethyl-2-{β-(3,5-di(α-methylbenzyl)-
4-hydroxyphenyl)propionyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5,5
Condecane, 3,9-bis[1,l-dimethyl-2-
{β-(3,5-di(α,α-dimethylbenzyl)-4
-hydroxyphenyl)propionyloxy)ethyl]
-2.4,8.10-tetraoxaspiro[5,5-oundecane, 3,9-bis[1,l-dimethyl-2-{β
-(3-1-butyl-4-hydroxy-5-methylphenyl)butylenyloxy)ethyl] -2,4,8,1
0-tetraoxaspiro[5,5]undecane, 3.9
-bis[1,1-dimethyl-2-{β-(3,5-di-
t-Butyl-4-hydroxyphenyl)butylenyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5-oundecane, 3,9-bis[1,1-dimethyl-2-{β-(3 ,5-diphenyl-4-hydroxyphenyl)butylenyloxy)ethyl] -2,4,8
, 10-tetraoxaspiro[5,5]undecane, 3
,9-bis[1,1-dimethyl-2-{β-(3,5-
dicyclohexyl-4-hydroxyphenyl)butylenyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-
Dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)hexonyloxy)ethyl]
-2.4,8.10-tetraoxaspiro[5,5-oundecane, 3,9-bis[1,1-dimethyl-2-{β
-(3,5-di-t-butyl-4-hydroxyphenyl)hexonyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5-oundecane, 3,9-bis[1,1- Dimethyl-2-{β・(3,5-diphenyl-4-hydroxyphenyl)hexonyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5,5
] undecane, 3,9-bis[l,1-dimethyl-2-
{β-(3,5-dicyclohexyl-4-hydroxyphenyl)hexonyloxy)ethyl]-2.4,8.1
0-tetraoxaspiro[5,5]undecane, 3,9
-bis[l,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)octonyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5 ,5] undecane, 3,9-bis[1,l-dimethyl-2-{β-(3,5-di-t-butyl-4-hydroxyphenyl)octonyloxy)ethyl] -2
, 4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[l, 1-dimethyl-2-{β-(
3,5-diphenyl-4-hydroxyphenyl)octonyloxy)ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane and 3,9-bis[
l,1-dimethyl-2-{β-(3,5-dicyclohegysylatehydroxyphenyl)octonyloxy)dityl]-2.4,8.10-tetraoxaspiro[5,5
] undecane, etc., and in particular, 3,9-bis[1,
1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl2.4,8.10-tetraoxaspiro[5,
5] Undecane, 3,9-bis[1,1-dimethyl-2
-{β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2.4,8.
10-tetraoxaspiro[5,5-oundecane, 3,
9-bis[1,1-dimethyl-2-{β-(3゜5-diphenyl-4-hydroxyphenyl)propionyloxy)ethyl]-2.4,8.10-tetraoxasbiC
I[5,5-oundecane and 3,9-bis[1,1-
Dimethyl-2-{β-(3,5-dicyclohexyl=4
-hydroxyphenyl)propionyloxy)ethyl]
-2,4,8,10-tetraoxaspiro[5,5-oundecane is preferred. These phenolic compounds can be used alone, but two or more phenolic compounds can also be used in combination.

Compound C used in the present invention is 1,3.5-)
Riskuchi (3-methyl-5-t-butyl-4-hydroxyphenyl) carbonyloxyethyl coisocyanurate,! , 3.5- ) lis [(3,5-di-t-butyl-
4-Hydroxyphenyl)carbonyloxyethyl coisocyanurate, 1,3.5-)lis[(3-methyl-5-t-butyl-4-hydroxyphenyl)acetyloxyethyl]isocyanurate,! , 3.5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)acetyloxyethyl coisocyanurate, 1,3.
5-) Lis[(3-t-butyl 4-hydroxyphenyl)probionyloxyethyl coisocyanurate,
1,3.5-tris[(3-t-amyl-4-hydroxyphenyl)probionyloxyethyl coisocyanurate, 1,3.5-tris[(3-t-octyl-4-
hydroxyphenyl)propionyloxyethyl]isocyanurate, 1,3.5-tris[(3-methyl-
4-Hydroxy-5-t-butylphenyl)propionyloxyethyl]isocyanurate, 1,3.5-)
Lis[(3-methyl-4-hydroxy-5-t-amylphenyl)propionyloxyethyl]isocyanurate, 1,3.5-tris[(3-methyl-4-hydroxy-5-t-octylphenyl)probio Nyloxyethyl coisocyanurate, 1,3.5-)lis[(3
-ethyl-4-hydroxy-5-t-butylphenyl)
Probionyloxyethyl coisocyanurate, 1,3
．． 5-) Lis[(3-i-propyl-4-hydroxy-5-t-butylphenyl)propionyloxyethyl]isocyanurate, 1,3.5-tris[(3-i-
Butyl-4-hydroxy-5-t-butylphenyl)propionyloxyethyl coisocyanurate, 1,3.
5-Tris[(3-s-butyl-4-hydroxy-5-
t-butylphenyl)propionyloxyethyl coisocyanurate, 1,3.5-tris[:(3,5-di-
t-butyl-4-hydroxyphenyl)probionyloxyethyl coisocyanurate, 1,3.5-)lis[(3-t-butyl-4-hydroxy-5-doamylphenyl)propionyloxyethyl]isocyanurate, 1,3.5-Tris[(3-t-butyl-4-hydroxy-5-t-octylphenyl)propionyloxyethyl coisocyanurate, 1,3.5-Tris[(3
, 5-di-t-amyl-4-hydroxyphenyl)propionyloxyethyl coisocyanurate, 1,3.5
-Tris[(3,5-di-t-octyl-4-hydroxyphenyl)probionyloxyethyl coisocyanurate, 1,3.5-tris[(3゜5-di-t-dodecyl-4-hydroxyphenyl) ) propionyloxyethyl] isocyanurate, 1,3.5-tris[(2-methyl-4-hydroxy-5-t-butylphenyl)propionyloxyethyl] isocyanurate, 1,3.5
-Tris[(2,5-di-t-butyl-4-hydroxyphenyl)brobionyloxyethyl coisocyanurate, 1,3.5-tris[(2-methyl-4-hydroxy-5-t-octyl) phenyl)probionyloxyethyl coisocyanate, 1,3.5.tris[(2-
t-Butyl-4-hydroxy-5-methylphenyl)propionyloxyethyl]isocyanurate, 1,3.
5-) Lis[(3-methyl-5-t-butyl-4-hydroxyphenyl)butenyloxyethyl coisocyanurate, 1,3.5-tris[(3,5-di-7-butyl-4-hydroxyphenyl) ) Butenyloxyethyl coisocyanurate, 1,3.5-tris[(3-methyl-5-t-butyl-4-hydroxyphenyl)hexonyloxyethyl coisocyanurate, 1,3.5-tris[ (3,5-di-t-butyl-h-hydroxyphenyl)hexoloxyethyl coisocyanurate, 1,3
．． 5-Tris[(3-methyl-5-t-butyl-4-hydroxyphenyl)octenyloxyethyl]isocyanurate, 1,3.5-)lis[(3,5-di-t-
Butyl-4-hydroxyphenyl)octenyloxyethyl coisocyanurate, 1,3.5-tris[(3-
methyl-5-t-butyl-4-hydroxyphenyl),
Propionyloxymethyl] isocyanurate, 1,3
．． 5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]isocyanurate, 1,3.5-)lis[(3-methyl-5-t
-butyl-4-hydroxyphenyl)probionyloxybrobyl coisocyanurate, 1,3,5-tris[
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxyprobyl] isocyanurate, 1,
3.5-Tris[(3-methyl-5-t-butyl-4-
hydroxyphenyl)propionyloxyhexyl]isocyanurate, 1,3.5-tris[(3,5-di-
t-Butyl-4-hydroxyphenyl)propionyloxyhexyl]isocyanurate, 1.3.5-)lis[(3-methyl-5-t-butyl-4-hydroxyphenyl)probionyloxyoctylcoisocyanurate, 1,3.5-)Lis[(3,5-di-t-butyl-4-hydroxyphenyl)probionyloxyoctylcoisocyanurate, 1,3.5-)Lis[(3-
Methyl-5-t-butyl-4-hydroxyphenyl)propionyloxydecyl]isocyanurate, 1,3゜5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxydecyl]isocyanurate , 1,3.5-tris[(3-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxidedodecyl]isocyanurate and 1,3.5-)lis[(3°5-di-t- Examples include butyl-4-hydroxyphenyl)probionyl oxide dodecyl coisocyanurate, particularly 1,3,5-tris[(3-methyl-
5-tert-butyl-4-hydroxyphenyl)probionyloxyethyl coisocyanurate and 1,3.5-
) Lis[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate is preferred. These phenolic compounds can be used alone, but two or more phenolic compounds can also be used in combination.

