JPH06102739B2 - Flame-retardant polyolefin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant polyolefin composition. More specifically, it relates to a flame-retardant polyolefin composition having excellent oxidative deterioration-preventing property of polyolefin during practical use.

[Prior Art] Generally, various halogen-based flame retardants have been blended with the polyolefin for the purpose of making the polyolefin flame-retardant, and have been widely put to practical use. However, a flame-retardant polyolefin composition containing a halogen-based flame retardant is oxidatively deteriorated by a halogen radical generated by decomposition of the halogen-based flame retardant due to heat during melt-kneading during molding. Therefore, there arises a problem that the thermal oxidation deterioration resistance in practical use (hereinafter, referred to as long-term thermal stability) is significantly reduced. In particular, since the propylene-based polymer has a tertiary carbon which is easily oxidized in the polymer, the above-mentioned problem of long-term thermal stability becomes remarkable.

Further, the flame-retardant polyolefin composition, when the molded product obtained by molding the composition is used for various automobile parts and electric and electronic parts, the molded product is treated with heavy metals such as copper, brass, iron and nickel. May be used for contact purposes.
However, since the polyolefin undergoes catalytic oxidative deterioration due to the heavy metal ions contained in the above-mentioned various heavy metals, the flame-retardant polyolefin composition has remarkable resistance to thermal oxidative deterioration (hereinafter referred to as heavy metal resistance) when brought into contact with heavy metals. Problems such as lowering occur.

Therefore, for the purpose of improving the long-term thermal stability of a flame-retardant polyolefin composition containing a halogen-based flame retardant, a metal soap is conventionally added to the flame-retardant polyolefin composition (Japanese Patent Laid-Open No. 49-31749). ), An epoxy compound (JP-A-52-92258)
JP-A-52-119655), stearic acid metal salts, that is, metal soaps and epoxy compounds (JP-A-52-119655).
48-60135), a phenolic antioxidant (Japanese Patent Application Laid-Open No. 54-54135).
-135838, JP-A-55-120644 and JP-A-57
-145136), a phenolic antioxidant and a saturated ester of bis-dithiopropionic acid (JP-A-53-86744).
Flame retardant polyolefin compositions each of which has been incorporated. Further, for the purpose of improving the flame retardancy of the flame-retardant polyolefin composition, a flame-retardant polyolefin composition obtained by blending the flame-retardant polyolefin composition with melamine (JP-A-51-106153 and JP-A-51-106153). 54-73
No. 843) is proposed. On the other hand, for the purpose of improving the heavy metal resistance of the polyolefin, a polyolefin composition obtained by blending a phenol compound having a specific spiro ring structure and a metal deactivator with the polyolefin (JP-A-62-112643). Is proposed.

[Problems to be Solved by the Invention] However, in recent years, the demand for flame retardancy has become more and more stringent in applications such as electrical and electronic parts or automobile parts, and molded articles obtained from flame-retardant polyolefin compositions. With the diversification of applications and the increase in size, the requirements for the practical use conditions (long-term thermal stability, heavy metal resistance, electrical insulation, etc.) of the molded articles are becoming stricter. That is, it is necessary to develop a flame-retardant polyolefin composition that is more excellent in thermal oxidation resistance than before. In order to solve these problems, a flame-retardant polyolefin composition containing a halogen-based flame retardant is blended with one or two selected from metal soaps and epoxy compounds. 31749, JP-A-52-92258, JP-A-52-11965
The flame-retardant polyolefin compositions proposed in JP-A No. 5-60 and JP-A No. 48-60135 are not yet sufficiently satisfactory in terms of long-term thermal stability and heavy metal resistance.
35838, JP 55-120644, JP 57-14513
No. 6 and JP-A No. 53-86744, a flame-retardant polyolefin composition in which a phenolic antioxidant is blended alone or a saturated ester of bis-dithiopropionic acid is used in combination with the phenolic antioxidant. Is considerably satisfactory in terms of long-term thermal stability, but is still unsatisfactory when it is used in applications requiring a high degree of long-term thermal stability, and is still not sufficiently satisfactory in terms of heavy metal resistance. In addition, JP-A-51-106153 and JP-A-5-106153
The flame-retardant polyolefin composition prepared by blending melamine proposed in JP-A-4-73843 is not yet sufficiently satisfactory in terms of long-term thermal stability and heavy metal resistance. Further, long-term thermal stability and heavy metal resistance of a polyolefin composition prepared by blending a phenolic compound having a specific spiro ring structure and a metal deactivator proposed in JP-A-62-112643 are considerably excellent. However, the long-term thermal stability and heavy metal resistance of the flame-retardant polyolefin composition obtained by blending the halogen-based flame retardant with the polyolefin composition are not yet sufficiently satisfactory. It is considered that this is because the scavenging action of halogen radicals generated from the halogen-based flame retardant is insufficient. In addition, the present inventor
The long-term thermal stability of a flame-retardant polyolefin composition prepared by blending a specific phenol-based antioxidant, a specific phosphorus-based antioxidant and an epoxy compound proposed in Japanese Patent No. 67338 is considerably excellent, but heavy metal resistance. Yes, I'm still not satisfied.

The present inventor has conducted extensive studies in order to solve the above-mentioned problems regarding the flame-retardant polyolefin composition obtained by blending the halogen-based flame retardant, that is, the problems of long-term thermal stability and heavy metal resistance.

As a result, a phenolic compound represented by the following general formula [II] (hereinafter referred to as compound B) and a phenolic compound represented by the following general formula [III] are added to a flame-retardant composition comprising a polyolefin and a halogen-based flame retardant. (Hereinafter, referred to as compound C.) The above flame-retardant polyolefin composition is a composition prepared by blending one or two or more phenolic compounds selected from the following, a heavy metal deactivator and an epoxy compound in specific amounts. It was found that the problem of (1) can be solved, and the present invention was completed based on this finding.

