JPH0436333A - Flame-retarding polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in heavy metal resistance by mixing a composition comprising a polyolefin and Mg(OH)2 with a phenolic compound, a specified compound, a heavy metal inactivator and an epoxy compound. CONSTITUTION:100 pts.wt. composition comprising a polyolefin and 30-70wt.% Mg(OH)2 of a mean particle diameter of 0.1-1mum is mixed with 0.01-1 pt.wt. phenolic compound of formula I (wherein R1 is 1-8C alkyl; R2 is H or R1; R3 is 2-4C alkylene; and (n) is 0 or 1), 0.01-1 pt.wt. at lest one compound selected from among thioethers and dialkyl disulfide compounds of formulas II and III (wherein R4 and R5 are each H or they are combined with each other to represent a group of formula IV which forms a five-membered ring; R6 and R8 are each 8-28C alkyl; and R7 and R9 are each H or they are combined with each other to represent a group of formula V which forms a five-membered ring), e.g. distearyl disulfide, 0.01-1 pt.wt. heavy metal inactivator [e.g. oxalic acid bis(benzylidenehydrazide)] and 0.01-1 pt.wt. epoxy compound of an epoxy equivalent of 100-1000 (e.g. epoxidized soybean oil), and the mixture is melt- kneaded at 150-300 deg.C.

Description

[Detailed description of the invention] [Industrial application fields] FIELD OF THE INVENTION This invention relates to 11 flammable polyolefin compositions.

More specifically, the present invention relates to a flame-retardant polyolefin composition that is excellent in preventing oxidative deterioration of polyolefin in practical use.

[Prior Art] Generally, various halogen-based flame retardants are blended into polyolefins as a means of making them flame retardant, and this has been widely used in practice.

However, since flame-retardant polyolefin compositions containing halogen-based flame retardants generate harmful halogen-based gases when burned, non-halogen-based flame retardants have recently been in demand as flame retardants. Among various non-halogen flame retardants, inorganic flame retardants that do not generate harmful combustion gases, especially magnesium hydroxide, have a high dehydration decomposition temperature.
It is also widely used in practical use because of its excellent smoke suppression effect during combustion. Furthermore, polyolefins, particularly propylene-based polymers, have a disadvantage in that they are susceptible to thermal oxidative deterioration during molding and practical use because they contain jI tertiary carbon that is susceptible to oxidation.

For this reason, various antioxidants have been widely used for the purpose of preventing thermal oxidative deterioration.

Molded products made from flame-retardant polyolefin compositions made by blending polyolefin with magnesium hydroxide and various antioxidants can be used in applications that come into contact with heavy metals such as copper, brass, iron, and nickel. be. However, since polyolefins undergo catalytic oxidative deterioration due to heavy metal ions contained in the various heavy metals mentioned above, molded products using the above-mentioned flame-retardant polyolefin compositions have poor Wt oxidative deterioration resistance (hereinafter referred to as resistance) upon contact with heavy metals. It has the disadvantage that the metallurgical properties (referred to as heavy metal properties) are significantly reduced.

For this reason, in order to improve the heavy metal resistance of molded products using flame-retardant polyolefin compositions containing magnesium hydroxide, magnesium hydroxide, phenolic antioxidants, and sulfur-based antioxidants have been added to polyolefins. A composition containing a copper inhibitor and a copper damage inhibitor (Japanese Patent Application Laid-Open No. 52-1123
8 and JP-A No. 63-56544 II), compositions containing magnesium hydroxide and epoxy compounds in polyolefins (JP-A No. 59-2193,12, JP-A No. 63-137963, JP-A-63-137963, Kaisho 63-1
No. 59473 and Japanese Unexamined Patent Application Publication No. 189462/1989 [) have been proposed.

However, in recent years, requirements for flame retardancy have become increasingly strict in applications such as electrical and electronic parts or automobile parts, and as molded products obtained from flame-retardant polyolefin compositions have diversified applications and become larger in size. and the conditions of use of the molded product in practical use (Pt heavy metal properties, electrical insulation, etc.)
The requirements for this are also becoming stricter. That is, there is a need to develop a W flammable polyolefin composition that has better resistance to heavy metals than ever before. In order to solve these problems, the above-mentioned Japanese Patent Application Laid-Open No. 52-11 contains magnesium hydroxide.
No. 238, JP-A-63-56544, JP-A-59-219352, JP-A-63-. 13796
The R-flammable polyolefin compositions proposed in Publication No. 3, JP-A-63-159473, and JP-A-63-189462 are still not fully satisfactory in terms of heavy metal resistance.

For this reason, the present inventor first prepared a flame-retardant polyolefin composition in which specific amounts of magnesium hydroxide, a specific phenol compound, a specific thioether compound, a heavy metal deactivator, and an epoxy compound are blended into polyolefin. (Japanese Patent Application No. 1-35792 and Patent Application No. 1-62845).

[Problem to be Solved by the Invention] The present inventor has disclosed the following patent application in Japanese Patent Application No. 1-35792 and Japanese Patent Application No. 1-35792
Unsatisfied with the flame-retardant polyolefin composition proposed in No. 62845, they conducted further research.

As a result, a flame retardant composition consisting of a polyolefin and magnesium hydroxide was added with a phenolic compound represented by the following formula [I], one or two selected from the following 1 to 3.
It was discovered that a flame-retardant polyolefin composition with improved heavy metal resistance can be obtained by blending specific amounts of at least one compound, a heavy metal deactivator, and an epoxy compound, and based on this knowledge, the present invention was developed. completed.

■Thioether compounds represented by the following general formula [■]■Thioether compounds represented by the following general formula [II[] (wherein R4 is an alkyl group having 1 to 8 carbon atoms, R
2 is hydrogen or an alkyl group having 1 to 8 carbon atoms, R3 is an alkylene group having 2 to 4 carbon atoms, R4 is an alkyl group having 228 carbon atoms, R7 and Ro are an alkylene group having 2 or 3 carbon atoms, R16 and R7 are hydrogen or >CH-RoSR8 group in which both form a 5-membered ring, n
represents O or 1, respectively) As is clear from the above description, the purpose of the present invention is to provide a flame-retardant polyolefin composition that has excellent heavy metal resistance when molded into a molded product. be.

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

(1) Magnesium hydroxide 30-70% in polyolefin
A phenolic compound represented by the following general formula [I] (hereinafter referred to as compound A), one or two selected from the following 1 to 3, to 100 parts by weight of the composition containing 1% by weight.
compound (hereinafter referred to as compound B), a heavy metal deactivator, and an epoxy compound, each in an amount of 0.01 to 1
1 to 1 part by weight of a flame retardant polyolefin composition.

■Thioether compounds represented by the following general formula [II] ■Thioether compounds represented by the following general formula [m] ■Dialkyl disulfide compounds (wherein R4 is an alkyl group having 1 to 8 carbon atoms, R
2 is hydrogen or an alkyl group having 1 to 8 carbon atoms, R3 is an alkylene group having 2 to 4 carbon atoms, R and 28 are an alkyl group, R7 and R9 are alkylene groups having 2 or 3 carbon atoms, R2 , and R2, are hydrogen or both are 5
>CH-Re 5-Re group forming a membered ring, n represents O or 1, respectively) (2) Composition 1 in which 30 to 70% by weight of magnesium hydroxide is blended with polyolefin
A flame-retardant polyolefin composition containing 0.01 to 1 part by weight of Compound A, Compound B, a heavy metal deactivator, and an epoxy compound, and 0.5 to 5 parts by weight of a fatty acid, based on 0.00 parts by weight. .

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, or two or more of these. Crystalline, low crystallinity or non-crystalline solid copolymers or crystalline block copolymers of α-olefins, amorphous ethylene-propylene-nonconjugated diene ternary copolymers, and the above-mentioned α-olefins. Copolymers with vinyl acetate or acrylic esters, saponified products of said copolymers, copolymers of these α-olefins with unsaturated silane compounds, copolymers of these α-olefins with unsaturated carboxylic acids or their anhydrides. Copolymers, reaction products of the copolymers and metal ion compounds, crystalline homopolymers of the above-mentioned α-olefins, crystalline, low-crystalline, non-quality random copolymers or crystalline block copolymers Modified polyolefin obtained by modifying a combined or amorphous ethylene-propylene-nonconjugated diene ternary copolymer with an unsaturated carboxylic acid or its derivative, a crystalline homopolymer of the above-mentioned α-olefin, crystallinity, low crystallinity, Examples include silane-modified polyolefins obtained by modifying non-quality random copolymers, crystalline block copolymers, or amorphous ethylene-propylene-nonconjugated diene ternary copolymers with unsaturated silane compounds. It is natural to use a single polyolefin, but it is also possible to use a mixture of two or more polyolefins. Additionally, various synthetic rubbers such as polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber,
(styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (For example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, fluororesin, petroleum resin (for example, C5 petroleum resin, hydrogenated C5
petroleum resin, C0 petroleum resin, hydrogenated C0 petroleum resin, C
-C, copolymerized petroleum resin, hydrogenated C, -C, copolymerized petroleum resin, acid-modified C8 petroleum resin, etc.), DCPD resin (e.g., cyclopentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, Cyclopentadiene-C5 copolymerized petroleum resin, hydrogenated cyclopentadiene-C5 copolymerized petroleum resin, cyclopentadiene-〇〇 copolymerized petroleum resin, hydrogenated cyclopentadiene-C8 copolymerized petroleum resin, cyclopentadiene-C5 Softening point of -C, copolymerized petroleum resin, hydrogenated cyclopentadiene-C5-C, copolymerized petroleum resin, etc. 80-2
00° C. DCPD resin) etc.) can also be used in combination. Crystalline propylene homopolymer, crystalline propylene copolymer containing 70% by weight or more of a propylene component, including crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene- Particularly preferably used are butene-1 random copolymer, crystalline ethylene-propylene-butene-13-element copolymer, crystalline propylene-hexene-butene-13-element copolymer, and mixtures of two or more thereof.