It is natural to use a single phenolic compound selected from Compound A, Compound B and Compound C, but it is also possible to use two or more kinds of phenolic compounds in combination. The blending ratio of the phenolic compound is 100% polyolefin.
0.01 to 1 part of IMf, preferably 0.3411 parts. O1 to 0.5 parts by weight.

If the groove content is less than 0.01 part by weight, the effect of preventing oxidative deterioration of the flame-retardant polyolefin composition will not be sufficiently exhibited;
Although it is possible to exceed more than 1 part by weight, it is not only impractical but also uneconomical as no further improvement in the effect of preventing oxidative deterioration can be expected.

Heavy metal deactivators used in the present invention include benzotriazole, 2,4.6-)riamino-1,3,5-
) riazine, 3,9-bis[2-(3,5-diamino-
2,4,6-)Ryazaphenyl)ethylco2.4,8
．． 10-tetraoxaspiro[5,5]undecane, ethylenediamine-tetraacetic acid, alkali metal salt of ethylenediamine-tetraacetic acid, N.

N'-disalicylidene-ethylenediamine, N,N
'-disalicylidene-1,2-propylenediamine, N
.

N ++-disalicylidene-N'-methyl-dipropylenetriamine, 3-salicyloyl amino-1,2,4-
) Riazole, decamethylenedicarboxylic acid-bis(N'-salicyloylhydrazide), nickel-bis(l-phenyl-3-methyl-4-decanoyl-)
5-virazolate), 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), thiodibrobionic 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)brobionylcohydrazine, 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)
Examples include propionyloxy[ethyl]oxamide, particularly oxalic acid-bis(benzylidene hydrazide), N,N'-bis[:3-(3,S-di-t
-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris[2-t-butyl-4-thio(2'-
Methyl-41-hydroxy-5'-1-butylphenyl)-5-methylphenylcottosphite and N,N
'-Bis[2-(3-(3,5-di-t-butyl-4-
Hydroxyphenyl)propionyloxy]ethylcoxamide is preferred. Of course, these heavy metal deactivators can be used alone, but two or more types of heavy metal deactivators can also be used in combination.

The blending ratio of the heavy metal deactivator is 10% of the polyolefin.
0.01 to 1 part by weight, preferably 0.01 to 1 part by weight.
05 to 0.5 parts by weight. If the amount is less than 0.01 part by weight, the effect of preventing oxidative deterioration of the flame-retardant polyolefin composition will not be sufficiently exhibited, and if it is more than 1 part by weight, the effect of preventing oxidative deterioration will not be further improved. Not only is this not promising and impractical, but it is also uneconomical.