(However, in the formula, 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 R ₄ is hydrogen or a carbon number of 1
~ 9 alkyl group, 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, k is an integer of 0-8,
x represents an integer of 1 to 12, and y represents an integer of 0 to 8. ) As is clear from the above description, an object of the present invention is to provide a flame-retardant polyolefin composition which is excellent in long-term thermal stability and heavy metal resistance of a molded product.

[Means for Solving Problems] The present invention has the following configurations.

In a flame-retardant composition comprising a polyolefin and a halogen-based flame retardant, a phenolic compound represented by the following general formula [II] (hereinafter referred to as compound B) and the following general formula [III] per 100 parts by weight of the polyolefin. ] 1 type or 2 or more types of phenolic compounds selected from the phenolic compound (henceforth compound C) shown by these, a heavy metal deactivator, and an epoxy compound are 0.01-1 respectively.
A flame-retardant polyolefin composition containing parts by weight.

(However, in the formula, 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 R ₄ is hydrogen or a carbon number of 1
~ 9 alkyl group, 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, k is an integer of 0-8,
x represents an integer of 1 to 12, and y represents an integer of 0 to 8. 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 these two types. A crystalline, low crystalline or amorphous random copolymer or crystalline block copolymer of the above α-olefin, an amorphous ethylene-propylene-nonconjugated diene terpolymer, and the above α-olefin. Copolymer with vinyl acetate or acrylic ester, saponified product of the copolymer, copolymer of these α-olefins and unsaturated silane compounds, of these α-olefins and unsaturated carboxylic acids or their anhydrides Copolymers, reaction products of the copolymers with metal ion compounds, and modified polyols obtained by modifying polyolefins with unsaturated carboxylic acids or their derivatives. Fins, polyolefin can be exemplified a modified silane modified polyolefin with an unsaturated silane compound, single use of these polyolefins can of course, also possible to use a mixture of two or more polyolefins. Further, the above-mentioned polyolefin 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 resin (for example, polystyrene,
Styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, fluororesin, etc.) can be mixed and used. Crystalline propylene homopolymer, 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-
A 1-terpolymer, a crystalline propylene-hexene-butene-1 terpolymer and a mixture of two or more thereof are particularly preferably used.

The compound B used in the present invention is 3,9-bis [1,1-
Dimethyl-2-{(3-t-butyl-4-hydroxy-5-
Methylphenyl) carbonyloxy} ethyl] -2,4,8,
10-Tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2-{(3,5-di-t-butyl-4-hydroxyphenyl) carbonyloxy} ethyl] -2 ,Four,
8,10-Tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2-{(3,5-diphenyl-4-hydroxyphenyl) carbonyloxy} ethyl] -2,4 , 8,
10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-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] -2,4,8,10-tetraoxaspiro [5,5]
Undecane, 3,9-bis [1,1-dimethyl-2- {β- (3,
5-di-t-butyl-4-hydroxyphenyl) acetyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2] -
{Β (3,5-diphenyl-4-hydroxyphenyl) acetyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl- 2-
{Β- (3,5-Dicyclohexyl-4-hydroxyphenyl) acetyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl -2- {β- (3-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1, 1-Dimethyl-2- {β- (3-t-amyl-4-hydroxyphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-
Dimethyl-2- {β- (3-t-octyl-4-hydroxyphenyl) propionyloxy} ethyl] -2,4,8,10-
Itraoxaspiro [5,5] undecane, 3,9-bis [1,
1-dimethyl-2- {β- (3-methyl-4-hydroxy-5-t-amylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3 , 9-Bis [1,1-dimethyl-2- {β- (3-methyl-4-hydroxy-5-t-octylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [ 5,5] Undecane, 3,9-bis [1,1-dimethyl-2-
{Β- (3-Ethyl-4-hydroxy-5-t-butylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1 , 1
-Dimethyl-2- {β- (3-i-propyl-4-hydroxy-5-t-butylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-Bis [1,1-dimethyl-2- {β- (3-i-butyl-4-hydroxy-5-t-butylphenyl) propionyloxy} ethyl] -2,4,8,10-tetra Oxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2-
{Β (3-s-Butyl-4-hydroxy-5-t-butylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 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, 3,9
-Bis [1,1-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 , 10-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-hydroxyphenyl) propionyloxy} ethyl] -2,
4,8,10-Tetraoxaspiro [5,5] undecane, 3,9-
Bis [1,1-dimethyl-2- {β- (3,5-di-t-octyl-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-butylphenyl) propionyloxy} ethyl] -2,4,8,10-tetra Oxaspiro [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-tetraoxaspiro [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] undecane, 3,9
-Bis [1,1-dimethyl-2- {β- (3,5-diphenyl-
4-hydroxyphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2- {β- (3,5 -Dibenzyl-4-hydroxyphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxyspiro [5,5]
Undecane, 3,9-bis [1,1-dimethyl-2- {β- (3,
5-di (α-methylbenzyl) -4-hydroxyphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl -2- {β- (3,5-di (α, α-dimethylbenzyl) -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-methylphenyl) butylenyloxy} ethyl] -2,4,8,10-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] undecane, 3,9-bis [1, 1-Dimethyl-2- {β- (3,5-diphenyl-4-hydroxyphenyl) butenylenyloxy} 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] undecane, 3,9-bis [1,1-dimethyl-2- {β- (3,5-di-
t-Butyl-4-hydroxyphenyl) hexonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5]
Undecane, 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 [1,1-dimethyl-2- {β-
(3,5-dicyclohexyl-4-hydroxyphenyl)
Hexonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy -5-Methylphenyl) octonyloxy} ethyl] -2,4,8,10-
Tetraoxaspiro [5,5] undecane, 3,9-bis [1,
1-dimethyl-2- {β- (3,5-di-t-butyl-4-hydroxyphenyl) octonyloxy} ethyl] -2,4,
8,10-Tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2- {β- (3,5-diphenyl-4-
Hydroxyphenyl) octonyloxy} ethyl] -2,
4,8,10-tetraoxaspiro [5,5] undecane and
3,9-Bis [1,1-dimethyl-2- {β- (3,5-dicyclohexyl-4-hydroxyphenyl) octonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5, Five]
Undecane and the like can be exemplified, and particularly 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, 3,9-bis [1,1-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- (3,5 -Diphenyl-4-hydroxyphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5]
Undecane and 3,9-bis [1,1-dimethyl-2- {β-
(3,5-dicyclohexyl-4-hydroxyphenyl)
Propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred. These phenolic compounds can be used alone, and two or more phenolic compounds can be used in combination.