As the magnesium hydroxide used in the present invention, plate-like and fibrous forms can be used without any restriction. The average particle size of the plate-like magnesium hydroxide is not particularly limited, but is usually 0.1μ to 10μ, preferably 0.2μ to 10μ.
2μ, most preferably 0.5μ to 1μ, and the fiber diameter of fibrous magnesium hydroxide is 0.1μ to 0.5μ
, the length is preferably 5μ to 20μ. These magnesium hydroxides can also be used with surface treatment agents such as metal soaps, higher fatty acid esters, higher alcohols, higher fatty acid monoamides, higher fatty acid bisamides, higher aliphatic phosphate metal salts, silane coupling agents, titanate camping agents, and boron. If the surface is treated in advance with a known surface treatment agent such as a type coupling agent, an aluminate type coupling agent, or a zircoaluminate type coupling agent, the compatibility and dispersibility of the magnesium hydroxide and the polyolefin will be improved. This improves the mechanical strength of the molded product.
It is preferable to use magnesium hydroxide whose surface has been treated with a surface treatment agent.These magnesium hydroxides can be used alone, but two or more types of magnesium hydroxide can also be used in combination. The blending ratio of the magnesium hydroxide is 30 to 70% by weight, preferably 50 to 65% by weight, based on the composition consisting of polyolefin and magnesium hydroxide.
Weight%. If the amount is less than 30% by weight, the resulting molded product will have insufficient flame retardancy, and if it exceeds 70% by weight, the molding processability will be difficult and the mechanical strength of the resulting molded product will be reduced, which is not practical.

Compound A used in the present invention is 1,3,2,4-
Bis(3-methyl-4-hydroxybenzylidene)sorbitol, 1,3,2,4-bis(3-t-butyl-4
-hydroxybenzylidene) sorbitol, 1,3,2
・4-bis(3-methyl-5-t-butyl-4-hydroxybenzylidene) sorbitol, 1,3,2,4-bis(3-ethyl-5-t-butyl-4-hydroxybenzylidene) sorbitol, 1・3,2・4-screw (3,
5-di-butyl-4-hydroxybenzylidene) sorbitol, 1,3,2,4-bis(3,5-di-t-
amyl-4-hydroxybenzylidene) sorbitol,
1, 3, 2, 4-bis (3, 5-gee, one octyl-4)
-hydroxybenzylidene) sorbitol, 1.3.2
・4-His[3-(3-t-butyl-4-hydroxyphenyl)propylidenecotrubitol, 1.3,2.4
-bis[3-(3-t-amyl-4-hydroxyphenyl)propylidene turbitol, 1,3,2,4-bis[3-(3-t-octyl-4-hydroxyphenyl)propylidenecot] Rubitol, 1,3,2,4-bis(3-(3-methyl-4-hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1,3,2,
4-bis[3-(3-methyl-4-hydroxy-5-t
-amyl phenyl) propylidenecotrubitol, 1.
3,2,4-bis(3-(3-methyl-4-hydroxy-5-t-octylphenyl)propylidenecotrubitol, 1,3,2,4-bis[3-(3-ethyl-4 −
Hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1,3,2,4-bis(3-(3-i-
propyl-4-hydroxy-5-t-butylphenyl)
Propylidenecotrubitol, 1,3,2,4-bis[
3-(3-i-butyl-4-hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1,3,2
・4-bis[3-(3-s-butyl-4-hydroxy-
5-tert-butylphenyl)propylideneco turbitol, l-3,2-4-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propylideneco turbitol, 1.3 ,2,4-bis[3-(3-t-butyl-
4-Hydroxy-5-t-amylphenyl) propylidene Sorbitol, 1,3,2,4-bis[3-(3
-t-butyl-4-hydroxy-5-t-octylphenyl)propylidenecoturbitol, 1,3,2,4-
Bis[3-(3,5-di-t-amyl-4-hydroxyphenyl)propylidenecotrubitol, 1.3,2.
4-bis[3-(3,5-di-t-octyl-4-hydroxyphenyl)propylidenecoturbitol, 1.3
．． 2,4-bis[3-(2-methyl-4-hydroxy-
5-tert-butylphenyl)propylidenecoturbitol, 1,3.2,4-bis[3-(3-methyl-4-hydroxy-5-t-amylphenyl)propylidenecoturbitol, 1,3 .2,4-bis[3-(2,5-di-
t-Butyl-4-hydroxyphenyl)propylidenecotrubitol, 1.3.2.4-bis[3-(3,5-
di-t-amyl-4-hydroxyphenyl)propylidenecotrubitol, l.3,2.4-bis[3-(2-
methyl-4-hydroxy-5-t-octylphenyl)
Propylidenecotrubitol, 1,3,2,4-bis[
3-(2-tert-butyl-4-hydroxy-5-methylphenyl)propylidenecoturbitol, ]・3,2・4
-bis[3-(3-t-butyl-4-hydroxyphenyl)butylidenecoturbitol, 1,3,2,4-bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl) ) Butylidenecotrubitol, 1, 3, 2, 4
-bis[3-(3,5-di-butyl-4-hydroxyphenyl)butylidenecoturbitol, 1.3,2.
4-bis[3-(3-methyl-4-hydroxy-5-t
-amyl phenyl) butylidene trubitol, l.3
,2,4-bis[3-(3,5-di-amyl-4-
Hydroxyphenyl) butylidene trubitol, 1.
3,2,4-bis[3-(3-methyl-4-hydroxy-5-t-octylphenyl)butylidenecotrubitol, l.3,2,4-bis[3-(3,5-di -t-octyl-4-hydroxyphenyl)butylidenecoturbitol, 1,3,2,4-bis[2-methyl-3-(3
-t-butyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4-bis[2-methyl-
3-(3-methyl-4-hydroxy-5-t-butylphenyl)propylidenecoturbitol, 1.3,2.4
-bis[2-methyl-3-(3,5-di-butyl-4-hydroxyphenyl)propylidenecosorbitol, 1,3,2,4-bis[2-methyl-3-(3-methyl-4 -Hydroxy-5-t-amylphenyl) propylideneco trubitol, 1,3,2,4-bis[2-methyl-3-(3,5-di-amylphenyl)propylideneco trubitol Thor, 1.3.2.
4-bis[2-methyl-3-(3-methyl-4-hydroxy-5-t-octylphenyl)propylidenecotrubitol, 1,3,2,4-bis[2-methyl-3-(
3,5-di-t-octyl-4-hydroxyphenyl)
Propylidenecotrubitol, 1,3゜2,4-bis[
2,2-dimethyl-3-(3-t-butyl-4-hydroxyphenyl)propylidenecotrubitol, 1.3,
2,4-bis[2,2-dimethyl-3-(3-t-amyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4-bis[2,2-dimethyl-3-
(3-t-octyl-4-hydroxyphenyl)propylidenecotrubitol, 1.3.2.4-bis[2,2
-dimethyl-3-(3-methyl-4-hydroxy-5-
t-butylphenyl)propylidenecotrubitol, 1
・3,2,4-bis[2,2-dimethyl-3-(3-methyl-4-hydroxy-5-t-amylphenyl)propylidenecotrubitol, 1,3,2,4-bis[2 ，
2-dimethyl-3-(3-methyl-4-hydroxy-5
-t-octylphenyl)propylidenecotrubitol 1,3,2,4-bis[2,2-dimethyl-3-(3-
Ethyl-4-hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1,3,2,4-bis[2
, 2-dimethyl-3-(3-i-propyl-4-hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1,3,2,4-bis[2.

2-dimethyl-3-(3-i-butyl-4-hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1,3,2,4-bis[2,2-dimethyl-3-
(3-s-butyl-4-hydroxy-5-t-butylphenyl)propylidenecoturbitol, 1.3.2.
4-bis[2,2-dimethyl-3-(3,5-di-butyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4-bis[2,2-dimethyl-
3-(3-t-butyl-4-hydroxy-5-t-amylphenyl)propylidenecotrubitol, 1.3,
2,4-bis[2,2-dimethyl-3-(3-t-butyl-4-hydroxy-5-t-octylphenyl)propylidenecotrubitol, 1,3,2,4-bis[2
,2-dimethyl-3-(3.5-di-t-amyl-4
-hydroxyphenyl)propylidenecotrubitol,
1,3,2,4-bis[2,2-dimethyl-3-(3,
5-di-t-octyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4-bis[2.
2-dimethyl-3-(2-methyl-4-hydroxy-5
-t-butylphenyl)propylidenecotrubitol,
1,3,2,4-bis[2,2-dimethyl-3-(3-
Methyl-4-hydroxy-5-t-amylphenyl)propylidenecotrubitol, 1,3,2,4-bis[2
,2-dimethyl-3-(2.5-di-t-butyl-4-
hydroxyphenyl) propylidenecotrubitol, 1
・3,2,4-bis[2,2-dimethyl-3-(3,5
-diamyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4-bis[2,2-
dimethyl-3-(2-methyl-4-hydroxy-5-t
-octylphenyl)propylidenecotrubitol, 1
・3,2,4-bis[2,2-dimethyl-3- (2-
t-Butyl-4-hydroxy-5-methylphenyl)propylidenecotrubitol, 1,3,2,4-bis[4
- (3-t-butyl-4-hydroxyphenyl)butylidenecotrubitol, 1.3.2.4-bis[4-
(3-Methyl-4-hydroxy-5-t-butylphenyl)butylidene trubitol, 1.3.2.4-bis[4-(3.5-di-butyl-4-hydroxyphenyl)butylidene Cotrubitol, 1, 3, 2, 4-
bis[4-(3-methyl-4-hydroxy-5-t-
amyl phenyl)butylidenecotrubitol, 1.3,
2,4-bis[4-(3,,1-di-t-amyl-4-hydroxyphenyl)butylidenecotrubitol, 1,3.2,4-bis[4-(3-methyl-4- Hydroxy-5-t-octylphenyl)butylidenecoturbitol, 1,3,2,4-bis(4-(3.5-di-octyl-4-hydroxyphenyl)butylidenecoturbitol, 1,3 ,2・4,5・6-tris(3
-methyl-4-hydroxybenzylidene) sorbitol, 1,3,2,4,5,6-tris(3-t-butyl-
4-hydroxybenzylidene) sorbitol, 1.3,
2,4,5,6-tris(3-methyl-5-t-butyl-4-hydroxybenzylidene)sorbitol, 1,3
, 2.4,5.6-tris(3-ethyl-5-t-butyl-4-hydroxybenzylidene) sorbitol, 1.
3.

