JPH0436331A - 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 30-70 pts.wt. Mg(OH)2 of a mean particle diameter of 0.1-10mum 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. thioether compound and/or dialkyl disulfide compound of formula II (wherein R4 is 8-28C alkyl; R5 is 2-3C alkylene; and R6 and R7 are each H or they are combined with each other to represent a group of formula III which forms a five-membered ring), distearyl disulfide, 0.01-1 pt.wt. heavy metal inactivator [e.g. oxalic acid bis(benzylidenehydrazide)] and an 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 [Field of Industrial Application] The present invention relates to a flame-retardant polyolefin composition, and more particularly to a flame-retardant polyolefin composition that is excellent in preventing oxidative deterioration of polyolefin in practical use.

[Prior Art] Generally, as a means to make polyolefin flame retardant, various halogen flame retardants are blended into polyolefin, and this is 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 required 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 the disadvantage of being susceptible to thermal oxidative deterioration during molding and practical use, since they contain 313-grade carbon, which 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 are subject to catalytic oxidative deterioration by the heavy metal ions contained in the various heavy metals mentioned above, molded products using the above-mentioned flame-retardant polyolefin compositions have high resistance to oxidative deterioration (hereinafter referred to as resistance) upon contact with heavy metals. It has the disadvantage that 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 (JP-A-52-1) The following general formula [II238 publication and JP-A-63-5654]
4), a composition in which magnesium hydroxide and an epoxy compound are blended with polyolefin (Japanese Unexamined Patent Publication No. 59-21
9352, JP 63-137963, JP 63-159473, and JP 63-18
No. 9462) have been proposed.

However, in recent years, requirements for flame retardancy have become increasingly strict in applications such as electrical and electronic parts and automobile parts, and as molded products obtained from flame-retardant polyolefin compositions have diversified applications and become larger. and the actual usage conditions of the molded product (heavy metal properties, electrical insulation, etc.)
The requirements for this are also becoming stricter. That is, it is necessary to develop a flame-retardant polyolefin composition that has better resistance to heavy metals than ever before. In order to solve these problems, magnesium hydroxide is added to the above-mentioned JP-A-52-1]
The following general formula [II238 publication, JP-A-63-5654
Publication No. 4, JP-A-59-219352, JP-A-6
The flame-retardant polyolefin compositions proposed in JP-A No. 3-137963, JP-A-63-159473, and JP-A-83-189462 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 phenolic compound represented by the following formula CI], one or two selected from the following 1 to 2 was added to a flame retardant composition consisting of a polyolefin and magnesium hydroxide.
The inventors have 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 completed. .

■Thioether compounds represented by the following general formula [I[] ■Dialkyl disulfide compounds (in formula 1, R2 is an alkyl group having 1 to 8 carbon atoms, R
2 is hydrogen or an alkyl group having 1 to 8 carbon atoms, R8 is an alkylene group having 2 to 4 carbon atoms, and R4 is 8 to 28 carbon atoms.
R5 is an alkylene group having 2 or 3 carbon atoms, R6 and Rt are hydrogen or both form a 5-membered ring>CH-R2S-R, and n is 0 or 1
) As is clear from the above description, an object of the present invention is to provide a flame-retardant polyolefin composition that has excellent heavy metal resistance when formed into a molded article.

[Means to solve the 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 or more selected from the following 1 to 2, per 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 at a concentration of 0.01 to 0.0, respectively.
A flame-retardant polyolefin composition containing 1 part by weight.

■Thioether compounds represented by the following general formula [nl ■Dialkyl disulfide compounds (in formula 1, R8 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, and R4 is 8 to 28 carbon atoms.
R6 is an alkylene group having 2 or 3 carbon atoms, R6 and R7 are hydrogen or both form a 5-membered ring>CH-Rt 5-Ra group, n is O or 1
) (2) Magnesium hydroxide in polyolefin 30-70
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.

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-crystalline or non-crystalline random copolymers or crystalline block copolymers of α-olefins, amorphous ethylene-propylene-nonconjugated diene ternary copolymers, the above-mentioned α-olefins and # copolymers with vinyl acids 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. A copolymer, a reaction product of the copolymer and a metal ion compound, a crystalline homopolymer of the above-mentioned α-olefin, and crystallinity.