The epoxy compound used in the present invention is not particularly limited as long as it does not significantly evaporate or decompose during melt-kneading, and has an epoxy equivalent of 100 to 1.
,000 can be suitably used, and epichlorohydrin or epichlorohydrin derivatives (such as 2-methylepichlorohydrin, 2-ethylepichlorohydrin, and 2-propylepichlorohydrin) and bisphenol or bisphenol derivatives (such as bisphenol A1 and bisphenol F1) can be suitably used.
condensates with bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, etc.), epoxidized fats and oils (such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized castor oil), epoxidized fats and oils , alkyl esters of epoxidized fatty acids (e.g. epoxidized octyl stearate, fatty acid esters of 3,4-epoxycyclohexylmethanol, alkyl esters of 3°4-epoxycyclohexylcarboxylic acids, 4,5-epoxycyclohexane-1, Dialkyl ester of 2-dicarboxylic acid, 3
, 4-epoxy-6-methylcyclohexylmethyl and 3,4-epoxy-6-methylcyclohexanecarboxylate), tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, novolak glycidyl ether, polyalkylene glycol diglycidyl ether, Glycerin triglycidyl ether, pentaerythritol diglycidyl ether, p-oxybenzoic acid glycidyl ether
Esters, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic late glycidyl ester, dimer acid diglycidyl 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 dieboxide, dicyclopentadiene oxide, bis (2
, 3-epoxycyclopentyl) ether, and limonene dioxide. Particularly preferred are a condensate of epichlorohydrin and bisphenol A, a condensate of 2-methylepichlorohydrin and bisphenol A, triglycidyl isocyanurate, and epoxidized soybean oil. It is controversial to use these epoxy compounds alone,
Two or more types of epoxy compounds can also be used in combination.

The blending ratio of the epoxy compound is 100% polyolefin.
0.01 to 1 part by weight, preferably 0.0 part by weight
It is 5 to 0.5 parts by weight. If the amount is less than 0.01 part by weight, the effect of preventing oxidative deterioration of the flame-retardant polyolefin composition will not be sufficiently exhibited, and if it is more than 1 part by weight, it is fine.
No further improvement in the effect of preventing oxidative deterioration can be expected (if the epoxy compound exceeds 1 part by weight, stickiness will occur).
Not only is this impractical, but it is also uneconomical.

The halogen flame retardants used in the present invention include ammonium bromide, ammonium chloride, 2-chlorotetrabromobutane, 2,2-bis[p-(chloroformyloxy)]
Phenyl-3]propane, 1,2-dibromo-3-chloropropane, 1.2.3-)ribromobroban, 1.1
, 2.2-tetrabromoethane, tetrabromobutane,
hexabromocyclododecane, hexabromooctane,
Hexabromobutane, pentabromocyclohexane, tribromotrichlorocyclohexane, pentabromochlorocyclohexane, 1,2-dibromo-1,1,2,2
-tetrachloroethane, 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane, vinylchloroacetate, 2,4.6-)ribromophenyl methacrylate, 2,3.3'-tribromoallyl formate, 2,2-dibromopropyl methacrylate,
Bis(2,3-dibromopropyl)-2,3-dibromofumarate, tribromophenyl acrylate, chloroendo acid, diallyl chloroendo acid, chloroendo acid anhydride, bromostyrene, tetrachlorophthalic anhydride, tetrabromophthalic anhydride , chloropropanediol, 3-
bromo-2,2-bis(bromomethyl)propertool,
2,2-dibromobutene-1,4-diol, tribromophenol, dibromoneopentyl glycol, tribromoneopentyl alcohol, 2,3-dibromopropanol, 2.3.3'-)ribromoallyl alcohol, chloropenta Bromophenyl allyl ether, pentachlorophenoxyglycerin ether, bromophenyl allyl ether, tribromophenol allyl ether, pentabromophenol furyl ether, pentabromophenyl allyl ether, bromoalkenyl ether, sorbitol-1,6-bis(2').

3'-dibromopropyl) ether, decabromodiphenyl ether, 1,2-bis(2', 3', 4'
, 5', 6'-pentabromophenoxy)ethane, hexabromodiphenyl ether, dibromocresyl glycidyl ether, pentabromoallyl ether, 1.2
-dibromopropyl-tribromophenyl ether, decachlorodiphenyl carbonate, decabromodiphenyl carbonate, 2,3.3-tribromoallylcarboxylate, 2,3,5,6.2', 3', 5', 6'
-octachloro-4,4″-dioxydiphenyl, tetrabromobenzene, α,β-dibromoethylbenzene,
2-bromo-α,β-dibromoethylbenzene, hexabromobenzene, perchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran,
Tetrabromobisphenol A, tetrabromobisphenol A jetoxylate, bis(2-hydroxyethyl ether)tetrabromobisphenol A, 2.2
'-Bis[(3,5-dibromo-4-(2',3'-dibromopropyloxy)]phenylcobroban, 2,2
'-Bis[(3,5-dibromo-4-(2'13'-dibromo-2'-methylpropyloxy)]phenyl]propane, tetrabromobisphenol F, bis[(3,
5-dibromo-4-(2',3'-dibromopropyloxy)]phenylcomethane, bis[(3,5-dibromo-4-(2',3'-dibromo-2''-methylpropyloxy)] Pphenyldmethane bis[(3,5-dibromo-4-(2',3'-dibromopropyloxy)]phenyl]oxide, bis[(3,5-dibromo-4-
(2'.

3'-dibromo-2'-methylpro-ruoxy)]phenyl]oxide, bis[: (3,5-dibromo-4
-(2'.

3'-dibromopropyloxy)] phenylkoketone,
Bis[(3,5-dibromo-4-(2',3'-dibromo-2'-methylpropyloxy)]phenylkoketone, bis[(3,5-dibromo-4-(2'',3'- dibromopropyloxy)]phenyl]sulfite, bis[(3,5-dibromo-4-(2',3'-dibromo-
2'-Methylprooxy)]phenyl]sulfite, tetrabromobisphenol S, bis[(3,5-
dibromo-4-(2',3'-dibromopropyloxy)]]phenylcosulfone bis[(3,5-dibromo-4-(2',3'-dibromo-2'-methylpropyloxy)]phenyl] sulfone, pentabromotoluene, tribromoaniline, acetylenetetrapromide, 1ip-tosyl)-3-(2'-bromo-4',4
Examples include inorganic and organic halogen flame retardants such as ',4'-trichlorobutyl) urea, 2,3-dibromopropanol ester, chlorinated paraffin, chlorinated polyethylene or chlorinated polypropylene, in particular decabromodiphenyl ether, Chloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, tetrabromobisphenol A, tetrabromobisphenol S, 2.2″-bis[(3,5-dibromo-
4-(2',3'-dibromopropyloxy)]phenyl]propane and bis[(3,5-dibromo-4-(
2',3'-dibromopropyloxy)]phenyl]sulfone is preferred. Although these halogen flame retardants can be used alone, two or more halogen flame retardants can also be used in combination. The blending ratio of the halogen flame retardant is
The amount may be blended depending on the desired flame retardance and is not particularly limited, but it is usually preferably 5 to 30 parts by weight per 100 parts by weight of the polyolefin.