2,4,5,6-tris (3,5-di-L-butyl 4
-hydroxybenzylidene) sorbitol, 1,3,2
・4,5,6-tris(3.5-di-t-amyl-4-
hydroxybenzylidene) sorbitol, 1, 3, 2,
4,5・6-tris (3,5-Gt・octyl 4
-hydroxybenzylidene) sorbitol, 1,3,2
・4,5・6-Doris:3- (3-t-butyl-4-
hydroxyphenyl) propylidenecotrubitol, 1
・3゜2.4,5.6-Tris[3-(3-t-amyl-4-hydroxyphenyl)propylidenecoturbitol, 1.3,2.4゜5.6-Tris[3-( 3-t-
Octyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4,5,6-tris[3-(
3-Methyl-4-hydroxy-5-t-butylphenyl)propylidenecoturbitol, l・3゜2・4,5・
6-tris[3-(3-methyl-4-hydroxy-5-
t-Amyl phenyl) propylidenecotrubitol, 1
・3,2.4,5.6-Tris[3-(3-methyl-4
-Hydroxy-5-t-octylphenyl)propylidenecotrubitol, 1,3,2,4,5,6-tris[
3-(3-ethyl-4-hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1.3,2.4
, 5,6-Tris[3-(3-i-propyl-4-hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1,3,2,4,5,6-Tris[3-( 3
-i-butyl-4-hydroxy-5-t-butylphenyl)propylidenecoturbitol, 1, 3, 2, 4, 5
・6-Tris[3-(3-s-butyl-4-hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1.3,2.4°5.6-Tris[3-(3, 5-
di-t-butyl-4-hydroxyphenyl)propylidenecotrubitol, l.3,2.4.5.6-tris[
3-(3-t-butyl-4-hydroxy-5-t-amylphenyl)propylidenecotrubitol, 1,3,2
・4,5,6-Tris[3-(3-t-butyl-4-hydroxy-5-t-octylphenyl)propylidenecoturbitol, 1,3,2,4,5,6-Tris E3
- (3,5-di-t-amyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4,5
・6-tris [3-(3,5-gee and one octyl 4
-hydroxyphenyl)propylidenecotrubitol,
1,3,2,4,5,6-tris[3-(2-methyl-
4-Hydroxy-5-t-butylphenyl)propylidenecotrubitol, 1,3,2,4,5,6-tris[
3-(3-methyl-4-hydroxy-5-t-amylphenyl)propylidenecoturbitol, 1.3,2.4
,5,6-tris[3-(2,5-di-t-butyl-4
-hydroxyphenyl)propylidenecotrubitol,
l・3,2・4,5・6-tris[3(3,5-di-t
-amyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4,5,6-tris[3-(
2-Methyl-4-hydroxy-5-t-octylphenyl)propylidenecotrubitol, 1, 3, 2, 4, 5
・6-tris[3-(2-t-butyl-4-hydroxy-5-methylphenyl)propylidenecoturbitol,
1.3,2.4.5.6-Tris[3-(3-t-butyl-4-hydroxyphenyl)butylidenecotrubitol, l.3,2.4,5.6-Tris[3- (3-Methyl-4-hydroxy-5-t-butylphenyl)butylidenecotrubitol, 1,3,2,4゜5,6-tris[3-(3,5-di-t-butyl-4 -Hydroxyphenyl) butylidene trubitol, 1, 3, 2, 4°5
・6-Tris[3-(3-methyl-4-hydroxy-5
-t-amylphenyl)butylidenecotrubitol, 1
・3゜2・4,5・6-tris[3-(3,5-di-t
-amyl-4-hydroxyphenyl)butylidenecotrubitol, 1.3゜2.4,5.6-tris[3-(3
-Methyl-4-hydroxy-5-t-octylphenyl)butylidenecotrubitol, 1, 3, 2, 4, 5, 6
-TrisC3~(3,5-di-1-.1cutyl-4-hydroxyphenyl)butylidenecotrubitol, 1.3
,2,4,5,6-tris[2-methyl-3-(3-t
-butyl-4-hydroxyphenyl) propylidenecotrubitol, 1,3,2,4,5,6-tris[2-methyl-3-(3-methyl-4-hydroxy-5-t-butylphenyl) Propylidenecotrubitol, 1.3,
2,4,5,6-tris[2-methyl-3-(3,5-
Di-butyl-4-hydroxyphenyl) propylidene turbitol, 1,3,2,4,5,6-tris[
2-Methyl-3-(3-methyl-4-hydroxy-5-
t-Amyl phenyl) propylidenecotrubitol, 1
3.2.4,5.6-tris[2-methyl-3-(3,
5-diamyl-4-hydroxyphenyl)propylidenecotrubitol, octylphenyl) propylidenecotrubitol, 1,3,2,4,5,6-tris[2-methyl-
3-(3,5-di-t-octyl-4-hydroxyphenyl)propylidenecotrubitol, 1.3.2.4°5.6-tris[2,2-dimethyl-3-(3-t -butyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4,5,6-tris[2,2-dimethyl-3-(3-t-amyl-4-hydroxyphenyl)propylidene Cotrubitol, 1, 3, 2, 4, 5
・6-Tris[2,2-dimethyl-3-(3-t-octyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4,5,6-tris[2,2-dimethyl -3-(3-methyl-4-hydroxy-5-t-
butylphenyl) propylidenecotrubitol, 1.3
,2,4゜5,6-tris[2,2-dimethyl-3-(
3-Methyl-4-hydroxy-5-t-amylphenyl)propylidenecotrubitol, 1, 3, 2, 4, 5,
6-tris[2,2-dimethyl-3-(3-methyl-4
-Hydroxy-5-t-octylphenyl)propylideneco Sorbitol, 1,3,2,4,5,6-tris[2,2-dimethyl-3-(3-ethyl-4-hydroxy-5-1-butylphenyl) ) Flopylideneco trubitol, 1,3,2,4,5,6-tris[2,2-dimethyl-3-(3-i-propyl-4-hydroxyl 5-
t-butylphenyl) floylidenecotrubitol, 1
・3,2.4,5.6-tris[2゜2-dimethyl-3
-(3-i-butyl-4-hydroxy-5-savetylphenyl)propylidenecoturbitol, 1.3.2.
4,5,6-tris[2,2-dimethyl-3-(3-s
-butyl-4-hydroxy-3-t~butylphenyl)
Flobilidenko trubitol, 1, 3, 2, 4, 5, 6
-tris[2,2-dimethyl-3-(3,5-di-butyl-4-hydroxyphenyl)propylidenecotrubitol, 1,3,2,4,5,6-tris[2,2-
Dimethyl-3-(3-t-butyl-4-hydroxy-5
-t-amylphenyl)propylidenecotrubitol,
1,3,2,4,5,6-tris[2,2-dimethyl-
3-(3-t-butyl-4-hydroxy-5-t-octylphenyl)propylidenecotrubitol, 1.3,
2,4,5,6-tris[2,2-dimethyl-3-(3
,5-di-amy-4-hydroxyphenyl)propylidenecotrubitol, 1.3.2.4,5.6-tris[2,2-dimethyl-3-(3,5-di-t-octyl) -4-hydroxyphenyl) floylideneco trubitol, 1,3,2,4,5,6-tris[2,2-dimethyl-3-(2-methyl-4-hydroxy-5-t-
butylphenyl) floylideneco trubitol, 1.3
,2,4,5,6-tris[2,2-dimethyl-3-(
3-Methyl-4-hydroxy-5-t-amylphenyl) floylidenecotrubitol, 1, 3, 2, 4, 5,
6-Tris[2,2-dimethyl-3-(2,5-di-butyl-4-hydroxyphenyl)fluorylidenecotrubitol, 1,3,2,4,5,6-tris[2,2
-dimethyl-3-(3,5-di-t-amyl-4-hydroxyphenyl)phlobylidenecotrubitol, 1.3
,2,4,5,6-tris[2,2-dimethyl-3-(
2-Methyl-4-hydroxy-5-t-octylphenyl)propylidenecotrubitol, 1, 3, 2, 4, 5
・6-Tris[2,2-dimethyl-3-(2-t-butyl-4-hydroxy-5-methylphenyl)phlobylidenecoturbitol, 1.3,2.4,5.6-TrisC
4-(3-t-butyl-4-hydroxyphenyl)butylidenecotrubitol, 1,3,2,4,5,6-tris[4-(3-methyl-4-hydroxy-5-t-butyl) phenyl)butylidenecotrubitol, 1, 3, 2,
4,5,6-tris[4-(3,5-di-t-butyl-
4-hydroxyphenyl) butylidene trubitol,
1,3,2,4,5,6-tris[4-(3-methyl-
4-Hydroxy-5-t-amylphenyl)butylidenecotrubitol, 1,3,2,4,5,6-tris[4
-(3,5-di-t-amyl-4-hydroxyphenyl)butylidenecotrubitol, 1, 3, 2, 4, 5, 6
-tris[4-(3-methyl-4-hydroxy-5-t
-octylphenyl)butylidenecotrubitol and l.3゜2.4,5.6-tris[4-(3,5-di-
Examples include 1,3,2,4-bis[2-(3-methyl-4-hydroxy-5-t-butylphenyl)furylidene], and 1,3,2,4-bis[2-(3-methyl-4-hydroxy-5-t-butylphenyl)fluorylidene]. Cotrubitol, 1, 3, 2
・4-bis[2-(3,5-di-butyl-4-hydroxyphenyl)fluorylidenecotrubitol, 1.
3.2,4-bis[2,2-dimethyl-3-(3-methyl-4-hydroxy-5-t-butylphenyl)propylidenecoturbitol, 1,3,2,4-bis[2, 2
-dimethyl-3-(3,5-di-butyl-4-hydroxyphenyl)fluorylidenecotrubitol, 1.3
, 2.4,5.6-tris[2-(3-methyl-4-hydroxy-5-t-butylphenyl)propylidenecoturbitol, l.3,2.4,5.6-tris[2 −(
3,5-di-t-butyl-4-hydroxyphenyl)propylidenecoturbitol, 1,3,2,4゜5,6-
Tris[2,2-dimethyl-3-(3-methyl-4-hydroxy-5-t-butylphenyl)propylidenecoturbitol and 1,3,2,4,5,6-tris[2
,2-dimethyl-3-(3,5-di-butyl-4-
Hydroxyphenyl) propylidene turbitol is preferred, and the use of these compounds A alone is of interest; 2.
More than one type of compound A can also be used in combination. The compound A
The blending ratio is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, per 100 parts by weight of a composition in which 0 to 0% by weight of magnesium hydroxide is blended with polyolefin. If the amount is less than 0.01 part by weight, the effect of improving heavy metal resistance will not be sufficiently exhibited, and although it is possible to exceed 1 part by weight, it is not practical as no further improvement in heavy metal resistance can be expected. Not only that, but it is also uneconomical.