Examples of the compound C used in the present invention include 1,3,5-tris [(3-methyl-5-t-butyl-4-hydroxyphenyl) carbonyloxyethyl] isocyanurate, 1,3,
5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) carbonyloxyethyl] isocyanurate,
1,3,5-Tris [(3-methyl-5-t-butyl-4-hydroxyphenyl) acetyloxyethyl] isocyanurate, 1,3,5-Tris [(3,5-di-t-butyl- 4-hydroxyphenyl) acetyloxyethyl] isocyanurate, 1,3,5-tris [(3-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris [(3- t-amyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 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-tris [(3-methyl-4-hydroxy-5-t-amylphenyl) propionyloxyethyl] isocyanurate, 1,3,5- Tris [(3-methyl-4-hydroxy-5-t-octylphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris [(3-ethyl-4-hydroxy-5-t-butylphenyl) propionyl Oxyethyl] isocyanurate, 1,3,5-tris [(3-i-propyl-4-hydroxy-5-t-butylphenyl) propionyloxyethyl]
Isocyanurate, 1,3,5-tris [(3-i-butyl-4
-Hydroxy-5-t-butylphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris (3-s-
Butyl-4-hydroxy-5-t-butylphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate , 1,
3,5-Tris [(3-t-butyl-4-hydroxy-5-t-
Amylphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris [(3-t-butyl-4-hydroxy-5-t-octylphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris [(3,5-Di-
t-amyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris [(3,5
-Di-t-octyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 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) propionyloxyethyl] isocyanurate, 1,3,5-tris [(2-methyl-4-hydroxy-5-t-octylphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris [( 2-t−
Butyl-4-hydroxy-5-methylphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris [(3-methyl-5-t-butyl-4-hydroxyphenyl) butenyloxyethyl] isocyanurate, 1,3,
5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) butenyloxyethyl] isocyanurate, 1,
3,5-Tris [(3-methyl-5-t-bruch-4-hydroxyphenyl) hexonyloxyethyl] isocyanurate, 1,3,5-Tris [(3,5-di-t-butyl-4] -Hydroxyphenyl) hexoloxyethyl] isocyanurate, 1,3,5-tris [(3-methyl-5-t-butyl-
4-hydroxyphenyl) octenyloxyethyl] isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) octenyloxyethyl] isocyanurate, 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
-Tris [(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxypropyl] isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-)
Hydroxyphenyl) propionyloxypropyl] 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-tris [(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxyoctyl] isocyanurate,
1,3,5-Tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyoctyl] isocyanurate, 1,3,5-Tris [(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) propionyl oxide decyl] isocyanurate and 1,3,5-
Examples include tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxidedecyl] isocyanurate, and particularly 1,3,5-tris [(3-methyl-5)
-t-Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate and 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxyethyl] isocyanurate is preferred. These phenolic compounds can be used alone, and two or more phenolic compounds can be used in combination.

The phenolic compound selected from the compound B and the compound C is used alone, and it is also possible to use two or more phenolic compounds in combination. The blending ratio of the phenolic compound is 0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the polyolefin.

If the amount is less than 0.01 part by weight, the effect of preventing oxidative deterioration of the flame-retardant polyolefin composition is not sufficiently exhibited, and if it exceeds 1 part by weight, further improvement of the effect of preventing oxidative deterioration cannot be expected. Not only impractical but also uneconomical.

As the heavy metal deactivator used in the present invention, benzotriazole, 2,4,6-triamino-1,3,5-triazine,
3,9-Bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5,
5] Undecane, ethylenediamine-tetraacetic acid, alkali metal salt of ethylenediamine-tetraacetic acid, N, N'-disalicylidene-ethylenediamine, N, N'-disalicylidene-1,2-bropyrenediamine, 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'- Ethyl oxanilide, 5-t-butyl-2-ethoxy-2'-ethyl oxanilide, 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-methyl Examples include phenyl] phosphite and N, N′-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, 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-methyl Phenyl] phosphite and N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide are preferred. It goes without saying that these heavy metal deactivators are used alone, and two or more heavy metal deactivators can be used in combination. The compounding ratio of the heavy metal deactivator 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 polyolefin. If the amount is less than 0.01 part by weight, the effect of preventing oxidative deterioration of the flame-retardant polyolefin composition is not sufficiently exhibited, and if it exceeds 1 part by weight, further improvement of the effect of preventing oxidative deterioration cannot be expected. Not only impractical but also uneconomical.