Further, a flame retardant aid can be further used in the composition of the present invention. The flame retardant aids include antimony compounds (for example, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium picoantimonate, antimony trichloride, antimony trisulfide, antimony oxychloride, antimony dichloride perchloropentane, and potassium antimonate). ), boron compounds (e.g. zinc metaborate, zinc tetraborate, zinc borate and basic zinc borate), zirconium oxide, tin oxide and molybdenum oxide, in particular antimony dioxide, Antimony oxide, antimony pentoxide, antimony trichloride, antimony trisulfide and zinc borate are preferred. Although these flame retardant aids can be used alone, two or more kinds of flame retardant aids can also be used in combination. The blending ratio of these flame retardant aids is not particularly limited, but is preferably 20 to 60 parts by weight per 100 parts by weight of the halogen flame retardant. The blending of the flame retardant aid acts synergistically with the halogenated flame retardant in the composition of the present invention to improve flame retardancy, so the amount of the halogenated flame retardant to be blended can be reduced.

Therefore, it is preferable to include the flame retardant aid.

The composition of the present invention contains various additives that are usually added to polyolefins, such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, etc.
Nucleating agents, lubricants, antistatic agents, antifogging agents, antiblocking agents, anti-drop agents, pigments, radical generators such as peroxides,
Dispersants or neutralizing agents for metal soaps, inorganic fillers (
For example, talc, mica, clay, wollastonite,
Zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber , carbon black, graphite, metal fibers, etc.) or coupling agents (such as silane-based, titanate-based, boron-based,
For the purpose of the present invention, the inorganic filler or organic filler (for example, wood flour, valve, waste paper, synthetic fiber, natural fiber, etc.) that has been surface-treated with a surface treatment agent such as aluminate-based, zirco-aluminate-based, etc. They can be used together as long as they do not cause any damage. In particular, when a thioether antioxidant is used in combination, the effect of preventing oxidative deterioration is synergistically exhibited, so it is preferable to use them together.

Examples of thioether antioxidants include dilaurylthiodipropionate, ditridecylthiodipropionate, dimyristylthiodipropionate, dicetylthiodipropionate, distearylthiodipropionate, dilaurylthiodibutyrate, and ditridecylthiodipropionate. Decylthiodibutyrate, dimyristylthiodibutyrate, dicetylthiodibutyrate, distearylthiodibutyrate, laurylstearylthiodipropionate, laurylstearylthiodibutyrate, pentaerythritol-β laurylthiodipropionate, pentaerythritol- Tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), bis(4-t-amylphenyl) sulfide, Examples include distearyl disulfide, thioethylene glycol-bis(ρ-aminocrotonate) and poly[1,4-bis(hydroxymethyl)cyclohexane-thiodibropionate;
Particularly preferred are dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate.

The composition of the present invention contains compound A1 compound B in the polyolefin.
and one or more phenolic compounds selected from compound C, a heavy metal deactivator, an epoxy compound, and a halogen flame retardant.If necessary, a flame retardant aid and the aforementioned various additives that are usually added to polyolefins. A predetermined amount of the agent is mixed using a conventional mixing device such as a Hensel mixer (trade name).
, a super mixer, a ribbon blender, a bar mixer, etc., and melt-kneaded with a normal single-screw extruder, twin-screw extruder, Brabender or roll, etc. at a melt-kneading temperature of 150°C to 250°C, preferably 180℃～230℃
It can be obtained by melt-kneading and pelletizing. The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding.

[Action] In the present invention, compound A5, compound B and compound C
The phenolic compound selected from the above acts as a radical chain inhibitor, the heavy metal deactivator acts as an inactivator for the catalytic oxidative deterioration of polyolefins caused by heavy metal ions, and the epoxy compound acts as a scavenger for A-logen radicals. This is generally known. However, a phenol compound selected from Compound A, Compound B, and Compound C related to the present invention, a heavy metal deactivator, and an epoxy compound may be used in combination with a flame-retardant polyolefin composition containing a halogen flame retardant. As a result, a surprising synergistic effect that could not be expected from the combination of conventionally known compounds with anti-oxidative deterioration effects is exhibited, and a flame-retardant polyolefin composition with extremely excellent long-term thermal stability and heavy metal resistance is obtained. I found out.

[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 method used in Examples and Comparative Examples was as follows.

1) Long-term thermal stability: Evaluated by oven life test. That is, using the obtained pellets, the length is 50 mm.
A test piece with a width of 25 mm and a thickness of 1 mm was created by injection molding, and the test piece was placed in a circulating hot air oven adjusted to a temperature of 150°C to determine the time until the test piece completely deteriorated (tensile strength Measure the time taken to reach O (J
Long-term thermal stability was evaluated according to Is K 7212).

2) Heavy metal resistance: Evaluated by rust resistance test. That is, using the obtained pellets, a length of 50 mm, a width of 25 mm,
A test piece with a thickness of 1 mm was created by injection molding, and using this test piece, a test piece with a length of 25 mm, a width of 25 mm,
The test specimen was placed in contact with a 0.3 mm thick steel plate, fixed with a clip, and placed in a circulating hot air oven adjusted to a temperature of 150°C, and the time until the contact part of the test piece with the copper plate completely deteriorated (time until deterioration penetrated) was measured. (JISK?212
Heavy metal resistance was evaluated by

3) Flame retardancy: UL Subject 94 (Unde
rwri-ters Laboratories
A flame retardancy test was conducted according to the vertical combustion test method of INC.). That is, using the obtained pellets, the length is 125
A combustion test piece with a width of 12.5 mm and a thickness of 1.56 mm was prepared by injection molding, and the combustion test piece was evaluated based on the combustibility classification and the presence or absence of melt dripping.