Compound B used in the present invention is 3,9-bis(2
-(2-ethylhexyl)thioethyl) -2,4,8
゜10-Tetraoxaspiro [5,5 condecane, 3
,9-bis(2-n-octylthioethyl) -2,4
, 8,10-tetraoxaspiro[5,5]undecane, 3,9-bis(2-nonylthioethyl) -2,4,
8,10-tetraoxaspiro[5,5]undecane,
3,9-bis(2-decylthioethyl)-2,4,8,
10-tetraoxaspiro[5,5]undecane, 3,
9-bis(2-laurylthioethyl) -2,4,8,
10-tetraoxaspiro[5,5]undecane, 3
．． 9-bis(2-tridecylthioethyl) -2,4,
8,10-tetraoxaspiro[5,5] undecane, 3,9-bis(2-myristylthioethyl) -2,
4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis(2-/<lumitylthioethyl) -
2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis(2-stearylthioethyl)-
2,4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis(2-tocosylthioethyl)-2
, 4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis(2-tetracosylthioethyl)
-2,4,8゜10-tetraoxaspiro[5,5 undecane, 3,9-bis(2-bentacosylthioethyl) -2,4,8,10-tetraoxaspiro[5
,5] undecane, 3,9-bis(2-ophtacosylthioethyl)-2,4,8,10-tetraoxaspiro[
5,5] undecane, 3,9-bis(1-methyl-2-
(2-ethylhexyl)thioethyl) -2,4,8゜O-tetraoxaspiro[5,5oundecane, 3,
9-bis(1-methyl-2-n-octylthioethyl)
-2,4゜8.10-tetraoxaspiro[5,5 undecane 3゜9-bis(1-methyl-2-nonylthioethyl) -2,4,8゜10-tetraoxaspiro[5,5] Undecane, 3,9-bis(1-methyl-2
-decylthioethyl) -2,4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis(1-
Methyl-2-laurylthioethyl) -2,4,8,1
0-tetraoxaspiro[5,51 undecane, 3,9
-bis(1-methyl-2-tridecylthioethyl) -
2,4,8゜10-tetraoxaspiro[5,5]undecane, 3,9-bis(l-methyl-2-myristylthioethyl) -2,4゜8.10-tetraoxaspiro[5,5] ] Undecane, 3゜9-bis(1-methyl-2
-balmitylthioethyl)-2゜4.8.10-tetraoxaspiro[5,5-oundecane, 3.9-bis(1
-methyl-2-stearylthioethyl)-2,4,8,
10-tetraoxaspiro[5,5]undecane, 3.
9-bis(1-methyl-2-tocosylthioethyl)-2
゜4.8.10-Tetraoxaspiro[5,5oundecane, 3,9-bis(1-methyl-2-tetracosylthioethyl)-2,4,8,10-tetraoxaspiro[
5,5] undecane, 3,9-bis(1-methyl-2-
hexacosylthioethyl)-2,4,li, 10-tetraoxaspiro[5,51 undecane, 3,9-bis(
1-methyl-2-ophtacosylthioethyl)-2,4,
8,10-tetraoxaspiro[5,5]undecane,
3.9-bis(2-(2-ethylhexyl)thiopropyl)-2,4,8,10-tetraoxaspiro[5,5
] Undecane, 3,9-bis(2-n-octylthiopropyl) -2,4,8°10-tetraoxaspiro[
5,5-oundecane, 3,9-bis(2-nonylthiopropyl)-2,4,8,10-tetraoxaspiro[5
,5-oundecane, 3,9-bis(2-decylthiopropyl)-2,4,8,10-tetraoxaspiroC5
,5] undecane, 3,9-bis(2-laurylthiopropyl)-2,4,8,10-tetraoxaspiro[
5,5]undecane, 3,9-bis(2-tridecylthiopropyl)-2,4,8,10-tetraoxaspiro[5,5undecane, 3,9-bis(2-myristylthiopropyl)- 2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis(2-palmitylthioprobyl) -2,4,8°10-tetraoxaspiro[5,5]undecane , 3,9-bis(2-stearylthiopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis(2
-tocosylthiopropyl) -2,4,il! , 10-
Tetraoxaspiro[5,5] undecane, 3,9-
Bis(2-tetracosylthiopropyl) -2,4,
8,10-tetraoxashyo[5,5]undecane, 3,9-bis(2-hexacosylthioprobil)
-2,4,8,10-tetraoxasbiro[5,5]
Undecane, 3,9-bis(2-ophtacosylthiopropyl)-2,4,8,10-tetraoxaspiro[5°5]undecane, 3,9-bis(3-(2-ethylhexyl)thiopropyl)- 2,4,8,10-tetraoxaspiro[5,5-undecane, 3,9-bis(3-
n-octylthiopropyl)-2,4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis(
3-nonylthiopropyl)-2,4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis(3
-decylthiopropyl) -2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis(3
-laurylthiopropyl) -2,4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis(
3-tridecylthiopropyl) -2,4,8,10
-tetraoxaspiro[5,5]undecane, 3,9-
Bis(3-myristylthiopropyl)-2,4,8,1
0-Tetraoxaspiro[5°5]undecane, 3,9
-bis(3-palmitylthiopropyl)-2,4,8,
10-tetraoxaspiro[5,5]undecane, 3,
9-bis(3-stearylthiopropyl)-2,4,8
, 10-tetraoxaspiro [5,5 condecane, 3
．． 9-bis(3-tocosylthiopropyl) -2,4,
8,10-tetraoxaspiro [5,5 condecane,
3.9-bis(3-tetracosylthioprobyl)-2
, 4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis(3-hexacosylthiopropyl)
-2,4,8,10-tetraoxaspiro[5,5]
Undecane, 3,9-bis(3-ophtacosylthioprobil)-2,4,8,10-tetraoxaspiro[
5,5 undecane, 1,3,2,4-bis(3-(2
-ethylhexyl)thiopropylidene)sorbitol,
1,3,2,4-bis(3-n-octylthiopropylidene) sorbitol, 1,3,2,4-bis(3-nonylthiopropylidene) sorbitol, 1,3,2,4-
Bis(3-decylthiopropylidene) sorbitol, 1
・3,2,4-bis(3-laurylthiopropylidene)
Sorbitol, 1,3,2,4-bis(3-tridecylthiopropylidene) sorbitol, 1,3,2,4-bis(3-myristylthiopropylidene) sorbitol,
1,3,2,4-bis(3-palmitylthiopropylidene) sorbitol, 1,3,2,4-bis(3-stearylthiopropylidene) sorbitol, 1,3,2,4
-bis(3-tocosylthiopropylidene) sorbitol, 1,3,2,4-his(3-tetracosylthiopropylidene) sorbitol, 1,3,2,4-bis(3-hexacosylthiopropylidene) ) Sorbitol, 1・3,
2,4-bis(3-ophtacosylthiopropylidene)sorbitol, l.3.2.4-bis(2-methyl-3-
(2-ethylhexyl)thiopropylidene) sorbitol, 1.3.2.4-bis(2-methyl-3-n-octylthiopropylidene) sorbitol, 1.3.2.4
-bis(2-methyl-3-nonylthiopropylidene)sorbitol, 1,3,2,4-bis(2-methyl-3-
decylthiopropylidene) sorbitol, 1, 3, 2,
4-bis(2-methyl-3-laurylthiopropylidene) sorbitol, 1.3.2.4-bis(2-methyl-
3-tridecylthiopropylidene) sorbitol, 1.
3,2,4-bis(2-methyl-3-myristylthiopropylidene) sorbitol, 1,3,2,4-bis(2
-Methyl-3-palmitylthiopropylidene) sorbitol, 1,3,2,4-bis(2-methyl-3-stearylthiopropylidene) sorbitol, 1,3,2,4
-bis(2-methyl-3-tocosylthiopropylidene)
Sorbitol, 3,2,4-bis(2-methyl-3
-tetracosylthiopropylidene) sorbitol, 1.
3,2,4-bis(2-methyl-3-hexacosylthiopropylidene) sorbitol, 1,3,2,4-bis(
2-Methyl-3-ophtacosylthiopropylidene) sorbitol, 1,3,2,4-bis(3-(2-ethylhexyl)thiobutylidene) sorbitol, 1,3,2,
4-bis(3-n-octylthiobutylidene) sorbitol, 1,3,2,4-bis(3-nonylthiobutylidene) sorbitol, 1,3,2,4-bis(3-decylthiobutylidene) ) Sorbitol, 1,3,2,4-bis(3-laurylthiobutylidene) sorbitol, 1,3
, 2,4-bis(3-tridecylthiobutylidene) sorbitol, 1,3,2,4-bis(3-myristylthiobutylidene) sorbitol, 1,3,2,4-bis(3
-palmitylthiobutylidene) sorbitol, 1.3,
2,4-bis(3-stearylthiobutylidene) sorbitol, 1,3,2,4-bis(3-tocosylthiobutylidene) sorbitol, 1,3,2,4-bis(3-tetracosylthiobutylidene) sorbitol Lyden) Sorbitol, 1, 3, 2
・4-bis(3-hexacosylthiobutylidene) sorbitol, 1,3,2,4-bis(3-ophtacosylthiobutylidene) sorbitol, 1,3,2,4-bis(4
-(2-ethylhexyl)thiobutylidene) sorbitol, 1,3,2,4-bis(4-n-octylthiobutylidene) sorbitol, 1,3,2,4-bis(4-nonylthiobutylidene) sorbitol, 1・3,2・4−
Bis(4-decylthiobutylidene) sorbitol, 1.
3゜2.4-bis(4-laurylthiobutylidene) sorbitol, l.3,2.4-bis(4-tridecylthiobutylidene) sorbitol, l.3,2.4-bis(4
- myristylthiobutylidene) sorbitol, 1.3.
2,4-bis(4-palmitylthiobutylidene) sorbitol, 1,3,2,4-bis(4-stearylthiobutylidene) sorbitol, 1,3,2,4-bis(4-
tocosylthiobutylidene) sorbitol, 1, 3, 2,
4-bis(4-tetracosylthiobutylidene) sorbitol, 1,3,2,4-bis(4-hexacylthiobutylidene) sorbitol, 1,3,2,4-bis(4-
(oftacosylthiobutylidene) sorbitol, l.3,
2,4,5,6-tris(3-(2-ethylhexyl)
thiopropylidene) sorbitol, 1, 3, 2, 4, 5
・6-Tris(3-n-octylthiopropylidene) sorbitol, l ・3,2.4,5.6-tris(3-nonylthiopropylidene) sorbitol, 1.3゜2.4
, 5,6-tris(3-decylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(3-laurylthiopropylidene) sorbitol, 1,3,2,4
,5,6-tris(3-tridecylthiopropylidene)
Sorbitol, 1, 3, 2, 4, 5, 6-tris (3-
myristylthiopropylidene) sorbitol, '1.3
, 2,4,5,6-tris(3-palmitylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(3-stearylthiopropylidene) sorbitol,
1, 3, 2, 4, 5, 6-tris (3-tocosylthiopropylidene) sorbitol, l, 3, 2, 4, 5, 6-
Tris(3-tetracosylthiopropylidene) sorbitol, 1.3,2.4,5.6-tris(3-hexacosylthiopropylidene) sorbitol, l.3,2.4
゜5,6-tris(3-ophtacosylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(2
-Methyl-3-(2-ethylhexyl)thiopropylidene)sorbitol, 1,3,2,4,5,6-tris
(2-methyl-3-n-octylthiopropylidene) sorbitol, 1.3,2.4゜5.6-tris(2-methyl-3-nonylthiopropylidene) sorbitol, 1
・3,2.4,5.6-tris(2-methyl-3-decylthiopropylidene) sorbitol, 1.3,2.4,
5,6-tris(2-methyl-3-laurylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(2-methyl-3-tridecylthiopropylidene) sorbitol, 1,3 , 2,4,5,6-tris(2-methyl-3-myristylthiopropylidene)sorbitol, 1,3,2,4,5,6-tris(2-methyl-3-
palmitylthiopropylidene) sorbitol, 1.3,
2,4,5,6-tris(2-methyl-3-stearylthiopropylidene) sorbitol, 1,3,2,4,5
・6-Tris(2-methyl-3-tocosylthiopropylidene) sorbitol, 1.3,2.4,5.6-tris(2-methyl-3-tetracosylthiopropylidene) sorbitol, 1.3, 2,4,5,6-tris(2-methyl-3-hexacosylthiopropylidene)sorbitol, 1,3.2,4,5,6-tris(2-methyl-3
-oftacosylthiopropylidene) sorbitol, 1.
3,2.4,5.6-tris(3-(2-ethylhexyl)thiobutylidene)sorbitol, 1.3,2.4,
5,6-tris (3-n-octylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (3-nonylthiobutylidene) sorbitol, 1,3,2,4,
5,6-tris (3-decylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (3-laurylthiobutylidene) sorbitol, 1,3,2,4,5
・6-tris(3-tridecylthiobutylidene) sorbitol, 1.3,2.4,5.6-tris(3-myristylthiobutylidene) sorbitol, 1.3,2.4,
5,6-tris (3-palmitylthiobutylidene) sorbitol, 1,3゜2,4,5,6-tris (3-stearylthiobutylidene) sorbitol, l,3,2,4
, 5,6-tris (3-tocosylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (3-tetracosylthiobutylidene) sorbitol, 1,3,2,
4,5,6-tris(3-hexacosylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris(3
-Ophtacosylthiobutylidene) sorbitol, 1.3
, 2, 4, 5, 6-tris (4- (2-ethylhexyl) thiobutylidene) sorbitol, 1, 3, 2, 4, 5
・6-tris(4-n-octylthiobutylidene) sorbitol, 1.3,2.4,5.6-tris(4-nonylthiobutylidene) sorbitol, 1.3,2.4,5
・6-Tris(4-decylthiobutylidene) sorbitol, 1.3,2.4,5.6-tris(4-laurylthiobutylidene) sorbitol, 1.3,2.4,5.6
- Tris(4-tridecylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris(4-myristylthiobutylidene) sorbitol, 1,3,2,4゜5.
6-tris(4-palmitylthiobutylidene) sorbitol, 1.3,2.4,5.6-tris(4-stearylthiobutylidene) sorbitol, 1.3,2.4,5
・6-Tris(4-tocosylthiobutylidene) sorbitol, 1.3,2.4,5.6-tris(4-tetracosylthiobutylidene) sorbitol, 1.3,2.4,
5,6-tris(4-hexacosylthiobutylidene) sorbitol, 1,3゜2,4,5,6-tris(4-ophtacosylthiobutylidene) sorbitol, dilauryl disulfide, similistyl disulfide, distearyl Examples include disulfide, didocosyl disulfide, ditetracosyl disulfide, dihexacosyl disulfide and dioctacosyl disulfide, particularly 3°9-bis(2-laurylthioethyl)-2,4, 8,
10-tetraoxaspiro[5,5]undecane, 3,
9-bis(2-myristylthioethyl) -2,4,8
, 10-tetraoxaspiro[5,5]undecane, 3
,9-bis(2-stearylthioethyl)-2,4,8
, 10-tetraoxaspiro[5,5]undecane, 1
・3,2,4-bis(3-laurylthiopropylidene)
Sorbitol, 1,3,2,4-bis(3-myristylthiopropylidene) sorbitol, 1,3,2,4-bis(3-stearylthiopropylidene) sorbitol,
1,3,2,4,5,6-tris(3-laurylthiopropylidene)sorbitol, 1,3,2,4,5,6-
Tris(3-myristylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(3-stearylthiopropylidene) sorbitol and distearyl disulfide are preferred; the use of these compounds B alone is of course In fact, two or more types of compounds B can also be used in combination. The blending ratio of the compound B is 100% of a composition in which 30 to 70% by weight of magnesium hydroxide is blended with polyolefin.
0.01 to 1 part by weight, preferably 0.0 part by weight
It is 5 to 0.5 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving heavy metal resistance will not be sufficiently exhibited;
Although it is possible to exceed more than 1 part by weight, it is not only impractical as no further improvement in heavy metal resistance can be expected, but is also uneconomical.