The epoxy compound used in the present invention is not particularly limited as long as it does not volatically escape or decompose during melt-kneading, and the epoxy equivalent is 100 to 1,000.
Those of a degree can be preferably used, and epichlorohydrin or a derivative of epichlorohydrin (for example, 2
-Methylepichlorohydrin, 2-ethylepichlorohydrin and 2-propylepichlorohydrin) and bisphenol or bisphenol derivatives (e.g. bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S) Condensates, epoxidized oils and fats (such as epoxidized soybean oil, epoxidized linseed oil and epoxidized castor oil), epoxidized oleic acids, alkyl esters of epoxidized oleic acids (eg epoxidized octyl stearate, 3,4-epoxy) Cyclohexylmethanol fatty acid ester, 3,
Alkyl ester of 4-epoxycyclohexylcarboxylic acid, dialkyl ester of 4,5-epoxycyclohexane-1,2-dicarboxylic acid, 3,4-epoxy-6-methylcyclohexylmethyl and 3,4-epoxy-6-methylcyclohexanecarboxy ), 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, phthalate Acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid 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) Examples thereof include adipate, vinylcyclohexene diepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether, and limonenedioxide. Particularly, a condensate of epichlorohydrin and bisphenol A, 2-methylepichlorohydrin and bisphenol A Condensates, triglycidyl isocyanurate and epoxidized soybean oil are preferred. It goes without saying that these epoxy compounds are used alone, and two or more kinds of epoxy compounds can be used in combination. The compounding ratio of the epoxy compound is 0.01 to 1 part by weight, preferably 100 parts by weight of the polyolefin.
0.05 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 is not sufficiently exhibited, and if it exceeds 1 part by weight, further improvement of the effect of preventing oxidative deterioration cannot be expected. (Stickiness occurs when the epoxy compound exceeds 1 part by weight.) Not only is it impractical, but also uneconomical.

As the halogen-based flame retardant used in the present invention, ammonium bromide, ammonium chloride, 2-chlorotetrabromobutane, 2,2-bis [p- (chloroformyloxy) phenyl-3] propane, 1,2-dibromo- 3-chloropropane, 1,2,3-tribromopropane, 1,1,2,2-tetrabromoethane, tetrabromobutane, hexabromocyclododecane, hexabromooctane, hexabromobutane, pentabromocyclohexane, tribromotrichloro Cyclohexane, pentabromochlorocyclohexane, 1,2-dibromo-1,1,2,2-tetrachloroethane, 2,
2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, vinyl chloroacetate, 2,4,6-tribromophenyl 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 (promomethyl) propanol,
2,2-dibromobutene-1,4-diol, tribromophenol, dibromoneopentyl glycol, tribromoneopentyl alcohol, 2,3-dibromopropanol, 2,3,3'-tribromoallyl alcohol, chloropentabromo Phenyl allyl ether, pentachlorophenoxy glycerin ether, bromophenyl allyl ether, tribromophenol allyl ether, pentabromophenol allyl 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, pentabromo Ryl ether, 1,2-dibromopropyl-tribromophenyl ether, decachlorodiphenyl carbonate, decabromodiphenyl carbonate, 2,3,3-tribromoallyl carboxylate, 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 diethoxylate, bis ( 2-hydroxyethyl ether)
Tetrabromobisphenol A, 2,2'-bis [[3,5-
Dibromo-4- (2 ', 3'-dibromopropyloxy)]
Phenyl] propane, 2,2'-bis [[3,5-dibromo-
4- (2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] propane, tetrabromobisphenol F, bis [[3,5-dibromo-4- (2', 3'-dibromopropyloxy)] ] Phenyl] methane, bis [[3,5
-Dibromo-4- (2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] methane, bis [[3,5-dibromo-4- (2', 3'-dibromopropyloxy)] phenyl ] Oxide, bis [[3,5-dibromo-4-
(2 ', 3'-Dibromo-2'-methylpropyloxy)] phenyl] oxide, bis [[3,5-dibromo-4- (2', 3'-dibromopropyloxy)] phenyl] ketone, bis [ [3,5-dibromo-4- (2 ', 3'-
Dibromo-2'-methylpropyloxy)] phenyl]
Ketone, bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfide, bis [[2,5-dibromo-4- (2', 3'-dibromo-2] ′-
Methylpropyloxy)] phenyl] sulfide, tetrabromobisphenol S, bis [[3,5-dibromo-4- (2 ′, 3′-dibromopropyloxy)] phenyl] sulfone, bis [[3,5-dibromo- 4- (2 ',
3'-Dibromo-2'-methylpropyloxy)] phenyl] sulfone, pentabromotoluene, tribromoaniline, acetylene tetrabromide, 1- (p-tosyl) -3- (2'-promo-4 ', 4'. Inorganic and organic halogen-based flame retardants such as 4,4'-trichlorobutyl) urea, 2,3-dibromopropanol ester, chlorinated paraffin, chlorinated polyethylene or chlorinated polypropylene can be exemplified, and especially decabromodiphenyl ether, perchloropenta Cyclodecane, didecachlorododecahydrodimethanodibenzocyclooctene, 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. These halogen-based flame retardants can be used alone, and two or more halogen-based flame retardants can be used in combination. The blending ratio of the halogen-based flame retardant is not particularly limited as long as it is blended according to the desired flame retardancy, but it is usually preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polyolefin.

Further, a flame retardant aid may be further used in the composition of the present invention. As the flame retardant aid, an antimony compound (for example, antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, antimony trichloride,
Antimony trisulfide, antimony oxychloride, antimony dichloride perchloropentane and potassium antimonate), boron compounds (such as zinc metaborate, zinc tetraborate, zinc borate and basic zinc borate), zirconium oxide, Examples thereof include tin oxide and molybdenum oxide, and antimony trioxide, antimony tetraoxide, antimony pentaoxide, antimony trichloride, antimony trisulfide and zinc borate are particularly preferable. It goes without saying that these flame retardant aids are used alone, and two or more flame retardant aids can be used in combination. The mixing ratio of these flame retardant aids is not particularly limited, but is preferably 20 to 60 parts by weight with respect to 100 parts by weight of the halogen-based flame retardant. The blending of the flame retardant aid acts synergistically with the halogen-based flame retardant in the composition of the present invention to enhance the flame retardancy, so that the blending amount of the halogen-based flame retardant can be reduced. Therefore, the blending of the flame retardant aid is preferred.