Examples 1 to 24, Comparative Examples 1 to 12 MFR (load 2 at 230°C) as polyolefin
．． Discharge f of molten resin for 10 minutes when adding 16 kg
f1) To 100 parts by weight of unstabilized powdered crystalline propylene homopolymer at 6.0 g/10 min, decabromodiphenyl ether as a halogenated flame retardant, antimony trioxide as a flame retardant aid, and tetrakis as compound A. Methylene-3-(3',5'-di-t-butyl-4'
-hydroxyphenyl)propionate comethane, 3,9-bis[1,l-dimethyl-2-{β as compound B
-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl] -2,4,8,
10-tetraoxaspiro[5,5]undecane, 1.3,5-tris((3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate as compound C, heavy metal deactivation N as an agent
, 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-methylphenylcottosphite, 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: 700-830
〉, mixture of condensate of epichlorohydrin and bisphenol A and condensate of 2-methylepichlorohydrin and bisphenol A (epoxy ff1180-200)
, triglycidyl isocyanurate (epoxy equivalent 10
0 to 110) or epoxidized soybean oil (epoxy
fi 220 to 240) and other additives in the proportions listed in Tables 1-1 and 1-2 below into a Hensel mixer (trade name), and stirred and mixed for 3 minutes. , 230℃ using a twin-screw pusher with a diameter of 30mm.
The mixture was melt-kneaded and pelletized. Also, comparative example 1~
12, a predetermined amount of each of the additives listed in Table 1-2 below was blended with 100 parts by weight of an unstabilized powdered crystalline propylene homopolymer with an MFR of 6.0 g/10 min. For the test pieces used in the oven life test, rust resistance test, and flammability test, pellets are obtained by melt-kneading according to 1 to 24, the obtained pellets are melt-kneaded at a resin temperature of 230°C,
It was prepared by injection molding at a mold temperature of 50°C.

Using the obtained test pieces, long-term thermal stability, heavy metal resistance, and flame retardancy were evaluated by the test method described above. These results are shown in Tables 1-1 and 1-2.

Examples 25 to 48, Comparative Examples 13 to 24 100 parts by weight of an unstabilized powdery crystalline propylene homopolymer with an MFR of 6.0 g/10 min as a polyolefin was added with 2,2'-2,2'- as a halogen flame retardant. bis[(3,5-dibromo.4-(2',3'-dibromopropyloxy)]phenyl]propane; antimony trioxide as a flame retardant aid; tetrakis[methylene-3-(3',5') as compound A; -di-t-butyl-4'-hydroxyphenyl)propionate comethane, compound B
as 3,9-bis[1,1-dimethyl-2-{β-(
3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl]-2.4,8.10-
Tetraoxaspiro[5,5]undecane, 1,3,5-)lis[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl coisocyanurate as compound C, heavy metal deactivator as N, N'
-bis[2-C3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]oxamide, tris[2-t-butyl-4-thio(2'-methyl-4'- hydroxy-5'-t-butylphenyl)
-5-Methylphenylkotosphite, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine or oxalic acid-bis(benzylidenehydrazide), epoxy compound as epichlorohydrin and bisphenol A
(Epoxy ffi 700-830), condensate of epichlorohydrin and bisphenol A and 2-
A mixture of condensates of methyl epichlorohydrin and bisphenol A (epoxy equivalent weight 180-200), triglycidyl isocyanurate (epoxy equivalent weight 11100-11
0) or epoxidized soybean oil (epoxy equivalent: 220~
240) and other additives in the mixing ratios listed in Tables 2-1 and 2-2 below, put them into a Hensel mixer (trade name), stirred and mixed for 3 minutes, and then mixed them with a diameter of 30 mm. The mixture was melt-kneaded at 200°C using a twin-screw extrusion machine to form pellets. Also, as Comparative Examples 13 to 24, M
To 100 parts by weight of an unstabilized powdered crystalline propylene homopolymer with an FR of 6.0 g/10 min,
Predetermined amounts of each of the additives listed in Table 2 were blended and melt-kneaded according to Examples 25 to 48 to obtain pellets.

For the test pieces used in the oven life test, rust resistance test, and flammability test, the obtained pellets were heated at a resin temperature of 200°C,
It was prepared by injection molding at a mold temperature of 50°C.

Using the obtained test pieces, long-term thermal stability, heavy metal resistance, and flame retardancy were evaluated by the test method described above. These results are shown in Table 2-1 and Table 2-2.

Examples 49 to 74, Comparative Examples 25 to 36 10 parts of unstabilized powdery crystalline propylene homopolymer with MFR6.0 g/10 min as a polyolefin was added with bis[[3] as a halogen flame retardant. ,5
-dibromo-4-(2',3'-dibromopropyloxy)]phenyl]sulfone, antimony trioxide as a flame retardant aid, tetrakis[methylene-3-
(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane, 3°9 as compound B
-Bis[1,1-dimethyl-2-{β-<3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl]-2.4,8.10-f Traoxashyguchi [5, 5] undecane, compound C as 1,3.
5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 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), a condensate of epichlorohydrin and bisphenol A (epoxy equivalent 700 to 830) as an epoxy compound, epichlorohydrin and A mixture of condensates with bisphenol A and condensates of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent ffi 1180-200), triglycidyl isocyanurate (epoxy equivalent ffi 100-110) or epoxidized soybean oil (epoxy equivalent ffi 220-200). 240)
and other additives in the mixing ratios listed in Tables 3-1 and 3-2 below, put them into a Hensel mixer (trade name), stirred and mixed for 3 minutes, and then
The mixture was melt-kneaded at 200° C. using a 0 mm twin-screw press ratio machine to form pellets. In addition, as Comparative Examples 25 to 36, MFR is 6
．． Predetermined amounts of each of the additives listed in Table 3-2 below were blended with 100 parts by weight of an unstabilized powdered crystalline propylene homopolymer of 0 g/10 minutes, and Examples 49-
A pellet was obtained by melt-kneading in accordance with 72.

The test pieces used for the oven life test, rust resistance test, and flammability test are the pellets obtained at a resin temperature of 200°C.
1 Prepared by injection molding at a mold temperature of 50°C.

Using the obtained test pieces, long-term thermal stability, heavy metal resistance, and flame retardancy were evaluated by the test method described above. These results are shown in Table 3-1 and Table 3-2.

