JPH0641357A - Flame-resistant polyolefion composition - Google Patents

Abstract

PURPOSE:To provide the flame-resistant polyolefin composition giving molded products excellent in an oxidized deterioration-preventing property by compounding the specific composition of a polyolefin with a specified compound, a thioether antioxidizing agent, a heavy metal-inactivating agent, etc., in specific amounts. CONSTITUTION:The composition comprises (A) a polyolefin composition containing 30-70wt.% of magnesium hydroxide, (B) one kind or more of (i) a compound of formula I (R1 is 1-4C alkylidene; R2 is 1-9C alkyl; R3 is H, 1-9C alkyl, cycloalkyl, etc.) (e.g. bis[2-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methyl-6- t-butylphenyl] isophthalate} and (ii) a compound of formula II (R4 is 1-8C alkyl; R5 is H, 1-8C alkyl; n is 1-4), [e.g. tris(3-t-butyl-4-hydroxybenzyl) isocyanurate], (C) a thioether antioxidizing agent, (D) a heavy metal-inactivating agent, (E) an epoxy compound, and (F) a fatty acid, the amounts of the components B-E being 0.01-1 pt.wt., respectively, and the amount of the component F being 0.5-5 pts.wt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to flame retardant polyolefin compositions. More specifically, it relates to a flame-retardant polyolefin composition having excellent oxidative deterioration-preventing property of polyolefin during practical use.

[0002]

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

A molded article molded from a flame-retardant polyolefin composition obtained by mixing magnesium hydroxide and various antioxidants in polyolefin is used for the purpose of coming into contact with heavy metals such as copper, brass, iron and nickel. Sometimes. However, since the polyolefin is catalytically deteriorated by the heavy metal ions contained in the above-mentioned various heavy metals, a molded article using the flame-retardant polyolefin composition described above is resistant to oxidation deterioration during contact with heavy metals (hereinafter,
It is called heavy metal resistance. ) Is significantly reduced.

Therefore, for the purpose of improving the heavy metal resistance of a molded product using a flame-retardant polyolefin composition which has been conventionally compounded with magnesium hydroxide, magnesium hydroxide, a phenolic antioxidant and sulfur are added to the polyolefin. Composition containing a system antioxidant and a copper damage inhibitor
No. 2-11238 and Japanese Patent Laid-Open No. 63-56544), and a composition obtained by mixing magnesium hydroxide and an epoxy compound with polyolefin (Japanese Patent Laid-Open No. 59-2193).
52, JP-A-63-137963, JP-A-63-159473 and JP-A-63-1894.
62), magnesium hydroxide in polyolefin,
Compositions containing a phenolic stabilizer, a higher fatty acid and a higher fatty acid metal salt (JP-A-53-33247 and JP-A-54-47746) have been proposed.

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 the applications of molded articles obtained from flame-retardant polyolefin compositions are diversified and large. Along with
The requirements for practical use conditions (heavy metal resistance, electrical insulation, etc.) of the molded product are becoming severe. That is, it is necessary to develop a flame-retardant polyolefin composition that is more excellent in heavy metal resistance than ever before. In order to solve these problems, magnesium hydroxide is added to the above-mentioned JP-A-52-1238, JP-A-63-56544, JP-A-59-219352, and JP-A-63-1.
37963, JP-A-63-159473,
JP-A-63-189462, JP-A-53-332
The flame-retardant polyolefin compositions proposed in Japanese Patent No. 47 and Japanese Patent Application Laid-Open No. 54-47746 are still not sufficiently satisfactory in terms of heavy metal resistance. For this reason, the present inventor has found that polyolefin has magnesium hydroxide, a specific phenol compound, a specific thioether compound,
A flame-retardant polyolefin composition prepared by mixing a heavy metal deactivator and an epoxy compound in specific amounts was previously proposed (JP-A-2-240148).

[0006]

DISCLOSURE OF THE INVENTION The inventor of the present invention has disclosed in
Further studies were conducted without being satisfied with the flame-retardant polyolefin composition proposed in JP-A-240148. As a result, a phenolic compound represented by the following chemical formula 3 (hereinafter referred to as compound A) and a phenolic compound represented by the following chemical formula 4 (hereinafter referred to as compound B) in a flame-retardant composition composed of polyolefin and magnesium hydroxide. Flame retardant polyolefin composition with improved heavy metal resistance by blending one or more compounds selected from the above), thioether-based antioxidants, heavy metal deactivators, epoxy compounds and fatty acids in specific amounts. It was found that a product was obtained, and the present invention was completed based on this finding.

[Chemical 3]

[Chemical 4] (In the formula, R ₁ is an alkylidene group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 9 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or an alkyl group. A cyclohexyl group, R ₄ is an alkyl group having 1 to 8 carbon atoms, R ₅ is hydrogen or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4.) As described above, an object of the present invention is to provide a flame-retardant polyolefin composition which is excellent in heavy metal resistance of a molded product when the molded product is formed.

[0007]

The present invention has the following constitution. A phenolic compound represented by the following chemical formula 5 (hereinafter referred to as compound A) based on 100 parts by weight of a composition obtained by mixing 30 to 70% by weight of magnesium hydroxide with polyolefin.
And a phenolic compound represented by the following chemical formula 6 (hereinafter,
It is called compound B. Flame retardancy obtained by blending 0.01 to 1 part by weight of one or more compounds selected from the above), thioether antioxidants, heavy metal deactivators and epoxy compounds, and 0.5 to 5 parts by weight of fatty acids. Polyolefin composition.

[Chemical 5]

[Chemical 6] (In the formula, R ₁ is an alkylidene group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 9 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or an alkyl group. (A cyclohexyl group, R ₄ is an alkyl group having 1 to 8 carbon atoms, R ₅ is hydrogen or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4.)

The polyolefin used in the present invention is a crystalline homopolymer of α-olefin such as ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, and the like. A crystalline, low crystalline or amorphous random copolymer or crystalline block copolymer of two or more α-olefins, an amorphous ethylene-propylene-nonconjugated diene terpolymer, the above α- Copolymer of olefin and vinyl acetate or acrylic ester, saponified product of the copolymer, copolymer of α-olefin and unsaturated silane compound, α-olefin and unsaturated carboxylic acid or anhydride thereof Copolymer, a reaction product of the copolymer and a metal ion compound, a crystalline homopolymer of the above α-olefin, a crystalline, low crystalline, amorphous random copolymer or binder. A modified polyolefin obtained by modifying a crystalline block copolymer or an amorphous ethylene-propylene-nonconjugated diene terpolymer with an unsaturated carboxylic acid or a derivative thereof, a crystalline homopolymer of the above α-olefin, and a crystalline property Examples include low crystallinity, amorphous random copolymers or crystalline block copolymers, or silane-modified polyolefins obtained by modifying an amorphous ethylene-propylene-nonconjugated diene terpolymer with an unsaturated silane compound. These polyolefins can be used alone or in combination of two or more.

In addition to the above-mentioned polyolefins, various synthetic rubbers (for example, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-rubber).
Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-
Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (eg polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, poly Butylene terephthalate, polycarbonate,
Polyvinyl chloride, fluororesin, petroleum resin (eg C ₅
Petroleum resin, hydrogenated C ₅ petroleum resin, C ₉ petroleum resin, hydrogenated C ₉ petroleum resin, C ₅ -C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉
Copolymerized petroleum resin, acid-modified C ₉ petroleum resin, etc.), DCP
D resin (eg, cyclopentadiene-based petroleum resin, hydrogenated cyclopentadiene-based petroleum resin, cyclopentadiene-
C ₅ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymerized petroleum resin, cyclopentadiene-C ₉ copolymerized petroleum resin,
Softening point of hydrogenated cyclopentadiene-C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, etc.
DCPD resin) and the like) may be mixed and used. Crystalline propylene homopolymer, propylene component 70
A crystalline propylene copolymer containing at least wt%, which is a crystalline ethylene-propylene random copolymer, a crystalline ethylene-propylene block copolymer, a crystalline propylene-butene-1 random copolymer, a crystalline ethylene. -
Propylene-butene-1 terpolymer, crystalline propylene
-Hexene-butene-1 terpolymers and mixtures of two or more thereof are particularly preferably used.

As the magnesium hydroxide used in the present invention, plate-like and fibrous ones can be used without any limitation. The average particle size of the plate-shaped magnesium hydroxide is not particularly limited, but is usually 0.1μ to 10μ, preferably 0.2.
μ-2 μ, most preferably 0.5 μ-1 μ, and the fibrous magnesium hydroxide preferably has a fiber diameter of 0.1 μ-0.5 μ and a length of 5 μ-20 μ.

These magnesium hydroxides are surface treatment agents such as metal soaps, higher fatty acid esters, higher alcohols, higher fatty acid monoamides, higher fatty acid bisamides, higher aliphatic metal phosphates, silane coupling agents, titanate couplings. Agent, a boron-based coupling agent, an aluminate-based coupling agent and a zircoaluminate-based coupling agent and the like, when used after being surface-treated with a known surface treatment agent, the compatibility between the magnesium hydroxide and the polyolefin and It is preferable to use magnesium hydroxide surface-treated with a surface-treating agent, because the dispersibility is improved, excellent moldability is obtained, and the mechanical strength of the molded product is improved. These magnesium hydroxides can be used alone or in combination of two or more.

The mixing ratio of the magnesium hydroxide is 30 to 70% by weight, preferably 50 to 65% by weight, based on the composition comprising polyolefin and magnesium hydroxide.
If the amount is less than 30% by weight, the flame retardancy of the obtained molded product is insufficient, and if it exceeds 70% by weight, the molding processability becomes difficult and the mechanical strength of the obtained molded product decreases, which is not practical.

The compound A used in the present invention is bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] isophthalate,
Bis [2- (3'-t-butyl-5'-ethyl-2'-hydroxybenzyl) -4-ethyl-6-t-butylphenyl] isophthalate, bis [2- (3'-nonyl-5 '-Methyl-2'-hydroxybenzyl) -4-methyl-6-nonylphenyl] isophthalate, bis [2- (3 ', 5'-dinonyl-2'-hydroxybenzyl) -4,6-dinonylphenyl] Isophthalate, bis [2
-(3'-cyclohexyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-cyclohexylphenyl] isophthalate, bis [2- (3 '-(1 "-methylcyclohexyl) -5'-
Methyl-2'-hydroxybenzyl) -4-methyl-6- (1'-methylcyclohexyl) phenyl] isophthalate, bis [2- (5'-nonyl-2'-hydroxy (α, α-dimethylbenzyl)) -4-nonylphenyl] isophthalate, bis [2
-(3 ', 5'-Dimethyl-2'-hydroxy (α-propylbenzyl))-4,6-dimethylphenyl] isophthalate, bis [2- (3', 5'-di-t-butyl-2) '-Hydroxybenzyl) -4,
6-di-t-butylphenyl] isophthalate, bis [2-
(3'-t-butyl-5'-s-butyl-2'-hydroxy (α-methylbenzyl))-4-s-butyl-6-t-butylphenyl] isophthalate, bis [2- (3 ' , 5'-Di-t-butyl-2'-hydroxy (α-methylbenzyl))-4,6-di-t-butylphenyl] isophthalate, bis [2- (3'-t-octyl-5 '] -Methyl-2'-hydroxybenzyl) -4-methyl-6-t-octylphenyl] isophthalate, bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy ( α-Propylbenzyl))-4-methyl-6- (1'-methylcyclohexyl) phenyl] isophthalate, bis [2- (3 ', 5'-dimethyl-2'-hydroxybenzyl) -4,6-dimethyl Phenyl] isophthalate,

Bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate, bis [2- (3'-t- Butyl-5'-ethyl-2'-
Hydroxybenzyl) -4-ethyl-6-t-butylphenyl]
Terephthalate, bis [2- (3'-nonyl-5'-methyl-2'-
Hydroxybenzyl) -4-methyl-6-nonylphenyl] terephthalate, bis [2- (3 ', 5'-dinonyl-2'-hydroxybenzyl) -4,6-dinonylphenyl] terephthalate, bis [2- ( 3'-cyclohexyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-cyclohexylphenyl] terephthalate, bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2 '-Hydroxybenzyl) -4-methyl-6- (1'-methylcyclohexyl) phenyl] terephthalate, bis [2- (5'-nonyl-2'-hydroxy (α, α
-Dimethylbenzyl))-4-nonylphenyl] terephthalate, bis [2- (3 ', 5'-dimethyl-2'-hydroxy (α
-Propylbenzyl))-4,6-dimethylphenyl] terephthalate, bis [2- (3 ', 5'-di-t-butyl-2'-hydroxybenzyl) -4,6-di-t-butylphenyl] Terephthalate, bis [2- (3'-t-butyl-5'-methyl-2'-hydroxy (α-methylbenzyl))-4-methyl-6-t-butylphenyl] terephthalate, bis [2- (3 '-t-Butyl-5'-ethyl-2'-hydroxy (α-methylbenzyl))-4-ethyl-6
-t-butylphenyl] terephthalate,

Bis [2- (3'-t-butyl-5'-s-butyl-2'-
Hydroxy (α-methylbenzyl))-4-s-butyl-6-t-
Butylphenyl] terephthalate, bis [2- (3 ', 5'-di
-t-Butyl-2'-hydroxy (α-methylbenzyl))-4,6
-Di-t-butylphenyl] terephthalate, bis [2- (3 '
-t-octyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-octylphenyl] terephthalate, bis [2
-(3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy (α-propylbenzyl))-4-methyl-6- (1'-
Methylcyclohexyl) phenyl] terephthalate and bis [2- (3 ', 5'-dimethyl-2'-hydroxybenzyl)
-4,6-Dimethylphenyl] terephthalate, etc., and particularly bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] Terephthalate, bis [2- (3'-t-butyl-5'-ethyl-2'-hydroxybenzyl) -4-ethyl-6-t-butylphenyl] terephthalate, bis [2- (3 ', 5'- Di-t-butyl-2'-hydroxybenzyl) -4,6-di-t-butylphenyl] terephthalate and bis [2- (3 ', 5'-di-t-butyl-2'-hydroxy (α- Methylbenzyl))-4,6-di-t-butylphenyl] terephthalate is preferred. These compounds A may be used alone or in combination of two or more kinds.

The compound B used in the present invention includes tris (3-t-butyl-4-hydroxybenzyl) isocyanurate, tris (3-t-amyl-4-hydroxybenzyl) isocyanurate, tris (3-t- Octyl-4-hydroxybenzyl) isocyanurate, tris (3-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris (3-methyl-4-hydroxy-5-t-amylbenzyl) isocyanurate, Tris (3-methyl-4-hydroxy-5-t-
Octylbenzyl) isocyanurate, tris (3-ethyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris (3-i-propyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris ( 3-i-Butyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris (3-s-butyl-4-hydroxy-5-t-butylbenzyl)
Isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris (3-t-butyl)
-4-Hydroxy-5-t-amylbenzyl) isocyanurate, tris (3-t-butyl-4-hydroxy-5-t-octylbenzyl) isocyanurate, tris (3,5-di-t-amyl-
4-hydroxybenzyl) isocyanurate, tris (3,
5-di-t-octyl-4-hydroxybenzyl) isocyanurate, tris (2-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris (2,5-di-t-butyl-4-)
Hydroxybenzyl) isocyanurate, tris (2-methyl-4-hydroxy-5-t-octylbenzyl) isocyanurate, tris (2-t-butyl-4-hydroxy-5-methylbenzyl) isocyanurate, tris (3- Methyl-4-hydroxy-5-t-butylphenylethyl) isocyanurate, tris (3-t-butyl-4-hydroxyphenylethyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl) Ethyl) isocyanurate, tris (3,5-di-t-amyl-4-hydroxyphenylethyl) isocyanurate, tris (3,5-di-t-octyl-4-hydroxyphenylethyl) isocyanurate, tris (3 -Methyl-4-hydroxy-5-t-butylphenylpropyl) isocyanurate, Tris (3,5-di-t-butyl-4-hydroxyphenylpropyl) isocyanurate, Tris (3-methyl
-4-Hydroxy-5-t-butylphenylbutyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenylbutyl) isocyanurate and tris (3,5-di-t-
Octyl-4-hydroxyphenylbutyl) isocyanurate and the like, and particularly tris (3,5-di-t-butyl-4-
Hydroxybenzyl) isocyanurate is preferred.

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

The thioether antioxidant used in the present invention includes dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, dicetyl thiodipropionate, distearyl thiodipropionate, Dilaurylthiodibutyrate, ditridecylthiodibutyrate, dimyristylthiodibutyrate, dicetylthiodibutyrate, distearylthiodibutyrate, laurylstearylthiodipropionate, laurylstearylthiodibutyrate, pentaerythritol-β-laurylthio Dipropionate,
Pentaerythritol-tetrakis (3-octylthiopropionate), Pentaerythritol-tetrakis (3
-Nonylthiopropionate), pentaerythritol-
Tetrakis (3-decylthiopropionate), Pentaerythritol-Tetrakis (3-laurylthiopropionate), Pentaerythritol-Tetrakis (3-Tridecylthiopropionate), Pentaerythritol-Tetrakis (3-myristylthiopropionate) Pionate), pentaerythritol-tetrakis (3-palmitylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), pentaerythritol
-Tetrakis (4-octylthiobutyrate), Pentaerythritol-Tetrakis (4-nonylthiobutyrate), Pentaerythritol-Tetrakis (4-decylthiobutyrate), Pentaerythritol-Tetrakis (4
-Laurylthiobutyrate), pentaerythritol-tetrakis (4-tridecylthiobutyrate), pentaerythritol-tetrakis (4-myristylthiobutyrate), pentaerythritol-tetrakis (4-palmitylthiobutyrate), pentaerythritol -Tetrakis (4-stearylthiobutyrate), Pentaerythritol-Tetrakis (3-octylthiobutyrate), Pentaerythritol-Tetrakis (3-nonylthiobutyrate), Pentaerythritol-Tetrakis (3-decylthiobutyrate), Pentaerythritol-Tetrakis (3
-Laurylthiobutyrate), pentaerythritol-tetrakis (3-tridecylthiobutyrate), pentaerythritol-tetrakis (3-myristylthiobutyrate), pentaerythritol-tetrakis (3-palmitylthiobutyrate), pentaerythritol -Tetrakis (3-stearyl thiobutyrate),

Tetrakis [3- {2- (octyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (nonyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (Decyloxycarbonyl) ethylthio}
Propionyloxymethyl] methane, tetrakis [3-
{2- (dodecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (tridecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (tetradecyloxycarbonyl) Ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (octadecyloxycarbonyl) ethylthio} propionyloxymethyl] methane,

1,3,5-Tris [3- {2- (octyloxycarbonyl) ethylthio} propionyl] hexahydro-
1,3,5-triazine, 1,3,5-tris [3- {2- (nonyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2- (decyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyl]
Hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2
-(Tridecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3, 5-triazine,
1,3,5-Tris [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-
Triazine, 1,3,5-tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 2,4,6-tris [3- {2- (octyloxy Carbonyl) ethylthio} propionyl] -1,
3,5-triazine, 2,4,6-tris [3- {2- (nonyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (Decyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine,
2,4,6-Tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-
Tris [3- {2- (tridecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl]- 1,3,5-triazine, 2,4,6-tris [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine,

Tris [3- {2- (octyloxycarbonyl) ethylthio} propionyl] isocyanurate, Tris [3- {2- (nonyloxycarbonyl) ethylthio}
Propionyl] isocyanurate, tris [3- {2- (decyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (Tridecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2-
(Hexadecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (octyloxycarbonyl) ethylthio} propionyloxyethyl] Isocyanurate, tris [3- {2- (nonyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (decyloxycarbonyl)
Ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (tridecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanate Nulate, tris [3- {2- (tetradecyloxycarbonyl)
Ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanate Nurate,

Bis (4-t-amylphenyl) sulfide,
Dilauryl disulfide, dimyristyl disulfide,
Distearyl disulfide, 3- (laurylthio) propionylamide, 3- (myristylthio) propionylamide, 3- (stearylthio) propionylamide, N, N '
-Methylene-bis (3-laurylthiopropionyl) amide, N, N'-methylene-bis (3-myristylthiopropionyl) amide, N, N'-methylene-bis (3-stearylthiopropionyl) amide, N, N '-Ethylene-bis (3-laurylthiopropionyl) amide, N, N'-ethylene-bis (3-myristylthiopropionyl) amide, N, N'-
Ethylene-bis (3-stearylthiopropionyl) amide, N, N'-bis (3-laurylthiopropionyl) hydrazide, N, N'-bis (3-myristylthiopropionyl) hydrazide, N, N'-bis (3 -Stearylthiopropionyl) hydrazide, sodium-β-laurylthiopropionate, sodium-β-myristylthiopropionate, sodium-β-stearylthiopropionate, thioethylene glycol-bis (β-aminocrotonate),

Bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, stearyl-3,5
-Dimethyl-4-hydroxybenzyl thioglycolate, 2,
4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t
-Butylanilino) -1,3,5-triazine, octylthiobis (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) cyanurate, 2,4-bis [(octylthio) methyl] -o- Cresol, bis [(2-hydroxy-3- (4'-ethoxyphenylamino) propyl)] sulfide, bis [2-methyl
-4- (3-octylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2-methyl-4- (3-nonylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2 -Methyl-4- (3-decylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2
-Methyl-4- (3-laurylthiopropionyloxy) -5-t
-Butylphenyl] sulfide, bis [2-methyl-4- (3-
Tridecylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2-methyl-4- (3-myristylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2-methyl-4- (3-pentadecylthiopropionyloxy) -5-t-butylphenyl] sulfide,
Bis [2-methyl-4- (3-palmitylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2-methyl-4- (3-stearylthiopropionyloxy) -5-t-
Butylphenyl] sulfide and poly [1,4-bis (hydroxymethyl) cyclohexane-thiodipropionate] can be exemplified, and particularly dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, Pentaerythritol-tetrakis (3-laurylthiopropionate), distearyl disulfide, N, N'-bis (3-laurylthiopropionyl) hydrazide, bis [2-methyl-4- (3-laurylthiopropionyloxy)- 5-t-butylphenyl] sulfide, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and 2,4- Bis [(octylthio) methyl] -o-cresol is preferred.

These thioether-based antioxidants may be used alone, or two or more thioether-based antioxidants may be used in combination. The blending ratio of the thioether antioxidant is 0.0 with respect to 100 parts by weight of a composition obtained by blending 30 to 70% by weight of magnesium hydroxide with polyolefin.
It is 1 to 1 part by weight, preferably 0.05 to 0.5 part by weight. 0.01
If the amount is less than 1 part by weight, the effect of improving heavy metal resistance is not sufficiently exerted, and if it exceeds 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is also uneconomical.

The heavy metal deactivators used in the present invention include benzotriazole, 2,4,6-triamino-1,3,5-triazine and 3,9-bis [2- (3,5-diamino-2 , 4,6-Triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, ethylenediamine-tetraacetic acid, ethylenediamine-tetraacetic acid alkali metal salt (Li, Na, K) salt, N, N'-disalicylidene-ethylenediamine, N, N'-disalicylidene-1,2-propylenediamine, N, N "-disalicylidene-
N'-methyl-dipropylenetriamine, 3-salicyloylamino-1,2,4-triazole, decamethylene dicarboxylic acid-bis (N'-salicyloyl hydrazide), nickel-bis (1-phenyl- 3-methyl-4-decanoyl-5-pyrazolate),

2-ethoxy-2'-ethyloxanilide, 5-t-
Butyl-2-ethoxy-2'-ethyloxanilide, N, N-diethyl-N ', N'-diphenyloxamide, N, N'-diethyl-N, N'-diphenyloxamide, oxalic acid- Bis (benzylidene hydrazide), thiodipropionic acid-bis (benzylidene hydrazide), isophthalic acid-bis (2-phenoxypropionyl hydrazide), bis (salicyloyl hydrazine), N
-Salicylidene-N'-Salicyloylhydrazone, N, N'-
Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, Tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t -Butylphenyl) -5-
Methylphenyl] phosphite, bis [2-t-butyl-4]
-Thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -pentaerythritol-diphosphite, tetrakis [2-t-butyl-4-thio (2'- Methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,6-hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2- t-Butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl]-
1,10-decamethylene-di-carboxylic acid-di-
Hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-
Hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid
-Di-salicyloyl hydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy
-5'-t-Butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy- 5'-t-Butylphenyl) -5-methylphenyl]-
N, N'-bis (hydroxyethyl) oxamide-diphosphite, and N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] Examples include oxamide,

Particularly oxalic acid-bis (benzylidene hydrazide), N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris [2-t-butyl] -4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite and N, N'-bis [2- [3- (3,5-di -t-Butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide is preferred. These heavy metal deactivators may be used alone or in combination of two or more. 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 composition obtained by mixing 30 to 70% by weight of magnesium hydroxide with polyolefin. If the amount is less than 0.01 part by weight, the effect of improving heavy metal resistance is not sufficiently exerted, and if it exceeds 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is uneconomical again.