In the composition of the present invention, various additives usually added to polyolefins such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifiers,
Radical generators such as nucleating agents, lubricants, antistatic agents, anticlouding agents, antiblocking agents, non-dripping agents, pigments and peroxides,
Dispersants or neutralizers such as metal soaps, inorganic fillers (eg 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 (eg, silane-based, titanate-based, boron-based,
For the purpose of the present invention, the inorganic or organic filler (eg, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with a surface treating agent such as aluminate-based, zirco-aluminate-based, etc. It can be used in combination as long as it does not deteriorate. Particularly, when a thioether-based antioxidant is used in combination, the effect of preventing oxidative deterioration is synergistically exhibited, and therefore it is preferable to use them together. As the thioether antioxidant, dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate,
Dicetylthiodipropionate, distearylthiodipropionate, dilaurylthiodibutyrate, ditridecylthiodibutyrate, dimyristylthiodibutyrate, dicetylthiodibutyrate, distearylthiodibutyrate, laurylstearylthiodipropionate ,
Lauryl stearyl thiodibutyrate, pentaerythritol-β-lauryl thiodibromopionate, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-
Myristyl thiopropionate), pentaerythritol-tetrakis (3-stearyl thiopropionate), bis (4-t-amylphenyl) sulfide, distearyl disulfide, thioethylene glycol-bis (β-amino crotonate) and poly Examples include [1,4-bis (hydroxymethyl) cyclohexane-thiodipropionate], and dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate are particularly preferable.

The composition of the present invention comprises a compound A, a compound B and a polyolefin.
And one or more phenolic compounds selected from the compound C, heavy metal deactivators, epoxy compounds, and halogen-based flame retardants, if necessary, a flame retardant aid and the above-mentioned various additives usually added to polyolefins. A predetermined amount of the agent is mixed using an ordinary mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, etc., and an ordinary single screw extruder, twin screw extruder, Brabender or roll is used. Then, it can be obtained by melt-kneading pelletizing at a melt-kneading temperature of 150 ° C to 250 ° C, preferably 180 ° C to 230 ° C. The obtained composition is used for producing a desired molded article by various molding methods such as an injection molding method, an extrusion molding method and a blow molding method.

[Function] In the present invention, the phenolic compound selected from the compound B and the compound C is used as a radical chain inhibitor, the heavy metal deactivator is used as a deactivator of the catalytic oxidative deterioration action of the polyolefin by heavy metal ions, and Epoxy compounds are generally known to act as scavengers of halogen radicals. However, by using a flame-retardant polyolefin composition containing a halogen-based flame retardant in combination with a phenolic compound selected from the compound B and the compound C of the present invention, a heavy metal deactivator and an epoxy compound, It has been found that a surprisingly synergistic effect which cannot be predicted from the compounding of a known compound having an antioxidative deterioration effect is exerted, and a flame-retardant polyolefin composition excellent in long-term thermal stability and heavy metal resistance is obtained.

[Examples] Hereinafter, the present invention will be specifically described 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) Long-term thermal stability: evaluated by an oven life test. That is, using the obtained pellets, length 50 mm, width 25
mm, 1 mm thick test piece was prepared by an injection molding method, and the test piece was placed in a circulating hot air oven adjusted to a temperature of 150 ° C., and the time until the test piece was completely deteriorated (tensile strength was 0
The long-term thermal stability was evaluated by measuring the time until it became (according to JIS K 7212).

2) Heavy metal resistance: evaluated by a copper resistance test. That is, using the obtained pellets, length 50 mm, width 25 mm, thickness 1 mm
Was prepared by injection molding method, the length of 25 mm using the test piece, width of 25 mm, and fixed by a clip in contact with a copper plate having a thickness of 0.3 mm, put in a circulating hot air oven adjusted to a temperature of 150 ° C, Measure the time until the copper plate contact part of the test piece completely deteriorates (the time until the deterioration penetrates) (JIS K 721
2), the heavy metal resistance was evaluated.

3) Flame retardance: UL Subject 94 (Underwriters Laborat
flame retardancy test was performed according to the vertical combustion test method of ories Inc.). That is, using the obtained pellets a length of 125 mm,
A combustion test piece having a width of 12.5 mm and a thickness of 1.56 mm was prepared by an injection molding method, and the combustion test piece was used to evaluate the flammability classification and the presence or absence of melt dripping.

Examples 1 to 16 and Comparative Examples 1 to 9 MFR as polyolefin (discharging amount of molten resin for 10 minutes when a load of 2.16 kg at 230 ° C. is applied for 10 minutes) 6.0 g / 10 minutes unstabilized powdery crystallinity Propylene homopolymer
100 parts by weight of decabromodiphenyl ether as a halogen-based flame retardant, antimony trioxide as a flame retardant aid, and 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, compound C as 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) 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 condensation product of epichlorohydrin and bisphenol A as an epoxy compound (epoxy equivalent of 700 to 830), a condensation product of epichlorohydrin and bisphenol A and 2-
Mixtures of condensates of methyl epichlorohydrin and bisphenol A (epoxy equivalent 180-200), triglycidyl isocyanurate (epoxy equivalent 100-110) or epoxidized soybean oil (epoxy equivalent 220-240) and other additives, respectively. Put the amount into the Henschel mixer (trade name) at the mixing ratios shown in Table 1-1 and Table 1-2 below, stir and mix for 3 minutes, and then use a twin-screw extruder with a diameter of 30 mm.
It was melt-kneaded at 230 ° C. and pelletized. Further, as Comparative Examples 1 to 9, 100 parts by weight of powdered crystalline propylene homopolymer having an MFR of 6.0 g / 10 min, which was not stabilized, was added to the first
-2. Predetermined amounts of the additives shown in Table 2 were mixed and melt-kneaded according to Examples 1 to 16 to obtain pellets.

The test pieces used in the oven life test, copper resistance test and flammability test were prepared by injection molding the obtained pellets at a resin temperature of 230 ° C and 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 above test methods. The results are shown in Tables 1-1 and 1-2.