Heavy metal deactivators used in the present invention include benzotriazole, 2,4.6-triamino-1,3,5-
triazine, 3,9-bis[2-(3,5-diamino-
2,4,6-)riazaphenyl)ethyl]-2.4,8
．． Alkali metals of 10-tetraoxaspiro[5,5]undecane, ethylenediamine-tetraacetic acid, and ethylenediamine-tetraacetic acid@
(Li.

Na, K) salt, N,N'-disalicylidene-ethylenediamine, N,N'-disalicylidene-1,2-propylenediamine, N,N"-disalicylidene-N'-methyl-dipropylenetriamine, 3-salicyloyl amino −
1,2,4-) lyazole, decamethylene dicarboxylin acid-bis(N'-salicyloylhydrazide), nickel-bis(1-phenyl-3-methyl-4-
Decanoyl-5-virazolate), 2-ethoxy-2'
-ethyloxanilide, 5-t-butyl-2-ethoxy-2'-ethyloxanilide, N,N-diethyl-N
I, N+-diphenyloxamide, N,N'-diethyl-N,N'-diphenyloxamide, oxalic acid bis(benzylidene hydrazide), thiodipropionic acid bis(benzylidene hydrazide), isophthalic acid Acid-bis(2-phenoxypropionylhydrazide), Bis(salicyloylhydrazine), N-salicylidene-N'-salicyloylhydrazone, N,Nξbis[3-(3,5-di-monobutyl-4-hydroxy) phenyl)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-5ξt-
butylphenyl)-5-methylphenyl]-pentaerythritol-siphosphite, tetrakis[2-t-
Butyl-4-thio(2'-methyl-4'-hydroxy-
5'-t-butylphenyl)-5-methylphenyl]-
1,6-hexamethylene-bis(N-hydroxyethyl-N-methylsemicarbazide)-siphosphite, tetrakis[2-t-butyl-4-thio(2'-methyl-
4'-hydroxy-5'-L-butylphenyl)-5-
Methylphenyl-1,10-decamethylene-dicarboxylin-acindo-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis[2-t
-butyl-4-thio(2'-methyl-4ξhydroxy-
5'-t-butylphenyl)-5-methylphenyl-1.10-decamethylene-dicarboxylic acid-di-salicyloylhydrazide diphosphorite,
Tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5
-Methylphenylkodi(hydroxyethylcarbonyl)hydrazide-siphosphite, tetrakis[2-t
-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenylcoN, N'-bis(hydroxyethyl)oxamide-siphosphite, and N, N'-bis[2-[
Examples include 3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxy]ethylcoxamide, particularly oxalic acid bis(benzylidene hydrazide), NN l-bis[3-(3,5 -G-
t-butyl-4-hydroxyphenyl)propionylcohydrazine, tris[2-t-butyl-4-thio(2'
-methyl-4'-hydroxy-51-t-butylphenyl)-5-methylphenylcottosphite and N,
N'-bis[2-[3-(3,5-di-t-butyl-4
-hydroxyphenyl)propionyloxy]ethylcoxamide is preferred. Of course, these heavy metal deactivators can be used alone, but two or more types of heavy metal deactivators can also be used in combination. The blending ratio of the heavy metal deactivator is 0.01 to 1 part by weight per 100 parts by weight of a composition in which 30 to 70% by weight of magnesium hydroxide is blended with polyolefin.
Part by weight, preferably 0.05 to 0.5 part by weight. 0
．． If the amount is less than 1 part by weight, the effect of improving heavy metal properties will not be sufficiently exhibited, and if it is more than 1 part by weight, it is fine.
Since no further improvement in heavy metal resistance can be expected, this is not only impractical but also uneconomical.

The epoxy compound used in the present invention is not particularly limited as long as it does not significantly evaporate or decompose during melt mixing, and has an epoxy equivalent of 100 to 1.
,000 or so, and epichlorohydrin or epichlorohydrin derivatives (e.g. 2-methylepichlorohydrin, 2-ethylepichlorohydrin and 2-propylepichlorohydrin) and bisphenol or bisphenol derivatives (e.g. bisphenol A, bisphenol F, bisphenol S, (e.g. hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S), epoxidized oils and fats (e.g. epoxidized soybean oil, epoxidized linseed oil and epoxidized castor oil), epoxidized oils and fats, epixidized Alkyl esters of fatty acids (e.g. epoxidized octyl stearate, fatty acid esters of 3,4-epoxycyclohexylmethanol, 3,
Alkyl ester of 4-epoxycyclohexylcarboxylic acid, dialkyl ester of 4゜5-epoxycyclohexane-1,2-dicarboxylic acid, 3,4-epoxy-6
-methylcyclohexylmethyl and 3,4-epoxy-6-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, glycidylaniline, tetraglycidyldiaminodiphenylmethane, 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
Examples include -epoxy-6-methylcyclohexylmethyl) adipate, vinylcyclohexene geboxide, dicyclopentadiene oxide, bis(2,3-epoxycyclopentyl) ether, and limonene dioxide, especially condensation of epichlorohydrin and bisphenol A. 2-methylepichlorohydrin and bisphenol A condensate, triglycidyl isocyanurate and epoxidized soybean oil are preferred. It is natural to use these epoxy compounds alone, but it is also possible to use two or more kinds of epoxy compounds in combination. The blending ratio of the epoxy compound is 30% to 30% magnesium hydroxide to the polyolefin.
0.0 for 100 parts by weight of a composition containing 70% by weight.
01 to 1 part by weight, preferably 0.05 to 0.5 part by weight. If the amount is less than 0.01 part by weight, the effect of improving heavy metal resistance will not be sufficiently exhibited, and although it is possible to exceed 1 part by weight, it is not practical because no further improvement in heavy metal resistance can be expected. Not only that, but it is also uneconomical.