The epoxy compound used in the present invention is not particularly limited as long as it does not significantly volatilize and escape or is decomposed during melt-kneading, and an epoxy equivalent of about 100 to 1,000 is suitable, and epichlorohydrin or Derivatives of epichlorohydrin (eg 2-
Condensation of methyl epichlorohydrin, 2-ethyl epichlorohydrin and 2-propyl epichlorohydrin) with bisphenol or a bisphenol derivative (for example, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S) Products, epoxidized oils and fats (eg, 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-epoxycyclohexyl) Fatty acid ester of methanol, 3,4-
Epoxycyclohexylcarboxylic acid alkyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid dialkyl ester, 3,4-epoxy-6-methylcyclohexylmethyl and 3,4-epoxy-6-methylcyclohexanecarboxylate ), Tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, novolac glycidyl ether,
Polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, p-oxybenzoic acid glycidyl ether-ester,

Phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid glycidyl ester, dimer acid 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,
Examples thereof include vinylcyclohexene diepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether and limonendioxide. Particularly, a condensate of epichlorohydrin and bisphenol A, 2-methylepichlorohydrin and bisphenol A
Condensates with triglycidyl isocyanurate and epoxidized soybean oil are preferred.

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

The fatty acid used in the present invention is acetic acid,
Propionic acid, n-butyric acid, i-butyric acid, n-valeric acid, i-valeric acid,
n-hexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid,
Oleic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, 12-hydroxyoctadecanoic acid,
Examples include ricinoleic acid and cerebronic acid.
2-Ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, montanic acid and 12-hydroxyoctadecanoic acid are preferred.

These fatty acids may be used alone or in combination of two or more. The blending ratio of the fatty acid is such that polyolefin is magnesium hydroxide.
0.5 to 0.5 to 100 parts by weight of a composition containing 30 to 70% by weight
It is 5 parts by weight, preferably 1 to 3 parts by weight. If the amount is less than 0.5 parts by weight, the effect of improving heavy metal resistance is not sufficiently exerted, and if it exceeds 5 parts by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is uneconomical again.

In the composition of the present invention, various additives usually added to polyolefins such as phenol-based compounds (excluding compound A and compound B), phosphorus-based antioxidants, light stabilizers, Clarifying agents, nucleating agents, lubricants (excluding fatty acids), antistatic agents, anti-fog agents, anti-blocking agents, non-dripping agents, flame retardants (excluding magnesium hydroxide), flame retardant aids, Antibacterial agents, pigments, radical generators such as peroxides, dispersants or neutralizers for metal soaps, inorganic fillers (eg talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous) Soil, asbestos, calcium carbonate, aluminum hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, silicic acid Calcium, aluminum silicate,
Surface treatment agent such as glass fiber, potassium titanate, carbon fiber, carbon black, graphite, metal fiber) or coupling agent (eg silane, titanate, boron, aluminate, zircoaluminate, etc.) The surface-treated inorganic or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used together within the range not impairing the object of the present invention.

The composition of the present invention comprises a polyolefin containing one or more compounds selected from magnesium hydroxide, compound A and compound B, a thioether antioxidant, a heavy metal deactivator, an epoxy compound and a fatty acid. In addition, a predetermined amount of each of the above-mentioned various additives that are usually added to polyolefins, and one or more compounds selected from magnesium hydroxide, compound A and compound B, which are surface-treated with a fatty acid, and thioethers. A predetermined amount of each of the above-mentioned antioxidants, heavy metal deactivators and epoxy compounds, and the above-mentioned various additives which are usually added to polyolefins is mixed with a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, or a bambar. Mix using a remixer, etc. Extruder, biaxial extruder, or the like Brabender or rolls, melt kneading temperature 0.99 ° C. to 300
It can be obtained by melt-kneading and pelletizing at ℃, preferably 200 ℃ -250 ℃. 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.

In the present invention, compound A and compound B
Is a radical chain inhibitor, a thioether antioxidant is a peroxide decomposer, a heavy metal deactivator is an inactivator of the catalytic oxidative deterioration of polyolefin by heavy metal ions, and an epoxy compound is an adsorption inhibitor. ,
It is generally known that fatty acids act as surface treatment agents for magnesium hydroxide. However, one or more compounds selected from the compound A and the compound B according to the present invention, a thioether-based antioxidant, and a heavy metal deactivator are added to a flame-retardant polyolefin composition containing magnesium hydroxide. By using an epoxy compound and a fatty acid in combination, a surprising synergistic effect that cannot be predicted from the compounding of a conventionally known compound having an oxidative deterioration preventing effect is exhibited, and a flame-retardant polyolefin composition excellent in heavy metal resistance is obtained. can get.

In addition, compound A is excellent as a radical chain inhibitor in a flame-retardant polyolefin composition containing magnesium hydroxide because compound A is an ester of phenol and an aromatic carboxylic acid, that is, an aromatic compound. Since it is an ester, the compound A has a chemical structure that is less susceptible to alkaline hydrolysis in the presence of magnesium hydroxide than a phenolic antioxidant having an aliphatic ester group or an aliphatic amide group other than the compound A, and It is presumed that this is due to the fact that the alkaline hydrolysis is further suppressed by the neutralizing effect of fatty acids on magnesium hydroxide.

It is generally known that the compound B is most susceptible to alkaline hydrolysis among the above-mentioned phenolic antioxidants having an aliphatic amide group. However, compound B is excellent as a radical chain inhibitor in a flame-retardant polyolefin composition containing magnesium hydroxide according to the present invention because compound B undergoes alkaline hydrolysis in the presence of magnesium hydroxide. Despite its easy chemical structure
It is presumed that this is due to the fact that the alkaline hydrolysis is significantly suppressed by the neutralizing action of fatty acids on magnesium hydroxide.

[0038]

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

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

Examples 1 to 8 and Comparative Examples 1 to 14 MFR as a polyolefin (load at 230 ° C. 2.16 k
Discharge amount of molten resin for 10 minutes when g is added) 43 g by weight of unstabilized powdery crystalline propylene homopolymer of 20 g / 10 minutes and average particle size as magnesium hydroxide of 0.
Bis [2- (5'-nonyl-2'-hydroxy (α, α-dimethylbenzyl))-4- as compound A was added to 100 parts by weight in total consisting of 6 to 0.8μ of 57% by weight of untreated surface. Nonylphenyl] isophthalate, tris (3-methyl as compound B
-4-Hydroxy-5-t-butylbenzyl) isocyanurate, dimyristylthiodipropionate or pentaerythritol-tetrakis (3-laurylthiopropionate) as a thioether antioxidant, 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 Alternatively, oxalic acid-bis (benzylidene hydrazide), a condensate of epichlorohydrin and bisphenol A as an epoxy compound (epoxy equivalent: 700 to 83
0) or a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 180 to 200), acetic acid as a fatty acid, 2-ethylhexanoic acid, stearic acid or oleic acid and others Add a specified amount of each of the additives to the Henschel mixer (trade name) at the blending ratio shown in Table 1 below, stir and mix for 3 minutes, and then calibrate 30 mm.
Was melt-kneaded at 250 ° C. in a twin-screw extruder to produce pellets. Further, as Comparative Examples 1 to 14, unstabilized powdery crystalline propylene homopolymer 43 having an MFR of 20 g / 10 min.
% By weight and magnesium hydroxide having an average particle size of 0.6 to
The pellets were melt-kneaded in accordance with Examples 1 to 8 by adding a predetermined amount of each of the additives shown in Table 1 below to a total of 100 parts by weight consisting of 0.8% of an untreated surface of 57% by weight. Got For the test pieces used for the copper resistance test and the flammability test, use the pellets obtained at a resin temperature of 250 ° C and a mold temperature of 50 ° C.
Was prepared by injection molding. The obtained test pieces were used to evaluate heavy metal resistance (150 ° C. copper resistance) and flame retardancy by the above-mentioned test method. The results are shown in Table 1.

Examples 9 to 16 and Comparative Examples 15 to 28 29.59% by weight of water-free crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) of MFR 30 g / 10 min as a polyolefin and water. Magnesium hydroxide [I], magnesium hydroxide [II], magnesium hydroxide [III] or magnesium hydroxide [IV] surface-treated as magnesium oxide
A total of 101.4 parts by weight (70.41% by weight) (100 parts by weight as the total of the crystalline ethylene-propylene block copolymer excluding the fatty acid used for the surface treatment and the surface-untreated magnesium hydroxide product) was added with bis as Compound A. [2- (3'-
t-Butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate, tris (3,5-di-t-butyl-4-hydroxybenzyl) as compound B
Isocyanurate, thioether type antioxidant as distearyl thiodipropionate or distearyl disulfide, and heavy metal deactivator as 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 mixture of a condensate of epichlorohydrin and bisphenol A as an epoxy compound (epoxy equivalent of 700 to 830) or a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy) Equivalent 180 to 200) and other prescribed amounts of other additives are put into a Henschel mixer (trade name) at the blending ratios shown in Table 2 below, and the mixture is stirred and mixed for 3 minutes, and then the caliber is 30 mm.
Was melt-kneaded at 250 ° C. in a twin-screw extruder to produce pellets. As Comparative Examples 15 to 28, powdery crystalline ethylene-propylene block copolymer having an MFR of 30 g / 10 minutes and not stabilized (ethylene content 8.5% by weight) 30% by weight
And a total of 100 parts by weight of 70% by weight of untreated surface having an average particle size of 0.6 to 0.8μ as magnesium hydroxide or an unstabilized powdery crystalline ethylene-propylene block copolymer weight of MFR of 30 g / 10 min. Combined (ethylene content 8.5% by weight) 29.59% by weight and magnesium hydroxide [II] 70.41% by weight surface-treated as magnesium hydroxide, a total of 101.4 parts by weight (crystalline ethylene-propylene excluding fatty acid used for surface treatment) A predetermined amount of each of the additives shown in Table 2 below was added to 100 parts by weight as the total of the surface-untreated block copolymer and magnesium hydroxide, and the melt-kneading treatment was carried out in accordance with Examples 9 to 16. To obtain pellets. The test pieces used for the copper resistance test and the flammability test were obtained by using the pellets with a resin temperature of 250
It was prepared by injection molding at a mold temperature of 50 ° C. Using the obtained test piece, the heavy metal resistance (150
(° C copper resistance) and flame retardancy were evaluated. The results are shown in Table 2.