Examples 17 to 32, Comparative Examples 10 to 18 100 parts by weight of powdered crystalline propylene homopolymer having an MFR of 6.0 g / 10 minutes as a polyolefin, 2,2'-bis [as a halogen-based flame retardant] [3,5-dibromo-
4- (2 ′, 3′-dibromopyroxy)] phenyl] propane, antimony trioxide as a flame retardant aid, 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-tris [(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-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 700-830), a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 180-200), triglycidyl isocyanurate (epoxy equivalent 100-110) or epoxidation. Put soybean oil (epoxy equivalent 220-240) and other additives in the Henschel mixer (trade name) in the proportions shown in Tables 2-1 and 2-2 below for 3 minutes. After stirring and mixing, the mixture was melt-kneaded at 200 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 10 to 18, MFR has a predetermined amount of each of the additives shown in Table 2-2 described below in 100 parts by weight of powdery crystalline propylene homopolymer which is not stabilized and has 6.0 g / 10 minutes. Then, in accordance with Examples 17 to 32, a melt kneading process was performed to obtain pellets.

The test pieces used for the oven life test, copper resistance test and flammability test were prepared by injection molding the obtained pellets at a resin temperature of 200 ° C and 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 above test methods. The results are shown in Table 2-1 and Table 2-2.

Examples 33 to 48, Comparative Examples 19 to 27 100 parts by weight of powdered crystalline propylene homopolymer having an MFR of 6.0 g / 10 min as a polyolefin, and bis [[3,5- Dibromo-4-
(2 ', 3'-Dibromopropyloxy)] phenyl] sulfone, antimony trioxide as a flame retardant aid, compound B
As 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) as compound C
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-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 700-830), a condensate of epichlorohydrin and bisphenol A and 2-
Mixtures of condensates of methyl epichlorohydrin and bisphenol A (epoxy equivalent 180-200), triglycidyl isocyanurate (epoxy equivalent 100-110) or epoxidized soybean oil (epoxy equivalent 220-240) and other additives, respectively. Put the amount into the Henschel mixer (trade name) at the blending ratio shown in Table 3-1 and Table 3-2 below, stir and mix for 3 minutes, and then use a twin-screw extruder with a diameter of 30 mm.
The mixture was melt-kneaded at 200 ° C. and pelletized. Further, as Comparative Examples 19 to 27, the MFR has an unstabilized powdery crystalline propylene homopolymer of 6.0 g / 10 min.
-2.
Melt-kneading was performed according to 33-48 to obtain pellets.

The test pieces used in the oven life test, copper resistance test and flame retardancy test were prepared by injection molding the obtained pellets at a resin temperature of 200 ° C and 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 above test methods. The results are shown in Table 3-1 and Table 3-2.

Examples 49 to 64, Comparative Examples 28 to 36 100 parts by weight of unstabilized powdery crystalline propylene homopolymer as MFR 6.0 g / 10 min as a polyolefin, dodecachlorododecahydrodimethanodibenzo as a halogen-based flame retardant Cyclooctene, antimony trioxide as flame retardant aid, 3,9-bis [1,1-dimethyl-2- as compound B
{Β- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, as compound C
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) 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), and epichlorohydrin and bisphenol A as epoxy compounds Condensation product (epoxy equivalent 700 to 8
30), a condensate of epichlorohydrin and bisphenol A, 2-methylepichlorohydrin and bisphenol A
A mixture of a condensate with (epoxy equivalent of 180 to 200), triglycidyl isocyanurate (epoxy equivalent of 100 to 110) or epoxidized soybean oil (epoxy equivalent of 220 to 240) and other additives are added in predetermined amounts described below. Put in a Henschel mixer (trade name) in the mixing ratios shown in Table 4-1 and Table 4-2, stir and mix for 3 minutes, and then melt-knead at 230 ° C with a twin-screw extruder with a diameter of 30 mm. Pelletized.
Further, as Comparative Examples 28 to 36, MFR was mixed with a prescribed amount of each of the additives shown in Table 4-2 below in 100 parts by weight of powdery crystalline propylene homopolymer having an unstabilized value of 6.0 g / 10 min. Then, in accordance with Examples 49 to 64, melt kneading treatment was performed to obtain pellets.

Test pieces used in the oven life test, copper resistance test and flame retardancy test were prepared by injection molding the obtained pellets at a resin temperature of 230 ° C and 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 above test methods. The results are shown in Table 4-1 and Table 4-2.

Examples 65 to 80, Comparative Examples 37 to 45 MFR as a polyolefin 4.0 g / 10 min Unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) 100 parts by weight, halogen Decabromodiphenyl ether as a flame retardant, antimony trioxide as a flame retardant aid, 3,9-bis [1,1-dimethyl-2- {β (3-t-butyl-4-hydroxy-5-methyl) as compound B (Phenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, compound C as 1,3,5-tris [(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-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), epichlorohydrin And bisphenol A condensate and 2-methylepichlorohydrin and bisphenol A condensate mixture (epoxy equivalent 180-200), triglycidyl isocyanurate (epoxy equivalent 100-110) or epoxidized soybean oil (epoxy equivalent 220- 240) and other additives in the Henschel mixer (trade name) at the blending ratios shown in Tables 5-1 and 5-2 below, and the mixture is stirred and mixed for 3 minutes. Was melt-kneaded at 230 ° C. with a twin-screw extruder to prepare pellets. Further, as Comparative Examples 37 to 45, MFR is 4.0 g /
Unstabilized powdery crystalline ethylene-propylene block copolymer for 10 minutes (ethylene content 8.5% by weight)
A predetermined amount of each of the additives shown in Table 5-2 described below was mixed with 100 parts by weight of the polymer, and the mixture was subjected to melt-kneading according to Examples 65 to 80 to obtain pellets.

Test pieces used in the oven life test, copper resistance test and flame retardancy test were prepared by injection molding the obtained pellets at a resin temperature of 230 ° C and 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 above test methods. The results are shown in Table 5-1 and Table 5-2.