In the composition of the present invention, heavy metal resistance can be improved by using a fatty acid in combination.

The fatty acids include 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, lylunic acid, arachic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid, 1
Examples include 2-hydroxyoctadecanoic acid, ricinoleic acid and cerebronic acid, in particular 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, montanic acid and 12-hydroxy Octadecanoic acid is preferred.

It is possible to use these fatty acids alone, but it is also possible to use two or more fatty acids together. The blending ratio of the fatty acids is
30-70% by weight of magnesium hydroxide in polyolefin
The amount is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, per 100 parts by weight of the composition.

In addition, fatty acids can be blended with untreated magnesium hydroxide, magnesium hydroxide whose surface has been treated with a surface treatment agent other than fatty acids, and other formulations, or where magnesium hydroxide is previously surface-treated with a fatty acid. Any method such as blending as magnesium hydroxide may be used.

In the composition of the present invention, various additives that are usually added to polyolefins, such as phenol type (however, compound A), thioether type (however, except compound B) are used.
, phosphorus-based, hydroxylamine-based antioxidants, light stabilizers, clarifying agents, nucleating agents, lubricants, antistatic agents, antifogging agents, anti-blocking agents, anti-drop agents, flame retardants (however, hydroxyl (excluding magnesium), flame retardant aids, antibacterial agents, pigments,
Radical generators such as peroxides, dispersants or neutralizing agents such as metal soaps, inorganic fillers (such as talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, carbonic acid) Calcium, aluminum hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite, metal fiber, etc. ) or cup song agents (e.g. silane, titanate, boron, aluminate, zircoaluminate, etc.)
The above-mentioned inorganic fillers or organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) whose surface has been treated with a surface treatment agent such as the following can be used in combination without impairing the purpose of the present invention. .

The composition of the present invention is prepared by adding predetermined amounts of magnesium hydroxide, compound A, compound B, a heavy metal deactivator, an epoxy compound, and each of the above-mentioned various additives that are normally added to polyolefin to a polyolefin using a conventional mixing device, for example. Mix using a Henschel mixer (trade name), super mixer, ribbon blender, Pan Bali mixer, etc., and melt and knead with a normal single screw extruder, twin screw extruder, Brabender or roll, etc. at a temperature of 150°C to 300°C. ℃
, preferably by melting, kneading, and pelletizing at 200°C to 250°C. The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding.

[Function] In the present invention, compound A is used as a radical chain inhibitor, compound B is used as a peroxide decomposer, and heavy metal deactivator is used as an inactivator for the catalytic oxidative deterioration of polyolefins caused by heavy metal ions. It is generally known that epoxy compounds each act as an anti-adsorption agent. However, the compound A according to the present invention cannot be used in a flame-retardant polyolefin composition containing magnesium hydroxide.
By using Compound B, a heavy metal deactivator, and an epoxy compound in combination, a surprising synergistic effect that cannot be predicted from the combination of conventionally known compounds with anti-oxidative deterioration effects is exhibited, resulting in extremely excellent heavy metal resistance. A flame retardant polyolefin composition is obtained.

In addition, Compound A is excellent as a radical chain inhibitor in a flame-retardant polyolefin composition containing magnesium hydroxide, because Compound A is a combination of pentaerythritol and phenol group-containing aldehyde in the coexistence of magnesium hydroxide. Since it is an acetal, it is presumed that this is due to the fact that Compound A has a chemical structure that is less susceptible to alkaline hydrolysis in the coexistence of magnesium hydroxide than other phenolic antioxidants having ester or amide groups. be done.

Furthermore, Compound B is excellent as a peroxide decomposer in a flame-retardant pyroolefin composition containing magnesium hydroxide, because Compound B is an acetal of pentaerythritol and alkylthioalkanal, sorbitol and alkylthioalkanal, Compound B is an acetal or dialkyl disulfide with an alkanal.
This is presumed to be due to the fact that Compound B has a chemical structure that is less susceptible to alkaline hydrolysis in the coexistence of magnesium hydroxide than thioether antioxidants having other aliphatic ester groups or aliphatic amide groups.

[Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The evaluation method used in Examples and Comparative Examples was as follows.

1) Heavy metal resistance: Evaluated by mold copper resistance test. That is, using the obtained pellets, a test piece with a length of 50 mm, a width of 25 mm, and a thickness of 1 inch was made by injection molding, and the test piece was used to make a copper plate with a length of 25 mm, a width of 25 mm, and a thickness of 0.3 mm. and fix it with a clip and heat it to 150℃ or 14℃.
Heavy metal resistance is evaluated by placing the test piece in a circulating hot air oven adjusted to a temperature of 0°C and measuring the time until the contact part of the test piece with the copper plate completely deteriorates (time until the deterioration penetrates) (based on JIS K7212). did.

2) Flame retardancy: A flame retardancy test was conducted according to the combustion test method for polymer materials using the oxygen index method. That is, using the obtained pellets, length 15 (he, medium 6.5I, thickness 3.0
m++ combustion test piece was created by injection molding method, and the oxygen index was measured using this combustion test piece (JISK7201
(Based on the following).

Production Example 1 100 parts by weight of a surface-untreated product with an average particle size of 0.6 to 0.8μ as magnesium hydroxide and 1 part of laurin as a fatty acid.
12 parts by weight of the mixture were placed in a Henschel mixer (trade name) adjusted to a temperature of 50° C., and stirred and mixed for 5 minutes to obtain surface-treated magnesium hydroxide [I].

Production Example 2 Henschel mixer (trade name) prepared by mixing 100 parts by weight of a surface-untreated product with an average particle size of 0.6 to 0.8 μ as magnesium hydroxide and 2 parts by weight of stearic acid as fatty acid at a temperature of 80°C. and stirred for 5 minutes to obtain surface-treated magnesium hydroxide [nl].

Production Example 3 100 parts by weight of a surface-untreated product with an average particle size of 0.6 to 0.8μ as magnesium hydroxide, and olein l as a fatty acid.
2 parts by weight of E were kept at room temperature using a Henschel mixer (trade name; hereinafter, if the temperature of the Henschel mixer is not stated, it means that the temperature is room temperature).

) and stirred and mixed for 5 minutes to obtain surface-treated magnesium hydroxide.

Production Example 4 100 parts by weight of a surface-untreated product with an average particle size of 0.6 to 0.8μ as magnesium hydroxide, and 1 part of linol as a fatty acid.
2 parts by weight of II were placed in a Henschel mixer (trade name) and mixed for 5 minutes to obtain surface-treated magnesium hydroxide [■].

Examples 1 to 8, Comparative Examples 1 to 15 MFR (load 2 at 230°C) as polyolefin
．． Discharge rate of molten resin in 10 minutes when adding 16 kg) 20 g/10 minutes 43% by weight of unstabilized powdered crystalline propylene homopolymer and magnesium hydroxide with an average particle size of 0.6-0. 8μ surface untreated product 5
7% by weight, 1,3,2,4-bis[2-(3,5-di-butyl-4-hydroxyphenyl)propylidenecoturbitol or 1,3 ,2・4,5・6-tris[2-(
3,5-di-butyl-4-hydroxyphenyl)propylidenecoturbitol, 3,9-bis(2-laurylthioethyl)-2,4,8,10- as compound B
Tetraoxaspiro [5,5 undecane, 1,3,2
・4-bis(3-laurylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(3-laurylthiopropylidene) sorbitol or dilauryl disulfide, N, N as a heavy metal deactivator '−bis[
2-(3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxy)ethylcoxamide,
Tris[2-butyl-4-thio(2'-methyl-4
'-Hydroxy-5'-t-butylphenyl)-5-methylphenylcottosphite, N,N'-bis[3-
(3,5-di-butyl-4-hydroxyphenyl)
Probionyl cohydrazine or oxalitic acid bis(benzylidene hydrazide), as an epoxy compound a condensate of epichlorohydrin and bisphenol A (epoxy equivalent: 700-830) or a condensate of epichlorohydrin and bisphenol A, 2-methylepichlorohydrin and bisphenol A A mixture of condensates (epoxy equivalent: 180 to 200) and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 1 below, and stirred and mixed for 3 minutes. The mixture was melt-kneaded and pelletized at 250° C. using a twin-screw extruder with a diameter of 30IIIT+. Also, Comparative Examples 1 to 1
5 from 43% by weight of unstabilized powdered crystalline propylene homopolymer with an MFR of 20 g/10 min and 57% by weight of a surface-untreated product with an average particle size of 0.6 to 0.8 μ as magnesium hydroxide. A total of 100 parts by weight was blended with predetermined amounts of each of the additives listed in Table 1 below, and melt-kneaded according to Examples 1 to 8 to obtain pellets.

3. The test pieces used in the copper property test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C.

The obtained test pieces were used to evaluate heavy metal resistance (150° C. hot copper type copper and flame retardance) according to the test method described above. The results are shown in Table 1.