Examples 17-24, Comparative Examples 29-42 MFR 7.0 g / 10 min as a polyolefin Unstabilized powdery crystalline ethylene-propylene-butene-13
Original copolymer (ethylene content 2.5% by weight, butene-1 content
4.5% by weight) and 50% by weight of magnesium hydroxide and 50% by weight of a surface-untreated product having an average particle size of 0.6 to 0.8μ, and 100 parts by weight of bis [2- (3 ', 5'- The-
t-Butyl-2'-hydroxy (α-methylbenzyl))-4,6-
Di-t-butylphenyl] terephthalate, tris (3-t-amyl-4-hydroxyphenylethyl) as compound B
Isocyanurate, N, N'-bis (3-laurylthiopropionyl) hydrazide or bis [2-methyl-4- (3-laurylthiopropionyloxy) -5-t-butylphenyl] sulfide as a thioether antioxidant, 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), triglycidyl isocyanurate (epoxy equivalent 100-110) or epoxidized soybean oil (epoxy equivalent 220-240) as an epoxy compound. ), Stearic acid, oleic acid, behenic acid or erucic acid as the fatty acid, and the respective prescribed amounts of the other additives are shown in Table 3 below.
The mixture was placed in a Henschel mixer (trade name) at the blending ratio described in 1 above, stirred and mixed for 3 minutes, and then melt-kneaded at 250 ° C. in a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 29 to 42, powdery crystalline ethylene-propylene-butene-1 terpolymer having an MFR of 7.0 g / 10 min and not stabilized (ethylene content 2.5% by weight, butene-1 content 4 .
5% by weight) and 50% by weight of magnesium hydroxide, and 50% by weight of surface-untreated product having an average particle size of 0.6 to 0.8μ as magnesium hydroxide, and 100 parts by weight in total of predetermined amounts of the additives shown in Table 3 below. Then, in accordance with Examples 17 to 24, melt-kneading treatment was performed to obtain pellets. The test piece used for the copper resistance test and the flammability test was obtained by pelletizing the pellets at a resin temperature of 250 ° C.,
It was prepared by injection molding at a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the heavy metal resistance (140 ° C. copper resistance) and the flame retardance by the above test method. The results are shown in Table 3.

Examples 25-32, Comparative Examples 43-56 55 wt% unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5 wt%) as MFR 7.0 g / 10 min as polyolefin , MI (190
Discharge amount of molten resin for 10 minutes when a load of 2.16 kg at 20 ° C.) 20 g / 10 minutes unstabilized powdered Ziegler-Natta high density ethylene homopolymer 10% by weight,
Unstabilized powdery amorphous ethylene-propylene random copolymer with Mooney viscosity ML1 + 4 (100 ° C) of 25% (propylene content 25% by weight) 5% by weight and magnesium hydroxide having an average particle size of 0.6 to 0.8 bis [2
-(3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy (α-propylbenzyl))-4-methyl-6- (1'-
Methylcyclohexyl) phenyl] terephthalate, tris (3,5-di-t-octyl-4-hydroxyphenylbutyl) isocyanurate as compound B, 2,4-bis (n-octylthio) -6- as thioether antioxidant (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine or 2,4-bis [(octylthio) methyl] -o-cresol, N, N 'as heavy metal deactivator -Bis [2- [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl
-4-Thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), triglycidyl isocyanurate as an epoxy compound (epoxy equivalent 100-1
10) or epoxidized soybean oil (epoxy equivalent 220 to 24
0), stearic acid, oleic acid, montanic acid or 12-hydroxyoctadecanoic acid as fatty acids and other additives in predetermined amounts in a Henschel mixer (trade name) at the compounding ratios shown in Table 4 below, and put for 3 minutes. After stirring and mixing, the mixture was melt-kneaded at 250 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 43 to 56, 55% by weight of unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) with MFR of 7.0 g / 10 minutes and MI of 20 g / 10 minutes Unstabilized powdery Ziegler-Natta high density ethylene homopolymer 10% by weight, Mooney viscosity ML1 + 4 (100 ° C) 25, unstabilized powdery amorphous ethylene-propylene random copolymer (Propylene content 25% by weight) 5% by weight and average particle size as magnesium hydroxide 0.6-0.8μ
A total of 100 parts by weight of the surface-untreated product of 30% by weight was added with a predetermined amount of each of the additives described in Table 4 below, and the mixture was melt-kneaded in accordance with Examples 25 to 32 to obtain pellets. It was The test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the heavy metal resistance (140 ° C. copper resistance) and the flame retardance by the above test method. The results are shown in Table 4.

The compounds and additives relating to the present invention shown in Tables 1 to 4 are as follows. Magnesium hydroxide [0]: Surface-untreated product with an average particle size of 0.6 to 0.8μ Magnesium hydroxide [I]: Surface-untreated product with an average particle size of 0.6 to 0.8μ 100 parts by weight of surface treatment with 2 parts by weight of lauric acid Surface-treated product Magnesium hydroxide [II]: Surface-treated product having an average particle size of 0.6 to 0.8 μ and surface-treated with 2 parts by weight of stearic acid 100 parts by weight Magnesium hydroxide [III]: Average particle size of 0.6 ~ 0.8μ surface-untreated 100 parts by weight surface-treated with 2 parts by weight oleic acid magnesium hydroxide [IV]: average particle size 0.6-0.8μ surface-untreated 100 parts by weight linoleic acid 2 parts Surface-treated product that has been surface-treated with parts by weight

Compound A [I]: Bis [2- (5'-nonyl-2 '
-Hydroxy (α, α-dimethylbenzyl))-4-nonylphenyl] isophthalate Compound A [II]: Bis [2- (3'-t-butyl-5'-methyl-
2'-Hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate Compound A [III]: Bis [2- (3 ', 5'-di-t-butyl-2'
-Hydroxy (α-methylbenzyl) -4,6-di-t-butylphenyl] terephthalate Compound A [IV]: Bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2 '-Hydroxy (α-propylbenzyl))-4-methyl-6- (1'-methylcyclohexyl) phenyl] terephthalate

Compound B [I]: Tris (3-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate Compound B [II]: Tris (3,5-di-t-butyl-4-hydroxybenzyl) ) Isocyanurate Compound B [III]: Tris (3-t-amyl-4-hydroxyphenylethyl) isocyanurate Compound B [IV]: Tris (3,5-di-t-octyl-4-hydroxyphenylbutyl) isocyanate Nurate

Thioether antioxidant [I]: dimyristyl thiodipropionate Thioether antioxidant [II]: Distearyl thiodipropionate Thioether antioxidant [III]: Pentaerythritol-tetrakis (3-lauryl) Thiopropionate) Thioether antioxidant [IV]: Distearyl disulfide Thioether antioxidant [V]: N, N′-bis (3-laurylthiopropionyl) hydrazide Thioether antioxidant [VI]: Bis [2-methyl-4
-(3-laurylthiopropionyloxy) -5-t-butylphenyl] sulfide thioether antioxidant [VII]: 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di -t-Butylanilino) -1,3,5-triazine thioether antioxidant [VIII]: 2,4-bis [(octylthio) methyl] -o-cresol

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-
Di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine Heavy metal deactivator [IV]: oxalic acid-bis (benzylidene hydrazide)

Epoxy compound [I]: Condensation product of epichlorohydrin and bisphenol A (epoxy equivalent 700 to 8
30; ARA-LDIT made by CIBA-GEIGY AG
E GT 7004) Epoxy compound [II]: a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent)
180-200; ADK CIZER manufactured by Asahi Denka Co., Ltd.
EP-17) Epoxy compound [III]: triglycidyl isocyanurate (epoxy equivalent 100 to 110; CIBA-GEIG)
ARALDITE PT 810 manufactured by YAG Epoxy compound [IV]: Epoxidized soybean oil (epoxy equivalent 220 to 240; ADK CIZE manufactured by Asahi Denka Co., Ltd.)
RO-130P)

Fatty acid [I]: Acetic acid Fatty acid [II]: 2-Ethylhexanoic acid Fatty acid [III]: Lauric acid Fatty acid [IV]: Stearic acid Fatty acid [V]: Oleic acid Fatty acid [VI]: Linoleic acid Fatty acid [VII] ]: Behenic acid Fatty acid [VIII]: Erucic acid Fatty acid [IX]: Montanic acid Fatty acid [X]: 12-Hydroxyoctadecanoic acid

Phosphorus-based antioxidant 1: Bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite Phosphorus-based antioxidant 2: bis (2,4-di-t) -Butylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 3: tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite

Phenol-based antioxidant 1: 2,6-di-t-butyl-p-cresol Phenol-based antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 3: 2,2-bis [4- [2- (3,5-di
-t-Butyl-4-hydroxyphenylpropionyloxy)
Ethoxy] phenyl] propane phenolic antioxidant 4: tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate phenolic antioxidant 5: tris [3- (3,5-di -t-Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate Phenolic antioxidant 6: 1,1,3-tris (5-t-butyl)
-4-Hydroxy-2-methylphenyl) -butane phenolic antioxidant 7: Bis [3,3-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] ethylene glycol ester phenolic oxidation Inhibitor 8: 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Carbon black: Carbon # 45 Mitsubishi Kasei Co., Ltd. Ca-St: Steer Calcium phosphate

The examples and comparative examples shown in Table 1 are cases where a crystalline propylene homopolymer was used as the polyolefin and a surface-untreated product was used as the magnesium hydroxide.
As can be seen from Table 1, in Examples 1 to 8, crystalline propylene homopolymer was added to magnesium hydroxide (untreated surface),
One or more compounds selected from Compound A and Compound B, a thioether-based antioxidant, a heavy metal deactivator, an epoxy compound and a fatty acid are blended, and Examples 1 to 8 and Comparative Example 1 7 to 7 (a compound containing a phenolic antioxidant other than the compound A or the compound B instead of the compound A or the compound B), Examples 1 to 8 are excellent in heavy metal resistance and It can be seen that in the presence of magnesium oxide, the phenolic antioxidants other than the compound A or the compound B do not sufficiently exhibit the radical chain inhibiting effect, that is, the antioxidant effect. Comparative Example 8 containing compound A, a thioether-based antioxidant and a heavy metal deactivator and not containing an epoxy compound and a fatty acid, compound A containing an epoxy compound, a compound A, a thioether-based antioxidant, a heavy metal deactivator and a fatty acid Comparative Example 9 in which compound A, a thioether-based antioxidant and an epoxy compound are not compounded and a heavy metal deactivator and a fatty acid are not compounded Comparative Example 10, compound A and a fatty acid are compounded in a thioether-based antioxidant and a heavy metal compound Compared with Comparative Example 11 containing no activator and epoxy compound, and Comparative Example 12 containing Compound A, thioether antioxidant and fatty acid and containing no heavy metal deactivator and epoxy compound, and Examples 1 to 8. As seen, the heavy metal resistance of Comparative Examples 8 to 12 is still insufficient.

Further, Comparative Example 13 containing compound A, a thioether antioxidant, a heavy metal deactivator and an epoxy compound but not a fatty acid (see Japanese Patent Application Laid-Open No. 2-240148 previously proposed by the present inventor) (Combustible polyolefin composition) and Compound A, a thioether-based antioxidant, a heavy metal deactivator and a fatty acid were mixed, and Comparative Example 14 was compared with Examples 1 to 8 and Comparative Example 13 was compared. The heavy metal resistance of Nos. 14 to 14 is improved as compared with Comparative Examples 8 to 12, but still not sufficient. Therefore, one selected from Compound A and Compound B according to the present invention
It is clear that the comparative examples that do not simultaneously satisfy the combination of the five components of one kind or two or more kinds of compounds, the thioether antioxidant, the heavy metal deactivator, the epoxy compound and the fatty acid do not exhibit the effect of the present invention. . That is, the heavy metal resistance obtained in the present invention is obtained by adding one or more compounds selected from the compound A and the compound B to the flame-retardant polyolefin composition containing magnesium hydroxide, and a thioether antioxidant. It can be said that this is a unique effect that can be seen only when the agent, the heavy metal deactivator, the epoxy compound and the fatty acid are used in combination.

The flame-retardant property according to the present invention, which comprises one or more compounds selected from Compound A and Compound B, a thioether antioxidant, a heavy metal deactivator, an epoxy compound and a fatty acid. It has been confirmed that the composition has a flame retardancy comparable to that of a conventionally known flame retardant composition.

Table 2 shows a crystalline ethylene-propylene block copolymer used as the polyolefin and a surface-treated product as the magnesium hydroxide, and the same effects as above were confirmed for these. Tables 3 to 4
Is a crystalline ethylene-propylene-butene-1 terpolymer or a crystalline ethylene as a polyolefin, respectively.
-Propylene random copolymer, a mixture of Ziegler-Natta high-density ethylene homopolymer and amorphous ethylene-propylene random copolymer, and a surface-untreated product used as magnesium hydroxide. The same effect was confirmed.