Examples 81-96, Comparative Examples 46-54 MFR 6.0 g / 10 min as a polyolefin Unstabilized powdery crystalline propylene homopolymer 70% by weight, MFR 7.0
g / 10 minutes unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 5% by weight, MI (melting at 190 ° C load 2.16 kg for 10 minutes) Resin discharge amount) 5.0g / 10min Unstabilized powdered Ziegler-Natta high density ethylene homopolymer 10wt% and Mooney viscosity ML1 + 4 (100
Unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content 25% by weight) 15% by weight in total of 100 parts by weight, decabromodiphenyl ether as a halogen-based flame retardant, Antimony trioxide as flame retardant aid, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] as compound B -2,4,8,10-Tetraoxaspiro [5,5] undecane, Compound C as 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] Isocyanurate, N as 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), epichlorohydrin And bisphenol A condensate and 2-methylepichlorohydrin and bisphenol A condensate mixture (epoxy equivalent 180-200), triglycidyl isocyanurate (epoxy equivalent 100-110) or epoxidized soybean oil (epoxy equivalent 220- 240) and other additives in the Henschel mixer (trade name) at the blending ratios shown in Tables 6-1 and 6-2 described below, and the mixture is stirred and mixed for 3 minutes, and then the diameter is 30 mm. Was melt-kneaded at 230 ° C. with a twin-screw extruder to prepare pellets. Further, as Comparative Examples 46 to 54, MFR was 6.0 g /
Unstabilized powdery crystalline propylene homopolymer for 10 minutes 70% by weight, MFR 7.0 g / 10 minutes unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% %) 5% by weight, unstabilized powdered Ziegler-Natta high density ethylene homopolymer 10% by weight and Mooney viscosity ML1
+4 (100 ° C.) is composed of 25 parts of unstabilized powdery amorphous ethylene-propylene random copolymer (15% by weight propylene content) and 15% by weight in total 100 parts by weight. Predetermined amounts of the additives shown in the table were mixed and melt-kneaded according to Examples 81 to 96 to obtain pellets.

The test pieces used in the oven life test, copper resistance test and flammability test were prepared by injection molding the obtained pellets at a resin temperature of 230 ° C and 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 above test methods. The results are shown in Table 6-1 and Table 6-2.

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

Compound B: 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 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 [II]: tris [2-t-butyl-4-]
Thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite Heavy metal deactivator [III]: N, N'-bis [3- (3,5 -The-
t-butyl-4-hydroxyphenyl) propionyl]
Hydrazine heavy metal deactivator [IV]: oxalic acid-bis (benzylidene hydrazide) epoxy compound [I]: condensate of epichlorohydridine and bisphenol A (epoxy equivalent 700-830; CIBA-G
EIGY AG ARA-LDITE GT 7004) Epoxy compound [II]: a mixture of a condensate of epichlorohydridine and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 180-200; ADEKA ARGUS CHEMICAL) MARK FP-1 manufactured by Co., Ltd.
7) Epoxy compound [III]: triglycidyl isocyanurate (epoxy equivalent 100 to 110; ARAL manufactured by CIBA-GEIGY AG
DITE PT810) Epoxy compound [IV]: Epoxidized soybean oil (epoxy equivalent 220-240; ADK CIZER manufactured by Adeka Argus Chemical Co., Ltd.)
O-130P Halogen flame retardant [I]: Decabromodiphenyl ether Halogen flame retardant [II]: 2,2'-bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] Phenyl] propane halogen-based flame retardant [III]: bis [[3,5-dibromo-4]
-(2 ', 3'-Dibromopropyloxy)] phenyl]
Sulfone Halogen flame retardant [IV]: Dodecachlorododecahydrodimethanodibenzocyclooctene Flame retardant aid: Antimony trioxide Thioether antioxidant: Dimyristyl thiodipropionate Phosphorus antioxidant 1: Bis (2,6 -Di-t-butyl-4-
Methylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 2: bis (2,4-di-t-butylphenyl) -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: 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) isocyanurate Phenolic antioxidant 4: 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene Ca-St: calcium stearate Examples and comparative examples described in Table 1-1 and Table 1-2,
Crystalline propylene homopolymer as polyolefin, decabromodiphenyl ether as halogen flame retardant,
This is the case when antimony trioxide is used as the flame retardant aid.
As can be seen from Table 1-1 and Table 1-2, Examples 1-16
Is a compound in which a phenolic compound selected from the compounds B and C according to the present invention, a heavy metal deactivator and an epoxy compound are blended. Examples 1 to 16 and Comparative Examples 1 to 3 (compounds B and C) In comparison with a phenolic compound other than the phenolic compound instead of the phenolic compound selected from Examples 1 to 16, Examples 1 to 16 are excellent in both long-term thermal stability and heavy metal resistance. You can see that Compounds B and C
Comparative Examples 4 to 5 in which a phenolic compound selected from the above and a heavy metal deactivator are blended and no epoxy compound is blended
Comparing Examples 1 to 16 with Comparative Examples 4 to 5, the long-term thermal stability and heavy metal resistance of Comparative Examples 4 to 5 are still insufficient. Moreover, the long-term thermal stability and heavy metal resistance of Comparative Examples 6 to 7 in which the compositions of Comparative Examples 4 to 5 were mixed with metal soap (calcium stearate) as a halogen scavenger were improved to some extent as compared with Comparative Examples 4 to 5. However, it is not enough. Further, comparing Comparative Examples 8 to 9 and Examples 1 to 16 in which a phenolic compound selected from Compound B and Compound C and an epoxy compound are not added and a heavy metal deactivator is not added, Comparative Examples 8 to 9 are compared. Although long-term thermal stability is fairly excellent, heavy metal resistance is still insufficient. Therefore, it is apparent that the comparative examples that do not simultaneously satisfy the combination of the three components of the phenolic compound selected from the compound B and the compound C according to the present invention, the heavy metal deactivator, and the epoxy compound do not exhibit the effect of the present invention. Is. That is, the long-term thermal stability and heavy metal resistance obtained in the present invention are obtained by adding a phenolic compound selected from compound B and compound C to a flame-retardant polyolefin composition obtained by blending a halogen-based flame retardant in the present invention, It can be said that this is a unique effect that can only be seen when a heavy metal deactivator and an epoxy compound are used in combination.