Examples 73 to 96, Comparative Examples 37 to 48 Dodecachlorododecahydrodi as a halogen flame retardant was added to 100 parts by weight of an unstabilized powdery crystalline propylene homopolymer with an MFR of 6.0 g/10 minutes as a polyolefin. Methanodibenzocyclooctene, antimony dioxide as a flame retardant aid, tetrakis[methylene-3-(3',5'-di-t-butyl-4') as compound A
-hydroxyphenyl)propionate comethane, 3,9-bis[l,1-dimethyl-2-{β as compound B
-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl] -2,4,8゜O-tetraoxaspiro[5,5]undecane, 1,3.5- as compound C ) squirrel [(3,5-di-t-
Butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 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-7-butyl-4-hydroxyphenyl)propionyl]hydrazine or oxalic acid -bis(benzylidene hydrazide), a condensate of epichlorohydrin and bisphenol A as an epoxy compound (epoxy equivalent: 700-830) ), mixture of condensates of epichlorohydrin and bisphenol A and condensates of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 180-200), triglycidyl isocyanurate (epoxy equivalent ffi+00-11
O) or epoxidized soybean oil (epoxy equivalent: 220~
240) and other additives at the mixing ratios listed in Tables 4-1 and 4-2 below, put them into a Hensel mixer (trade name), stir and mix for 3 minutes, and then mix the mixture with a diameter of 30 mm. The mixture was melt-kneaded and pelletized at 230°C using a twin-screw presser. Also, as Comparative Examples 37 to 48, M
100 parts by weight of an unstabilized powdered crystalline propylene homopolymer with an FR of 6.0 g/10 min,
Predetermined amounts of each of the additives listed in Table 2 were blended and melt-kneaded according to Examples 73 to 96 to obtain pellets.

For the test pieces used in the oven life test, rust resistance test, and flammability test, the obtained pellets were heated at a resin temperature of 230°C,
It was prepared by injection molding at a mold temperature of 50°C.

Using the obtained test pieces, long-term thermal stability, heavy metal resistance, and flame retardancy were evaluated by the test method described above. These results are shown in Tables 4-1 and 4-2.

Examples 97-120, Comparative Examples 49-60 Unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) toot m In the department,
Decabromodiphenyl ether as a halogen flame retardant, antimony dioxide as a flame retardant aid, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane] as a compound A, Compound B is 3,9-bis[1,l-dimethyl-
2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl]-2.4
, 8.10-tetraoxaspiro[5,5-oundecane, 1,3.5-tris[(3,5-di-
t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, N,N'-bis[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)) as a heavy metal deactivator Propionyloxy]ethyl]oxamide, tris[2-t-butyl-4-thio(2'-methyl-42-hydroxy-5'-t-butylphenyl)-5-methylphenylcottosphite, N
, N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionylcohydrazine or oxalic acid-bis(benzylidenehydrazide), a condensate of epichlorohydrin and bisphenol A as an epoxy compound ( Epoxy equivalent 700-830)
, mixture of condensates of epichlorohydrin and bisphenol A and condensates of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent: 180-200), triglycidyl isocyanurate (epoxy equivalent filoo~
+10) or epoxidized soybean oil (epoxy equivalent: 22
0 to 240) and other additives in the mixing ratios listed in Tables 5-1 and 5-2 below into a Hensel mixer (trade name), and stirred and mixed for 3 minutes. The mixture was melt-kneaded and pelletized at 230° C. using a twin-screw presser with a diameter of 30 mm. In addition, as Comparative Examples 49 to 60, an unstabilized powdery crystalline ethylene-propylene block copolymer with an MFR of 4.0 g/10 min (ethylene content: 8.5% by weight) was added to 100 parts by weight of the polymer. Predetermined amounts of each of the additives listed in Table 5-2 were blended, followed by melt-kneading treatment similar to Examples 97 to 120 to obtain pellets.

For the test pieces used in the oven life test, rust resistance test, and flammability test, the obtained pellets were heated at a resin temperature of 230°C,
It was prepared by injection molding at a mold temperature of 50°C.

Using the obtained test pieces, long-term thermal stability, heavy metal resistance, and flame retardancy were evaluated by the test method described above. These results are shown in Tables 5-1 and 5-2.

Examples 121-144, Comparative Examples 61-72 As polyolefin, MFR6,0g/10min unstabilized powdery crystalline propylene homopolymer 70% by weight;
MFR7,0g/10min unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 5% by weight, MI (190°C
Discharge of molten resin for 10 minutes when a load of 2.16 kg is applied at L 11
A total of 100 parts by weight of an unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content: 25%) and 15% by weight (at 100°C) were added with a halogen flame retardant. decabromodiphenyl ether as flame retardant, antimony dioxide as flame retardant aid, compound A
Tetrakis[methylene-3-(3',5'-di-
t-butyl-4'-hydroxyphenyl) propionate comethane, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl) as compound B ) propionyloxy)ethyl]
-2.4,8.10-Tetraoxaspiro[5,5]undecane, 1,3.5- as compound C) Lis[:(
3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, N,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-methylphenylcottosphite, N,N'-bis[3-(3,5-di-t-
butyl-4-hydroxyphenyl)probionyl cohydrazine or oxalic acid-bis(benzylidene hydrazide), a condensate of epichlorohydrin and bisphenol A as an epoxy compound (epoxy compound: 1
700-830), a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy mtso
~200), triglycidyl isocyanurate (epoxy equivalent: 100~11O) or epoxidized soybean oil (epoxy equivalent fIk: 220~240), and other additives in Tables 6-1 and 6-2 below. Put it into a Hensel mixer (product name) at the mixing ratio listed in
After stirring and mixing for 3 minutes, the mixture was melt-kneaded at 230° C. using a twin-screw presser with a diameter of 30 mm to form pellets. In addition, as Comparative Examples 61 to 72, unstabilized powder crystalline propylene homopolymer 70 with an MFR of 6.0 g and 710 min.
Unstabilized powdered crystalline ethylene-propylene random copolymer with a MFR of 7.0 g/10 minutes (ethylene content 2.5 wt.%), MFR of 5 wt.%, Ml of 5
．． 0 g/10 min unstabilized powdered Ziegler-Natsuta high density ethylene homopolymer 10% by weight and unstabilized powdered amorphous ethylene-propylene with Mooney viscosity M L 114 (100 °C) 250 A total of 100 parts by weight consisting of a random copolymer (propylene content 25% by weight) and 15% by weight was blended with predetermined amounts of each of the additives listed in Table 6-2 below, and Example 121 was prepared.
Pellets were obtained by melt-kneading in accordance with 144.