[0057]

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

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 10, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1]

(Wherein R ₁ is an alkylidene group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 9 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 9 carbon atoms, cyclo An alkyl group or an alkylcyclohexyl group, R ₄ is an alkyl group having 1 to 8 carbon atoms, R ₅ is hydrogen or 1 to 8 carbon atoms
8 represents an alkyl group, and n represents an integer of 1 to 4, respectively. )

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to flame retardant polyolefin compositions. More specifically, it relates to a flame-retardant polyolefin composition having excellent oxidative deterioration-preventing property of polyolefin during practical use.

[0002]

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

A molded article molded from a flame-retardant polyolefin composition obtained by mixing magnesium hydroxide and various antioxidants in polyolefin is used for the purpose of coming into contact with heavy metals such as copper, brass, iron and nickel. Sometimes. However, since the polyolefin is catalytically deteriorated by the heavy metal ions contained in the above-mentioned various heavy metals, a molded article using the flame-retardant polyolefin composition described above is resistant to oxidation deterioration during contact with heavy metals (hereinafter,
It is called heavy metal resistance. ) Is significantly reduced.

Therefore, for the purpose of improving the heavy metal resistance of a molded product using a flame-retardant polyolefin composition which has been conventionally compounded with magnesium hydroxide, magnesium hydroxide, a phenolic antioxidant and sulfur are added to the polyolefin. Composition containing a system antioxidant and a copper damage inhibitor
No. 2-11238 and Japanese Patent Laid-Open No. 63-56544), and a composition obtained by mixing magnesium hydroxide and an epoxy compound with polyolefin (Japanese Patent Laid-Open No. 59-2193).
52, JP-A-63-137963, JP-A-63-159473 and JP-A-63-1894.
62), magnesium hydroxide in polyolefin,
Compositions containing a phenolic stabilizer, a higher fatty acid and a higher fatty acid metal salt (JP-A-53-33247 and JP-A-54-47746) have been proposed.

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 the applications of molded articles obtained from flame-retardant polyolefin compositions are diversified and large. Along with
The requirements for practical use conditions (heavy metal resistance, electrical insulation, etc.) of the molded product are becoming severe. That is, it is necessary to develop a flame-retardant polyolefin composition that is more excellent in heavy metal resistance than ever before. In order to solve these problems, magnesium hydroxide is added to the above-mentioned JP-A-52-1238, JP-A-63-56544, JP-A-59-219352, and JP-A-63-1.
37963, JP-A-63-159473,
JP-A-63-189462, JP-A-53-332
The flame-retardant polyolefin compositions proposed in Japanese Patent No. 47 and Japanese Patent Application Laid-Open No. 54-47746 are still not sufficiently satisfactory in terms of heavy metal resistance. For this reason, the present inventor has found that polyolefin has magnesium hydroxide, a specific phenol compound, a specific thioether compound,
A flame-retardant polyolefin composition prepared by mixing a heavy metal deactivator and an epoxy compound in specific amounts was previously proposed (JP-A-2-240148).

[0006]

DISCLOSURE OF THE INVENTION The inventor of the present invention has disclosed in
Further studies were conducted without being satisfied with the flame-retardant polyolefin composition proposed in JP-A-240148. As a result, a phenolic compound represented by the following chemical formula 3 (hereinafter referred to as compound A) and a phenolic compound represented by the following chemical formula 4 (hereinafter referred to as compound B) in a flame-retardant composition composed of polyolefin and magnesium hydroxide. Flame retardant polyolefin composition with improved heavy metal resistance by blending one or more compounds selected from the above), thioether-based antioxidants, heavy metal deactivators, epoxy compounds and fatty acids in specific amounts. It was found that a product was obtained, and the present invention was completed based on this finding.

[Chemical 3]

Wherein R ₁ is an alkylidene group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 9 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 9 carbon atoms, cyclo Alkyl group or alkylcyclohexyl group, R ₄ has 1 carbon atom
~ 8 alkyl group, R ₅ is hydrogen or 1 to 8 carbon atoms
And an n is an integer of 1 to 4, respectively. )
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 heavy metal resistance of the molded product when it is formed.

[0007]

The present invention has the following constitution. With respect to 100 parts by weight of a composition obtained by mixing 30 to 70% by weight of magnesium hydroxide with polyolefin, a phenolic compound represented by the following chemical formula 5 (hereinafter referred to as compound A) and a phenolic compound represented by the following chemical formula 6 ( Hereinafter, one or two selected from Compound B).
A flame-retardant polyolefin composition comprising 0.01 to 1 part by weight of a compound of one or more kinds, a thioether antioxidant, a heavy metal deactivator and an epoxy compound, and 0.5 to 5 parts by weight of a fatty acid.

[Chemical 5]

(Wherein R ₁ is an alkylidene group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 9 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 9 carbon atoms, cyclo An alkyl group or an alkylcyclohexyl group, R ₄ is an alkyl group having 1 to 8 carbon atoms, R ₅ is hydrogen or 1 to 8 carbon atoms
8 represents an alkyl group, and n represents an integer of 1 to 4, respectively. )

The polyolefin used in the present invention is a crystalline homopolymer of α-olefin such as ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, and the like. A crystalline, low crystalline or amorphous random copolymer or crystalline block copolymer of two or more α-olefins, an amorphous ethylene-propylene-nonconjugated diene terpolymer, the above α- Copolymer of olefin and vinyl acetate or acrylic ester, saponified product of the copolymer, copolymer of α-olefin and unsaturated silane compound, α-olefin and unsaturated carboxylic acid or anhydride thereof Copolymer, a reaction product of the copolymer and a metal ion compound, a crystalline homopolymer of the above α-olefin, a crystalline, low crystalline, amorphous random copolymer or binder. A modified polyolefin obtained by modifying a crystalline block copolymer or an amorphous ethylene-propylene-nonconjugated diene terpolymer with an unsaturated carboxylic acid or a derivative thereof, a crystalline homopolymer of the above α-olefin, and a crystalline property Examples include low crystallinity, amorphous random copolymers or crystalline block copolymers, or silane-modified polyolefins obtained by modifying an amorphous ethylene-propylene-nonconjugated diene terpolymer with an unsaturated silane compound. These polyolefins can be used alone or in combination of two or more.

In addition to the above-mentioned polyolefins, various synthetic rubbers (for example, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-rubber).
Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-
Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (eg polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, poly Butylene terephthalate, polycarbonate,
Polyvinyl chloride, fluororesin, petroleum resin (eg C ₅
Petroleum resin, hydrogenated C ₅ petroleum resin, C ₉ petroleum resin, hydrogenated C ₉ petroleum resin, C ₅ -C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉
Copolymerized petroleum resin, acid-modified C ₉ petroleum resin, etc.), DCP
D resin (eg, cyclopentadiene-based petroleum resin, hydrogenated cyclopentadiene-based petroleum resin, cyclopentadiene-
C ₅ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymerized petroleum resin, cyclopentadiene-C ₉ copolymerized petroleum resin,
Softening point of hydrogenated cyclopentadiene-C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, etc.
DCPD resin) and the like) may be mixed and used. Crystalline propylene homopolymer, propylene component 70
A crystalline propylene copolymer containing at least wt%, which is a crystalline ethylene-propylene random copolymer, a crystalline ethylene-propylene block copolymer, a crystalline propylene-butene-1 random copolymer, a crystalline ethylene. -
Propylene-butene-1 terpolymer, crystalline propylene
-Hexene-butene-1 terpolymers and mixtures of two or more thereof are particularly preferably used.

As the magnesium hydroxide used in the present invention, plate-like and fibrous ones can be used without any limitation. The average particle size of the plate-shaped magnesium hydroxide is not particularly limited, but is usually 0.1μ to 10μ, preferably 0.2.
μ-2 μ, most preferably 0.5 μ-1 μ, and the fibrous magnesium hydroxide preferably has a fiber diameter of 0.1 μ-0.5 μ and a length of 5 μ-20 μ.

These magnesium hydroxides are surface treatment agents such as metal soaps, higher fatty acid esters, higher alcohols, higher fatty acid monoamides, higher fatty acid bisamides, higher aliphatic metal phosphates, silane coupling agents, titanate couplings. Agent, a boron-based coupling agent, an aluminate-based coupling agent and a zircoaluminate-based coupling agent and the like, when used after being surface-treated with a known surface treatment agent, the compatibility between the magnesium hydroxide and the polyolefin and It is preferable to use magnesium hydroxide surface-treated with a surface-treating agent, because the dispersibility is improved, excellent moldability is obtained, and the mechanical strength of the molded product is improved. These magnesium hydroxides can be used alone or in combination of two or more.

The mixing ratio of the magnesium hydroxide is 30 to 70% by weight, preferably 50 to 65% by weight, based on the composition comprising polyolefin and magnesium hydroxide.
If the amount is less than 30% by weight, the flame retardancy of the obtained molded product is insufficient, and if it exceeds 70% by weight, the molding processability becomes difficult and the mechanical strength of the obtained molded product decreases, which is not practical.

The compound A used in the present invention is bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] isophthalate,
Bis [2- (3'-t-butyl-5'-ethyl-2'-hydroxybenzyl) -4-ethyl-6-t-butylphenyl] isophthalate, bis [2- (3'-nonyl-5 '-Methyl-2'-hydroxybenzyl) -4-methyl-6-nonylphenyl] isophthalate, bis [2- (3 ', 5'-dinonyl-2'-hydroxybenzyl) -4,6-dinonylphenyl] Isophthalate, bis [2
-(3'-cyclohexyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-cyclohexylphenyl] isophthalate, bis [2- (3 '-(1 "-methylcyclohexyl) -5'-
Methyl-2'-hydroxybenzyl) -4-methyl-6- (1'-methylcyclohexyl) phenyl] isophthalate, bis [2- (5'-nonyl-2'-hydroxy (α, α-dimethylbenzyl)) -4-nonylphenyl] isophthalate, bis [2
-(3 ', 5'-Dimethyl-2'-hydroxy (α-propylbenzyl))-4,6-dimethylphenyl] isophthalate, bis [2- (3', 5'-di-t-butyl-2) '-Hydroxybenzyl) -4,
6-di-t-butylphenyl] isophthalate, bis [2-
(3'-t-butyl-5'-s-butyl-2'-hydroxy (α-methylbenzyl))-4-s-butyl-6-t-butylphenyl] isophthalate, bis [2- (3 ' , 5'-Di-t-butyl-2'-hydroxy (α-methylbenzyl))-4,6-di-t-butylphenyl] isophthalate, bis [2- (3'-t-octyl-5 '] -Methyl-2'-hydroxybenzyl) -4-methyl-6-t-octylphenyl] isophthalate, bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy ( α-Propylbenzyl))-4-methyl-6- (1'-methylcyclohexyl) phenyl] isophthalate, bis [2- (3 ', 5'-dimethyl-2'-hydroxybenzyl) -4,6-dimethyl Phenyl] isophthalate,

Bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate, bis [2- (3'-t- Butyl-5'-ethyl-2'-
Hydroxybenzyl) -4-ethyl-6-t-butylphenyl]
Terephthalate, bis [2- (3'-nonyl-5'-methyl-2'-
Hydroxybenzyl) -4-methyl-6-nonylphenyl] terephthalate, bis [2- (3 ', 5'-dinonyl-2'-hydroxybenzyl) -4,6-dinonylphenyl] terephthalate, bis [2- ( 3'-cyclohexyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-cyclohexylphenyl] terephthalate, bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2 '-Hydroxybenzyl) -4-methyl-6- (1'-methylcyclohexyl) phenyl] terephthalate, bis [2- (5'-nonyl-2'-hydroxy (α, α
-Dimethylbenzyl))-4-nonylphenyl] terephthalate, bis [2- (3 ', 5'-dimethyl-2'-hydroxy (α
-Propylbenzyl))-4,6-dimethylphenyl] terephthalate, bis [2- (3 ', 5'-di-t-butyl-2'-hydroxybenzyl) -4,6-di-t-butylphenyl] Terephthalate, bis [2- (3'-t-butyl-5'-methyl-2'-hydroxy (α-methylbenzyl))-4-methyl-6-t-butylphenyl] terephthalate, bis [2- (3 '-t-Butyl-5'-ethyl-2'-hydroxy (α-methylbenzyl))-4-ethyl-6
-t-butylphenyl] terephthalate,

Bis [2- (3'-t-butyl-5'-s-butyl-2'-
Hydroxy (α-methylbenzyl))-4-s-butyl-6-t-
Butylphenyl] terephthalate, bis [2- (3 ', 5'-di
-t-Butyl-2'-hydroxy (α-methylbenzyl))-4,6
-Di-t-butylphenyl] terephthalate, bis [2- (3 '
-t-octyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-octylphenyl] terephthalate, bis [2
-(3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy (α-propylbenzyl))-4-methyl-6- (1'-
Methylcyclohexyl) phenyl] terephthalate and bis [2- (3 ', 5'-dimethyl-2'-hydroxybenzyl)
-4,6-Dimethylphenyl] terephthalate, etc., and particularly bis [2- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] Terephthalate, bis [2- (3'-t-butyl-5'-ethyl-2'-hydroxybenzyl) -4-ethyl-6-t-butylphenyl] terephthalate, bis [2- (3 ', 5'- Di-t-butyl-2'-hydroxybenzyl) -4,6-di-t-butylphenyl] terephthalate and bis [2- (3 ', 5'-di-t-butyl-2'-hydroxy (α- Methylbenzyl))-4,6-di-t-butylphenyl] terephthalate is preferred. These compounds A may be used alone or in combination of two or more kinds.