A modified polyolefin obtained by modifying a low-crystalline, non-quality random copolymer or crystalline block copolymer or an amorphous ethylene-propylene-nonconjugated diene terpolymer with an unsaturated carboxylic acid or a derivative thereof, the above-mentioned Unsaturated crystalline homopolymers, crystalline, low-crystalline, unqualified random copolymers or crystalline block copolymers of α-olefins, or unsaturated ethylene-propylene-nonconjugated diene ternary copolymers Examples include silane-modified polyolefins modified with silane compounds, and these polyolefins can be used alone or in combination of two or more polyolefins. In addition, various synthetic rubbers such as IF/liptadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-propylene-butylene-styrene block copolymers, etc.) or thermoplastic synthetic resin fII
(For example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, fluororesin, petroleum resin (for example, CS petroleum resin, hydrogenated C5 petroleum resin, C9 petroleum resin, hydrogenated C9
petroleum resin, C, -C, copolymerized petroleum resin, hydrogenated C, -C
, copolymerized petroleum resin, acid-modified C8 petroleum resin, etc.), DC
PD resin (e.g. cyclopentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene-Cs copolymer petroleum resin, hydrogenated cyclopentadiene-Cs
Copolymerized petroleum resin, cyclopentadiene-C8 copolymerized petroleum resin, hydrogenated cyclopentadiene-〇, copolymerized petroleum resin,
Cyclopentadiene-〇s-Cs copolymerized petroleum resin,
DCPDI with a softening point of 80-200°C such as hydrogenated cyclopentadiene-Cs-Cs copolymerized petroleum resin! (l1l) etc.) can also be used in combination. A crystalline propylene homopolymer, a crystalline propylene copolymer containing 70% by weight or more of a propylene component, the crystalline ethylene-
Propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene-1
Random copolymers, crystalline ethylene-propylene-butene-13-element copolymers, crystalline propylene-hexene-butene-13-element copolymers, and mixtures of two or more thereof are particularly preferably used.

As the magnesium hydroxide used in the present invention, plate-like and fibrous forms can be used without any restriction. The average particle diameter of the plate-shaped magnesium hydroxide is not particularly limited, but is usually 0.1 to 10 microns.

Preferably it is 0.2 μ to 2 μ, most preferably 0.5 μ to 1 μ, and 1] The fiber diameter of the fibrous magnesium hydroxide is 0.1 μ to 0.5 μ, the length is 5 μ
μ to 20μ is preferable, and these magnesium hydroxides can be used as surface treatment agents such as metal soaps, higher fatty acid esters, higher alcohols, higher nwj acid monoamides, higher fatty acid bisamides, higher aliphatic metal phosphates, and silane coupling agents. If the surface is treated in advance with a known surface treatment agent such as a titanate coupling agent, a boron-based camping agent, an aluminate-based coupling agent, or a zirco-aluminate-based coupling agent, the magnesium hydroxide and Improved compatibility and dispersibility with polyolefins.

It is preferable to use magnesium hydroxide whose surface has been treated with a surface treatment agent because it provides excellent moldability and improves the mechanical strength of the molded article.
The use of magnesium hydroxide alone is a matter of course,
Two or more types of magnesium hydroxide can also be used together. The blending ratio of magnesium hydroxide is 30% to the composition consisting of polyolefin and magnesium hydroxide.
-70% by weight, preferably 50-65% by weight. 3
If the content is 0% 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 decrease, so it is not practical. .

Compound A used in the present invention is 3,9-bis(3
-methyl-4-hydroxyphenyl) -2,4,8,
10-tetraoxaspiro[5,51 undecane, 3,
9-bis(3-t-butyl-4-hydroxyphenyl)
-2,4,8,10-tetraoxaspiro[5-51
undecane, 3,9-bis(3-methyl-5-t-butyl-4-hydroxyphenyl)-2,4,8,10-tetraoxaspiro[5,5 undecane, 3,9-bis(3-ethyl -5-t-butyl-4-hydroxyphenyl)-2,4,8,10-tetraoxaspiro[5,5
Undecane, 3,9-bis(3,5-di-butyl-4-hydroxyphenyl)-2,4,8,10-tetraoxaspiro[5,5] Undecane, 3,9-bis(3,5- di-t-amyl-4-hydroxyphenyl)
-2,4,8,10-tetraoxaspiro[5,5]
Undecane, 3,9-bis(3,5-di-octyl-4-hydroxyphenyl)-2,4,8,10-tetraoxaspiro[5,5] Undecane, 3,9-bis[2-(3 -t-phthyl-4-hydroxyphenyl)
ethyl]-2゜4,8.10-tetraoxaspiro[5
, 5-oundecane, 3.9-bis[2-(3-t-amyl-4-hydroxyphenyl)ethyl2.4, 8.
10-tetraoxaspiro[5,5]undecane, 3,
9-bis[2-(3-t-octyl-4-hydroxyphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[2-(3
-methyl-4-hydroxy-5-t-butylphenyl)
Ethyltwo 2.4,8.10-tetraoxaspiro[5
, 5 Koun Decan.