Examples 9-16, Comparative Examples 16-30 Unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) with MFR 30g/10min as polyolefin29.
59% by weight and surface treated magnesium hydroxide as magnesium hydroxide [11, magnesium hydroxide [■
A total of 101% consisting of 70.41% by weight of magnesium hydroxide [■ or magnesium hydroxide [■]].
4 parts by weight (100 parts by weight as the total of the surface-untreated crystalline ethylene-propylene block copolymer and magnesium hydroxide excluding fatty acids used for surface treatment)
1,3,2,4-bis[2,2-dimethyl-3-(3-methyl-4-hydroxy-5-t-
butylphenyl)propylidenecotrubitol or 1,3,2,4,5,6-tris[2,2-dimethyl-
3-(3-methyl-4-hydroxy-5-savetylphenyl)propylidenecoturbitol, as compound B 3,9-bis(1-methyl-2.(2-ethylhexyl)thioethyl)-2,4, 8,10-tetraoxaspiro[5,5-oundecane, 1,3,2,4-bis(2-
Methyl-3-(2-ethylhexyl)thiopropylidene) sorbitol, 1,3,2,4,5,6-tris(2
- methyl-3-(2-ethylhexyl)thiopropylidene) sorbitol or similistyl disulfide,
NN l-bis[2-[3-(
3,5-di-butyl-4-hydroxyphenyl)propionyloxy]ethylcoxamide, tris[2-
t-Butyl-4-thio(2'-methyl-42-hydroxy-5'-t-'tylphenyl)-5-methylphenyl]phosphite, N,N'-bis[3-(3,5-di- t-Butyl-4-hydroxyphenyl) propionyl cohydrazine or oxalin acid-bis(benzylidene hydrazide), a condensate of epichlorohydrin and bisphenol A as an epoxy compound (epoxy compound ff1700-830) or a condensate of epichlorohydrin and bisphenol A A mixture of a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent: 180 to 200) and other additives were added to a Henschel mixer (trade name) at the mixing ratios listed in Tables 1 and 2 below. After stirring and mixing for 3 minutes, the mixture was melt-kneaded at 250° C. using a twin-screw extruder having a diameter of 30 mm to form pellets. Also, as Comparative Examples 16 to 30, MF
30% by weight of unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) with R of 30g/10min and an average particle size of 0.6-0.0% as magnesium hydroxide. A total of 100 parts by weight consisting of 70% by weight of 8μ surface untreated product or MFR of 30g
/ 10 minutes of unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene containing 118.
5% by weight) 29.59% by weight and surface treated magnesium hydroxide as magnesium hydroxide [n] 7
70.41 parts by weight in total (100 parts by weight as the total of the crystalline ethylene-propylene block copolymer excluding fatty acids used for surface treatment and the surface untreated product of magnesium hydroxide) as described below. Predetermined amounts of each of the additives listed in Table 2 were blended and melt-kneaded according to Examples 9 to 16 to obtain pellets.

3. The test pieces used in the copper property test and the flammability test were made into V4 by injection molding the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C.

Heavy metal resistance (copper resistance at 150° C.) 08 and flame retardance were evaluated using the obtained test piece according to the test method described above.

These results are shown in Table 112.

Examples 17-24, Comparative Examples 31-45 As polyolefin MFR7.0z/10 min unstabilized powdery crystalline ethylene-propylene-butene-13 copolymer (ethylene content 2.5 wt. %, butene-1 content 4.5% by weight) and 50% by weight of a surface-untreated product with an average particle size of 0.6 to 0.8μ as magnesium hydroxide, to a total of 100 parts by weight, compound A was added. as 1,3,2,4-bis(3,5-di-monooctyl-4-hydroxybenzylidene)sorbitol or l.3,2.4,5,6-tris(3,5
-di-t-octyl-4-hydroxybenzylidene) sorbitol, 3,9-bis(2-stearylthiopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane as compound B, 1. 3,2,4-bis(
3-stearylthiobutylidene) sorbitol, l.3
, 2,4,5,6-tris(3-stearylthiobutylidene) sorbitol or distearyl disulfide, N as a heavy metal deactivator.

N'-bis[2-(3-(3,5-di-t-butyl-4
-hydroxyphenyl)propionyloxy]ethylcoxamide, tris[2-t-butyl-4-thio(2'
-methyl-41-hydroxy-5'-t-butylphenyl)-5-methylphenyl]phosphite, N,
N'-bis[3-(3,5-di-butyl-4-hydroxyphenyl)propionylcohydrazine or oxalin acid-bis(benzylidene hydrazide), triglycidyl isocyanurate (epoxy equivalent 100 to 110) as an epoxy compound, or Predetermined amounts of epoxidized soybean oil (epoxy equivalent: 220-240) and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 3 below, and after stirring and mixing for 3 minutes, 250 with twin screw extruder
The mixture was melted and mixed at ℃ to form pellets. Also, comparative example 3
Unstabilized powdery crystalline ethylene-propylene-butene-13 copolymer (ethylene content 2.5% by weight, butene-1 content 4.0% by weight) with a MFR of 1-Ox/10 minutes as 1-45. 5% by weight) and 50% by weight of a surface-untreated product with an average particle size of 0.6 to 0.8μ as magnesium hydroxide to a total of 100 parts by weight, and 1 as described below.
Predetermined amounts of each of the additives listed in Table 3 were blended and melt-kneaded according to Examples 17 to 24 to obtain pellets.

3 The test pieces used in the copper property test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250°C and a mold temperature of 50''C.

The obtained test pieces were used to evaluate heavy metal resistance (140°C hot copper type copper and flame retardance) using the test method described above.The results are shown in Tables 1 and 3.

Examples 25-32, Comparative Examples 46-60 Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 55 with M F R7,0z/10 min as polyolefin
Weight %, MI (discharge amount of molten resin for 10 minutes when applying a load of 2.16 kg at 190°C) 20z/1
0 min unstabilized powdered Ziegler-Natsuta high density ethylene homopolymer 10% by weight, Mooney viscosity M
L 1+4 (100°C) 25% by weight of unstabilized powdered amorphous ethylene-propylene random copolymer (propylene content 25% by weight) and average particle size 0.6-0.5% as magnesium hydroxide. Compound A
as 1,3,2,4-bis[4-(3-t-butyl-
4-hydroxyphenyl)butylidenecotrubitol or 1,3,2,4,5,6-tris[4-(3-t
-butyl-4-hydroxyphenyl)butylidenecotrubitol, as compound B 3,9-bis(3-ophtacosylthioprobyl)-2,4,8,10-tetraoxaspiro[5,5-oundican, 1・3,2,4-bis(
4-ophtacosylthiobutylidene) sorbitol, 1.
3,2,4,5,6-tris(4-ophtacosylthiobutylidene) sorbitol or dioctacosyl disulfide, N,N'-bis[:L
(3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxy)ethylcoxamide, tris[2-t-butyl-4-thio(2'-methyl-4'
-Hydroxy-5'-t-butylphenyl)-5-methylphenylcottosphite, N,N'-bis(3-(
3,5-di-t-butyl-4-hydroxyphenyl)propionylcohydrazine or oxalic acid-bis(benzylidene hydrazide), triglycidyl isocyanurate as an epoxy compound (epoxy equivalent 1
00 to 110) or epoxidized soybean oil (epoxy equivalent 220 to 240) and other additives in the mixing ratios listed in Table 3 below in a Henschel mixer (trade name), and stirred and mixed for 3 minutes. After that, caliber 3
The mixture was melted and mixed in a 011I11 twin-screw extruder at 250°C to form pellets. In addition, as comparative examples 46 to 60, MF
Unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) with R of 7.0z/10 min, 55% by weight, MI of 20z/1
0 min unstabilized powdered Ziegler-Natsuta high density ethylene homopolymer 10% by weight, Mooney viscosity M
Unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content 25% by weight) with a LI÷4 (100°C) of 25 and an average particle size of 0.6 to 5% by weight as magnesium hydroxide. A total of 1.00 parts by weight consisting of 30% by weight of a 0.8 μ surface-untreated product was added with the 4th part described below.
Example 2
Pellets were obtained by melt-kneading treatment according to 5-32.

The test pieces used in the mold copper property 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.

Using the obtained test pieces, heavy metal resistance (140″C copper resistance) and flame retardance were evaluated according to the test method described above.

These results are shown in Table 4.

The compounds and additives related to the present invention shown in Tables 1 to 14 are as follows.