The compound B used in the present invention includes tris (3-t-butyl-4-hydroxybenzyl) isocyanurate, tris (3-t-amyl-4-hydroxybenzyl) isocyanurate, tris (3-t- Octyl-4-hydroxybenzyl) isocyanurate, tris (3-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris (3-methyl-4-hydroxy-5-t-amylbenzyl) isocyanurate, Tris (3-methyl-4-hydroxy-5-t-
Octylbenzyl) isocyanurate, tris (3-ethyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris (3-i-propyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris ( 3-i-Butyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris (3-s-butyl-4-hydroxy-5-t-butylbenzyl)
Isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris (3-t-butyl)
-4-Hydroxy-5-t-amylbenzyl) isocyanurate, tris (3-t-butyl-4-hydroxy-5-t-octylbenzyl) isocyanurate, tris (3,5-di-t-amyl-
4-hydroxybenzyl) isocyanurate, tris (3,
5-di-t-octyl-4-hydroxybenzyl) isocyanurate, tris (2-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, tris (2,5-di-t-butyl-4-)
Hydroxybenzyl) isocyanurate, tris (2-methyl-4-hydroxy-5-t-octylbenzyl) isocyanurate, tris (2-t-butyl-4-hydroxy-5-methylbenzyl) isocyanurate, tris (3- Methyl-4-hydroxy-5-t-butylphenylethyl) isocyanurate, tris (3-t-butyl-4-hydroxyphenylethyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl) Ethyl) isocyanurate, tris (3,5-di-t-amyl-4-hydroxyphenylethyl) isocyanurate, tris (3,5-di-t-octyl-4-hydroxyphenylethyl) isocyanurate, tris (3 -Methyl-4-hydroxy-5-t-butylphenylpropyl) isocyanurate, Tris (3,5-di-t-butyl-4-hydroxyphenylpropyl) isocyanurate, Tris (3-methyl
-4-Hydroxy-5-t-butylphenylbutyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenylbutyl) isocyanurate and tris (3,5-di-t-
Octyl-4-hydroxyphenylbutyl) isocyanurate and the like, and particularly tris (3,5-di-t-butyl-4-
Hydroxybenzyl) isocyanurate is preferred.

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

The thioether antioxidant used in the present invention includes dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, dicetyl thiodipropionate, distearyl thiodipropionate, Dilaurylthiodibutyrate, ditridecylthiodibutyrate, dimyristylthiodibutyrate, dicetylthiodibutyrate, distearylthiodibutyrate, laurylstearylthiodipropionate, laurylstearylthiodibutyrate, pentaerythritol-β-laurylthio Dipropionate,
Pentaerythritol-tetrakis (3-octylthiopropionate), Pentaerythritol-tetrakis (3
-Nonylthiopropionate), pentaerythritol-
Tetrakis (3-decylthiopropionate), Pentaerythritol-Tetrakis (3-laurylthiopropionate), Pentaerythritol-Tetrakis (3-Tridecylthiopropionate), Pentaerythritol-Tetrakis (3-myristylthiopropionate) Pionate), pentaerythritol-tetrakis (3-palmitylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), pentaerythritol
-Tetrakis (4-octylthiobutyrate), Pentaerythritol-Tetrakis (4-nonylthiobutyrate), Pentaerythritol-Tetrakis (4-decylthiobutyrate), Pentaerythritol-Tetrakis (4
-Laurylthiobutyrate), pentaerythritol-tetrakis (4-tridecylthiobutyrate), pentaerythritol-tetrakis (4-myristylthiobutyrate), pentaerythritol-tetrakis (4-palmitylthiobutyrate), pentaerythritol -Tetrakis (4-stearylthiobutyrate), Pentaerythritol-Tetrakis (3-octylthiobutyrate), Pentaerythritol-Tetrakis (3-nonylthiobutyrate), Pentaerythritol-Tetrakis (3-decylthiobutyrate), Pentaerythritol-Tetrakis (3
-Laurylthiobutyrate), pentaerythritol-tetrakis (3-tridecylthiobutyrate), pentaerythritol-tetrakis (3-myristylthiobutyrate), pentaerythritol-tetrakis (3-palmitylthiobutyrate), pentaerythritol -Tetrakis (3-stearyl thiobutyrate),

Tetrakis [3- {2- (octyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (nonyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (Decyloxycarbonyl) ethylthio}
Propionyloxymethyl] methane, tetrakis [3-
{2- (dodecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (tridecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (tetradecyloxycarbonyl) Ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (octadecyloxycarbonyl) ethylthio} propionyloxymethyl] methane,

1,3,5-Tris [3- {2- (octyloxycarbonyl) ethylthio} propionyl] hexahydro-
1,3,5-triazine, 1,3,5-tris [3- {2- (nonyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2- (decyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyl]
Hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2
-(Tridecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3, 5-triazine,
1,3,5-Tris [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-
Triazine, 1,3,5-tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 2,4,6-tris [3- {2- (octyloxy Carbonyl) ethylthio} propionyl] -1,
3,5-triazine, 2,4,6-tris [3- {2- (nonyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (Decyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine,
2,4,6-Tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-
Tris [3- {2- (tridecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl]- 1,3,5-triazine, 2,4,6-tris [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine,

Tris [3- {2- (octyloxycarbonyl) ethylthio} propionyl] isocyanurate, Tris [3- {2- (nonyloxycarbonyl) ethylthio}
Propionyl] isocyanurate, tris [3- {2- (decyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (Tridecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2-
(Hexadecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (octyloxycarbonyl) ethylthio} propionyloxyethyl] Isocyanurate, tris [3- {2- (nonyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (decyloxycarbonyl)
Ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (tridecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanate Nulate, tris [3- {2- (tetradecyloxycarbonyl)
Ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanate Nurate,

Bis (4-t-amylphenyl) sulfide,
Dilauryl disulfide, dimyristyl disulfide,
Distearyl disulfide, 3- (laurylthio) propionylamide, 3- (myristylthio) propionylamide, 3- (stearylthio) propionylamide, N, N '
-Methylene-bis (3-laurylthiopropionyl) amide, N, N'-methylene-bis (3-myristylthiopropionyl) amide, N, N'-methylene-bis (3-stearylthiopropionyl) amide, N, N '-Ethylene-bis (3-laurylthiopropionyl) amide, N, N'-ethylene-bis (3-myristylthiopropionyl) amide, N, N'-
Ethylene-bis (3-stearylthiopropionyl) amide, N, N'-bis (3-laurylthiopropionyl) hydrazide, N, N'-bis (3-myristylthiopropionyl) hydrazide, N, N'-bis (3 -Stearylthiopropionyl) hydrazide, sodium-β-laurylthiopropionate, sodium-β-myristylthiopropionate, sodium-β-stearylthiopropionate, thioethylene glycol-bis (β-aminocrotonate),

Bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, stearyl-3,5
-Dimethyl-4-hydroxybenzyl thioglycolate, 2,
4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t
-Butylanilino) -1,3,5-triazine, octylthiobis (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) cyanurate, 2,4-bis [(octylthio) methyl] -o- Cresol, bis [(2-hydroxy-3- (4'-ethoxyphenylamino) propyl)] sulfide, bis [2-methyl
-4- (3-octylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2-methyl-4- (3-nonylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2 -Methyl-4- (3-decylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2
-Methyl-4- (3-laurylthiopropionyloxy) -5-t
-Butylphenyl] sulfide, bis [2-methyl-4- (3-
Tridecylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2-methyl-4- (3-myristylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2-methyl-4- (3-pentadecylthiopropionyloxy) -5-t-butylphenyl] sulfide,
Bis [2-methyl-4- (3-palmitylthiopropionyloxy) -5-t-butylphenyl] sulfide, bis [2-methyl-4- (3-stearylthiopropionyloxy) -5-t-
Butylphenyl] sulfide and poly [1,4-bis (hydroxymethyl) cyclohexane-thiodipropionate] can be exemplified, and particularly dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, Pentaerythritol-tetrakis (3-laurylthiopropionate), distearyl disulfide, N, N'-bis (3-laurylthiopropionyl) hydrazide, bis [2-methyl-4- (3-laurylthiopropionyloxy)- 5-t-butylphenyl] sulfide, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and 2,4- Bis [(octylthio) methyl] -o-cresol is preferred.

These thioether-based antioxidants may be used alone, or two or more thioether-based antioxidants may be used in combination. The blending ratio of the thioether antioxidant is 0.0 with respect to 100 parts by weight of a composition obtained by blending 30 to 70% by weight of magnesium hydroxide with polyolefin.
It is 1 to 1 part by weight, preferably 0.05 to 0.5 part by weight. 0.01
If the amount is less than 1 part by weight, the effect of improving heavy metal resistance is not sufficiently exerted, and if it exceeds 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is also uneconomical.

The heavy metal deactivators used in the present invention include benzotriazole, 2,4,6-triamino-1,3,5-triazine and 3,9-bis [2- (3,5-diamino-2 , 4,6-Triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, ethylenediamine-tetraacetic acid, ethylenediamine-tetraacetic acid alkali metal salt (Li, Na, K) salt, N, N'-disalicylidene-ethylenediamine, N, N'-disalicylidene-1,2-propylenediamine, N, N "-disalicylidene-
N'-methyl-dipropylenetriamine, 3-salicyloylamino-1,2,4-triazole, decamethylene dicarboxylic acid-bis (N'-salicyloyl hydrazide), nickel-bis (1-phenyl- 3-methyl-4-decanoyl-5-pyrazolate),

2-ethoxy-2'-ethyloxanilide, 5-t-
Butyl-2-ethoxy-2'-ethyloxanilide, N, N-diethyl-N ', N'-diphenyloxamide, N, N'-diethyl-N, N'-diphenyloxamide, oxalic acid- Bis (benzylidene hydrazide), thiodipropionic acid-bis (benzylidene hydrazide), isophthalic acid-bis (2-phenoxypropionyl hydrazide), bis (salicyloyl hydrazine), N
-Salicylidene-N'-Salicyloylhydrazone, N, N'-
Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, Tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t -Butylphenyl) -5-
Methylphenyl] phosphite, bis [2-t-butyl-4]
-Thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -pentaerythritol-diphosphite, tetrakis [2-t-butyl-4-thio (2'- Methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,6-hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2- t-Butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl]-
1,10-decamethylene-di-carboxylic acid-di-
Hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-
Hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid
-Di-salicyloyl hydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy
-5'-t-Butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy- 5'-t-Butylphenyl) -5-methylphenyl]-
N, N'-bis (hydroxyethyl) oxamide-diphosphite, and N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] Examples include oxamide,

Particularly oxalic acid-bis (benzylidene hydrazide), N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris [2-t-butyl] -4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite and N, N'-bis [2- [3- (3,5-di -t-Butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide is preferred. These heavy metal deactivators may be used alone or in combination of two or more. 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 composition obtained by mixing 30 to 70% by weight of magnesium hydroxide with polyolefin. If the amount is less than 0.01 part by weight, the effect of improving heavy metal resistance is not sufficiently exerted, and if it exceeds 1 part by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is uneconomical again.