3.9-bis[2-(3-methyl-4-hydroxy-5
-t-amylphenyl)ethylco-2,4,8.10-
Tetraoxaspiro[5,5 undecane, 3,9-bis[2-(3-methyl-4-hydroxy-5-t-octylphenyl)ethyl2.4,8.10-tetraoxaspiro[5,5 undecane , 3.9-bis[2-
(3-ethyl-4-hydroxy-5-butylphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis[2-(3-i
-propyl-4-hydroxy-5-t-butylphenyl)ethyl2.4,8.10-tetraoxaspiro[
5,51 undecane, 3,9-bis[2-(3-i-butyl-4-hydroxy-5-t-butylphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5,
5] undecane, 3,9-bis[2-(3-s-butyl-4-hydroxy-5-t-butylphenyl)ethyl2.4,8.10-tetraoxaspiro[5,5 undecane, 3.9-bis[2-(3,5-di-butyl-4-hydroxyphenyl)ethyl] -2,4,
8,10-tetraoxaspiro[5,51 undecane,
3.9-bis[2-(3-t-butyl-4-hydroxy-5-t-amylphenyl)ethyl]-2゜4.8.1
0-tetraoxaspiro[5,5]undecane, 3.9
-bis[2-(3-t-butyl-4-hydroxy-5-
t-octylphenyl)ethyl] -2,4,8,10
-Tetraoxaspiro[5,5]undecane, 3.9-
BisC2-(3,5-di-amy-4-hydroxyphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[2.(3
,5-di-t-octyl-4-hydroxyphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5
, 5-oundecane, 3,9-bis[2-(2-methyl-
4-hydroxy-5-t-butylphenyl)ethylco2゜4.8.10-tetraoxaspiro[5,5]undecane, 3.9-bis[2-(3-methyl-4-hydroxy-5-t) -amylphenyl)ethyl] -2,4,
8,10-tetraoxaspiro [5,5 condecane,
3,9-bis[2-(2,5-di-butyl-4-hydroxyphenyl)ethyl] -2,4゜8.10-tetraoxaspiro[5,5]undecane, 3゜9-bis[2 -(3,5-di-t-amyl-4-hydroxyphenyl)ethyl-2.4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[2-(2-methyl-4 -hydroxy-5-t-octylphenyl)ethyl] -2,4゜8.10-tetraoxaspiro[5
, 51 undecane, 3゜9-bis[2-(2-t-butyl-4-hydroxy-5-methylphenyl)ethyl]
-2,4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis[1-methyl-2-(3-t-
Butyl-4-hydroxyphenyl)ethyl]-2゜4.
8.10-Tetraoxaspiro [5,5 condecane,
3.9-bis[1-methyl-2-(3-methyl-4-hydroxy-5-t-butylphenyl)ethyl] -2,
4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis[1-methyl-2-(3,5-di-t
-butyl-4-hydroxyphenyl)ethyl2.4
, 8.10-tetraoxaspiro[5,5-oundecane, 3,9-bis[1-methyl-2-(3-methyl-4-
Hydroxy-5-t-amylphenyl)ethylco2.
4゜8.10-tetraoxaspiro[5,5]undecane, 3゜9-bis[1-methyl-2-(3,5-di-t
-amyl-4-hydroxyphenyl)ethyl] -2,
4,8,10-tetraoxaspiro[5,5] undecane, 3,9-bis[1-methyl 2-(3-methyl-
4-Hydroxy-5-t-octylphenyl)ethyl2.4,8.10-tetraoxaspiro[5゜5oundecane, 3,9-bis[l-methyl-2-(3,5-
di-1-octyl-4-hydroxyphenyl)ethylco2.4,8.10-tetraoxaspiro[5,51 undecane.