For the test pieces used in the oven life test, rust resistance test, and flammability test, the obtained pellets were heated at a resin temperature of 230°C,
It was prepared by injection molding at a mold temperature of 50°C.

Using the obtained test pieces, long-term thermal stability, heavy metal resistance, and flame retardancy were evaluated by the test method described above. These results are shown in Tables 6-1 and 6-2.

The compounds and additives related to the present invention shown in Tables 1-1 to 6-2 are as follows.

Compound A: Tetrakis[methylene-3-(3',5'-
di-t-butyl-4'-hydroxyphenyl)propionate comethane compound B: 3,9-bis[l,1-dimethyl-2-{β
-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl] -2,4,8,
10-tetraoxaspiro[5,5]unde-iron compound C: 1,3,5-tris((3,5-di-t-
Butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate heavy metal deactivator [I]: N,N'-bis[2-(3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy]ethyl]oxamide heavy metal deactivator [■]: Tris[2-t-butyl-
4-thio(2'-methyl-4'-hydroxy-5'-t
-butylphenyl)-5-methylphenylcotiosphite heavy metal deactivator [ml: N,N'-bis[3
-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine Heavy metal deactivator [■] Nioxalic acid bis(benzylidene hydrazide) Epoxy compound [I]: Condensation of epichlorohydrin and bisphenol A (Epoxy equivalent: 700-830; C
IBA-C; ARA-L D manufactured by EIGY AG
I T E G T 7004) Epoxy compound [11: Mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 180-20
0; ADEKA ARGUS CHEMICAL! 41. Made by MARK
EP-17) Epoxy compound [ml:) liglycidyl isocyanurate (epoxy equivalent 100-110;
CI BA-C; El to Y AG ARALDI
TE PT epoxy compound [■]: Eboxidized soybean oil (epoxy equivalent 220-240; ADK CI ZER0-130P manufactured by Adeka Argus Chemical ■) Halogen flame retardant [11: Decabromodiphenyl ether halogen flame retardant [■1: 2 ,2'-bis[(3,
5-dibromo-4-(2',3'-dibromopropyloxy)] phenylcobroban halogen flame retardant [ml: bis[(3,5-dibromo-4-(2',3'-dibromopropyloxy)) ] Phenylcosulfone halogen flame retardant [■]: Hydrodimethanodibenzocyclooctene flame retardant aid: Antimony dioxide thioether antioxidant: Dimyristylthiodibrobionate phosphorus antioxidant 1: bis(2,6-di-t-butyl-
4-Methylphenyl)-pentaerythritol-shiphosphiterin-based antioxidant 2: Bis(2,4-di-t-butylphenyl)-pentaerythritol-shiphosphiterin-based antioxidant 3: Tetrakis(2, 4-di-t-butylphenyl) -4,4'-biphenylene-diphosphonite phenolic antioxidant 1: 2.6-di-t-butyl-
p-cresol phenolic antioxidant 2: n-octadecyl-β-(
3',5'-di-t-butyl-4'-hydroxyphenyl)propionate phenolic antioxidant 3: 1.3.5-tris(3
, 5-di-t-butyl-4-hydroxybenzyl) isocyanate phenolic antioxidant 4: 1,3.5-tris-tyl-2,4,6-tris(3,5-di-t-butyl-4 −
The examples and comparative examples listed in Tables 1-1 and 1-2 use crystalline propylene homopolymer as the polyolefin, decabromodiphenyl ether as the halogen flame retardant, and decabromodiphenyl ether as the halogen flame retardant. This is the case when antimony dioxide is used as a combustion aid. As seen from Table 1.1 and Table 1-2,
Examples 1 to 24 are compounds in which a phenolic compound selected from Compound A5, Compound B, and Compound C, a heavy metal deactivator, and an epoxy compound related to the present invention are blended, and Examples 1 to 24 and Comparative Examples 1 to Comparing Example 1 with Example 3 (instead of compound A1, a phenol compound selected from compound B and compound C, a phenol compound other than the phenol compound is blended).
It can be seen that Samples No. 24 to 24 are excellent in both long-term thermal stability and heavy metal resistance. Comparative Example 4 in which a phenolic compound selected from Compound A, Compound B, and Compound C and a heavy metal deactivator were blended, but no epoxy compound was blended.
Comparing Examples 1 to 24 with Comparative Examples 4 to 6
The long-term thermal stability and resistance to heavy metals are still insufficient. Comparative Example 7 in which metal soap (calcium stearate) was added to the compositions of Comparative Examples 4 to 6 as a halogen scavenger.
The long-term thermal stability and heavy metal resistance of Comparative Examples 4 to 6
Although this has been improved to some extent compared to the above, it is still not sufficient. Furthermore, compound A.

Comparing Examples 1 to 24 with Comparative Examples 7 to 9 in which a phenolic compound and an epoxy compound selected from Compound B and Compound C and no heavy metal deactivator were blended, it was found that the long-term performance of Comparative Examples 7 to 9 was Although the thermal stability is quite good, the heavy metal resistance is still insufficient. Compound A according to the present invention.

It is clear that comparisons that do not simultaneously satisfy the formulation of the three components of the phenolic compound separated from Compound B and Compound C, the heavy metal deactivator, and the epoxy compound do not exhibit the effects of the present invention. That is, the long-term thermal stability and heavy metal resistance obtained in the present invention are achieved by adding a phenol-based compound selected from Compound A1, Compound B, and Compound C to a flame-retardant polyolefin composition containing a halogen-based flame retardant. It can be said that this is a unique effect that can only be seen when a compound, a heavy metal deactivator, and an epoxy compound are used together.

In addition, the flame retardant composition according to the present invention, which contains a phenolic compound selected from Compound A, Compound B, and Compound C, a heavy metal deactivator, and an epoxy compound,
It was confirmed that the flame retardancy was comparable to that of conventionally known flame retardant compositions.