Further, the flame-retardant composition according to the present invention, which comprises a phenolic compound selected from compound B and compound C, a heavy metal deactivator, and an epoxy compound, is more difficult than conventionally known flame-retardant compositions. It was confirmed that the flammability was comparable.

Tables 2-1 to 4-2 show that crystalline propylene homopolymer as a polyolefin and halogen-based flame retardant 2, 2, respectively.
2'-bis [(3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] propane, bis [[3,
5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfone and dodecachlorododecahydrodimethanodibenzocyclooctene were used, and the effects similar to those described above were confirmed. .
Further, Tables 5-1 to 6-2 show that, as the polyolefin, crystalline ethylene-propylene block copolymer or crystalline propylene homopolymer, crystalline ethylene-propylene random copolymer, Ziegler-Natta high density A mixture of an ethylene homopolymer and an amorphous ethylene-propylene random copolymer and decabromodiphenyl ether as a halogen-based flame retardant were used, and the same effects as above were confirmed.

[Effects of the Invention] The composition of the present invention is (1) compared with a conventionally known flame-retardant polyolefin composition obtained by mixing a halogen-based flame retardant and a compound having various oxidative deterioration-preventing effects. The molded article is remarkably excellent in long-term thermal stability and heavy metal resistance. (2) Since the long-term thermal stability and heavy metal resistance are remarkably excellent, there is no deterioration in electrical insulation due to oxidative deterioration of polyolefin, so flame retardancy in various molding fields and long-term thermal stability and heavy metal resistance. Can be suitably used for the required applications (for example, electric and electronic functional parts such as a deflection yoke, CRT socket and connector, and automotive parts such as a distributor cap, car heater case and car air conditioner case).

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Claims (14)

[Claims] 1. A flame-retardant composition comprising a polyolefin and a halogen-based flame retardant, and a phenol compound represented by the following general formula [II] (hereinafter referred to as compound B) and 100 parts by weight of the polyolefin. The following general formula [II
I], and one or more phenolic compounds selected from the phenolic compounds (hereinafter referred to as compound C), a heavy metal deactivator, and an epoxy compound, each in an amount of 0.01 to 1 part by weight. Flame-retardant polyolefin composition. (However, in the formula, 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 R ₄ is hydrogen or a carbon number of 1
~ 9 alkyl group, 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, k is an integer of 0-8,
x represents an integer of 1 to 12, and y represents an integer of 0 to 8. ) 2. R ₃ and R in the general formulas [II] to [III]
The flame-retardant polyolefin composition according to claim 1, wherein _{5 to} R ₆ are t-butyl groups and R ₄ is a methyl group. 3. Compound B as 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4 , 8,10
-The flame-retardant polyolefin composition according to claim (1), which comprises tetraoxaspiro [5,5] undecane. 4. A compound C comprising 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate as compound C. ) Item, the flame-retardant polyolefin composition. 5. Oxalic acid-bis (benzylidene hydrazide), N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine as a heavy metal deactivator, 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 The flame-retardant polyolefin composition according to claim (1), which is prepared by blending one or two or more of these. 6. An epoxy compound selected from epichlorohydrin or a condensate of a derivative of epichlorohydrin and a bisphenol or a derivative of bisphenol, triglycidyl isocyanurate, an epoxidized oil / fat, an epoxidized oil / fat acid or an alkyl ester of an epoxidized oil / fat acid. The flame-retardant polyolefin composition according to claim (1), which is a mixture of two or more kinds. 7. A compound comprising one or more compounds selected from a condensate of epichlorohydrin or its derivative and bisphenol A, triglycidyl isocyanurate and epoxidized soybean oil as an epoxy compound. The flame-retardant polyolefin composition according to the item (1). 8. The halogen-based flame retardant is decabromodiphenyl ether, perchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, tetrabromobisphenol A, tetrabromobisphenol S, 2,2. 2'-bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] propane and bis [[3,5-dibromo-4- (2', 3'-dibromopropyl) The flame-retardant polyolefin composition according to claim (1), which is one or more selected from (oxy)] phenyl] sulfone. 9. The flame-retardant polyolefin composition according to claim 1, wherein the halogen-based flame retardant is mixed in an amount of 5 to 30 parts by weight with respect to 100 parts by weight of the polyolefin. 10. A crystalline propylene homopolymer as a polyolefin, a propylene copolymer containing 70% by weight or more of a propylene component, which is a crystalline ethylene-propylene random copolymer or a crystalline ethylene-propylene block copolymer. , Crystalline propylene-butene-1 random copolymer, crystalline ethylene-propylene-butene-1
Flame retardant polyolefin according to claim (1), wherein one or more terpolymers selected from terpolymers and crystalline propylene-hexene-butene-1 terpolymers are used. Composition. 11. The flame-retardant polyolefin composition according to claim 1, which further comprises a thioether antioxidant. 12. A compound comprising one or more selected from dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate as a thioether antioxidant. The flame-retardant polyolefin composition according to item (11). 13. A halogen-based flame retardant compounding amount of a flame retardant auxiliary is 10
The flame-retardant polyolefin composition according to claim (1), which is compounded in an amount of 20 to 60 parts by weight with respect to 0 parts by weight. 14. An antimony trioxide, antimony tetroxide, antimony pentoxide, antimony trichloride, as a flame retardant aid,
The flame-retardant polyolefin composition according to claim (13), which comprises one or more selected from antimony trisulfide and zinc borate.