3.9-bis[2-methyl-2-(3-t-butyl-4
-Hydroxyphenyl)ethyltwo2.4,8.10-
Tetraoxaspiro[5,5] undecane, 3,9-
Bis[2-methyl-2-(3-methyl-4-hydroxy-5-t-butylphenyl)ethyltwo 2.4,8.1
0-tetraoxaspiro[5,51 undecane, 3,9
-bis[2-methyl-2-(3,5-di-t-butyl-
4-hydroxyphenyl)ethyl] -2,4,8,1
0-tetraoxaspiro[5,5]undecane, 3,9
-bis[2-methyl-2-(3-methyl-4-hydroxy-5-t-amylphenyl)ethyl] -2,4,8
, 10-tetraoxaspiro[5-5]undecane, 3
,9-bis[2-methyl-2-(3,5-di-t-amyl-4-hydroxyphenyl)ethylco2.4,8.
10-tetraoxaspiro[5,5-oundecane, 3,
9-bis[2-methyl-2-(3-methyl-4-hydroxy-5-t-octylphenyl)ethyl] -2,4
゜8.10-tetraoxaspiro[5,5]undecane, 3゜9-bis[2-methyl-2-(3,5-di-t-
octyl-4-hydroxyphenyl)ethyl] -2,
4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,l-dimethyl-2-(3-t-
butyl-4-hydroxyphenyl)ethyl]-2.4,
8.10-tetraoxaspiro[5,51 undecane,
3,9-bis[1,1-dimethyl-2-(3-t-amyl-4-hydroxyphenyl)ethyl] -2,4,8
, 10-tetraoxaspiro[5,5]undecane, 3
,9-bis[1,1-dimethyl-2-(3-t-octyl-4-hydroxyphenyl)ethyl]-2.4,8.
10-tetraoxaspiro[5,5]undecane, 3
,9-bis[1,1-dimethyl-2-(3-methyl-4
-hydroxy-5-t-butylphenyl)ethyl]-2
．． 4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-(3-methyl-4-hydroxy-5-t-amylphenyl)ethylco2゜4 .8.10-tetraoxaspiro[5,5
Condecane, 3,9-bis[1,1-dimethyl-2-
(3-Methyl-4-hydroxy-5-t-octylphenyl)ethyl2.4.8.10-tetraoxaspiro[5,5]undecane, 3,9.bis[1,1-dimethyl-2-( 3-ethyl-4-hydroxy-5-t-butylphenyl)ethyl] -2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[1
,1-dimethyl-2-(3-i-propyl-4-hydroxy-5-t-butylphenyl)ethyl]-2.4,8
．． 10-tetraoxaspiro[5,5]undecane,
3,9-bis[1,1-dimethyl-2-(3-i-butyl-4-hydroxy-5-t-butylphenyl)ethyl]-2.4,8.10-tetraoxaspiro[5゜5 Condecane, 3,9-bis[1,1-dimethyl-2-(
3-5-Butyl-4-hydroxy-5-t-butylphenyl)ethyl2.4,8.10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2- (3,5-di-butyl-4-hydroxyphenyl)ethyl] -2,4,8゜10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1
-dimethyl-2-(3-t-butyl-4-hydroxy-
5-t-amylphenyl)ethyl] -2,4,8,1
0-tetraoxaspiro[5,5 condecane, 3,9
-bis[1,1-dimethyl-2-(3-t-butyl-4
-Hydroxy-5-cyoctylphenyl)ethyl]
-2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-(3
,5-di-amy-4-hydroxyphenyl)ethyl]-2.4,8.10-tetraoxaspiro[5゜5
] undecane, 3,9-bis[1,1-dimethyl-2-
(3゜5-di-1octyl-4-hydroxyphenyl)ethyl2.4,8.10-tetraoxaspiro[
5,5] undecane.