The epoxy compound used in the present invention is not particularly limited as long as it does not significantly volatilize and escape or is decomposed during melt-kneading, and an epoxy equivalent of about 100 to 1,000 is suitable, and epichlorohydrin or Derivatives of epichlorohydrin (eg 2-
Condensation of methyl epichlorohydrin, 2-ethyl epichlorohydrin and 2-propyl epichlorohydrin) with bisphenol or a bisphenol derivative (for example, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S) Products, epoxidized oils and fats (eg, 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-epoxycyclohexyl) Fatty acid ester of methanol, 3,4-
Epoxycyclohexylcarboxylic acid alkyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid dialkyl ester, 3,4-epoxy-6-methylcyclohexylmethyl and 3,4-epoxy-6-methylcyclohexanecarboxylate, etc. ), Tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, novolac glycidyl ether,
Polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, p-oxybenzoic acid glycidyl ether-ester,

Phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid glycidyl ester, dimer acid 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,
Examples thereof include vinylcyclohexene diepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether and limonendioxide. Particularly, a condensate of epichlorohydrin and bisphenol A, 2-methylepichlorohydrin and bisphenol A
Condensates with triglycidyl isocyanurate and epoxidized soybean oil are preferred.

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

The fatty acid used in the present invention is acetic acid,
Propionic acid, n-butyric acid, i-butyric acid, n-valeric acid, i-valeric acid,
n-hexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid,
Oleic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, 12-hydroxyoctadecanoic acid,
Examples include ricinoleic acid and cerebronic acid.
2-Ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, montanic acid and 12-hydroxyoctadecanoic acid are preferred.

These fatty acids may be used alone or in combination of two or more. The blending ratio of the fatty acid is such that polyolefin is magnesium hydroxide.
0.5 to 0.5 to 100 parts by weight of a composition containing 30 to 70% by weight
It is 5 parts by weight, preferably 1 to 3 parts by weight. If the amount is less than 0.5 parts by weight, the effect of improving heavy metal resistance is not sufficiently exerted, and if it exceeds 5 parts by weight, further improvement effect of heavy metal resistance cannot be expected and it is not practical. It is uneconomical again.

In the composition of the present invention, various additives usually added to polyolefins such as phenol-based compounds (excluding compound A and compound B), phosphorus-based antioxidants, light stabilizers, Clarifying agents, nucleating agents, lubricants (excluding fatty acids), antistatic agents, anti-fog agents, anti-blocking agents, non-dripping agents, flame retardants (excluding magnesium hydroxide), flame retardant aids, Antibacterial agents, pigments, radical generators such as peroxides, dispersants or neutralizers for metal soaps, inorganic fillers (eg talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous) Soil, asbestos, calcium carbonate, aluminum hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, silicic acid Calcium, aluminum silicate,
Surface treatment agent such as glass fiber, potassium titanate, carbon fiber, carbon black, graphite, metal fiber) or coupling agent (eg silane, titanate, boron, aluminate, zircoaluminate, etc.) The surface-treated inorganic or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used together within the range not impairing the object of the present invention.

The composition of the present invention comprises a polyolefin containing one or more compounds selected from magnesium hydroxide, compound A and compound B, a thioether antioxidant, a heavy metal deactivator, an epoxy compound and a fatty acid. In addition, a predetermined amount of each of the above-mentioned various additives that are usually added to polyolefins, and one or more compounds selected from magnesium hydroxide, compound A and compound B, which are surface-treated with a fatty acid, and thioethers. A predetermined amount of each of the above-mentioned antioxidants, heavy metal deactivators and epoxy compounds, and the above-mentioned various additives which are usually added to polyolefins is mixed with a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, or a bambar. Mix using a remixer, etc. Extruder, biaxial extruder, or the like Brabender or rolls, melt kneading temperature 0.99 ° C. to 300
It can be obtained by melt-kneading and pelletizing at ℃, preferably 200 ℃ -250 ℃. 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.

In the present invention, compound A and compound B
Is a radical chain inhibitor, a thioether antioxidant is a peroxide decomposer, a heavy metal deactivator is an inactivator of the catalytic oxidative deterioration of polyolefin by heavy metal ions, and an epoxy compound is an adsorption inhibitor. ,
It is generally known that fatty acids act as surface treatment agents for magnesium hydroxide. However, one or more compounds selected from the compound A and the compound B according to the present invention, a thioether-based antioxidant, and a heavy metal deactivator are added to a flame-retardant polyolefin composition containing magnesium hydroxide. By using an epoxy compound and a fatty acid in combination, a surprising synergistic effect that cannot be predicted from the compounding of a conventionally known compound having an oxidative deterioration preventing effect is exhibited, and a flame-retardant polyolefin composition excellent in heavy metal resistance is obtained. can get.

In addition, compound A is excellent as a radical chain inhibitor in a flame-retardant polyolefin composition containing magnesium hydroxide because compound A is an ester of phenol and an aromatic carboxylic acid, that is, an aromatic compound. Since it is an ester, the compound A has a chemical structure that is less susceptible to alkaline hydrolysis in the presence of magnesium hydroxide than a phenolic antioxidant having an aliphatic ester group or an aliphatic amide group other than the compound A, and It is presumed that this is due to the fact that the alkaline hydrolysis is further suppressed by the neutralizing effect of fatty acids on magnesium hydroxide.

It is generally known that the compound B is most susceptible to alkaline hydrolysis among the above-mentioned phenolic antioxidants having an aliphatic amide group. However, compound B is excellent as a radical chain inhibitor in a flame-retardant polyolefin composition containing magnesium hydroxide according to the present invention because compound B undergoes alkaline hydrolysis in the presence of magnesium hydroxide. Despite its easy chemical structure
It is presumed that this is due to the fact that the alkaline hydrolysis is significantly suppressed by the neutralizing action of fatty acids on magnesium hydroxide.

[0038]

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

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

Examples 1 to 8 and Comparative Examples 1 to 14 MFR as a polyolefin (load at 230 ° C. 2.16 k
Discharge amount of molten resin for 10 minutes when g is added) 43 g by weight of unstabilized powdery crystalline propylene homopolymer of 20 g / 10 minutes and average particle size as magnesium hydroxide of 0.
Bis [2- (5'-nonyl-2'-hydroxy (α, α-dimethylbenzyl))-4- as compound A was added to 100 parts by weight in total consisting of 6 to 0.8μ of 57% by weight of untreated surface. Nonylphenyl] isophthalate, tris (3-methyl as compound B
-4-Hydroxy-5-t-butylbenzyl) isocyanurate, dimyristylthiodipropionate or pentaerythritol-tetrakis (3-laurylthiopropionate) as a thioether antioxidant, 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 Alternatively, oxalic acid-bis (benzylidene hydrazide), a condensate of epichlorohydrin and bisphenol A as an epoxy compound (epoxy equivalent: 700 to 83
0) or a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 180 to 200), acetic acid as a fatty acid, 2-ethylhexanoic acid, stearic acid or oleic acid and others Add a specified amount of each of the additives to the Henschel mixer (trade name) at the blending ratio shown in Table 1 below, stir and mix for 3 minutes, and then calibrate 30 mm.
Was melt-kneaded at 250 ° C. in a twin-screw extruder to produce pellets. Further, as Comparative Examples 1 to 14, unstabilized powdery crystalline propylene homopolymer 43 having an MFR of 20 g / 10 min.
% By weight and magnesium hydroxide having an average particle size of 0.6 to
The pellets were melt-kneaded in accordance with Examples 1 to 8 by adding a predetermined amount of each of the additives shown in Table 1 below to a total of 100 parts by weight consisting of 0.8% of an untreated surface of 57% by weight. Got For the test pieces used for the copper resistance test and the flammability test, use the pellets obtained at a resin temperature of 250 ° C and a mold temperature of 50 ° C.
Was prepared by injection molding. The obtained test pieces were used to evaluate heavy metal resistance (150 ° C. copper resistance) and flame retardancy by the above-mentioned test method. The results are shown in Table 1.

Examples 9 to 16 and Comparative Examples 15 to 28 29.59% by weight of water-free crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) of MFR 30 g / 10 min as a polyolefin and water. Magnesium hydroxide [I], magnesium hydroxide [II], magnesium hydroxide [III] or magnesium hydroxide [IV] surface-treated as magnesium oxide
A total of 101.4 parts by weight (70.41% by weight) (100 parts by weight as the total of the crystalline ethylene-propylene block copolymer excluding the fatty acid used for the surface treatment and the surface-untreated magnesium hydroxide product) was added with bis as Compound A. [2- (3'-
t-Butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate, tris (3,5-di-t-butyl-4-hydroxybenzyl) as compound B
Isocyanurate, thioether type antioxidant as distearyl thiodipropionate or distearyl disulfide, and heavy metal deactivator as 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 mixture of a condensate of epichlorohydrin and bisphenol A as an epoxy compound (epoxy equivalent of 700 to 830) or a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy) Equivalent 180 to 200) and other prescribed amounts of other additives are put into a Henschel mixer (trade name) at the blending ratios shown in Table 2 below, and the mixture is stirred and mixed for 3 minutes, and then the caliber is 30 mm.
Was melt-kneaded at 250 ° C. in a twin-screw extruder to produce pellets. As Comparative Examples 15 to 28, powdery crystalline ethylene-propylene block copolymer having an MFR of 30 g / 10 minutes and not stabilized (ethylene content 8.5% by weight) 30% by weight
And a total of 100 parts by weight of 70% by weight of untreated surface having an average particle size of 0.6 to 0.8μ as magnesium hydroxide or an unstabilized powdery crystalline ethylene-propylene block copolymer weight of MFR of 30 g / 10 min. Combined (ethylene content 8.5% by weight) 29.59% by weight and magnesium hydroxide [II] 70.41% by weight surface-treated as magnesium hydroxide, a total of 101.4 parts by weight (crystalline ethylene-propylene excluding fatty acid used for surface treatment) A predetermined amount of each of the additives shown in Table 2 below was added to 100 parts by weight as the total of the surface-untreated block copolymer and magnesium hydroxide, and the melt-kneading treatment was carried out in accordance with Examples 9 to 16. To obtain pellets. The test pieces used for the copper resistance test and the flammability test were obtained by using the pellets with a resin temperature of 250
It was prepared by injection molding at a mold temperature of 50 ° C. Using the obtained test piece, the heavy metal resistance (150
(° C copper resistance) and flame retardancy were evaluated. The results are shown in Table 2.

Examples 17-24, Comparative Examples 29-42 MFR 7.0 g / 10 min as a polyolefin Unstabilized powdery crystalline ethylene-propylene-butene-13
Original copolymer (ethylene content 2.5% by weight, butene-1 content
4.5% by weight) and 50% by weight of magnesium hydroxide and 50% by weight of a surface-untreated product having an average particle size of 0.6 to 0.8μ, and 100 parts by weight of bis [2- (3 ', 5'- The-
t-Butyl-2'-hydroxy (α-methylbenzyl))-4,6-
Di-t-butylphenyl] terephthalate, tris (3-t-amyl-4-hydroxyphenylethyl) as compound B
Isocyanurate, N, N'-bis (3-laurylthiopropionyl) hydrazide or bis [2-methyl-4- (3-laurylthiopropionyloxy) -5-t-butylphenyl] sulfide as a thioether antioxidant, 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), triglycidyl isocyanurate (epoxy equivalent 100-110) or epoxidized soybean oil (epoxy equivalent 220-240) as an epoxy compound. ), Stearic acid, oleic acid, behenic acid or erucic acid as the fatty acid, and the respective prescribed amounts of the other additives are shown in Table 3 below.
The mixture was placed in a Henschel mixer (trade name) at the blending ratio described in 1 above, stirred and mixed for 3 minutes, and then melt-kneaded at 250 ° C. in a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 29 to 42, powdery crystalline ethylene-propylene-butene-1 terpolymer having an MFR of 7.0 g / 10 min and not stabilized (ethylene content 2.5% by weight, butene-1 content 4 .
5% by weight) and 50% by weight of magnesium hydroxide, and 50% by weight of surface-untreated product having an average particle size of 0.6 to 0.8μ as magnesium hydroxide, and 100 parts by weight in total of predetermined amounts of the additives shown in Table 3 below. Then, in accordance with Examples 17 to 24, melt-kneading treatment was performed to obtain pellets. The test piece used for the copper resistance test and the flammability test was obtained by pelletizing the pellets at a resin temperature of 250 ° C.,
It was prepared by injection molding at a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the heavy metal resistance (140 ° C. copper resistance) and the flame retardance by the above test method. The results are shown in Table 3.