Magnesium hydroxide [average particle size 0.6-0.8μ
Surface-untreated magnesium hydroxide [average particle size of 0.6 to 0.8μ]
Magnesium hydroxide, a surface-treated product obtained by surface-treating 100 parts by weight of an untreated product with 2 parts by weight of lauric acid [■]: Koni average particle size 0.6-0.
Surface-treated magnesium hydroxide obtained by adding 2 parts by weight of stearic acid to 100 parts by weight of an untreated 8μ surface [■Koni average particle size 0.6 to 0.8μ]
Magnesium hydroxide, a surface-treated product obtained by surface-treating 100 parts by weight of an untreated product with 2 parts by weight of oleic acid [■]: Koni average particle size 0.6-0.
Surface-treated product Compound A [1Coni 1,3,2,4-bis[2-(3,5
-di-t-butyl-4-hydroxyphenyl)propylidenecoturbitol Compound A [I+]: 1.3,2.4-bis[2,
2-dimethyl-3(3-methyl-4-hydroxy-5-
t-butylphenyl) propylideneco trubitol compound A [mconi 1,3,2,4-bis(3,5-di-monooctyl-4-hydroxybenzylidene) sorbitol compound A [IV coni 1,3,2, 4-bis[4-(
3-t-butyl-4-hydroxyphenyl)butylidene turbitol compound A [Vconi 1,3,2,4,5,6-tris[2
-(3,5-di-t-'thi-4-hydroxyphenyl)propylidenecoturbitol Compound A [VInconi13,2.4,5.6-tris[
2,2-dimethyl-3-(3-methyl-4-hydroxy-5-t-butylphenyl)propylidenecoturbitol Compound A [■Coni 1,3,2,4,5,6-tris(3
, 5-di-t-octyl-4-hydroxybenzylidene) sorbitol compound A [mconi 1,3,2,4,5,6-tris[4
-(3-t-butyl-4-hydroxyphenyl)butylidenecoturbitol compound B [11: 3.9-bis(2-laurylthioethyl)-2,4,8,10-tetraoxaspiro[5
,51 undecane compound B [nconi-3,9-bis(1-methyl-2-(2
-ethylhexyl)thioethyl) -2,4,8,10
-Tetraoxaspiro[5,5]undecane compound B [m]:'3,9-bis(2-stearylthiopropyl) -2,4,8,10-tetraoxaspiro[5,5]undecane compound B [TV ]: 3.9-bis(3-oftacosylthioprobil)-2,4,8,10-tetraoxaspiro[5゜5koundican compound B [:V]: 1.3,2.4-bis( 3-
laurylthiopropylidene) sorbitol compound B [W]: 1,3,2,4-bis(2-methyl-3-(2-ethylhexyl)thiopropylidene)
Sorbitol Compound B [■ Coni 1,3,2,4-bis(3-stearylthiobutylidene) Sorbitol Compound B [mConi 1,3,2,4-bis(4-ophtacosylthiobutylidene) Sorbitol Compound B []
-Methyl-3-(2-ethylhexyl)thiopropylidene) sorbitol compound B [XInconi13,2.4,5.6-tris(3-stearylthiobutylidene)sorbitol compound B [XInconi1.3,2.4 , 5,6-tris(4-ophtacosylthiobutylidene) sorbitol compound B [Xm conidilauryl disulfide compound B [
XrV]: Similistyl disulfide compound B [XV
]: Distearyl disulfide compound B [XVI:
Dioctacosyl disulfide heavy metal deactivator Activator [II]:) Lis[2-t-butyl-
4-thio(2'-methyl-4'-hydroxy-5'-t
-butylphenyl)-5-methylphenylcotiosphite heavy metal deactivator [■Koni N,N'-bis[3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionylcohydrazine heavy metal deactivator "■": Oxalinkacindobis (benzylidene hydrazide) Epoxy compound [■]: Condensate of shrimp chlorohydrin and bisphenol A (epoxy equivalent: 700-830;
CIBA-GEIGY AG ARA-LDITE
GT 7004) Epixy compound [II]: A mixture of a condensate of shrimp chlorohydrin and bisphenol A and a mixture of 2-methyl epichlorohydrin and bisphenol A (epoxy compound 11180-200; manufactured by Adeka Argus Chemical M)
ARK EP-17) Epoxy compound [2] Following general formula [III]: ) Liglycidyl isocyanurate (t100-110 per epoxy; CIBA-GEIGY
ARALDITE PT epoxy compound []Vl manufactured by AG: Epoxidized soybean oil (epoxy equivalent: 220~
240; ADK CIZE manufactured by Adeka Argus Chemical ■
RO-130F) Fat ill: Acetate fat 112: 2-ethylhexanoate fat IE3: Lauric acid fat j1! ! 4 Nistearic acid fatty acid 5 Nioleic acid fat W16: Linoleic acid fat 117: Behenic acid fat 118: Erucic acid fat 119: Montanic acid fat [I! 10: 12-hydroxyoctadecanoic acid phosphorus antioxidant 1: Bis(2,6-di-t-butyl-4
-Methylphenyl)-Pentaerythritol-Shiphosphiterin-based antioxidant 2: Bis(2,4-di-butylphenyl)-Pentaerythritol-Sifosphiterin-based antioxidant 3: Tetrakis(2,4- di-t-butylphenyl) -4,4'-biphenylene-diphosphonite phenolic antioxidant 1: 2,6-di-t-butyl-
P-cresol phenolic antioxidant 2: Tetrakis [methylene-3
-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane phenolic antioxidant 3: 2,2-bis[4-C2-
(3,5-dibutyl-4-hydroxyphenylpropionyloxy)ethoxy]phenyl]propanephenolic antioxidant 4: Tris(4-thibutyl-3
-Hydroxy-2,6-cyphthylbenzyl)incyanurate phenolic antioxidant 5: Tris[3-(3,5-
di-t-phthyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate phenolic antioxidant 6: 1,1,3-tris(5
-t-butyl-4-hydroxy-2-methylphenyl)
-Butanephenolic antioxidant 7: bis[3,3-bis(4'
-Hydroxy-3'-t-butylphenyl)butyrin acid coethylene glycol ester phenolic antioxidant 8:2,2-thio-diethylenebis[3-(3
,5-di-7-butyl-4-hydroxyphenyl)propionate-tocophenol antioxidant 9:1,3.5-trimethyl-
2,4,6-)Lis(3,5-di-t-butyl-4-hydroxybenzyl)benzenephenolic antioxidant 10: Bis[2-(3'-t
-butyl-5'-methyl-22-hydroxybenzyl)
-4-Methyl-6-t-butylphenyl] terephthalate thioether antioxidant 1 Nidimyristylthiodipropionate thioether antioxidant 2: Pentaerythritol -
Tetrakis(3-laurylthiopropionate) Thioether antioxidant 3: N,N'-bis(3-laurylthiopropionyl)hydrazide Carbon blank: Carbon #45 C manufactured by Mitsubishi Kasei ■
a-8t: Calcium stearate 311 In the Examples and Comparative Examples shown in Table 1, 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, magnesium hydroxide (surface untreated product), Compound A, Compound B,
It is a mixture of a heavy metal deactivator and an epoxy compound, and Examples 1 to 8 and Comparative Examples 1 to 7 (in Examples 1 to 4, phenolic antioxidants 2 to 8 other than compound A were used instead of compound A). Comparing Examples 1 to 8 with the compound A), Examples 1 to 8 have excellent heavy metal resistance, and in the coexistence of magnesium hydroxide, phenolic antioxidants 2 to 8 other than Compound A have a radical chain inhibiting effect, i.e. It can be seen that the antioxidant effect is not sufficiently exhibited. In addition, Example 1~
8 and Comparative Examples 8 to 10 (in Examples 1 to 4, thioether antioxidants 1 to 1 other than compound B were used instead of compound B).
3), Comparative Examples 8 to 1
Although the heavy metal resistance of No. 0 is improved compared to Comparative Examples 1 to 7, it is still not sufficient, and in the coexistence of magnesium hydroxide, thioether antioxidants 1 to 3 other than Compound B have a peroxide decomposition effect, that is, oxidation prevention. It can be seen that the effect is not fully exerted. In addition, the patent application No.
-35792 and Japanese Patent Application No. 1-62845, that is, in Examples 1 to 4, the phenolic antioxidant 9 was used instead of Compound A.
and thioether antioxidant 1 instead of compound B
or Comparative Examples 11 to 12 in which phenolic antioxidant 10 was blended in place of compound A and thioether antioxidant 2 was blended in place of compound B.
Comparing Examples 1 to 8, the heavy metal resistance of Comparative Examples 11 to 12 is improved over Comparative Examples 1 to 7, but is still not sufficient. Furthermore, Comparative Example 13 which contains Compound A, Compound B and a heavy metal deactivator but does not contain an epoxy compound, Comparative Example 14 which contains an epoxy compound but does not contain Compound A, Compound B and a heavy metal deactivator, and Compound A , Comparative Example 15 and Examples 1 to 1, which contain Compound B and an epoxy compound but do not contain a heavy metal deactivator.
When compared with Comparative Examples 13 to 15, the heavy metal resistance of Comparative Examples 13 to 15 is still not sufficient.

Therefore, it is clear that comparisons that do not simultaneously satisfy the four components of compound A, compound B, heavy metal deactivator, and epoxy compound according to the present invention do not exhibit the effects of the present invention. That is, the heavy metal resistance obtained in the present invention can only be seen when Compound A, Compound B, a heavy metal deactivator, and an epoxy compound are used in combination with a flame-retardant polyolefin composition containing magnesium hydroxide. This can be said to be a unique effect. Furthermore, Examples 1-
In Examples 5 to 8, in which various fatty acids were used in combination in 4, compared to Examples 1 to 4, the excellent effect of improving heavy metal resistance of compound A, compound B, heavy metal deactivator, and epoxy compound was inhibited. It can be seen that a remarkable synergistic effect is observed due to the combined use of fatty acids.

Furthermore, the flame retardant composition according to the present invention, which is a mixture of Compound A, Compound B, a heavy metal deactivator, and an epoxy compound, has no inferior flame retardancy compared to conventionally known flame retardant compositions. It was confirmed that there was no such thing.

Table 2 shows results in which a crystalline ethylene-propylene block copolymer was used as the polyolefin and a surface-treated product was used as magnesium hydroxide, and the same effects as described above were confirmed for these as well. In addition, Tables 3 and 4 list crystalline ethylene-propylene-butene-13-element copolymer, crystalline ethylene-propylene random copolymer, Ziegler-Natsuta high-density ethylene homopolymer, and amorphous polyolefin, respectively. A mixture of ethylene-propylene random copolymer and a surface-untreated magnesium hydroxide were used, and the same effects as described above were confirmed for these as well.

[Effects of the Invention] Compared to conventionally known flame-retardant polyolefin compositions containing magnesium hydroxide and having improved heavy metal resistance, the composition of the present invention has the following advantages: The molded product has extremely high resistance to heavy metals. (2) It has extremely high resistance to heavy metals, so there is no decrease in electrical insulation properties caused by oxidative deterioration of polyolefin, so it can be used in applications that require flame retardancy and heavy metal resistance in various molding fields (for example, deflection yokes). , electrical and electronic functional parts such as CRT sockets and connectors, and distributor camps.

It can be suitably used for automobile parts such as car heater cases and car air conditioner cases, and insulating materials such as electric wire covering materials.

that's all

Claims (2)

[Claims] (1) Magnesium hydroxide 30-70% in polyolefin
A phenolic compound represented by the following general formula [I] (hereinafter referred to as compound A), one or two or more selected from the following 1 to 3 is added to 100 parts by weight of the composition containing % by weight. compound (hereinafter referred to as compound B), a heavy metal deactivator, and an epoxy compound, each in an amount of 0.01 to
A flame-retardant polyolefin composition containing 1 part by weight. [1] Thioether compounds represented by the following general formula [II] [2] Thioether compounds represented by the following general formula [III] [3] Dialkyl disulfide compounds ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (However, in the formula, R_1 is an alkyl group with 1 to 8 carbon atoms,
R_2 is hydrogen or an alkyl group having 1 to 8 carbon atoms,
_3 is an alkylene group having 2 to 4 carbon atoms, R_4 and R
_5 is hydrogen or both form a 5-membered ring＞CH-▲There are mathematical formulas, chemical formulas, tables, etc.▼The group is R_6 and
8 is an alkyl group having 8 to 28 carbon atoms, R_7 and R_
9 is an alkylene group having 2 or 3 carbon atoms, R_1_0
and R_1_1 represent hydrogen or a >CH-R_9-S-R_8 group in which both of them form a 5-membered ring, and n represents 0 or 1, respectively. ) (2) Magnesium hydroxide 30-70% in polyolefin
Compound A, compound B, heavy metal deactivator, and epoxy compound are each mixed in 0.01 to 1 part by weight, and fatty acid is blended in 0.5 to 5 parts by weight to 100 parts by weight of the composition. A flame-retardant polyolefin composition.