3.9.bis[1,1-dimethyl-2-(2-methyl-
4-hydroxy-5-t-butylphenyl)ethyl]
-2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-(3
-methyl-4-hydroxy-5-t-amylphenyl)
ethyl] -2,4,8,10-tetraoxaspiro[
5,5]undecane, 3,9-bis[1,1-dimethyl-2-(2,5-di-t-butyl-4-hydroxyphenyl)ethyl]-2.4,8.10-tetraoxaspiro [5,5]Undecane, 3,9-bis[1,1-dimethyl-2-(3,5-di-t-amyl-4-hydroxyphenyl)ethylco-2,4°8.10-tetraoxaspiro[5 ,5 undecane, 3゜9-bis[1,1-
Dimethyl-2-(2-methyl-4-hydroxy-5-t
-octylphenyl)ethyl] -2,4,8,10-
Tetraoxaspiro[5,5-oundecane, 3,9-bis[1,1-dimethyl-2-(2-t-butyl-4-hydroxy-5-methylphenyl)ethyl] -2,4,
8,10-tetraoxaspiro [5,5 condecane,
3,9-bis[3-(3-t-butyl-4-hydroxyphenyl)butyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 3,9-bis[3-(
3-Methyl-4-hydroxy-5-t-butylphenyl)butyl]-2.4,8.10-tetraoxaspiro[
5,5]undecane, 3,9-bis[3-(3,5-di-butyl-4-hydroxyphenyl)butyl] -
2,4,8,10-tetraoxaspiro[5,5oundecane, 3,9-bis[3-(3-methyl-4-hydroxy-5-t-amylphenyl)-jf]-2,4,
8,10-tetraoxaspiro[5,5]undecane,
3,9-bis[3-(3,5-diamyl-4-hydroxyphenyl)butyl]-2,4,8,10-tetraoxaspiro[5,5] undecane, 3,9-bis[3 -(3-methyl-4-hydroxy-5-t-octylphenyl)butyl]-2.4,8.10-tetraoxaspiro[5,5]undecane and 3,9-bis[
3-(3,5-di-t-octyl.

4-hydroxyphenyl)butyl] -2,4,8,1
Examples include 0-tetraoxaspiro[5,5-oundecane, particularly 3,9-bis[2-(3-methyl-4-hydroxy-5-t-butylphenyl)ethyl]-2,
4,8,10-tetraoxaspiro[5,5-oundecane, 3,9-bis[2-(3,5-di-t-butyl-4
-Hydroxyphenyl)ethylco2.4,8.10-
Tetraoxaspiro[5,5] undecane, 3.9-
Bis[1,1-dimethyl-2-(3-methyl-4-hydroxy-5-t-butylphenyl)ethyl] -2,4
, 8,10-tetraoxaspiro[5,5-oundecane and 3,9-bis[1,1-dimethyl-2-(3,5
-di-savetyl-4-hydroxyphenyl)ethyl]
-2.4,8.10-tetraoxaspiro[5,51 undecane is preferred. These compounds A can be used alone, but two or more kinds of compounds A can also be used in combination. The blending ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 parts by weight, based on 100 parts by weight of a ready-made product in which 30 to 70% by weight of magnesium hydroxide is blended with polyolefin.
~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.

Compound B used in the present invention is 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-myristylthiobropylidene)
Sorbitol, l.3.2.4-bis(3-palmitylthiopropylidene) sorbitol, 1.3,2.4-bis(3-stearylthiopropylidene) sorbitol,
1.3,2.4-bis(3-tocosylthiopropylidene) sorbitol, l.3,2.4-bis(3-tetracosylthiopropylidene) sorbitol, 1.3.2.4
-bis(3-hexacosylthiopropylidene) sorbitol, 1,3,2,4-bis(3-ophtacosylthiopropylidene) sorbitol, 1,3,2,4-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-balmitylthiopropylidene) sorbitol, 1.3.2.4-bis(2-methyl-3-stearylthiopropylidene) sorbitol,
1,3,2,4-bis(2-methyl-3-tocosylthiopropylidene) sorbitol, 1,3,2,4-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, ■・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-balmitylthiobutylidene) 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, 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, 1,3,2,4-bis(4-
tridecylthiobutylidene) sorbitol, 1, 3, 2
・4-bis(4-myristylthiobutylidene) sorbitol, 1.3,2.4-bis(4-balmitylthiobutylidene) sorbitol, l.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-hexacosylthiobutylidene) ) Sorbitol, 1, 3, 2,
4-bis(4-ophtacosylthiobutylidene) sorbitol, 1.3,2.4,5.6-tris(3-(2-ethylhexyl)thiopropylidene) sorbitol, 1.
3.2.4,5.6-tris(3-n-octylthiopropylidene) sorbitol, 1.3゜2.4,5.6-
tris(3-nonylthiopropylidene) sorbitol,
l.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-balmitylthiopropylidene) sorbitol, l,3,2,4,
5,6-tris(3-stearylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(3-tocosylthiopropylidene) sorbitol, 1,3,2,
4,5,6-tris(3-tetracosylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(
3-hexacosylthiopropylidene) sorbitol, 1
・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-balmitylthiopropylidene) 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, l.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-ophtacosylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris(3-(2-ethylhexyl)thiobutylidene) sorbitol, 1,3
, 2.4,5.6-tris(3-n-octylthiobutylidene) sorbitol, l.3,2.4,5.6-tris(3-nonylthiobutylidene) sorbitol, 1.3
, 2.4,5.6-tris(3-decylthiobutylidene) sorbitol, l.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-balmitylthiobutylidene) sorbitol, 1.3,2.4,5.6-tris(
3-stearylthiobutylidene) sorbitol, 1.3
, 2.4,5.6-tris(3-tocosylthiobutylidene) sorbitol, l.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, l.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-valmitylthiobutylidene)
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, simiristyl Examples include disulfide, distearyl disulfide, didocosyl disulfide, ditetracosyl disulfide, dihexacosyl disulfide, and dioctacosyl disulfide.
In particular, 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; single use of these compounds B is Of course, two or more types of compounds B can also be used in combination. The blending ratio of the compound B is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of a composition in which 30 to 70% 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.
Although it is possible to exceed 1 part by weight, it is not only impractical but also uneconomical since no further improvement in heavy metal resistance can be expected.