Tables 2-1 to 4-2 show crystalline propylene homopolymer as polyolefin and 2,2'-bis[(3,5-dibromo-4-(2'
,3'-dibromopropyloxy)]phenyl]propane bis[: (3,5-dibromo-4-(2',3'
-dibromopropyloxy)] phenylcosulfone,
Dodecachlorododecahydrodimethanodibenzocyclooctene was used, and the same effects as described above were confirmed with these as well. In addition, Tables 5-1 to 6-2 are
Polyolefins include crystalline ethylene-propylene block copolymer or crystalline propylene homopolymer, crystalline ethylene-propylene random copolymer, Ziegler-Natsuta high-density ethylene homopolymer, and amorphous ethylene-propylene random copolymer, respectively. mixture of coalescence,
Decabromodiphenyl ether was used as a halogen-based flame retardant, and the same effects as described above were confirmed with these as well.

[Effects of the Invention] Compared to conventionally known flame-retardant polyolefin compositions containing a halogenated flame retardant and various compounds having an oxidative deterioration prevention effect, the composition of the present invention has the following advantages: The long-term thermal stability and resistance to heavy metals of the molded article are extremely excellent. (2) It has extremely excellent long-term thermal stability and heavy metal resistance, so there is no decrease in electrical insulation properties caused by oxidative deterioration of polyolefin, so it has flame retardancy, long-term thermal stability, and heavy metal resistance in various molding fields. It can be suitably used in applications that require the following properties (for example, electrical and electronic functional parts such as deflection yokes, CRT sockets and connectors, and automotive parts such as distributor caps, car heater cases and car air conditioner cases). .

that's all

Claims (15)

[Claims] (1) A phenolic compound represented by the following general formula [I] (hereinafter referred to as compound A), a phenolic compound represented by the following general formula [I] (hereinafter referred to as compound A), a flame retardant composition consisting of a polyolefin and a halogen flame retardant, and a One or two selected from the phenolic compound represented by formula [II] (hereinafter referred to as compound B) and the phenolic compound represented by the following general formula [III] (hereinafter referred to as compound C)
A flame-retardant polyolefin composition comprising 0.01 to 1 part by weight of each of at least one phenolic compound, a heavy metal deactivator, and an epoxy compound. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (However, R_1 in the formula is a carbon number of 1 to 8 alkyl group,
R_2 is hydrogen or an alkyl group having 1 to 8 carbon atoms,
_3 is an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group,
cyclohexylalkyl group, aryl group or arylalkyl group, R_4 is hydrogen or an alkyl group having 1 to 9 carbon atoms, cycloalkyl group, cyclohexylalkyl group, aryl group or arylalkyl group, R_5
is an alkyl group having 1 to 12 carbon atoms, R_6 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and m and n are 1 to 6
k is an integer of 0 to 8, x is an integer of 1 to 12, and y is an integer of 0 to 8. ) (2) R_1 to R_2 in general formulas [I] to [III]
The flame-retardant polyolefin composition according to claim (1), wherein R_5 and R_6 are t-butyl groups and R_4 is a methyl group. (3) Compound A is tetrakis[methylene-3-(3
',5'-di-t-butyl-4'-hydroxyphenyl)propionate] methane. The flame-retardant polyolefin composition according to claim (1). (4) Compound B is 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-
methylphenyl)propionyloxy}ethyl]-2,
The flame-retardant polyolefin composition according to claim (1), which contains 4,8,10-tetraoxaspiro[5,5]undecane. (5) Compound C as 1,3,5-tris[(3,5-
The flame-retardant polyolefin composition according to claim (1), which comprises di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate. (6) Oxalic acid as a heavy metal deactivator
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-
Claim (1) comprising one or more selected from di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]oxamide
The flame-retardant polyolefin composition described in . (7) As an epoxy compound, one selected from epichlorohydrin or a condensate of an epichlorohydrin derivative and bisphenol or a bisphenol derivative, triglycidyl isocyanurate, epoxidized fat, epoxidized fatty acid, and alkyl ester of epoxidized fatty acid, or The flame-retardant polyolefin composition according to claim (1), which is a mixture of two or more types. (8) As an epoxy compound, one or more selected from the group consisting of a condensate of epichlorohydrin or its derivatives and bisphenol A, triglycidyl isocyanurate, and epoxidized soybean oil is blended. The flame-retardant polyolefin composition according to item 1). (9) The halogen flame retardant is decabromodiphenyl ether, perchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, tetrabromobisphenol A, tetrabromobisphenol S, 2
,2'-bis[[3,5-dibromo-4-(2',3'
-dibromopropyloxy)]phenyl]propane and bis[[3,5-dibromo-4-(2',3'-dibromopropyloxy)]phenyl]sulfone or two or more selected from A flame-retardant polyolefin composition according to claim (1). (10) The flame-retardant polyolefin composition according to claim (1), which contains 5 to 30 parts by weight of a halogen flame retardant per 100 parts by weight of the polyolefin. (11) A crystalline propylene homopolymer or a propylene copolymer containing 70% by weight or more of a propylene component as a polyolefin, such as a crystalline ethylene-propylene random copolymer, a crystalline ethylene-propylene block copolymer, or a crystalline propylene copolymer. propylene-butene-1 random copolymer, crystalline ethylene-propylene-butene-1 terpolymer and crystalline propylene-hexene-butene-1
1. The flame-retardant polyolefin composition according to claim 1, which uses one or more ternary copolymers. (12) The flame-retardant polyolefin composition according to claim (1), which contains a thioether antioxidant. (13) Claims comprising one or more thioether antioxidants selected from dilaurylthiodipropionate, dimyristylthiodipropionate, and distearylthiodipropionate. The flame-retardant polyolefin composition according to item (12). (14) The flame-retardant polyolefin composition according to claim (1), which contains 20 to 60 parts by weight of the flame-retardant aid per 100 parts by weight of the halogenated flame retardant. (15) A patent claim in which the flame retardant aid is one or more selected from antimony trioxide, antimony tetroxide, antimony pentoxide, antimony trichloride, antimony trisulfide, and zinc borate. The flame-retardant polyolefin composition according to item (14).