Examples 25-32, Comparative Examples 43-56 55 wt% unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5 wt%) as MFR 7.0 g / 10 min as polyolefin , MI (190
Discharge amount of molten resin for 10 minutes when a load of 2.16 kg at 20 ° C.) 20 g / 10 minutes unstabilized powdered Ziegler-Natta high density ethylene homopolymer 10% by weight,
Unstabilized powdery amorphous ethylene-propylene random copolymer with Mooney viscosity ML1 + 4 (100 ° C) of 25% (propylene content 25% by weight) 5% by weight and magnesium hydroxide having an average particle size of 0.6 to 0.8 bis [2
-(3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy (α-propylbenzyl))-4-methyl-6- (1'-
Methylcyclohexyl) phenyl] terephthalate, tris (3,5-di-t-octyl-4-hydroxyphenylbutyl) isocyanurate as compound B, 2,4-bis (n-octylthio) -6- as thioether antioxidant (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine or 2,4-bis [(octylthio) methyl] -o-cresol, N, N 'as heavy metal deactivator -Bis [2- [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl
-4-Thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), triglycidyl isocyanurate as an epoxy compound (epoxy equivalent 100-1
10) or epoxidized soybean oil (epoxy equivalent 220 to 24
0), stearic acid, oleic acid, montanic acid or 12-hydroxyoctadecanoic acid as fatty acids and other additives in predetermined amounts in a Henschel mixer (trade name) at the compounding ratios shown in Table 4 below, and put for 3 minutes. After stirring and mixing, the mixture was melt-kneaded at 250 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 43 to 56, 55% by weight of unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) with MFR of 7.0 g / 10 minutes and MI of 20 g / 10 minutes Unstabilized powdery Ziegler-Natta high density ethylene homopolymer 10% by weight, Mooney viscosity ML1 + 4 (100 ° C) 25, unstabilized powdery amorphous ethylene-propylene random copolymer (Propylene content 25% by weight) 5% by weight and average particle size as magnesium hydroxide 0.6-0.8μ
A total of 100 parts by weight of the surface-untreated product of 30% by weight was added with a predetermined amount of each of the additives described in Table 4 below, and the mixture was melt-kneaded in accordance with Examples 25 to 32 to obtain pellets. It was The test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the heavy metal resistance (140 ° C. copper resistance) and the flame retardance by the above test method. The results are shown in Table 4.

The compounds and additives relating to the present invention shown in Tables 1 to 4 are as follows. Magnesium hydroxide [0]: Surface-untreated product with an average particle size of 0.6 to 0.8μ Magnesium hydroxide [I]: Surface-untreated product with an average particle size of 0.6 to 0.8μ 100 parts by weight of surface treatment with 2 parts by weight of lauric acid Surface-treated product Magnesium hydroxide [II]: Surface-treated product having an average particle size of 0.6 to 0.8 μ and surface-treated with 2 parts by weight of stearic acid 100 parts by weight Magnesium hydroxide [III]: Average particle size of 0.6 ~ 0.8μ surface-untreated 100 parts by weight surface-treated with 2 parts by weight oleic acid magnesium hydroxide [IV]: average particle size 0.6-0.8μ surface-untreated 100 parts by weight linoleic acid 2 parts Surface-treated product that has been surface-treated with parts by weight

Compound A [I]: Bis [2- (5'-nonyl-2 '
-Hydroxy (α, α-dimethylbenzyl))-4-nonylphenyl] isophthalate Compound A [II]: Bis [2- (3'-t-butyl-5'-methyl-
2'-Hydroxybenzyl) -4-methyl-6-t-butylphenyl] terephthalate Compound A [III]: Bis [2- (3 ', 5'-di-t-butyl-2'
-Hydroxy (α-methylbenzyl) -4,6-di-t-butylphenyl] terephthalate Compound A [IV]: Bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2 '-Hydroxy (α-propylbenzyl))-4-methyl-6- (1'-methylcyclohexyl) phenyl] terephthalate

Compound B [I]: Tris (3-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate Compound B [II]: Tris (3,5-di-t-butyl-4-hydroxybenzyl) ) Isocyanurate Compound B [III]: Tris (3-t-amyl-4-hydroxyphenylethyl) isocyanurate Compound B [IV]: Tris (3,5-di-t-octyl-4-hydroxyphenylbutyl) isocyanate Nurate

Thioether antioxidant [I]: dimyristyl thiodipropionate Thioether antioxidant [II]: Distearyl thiodipropionate Thioether antioxidant [III]: Pentaerythritol-tetrakis (3-lauryl) Thiopropionate) Thioether antioxidant [IV]: Distearyl disulfide Thioether antioxidant [V]: N, N′-bis (3-laurylthiopropionyl) hydrazide Thioether antioxidant [VI]: Bis [2-methyl-4
-(3-laurylthiopropionyloxy) -5-t-butylphenyl] sulfide thioether antioxidant [VII]: 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di -t-Butylanilino) -1,3,5-triazine thioether antioxidant [VIII]: 2,4-bis [(octylthio) methyl] -o-cresol

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-
Di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine Heavy metal deactivator [IV]: oxalic acid-bis (benzylidene hydrazide)

Epoxy compound [I]: Condensation product of epichlorohydrin and bisphenol A (epoxy equivalent 700 to 8
30; ARA-LDIT made by CIBA-GEIGY AG
E GT 7004) Epoxy compound [II]: a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent)
180-200; ADK CIZER manufactured by Asahi Denka Co., Ltd.
EP-17) Epoxy compound [III]: triglycidyl isocyanurate (epoxy equivalent 100 to 110; CIBA-GEIG)
ARALDITE PT 810 manufactured by YAG Epoxy compound [IV]: Epoxidized soybean oil (epoxy equivalent 220 to 240; ADK CIZE manufactured by Asahi Denka Co., Ltd.)
RO-130P)

Fatty acid [I]: Acetic acid Fatty acid [II]: 2-Ethylhexanoic acid Fatty acid [III]: Lauric acid Fatty acid [IV]: Stearic acid Fatty acid [V]: Oleic acid Fatty acid [VI]: Linoleic acid Fatty acid [VII] ]: Behenic acid Fatty acid [VIII]: Erucic acid Fatty acid [IX]: Montanic acid Fatty acid [X]: 12-Hydroxyoctadecanoic acid

Phosphorus-based antioxidant 1: Bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite Phosphorus-based antioxidant 2: bis (2,4-di-t) -Butylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 3: tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite

Phenol-based antioxidant 1: 2,6-di-t-butyl-p-cresol Phenol-based antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 3: 2,2-bis [4- [2- (3,5-di
-t-Butyl-4-hydroxyphenylpropionyloxy)
Ethoxy] phenyl] propane phenolic antioxidant 4: tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate phenolic antioxidant 5: tris [3- (3,5-di -t-Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate Phenolic antioxidant 6: 1,1,3-tris (5-t-butyl)
-4-Hydroxy-2-methylphenyl) -butane phenolic antioxidant 7: Bis [3,3-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] ethylene glycol ester phenolic oxidation Inhibitor 8: 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Carbon black: Carbon # 45 Mitsubishi Kasei Co., Ltd. Ca-St: Steer Calcium phosphate

The examples and comparative examples shown in Table 1 are cases where a crystalline propylene homopolymer was used as the polyolefin and a surface-untreated product was used as the magnesium hydroxide.
As can be seen from Table 1, in Examples 1 to 8, crystalline propylene homopolymer was added to magnesium hydroxide (untreated surface),
One or more compounds selected from Compound A and Compound B, a thioether-based antioxidant, a heavy metal deactivator, an epoxy compound and a fatty acid are blended, and Examples 1 to 8 and Comparative Example 1 7 to 7 (a compound containing a phenolic antioxidant other than the compound A or the compound B instead of the compound A or the compound B), Examples 1 to 8 are excellent in heavy metal resistance and It can be seen that in the presence of magnesium oxide, the phenolic antioxidants other than the compound A or the compound B do not sufficiently exhibit the radical chain inhibiting effect, that is, the antioxidant effect. Comparative Example 8 containing compound A, a thioether-based antioxidant and a heavy metal deactivator and not containing an epoxy compound and a fatty acid, compound A containing an epoxy compound, a compound A, a thioether-based antioxidant, a heavy metal deactivator and a fatty acid Comparative Example 9 in which compound A, a thioether-based antioxidant and an epoxy compound are not compounded and a heavy metal deactivator and a fatty acid are not compounded Comparative Example 10, compound A and a fatty acid are compounded in a thioether-based antioxidant and a heavy metal compound Compared with Comparative Example 11 containing no activator and epoxy compound, and Comparative Example 12 containing Compound A, thioether antioxidant and fatty acid and containing no heavy metal deactivator and epoxy compound, and Examples 1 to 8. As seen, the heavy metal resistance of Comparative Examples 8 to 12 is still insufficient.

Further, Comparative Example 13 containing compound A, a thioether antioxidant, a heavy metal deactivator and an epoxy compound but not a fatty acid (see Japanese Patent Application Laid-Open No. 2-240148 previously proposed by the present inventor) (Combustible polyolefin composition) and Compound A, a thioether-based antioxidant, a heavy metal deactivator and a fatty acid were mixed, and Comparative Example 14 was compared with Examples 1 to 8 and Comparative Example 13 was compared. The heavy metal resistance of Nos. 14 to 14 is improved as compared with Comparative Examples 8 to 12, but still not sufficient. Therefore, one selected from Compound A and Compound B according to the present invention
It is clear that the comparative examples that do not simultaneously satisfy the combination of the five components of one kind or two or more kinds of compounds, the thioether antioxidant, the heavy metal deactivator, the epoxy compound and the fatty acid do not exhibit the effect of the present invention. . That is, the heavy metal resistance obtained in the present invention is obtained by adding one or more compounds selected from the compound A and the compound B to the flame-retardant polyolefin composition containing magnesium hydroxide, and a thioether antioxidant. It can be said that this is a unique effect that can be seen only when the agent, the heavy metal deactivator, the epoxy compound and the fatty acid are used in combination.

The flame-retardant property according to the present invention, which comprises one or more compounds selected from Compound A and Compound B, a thioether antioxidant, a heavy metal deactivator, an epoxy compound and a fatty acid. It has been confirmed that the composition has a flame retardancy comparable to that of a conventionally known flame retardant composition.

Table 2 shows a crystalline ethylene-propylene block copolymer used as the polyolefin and a surface-treated product as the magnesium hydroxide, and the same effects as above were confirmed for these. Tables 3 to 4
Is a crystalline ethylene-propylene-butene-1 terpolymer or a crystalline ethylene as a polyolefin, respectively.
-Propylene random copolymer, a mixture of Ziegler-Natta high-density ethylene homopolymer and amorphous ethylene-propylene random copolymer, and a surface-untreated product used as magnesium hydroxide. The same effect was confirmed.

[0057]

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

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area C08K 5/3477 KFB 7242-4J 5/36 KFD 7242-4J

Claims (1)

[Claims] 1. A polyolefin containing magnesium hydroxide 30
To 100 parts by weight of a composition containing 70 to 70% by weight, a phenolic compound represented by the following chemical formula 1 (hereinafter referred to as compound A) and a phenolic compound represented by the following chemical formula 2 (hereinafter referred to as compound B). ) 1 or 2 selected from
A flame-retardant polyolefin composition comprising 0.01 to 1 part by weight of a compound of one or more kinds, a thioether antioxidant, a heavy metal deactivator and an epoxy compound, and 0.5 to 5 parts by weight of a fatty acid. [Chemical 1] [Chemical 2] (In the formula, R ₁ is an alkylidene group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 9 carbon atoms, R ₃ is hydrogen or an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or an alkyl group. (A cyclohexyl group, R ₄ is an alkyl group having 1 to 8 carbon atoms, R ₅ is hydrogen or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4.)