Heavy metal deactivators used in the present invention include benzotriazole, 2,4.8-)riamino-1,3,5-
) riazine, 3,9-bis(2-(3,5-diamino-
2,4,6-)riazaphenyl)ethyl] -2,4,
8,10-tetraoxaspiro [5,5 condecane,
Ethylenediamine-tetraacetic acid, alkali metal salt of ethylenediamine-tetraacetic acid (Li.

Na, K) @, N, N'-disalicylidene-ethylenediamine, N, N'-disalicylidene-1,2-propylenediamine, N, N l-disalicylidene-N
'-Methyl-dipropylene triamine, 3-salicyloylamino-1,2,4-) lyazole, decamethylene dicarboxylic acid-bis(N'-salicyloyl hydrazide), nickel-bis(1-phenyl-3-methyl -4-decanoyl-5-virazolate), 2-ethoxy-2'-ethyloxanilide, 5-t-butyl-2
-Ethoxy-21-ethyloxanilide, N,N-diethyl-N',N'-diphenyloxamide, N,N
'-diethyl-N,N'-diphenyloxamide, oxalic acid-bis(benzylidene hydrazide),
Thiodipropionine quacid bis(benzylidene hydrazide), isophthalic acid bis(2-phenoxypropionyl hydrazide), bis(salicyloylhydrazine), N-salicylidene-N'-salicyloylhydrazone, N, N'- Bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)probionylcohydrazine, tris[2-t-butyl-4-thio(2
1-Methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]phosphite, bis[
2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenylcopentaerythritol-diphosphite, tetrakis[2-L-butyl-4 -thio(2'-methyl-
42-Hydroxy-5'-butylphenyl)-5-
methylphenyl]-1,6-hexamethylene-bis(N
-Hydroxyethyl-N-methylsemicarbazide)-siphosphite, tetrakis[2-t-butyl-4-thio(2'-methyl4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl2 1,10-decamethylene dicarboxylic acid dihydroxyethyl carbonyl hydrazide diphosphorite,
Tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-51-t-butylphenyl)-5
-Methylphenylco1.10-decamethylene-dicarboxylic acid-disalicyloylhydrazide diphosphite, tetrakis[2-t-butyl-4
-thio(2ζmethyl-41-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-di(hydroxyethylcarbonyl)hydrazide-siphosphite,
Tetrakis[2-t-butyl-4-thio(2'-methyl-4ξhydroxy-5'-t-butylphenyl)-5-
Methylphenylco N,N'-bis(hydroxyethyl)oxamide-siphosphite.

and N,N'-bis[2-[3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxy]ethyl]oxamide, in particular oxalic acid-bis(benzylidene hydrazide), NN
j-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris[2
-t-butyl-4-thio(2'-methyl-41-hydroxy-5'-butylphenyl)-5-methylphenyl]phosphite and N,Nξbis[2-[3-(
3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethylcoxamide is preferred; these heavy metal deactivators can be used alone, but two or more heavy metal deactivators can be used together. They can also be used together. The blending ratio of the heavy metal deactivator is as follows: 100 g
0.01 to 1 part by weight, preferably 0.0 part by weight
The amount 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 but also uneconomical since no further improvement in heavy metal resistance can be expected.

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 is suitable, and epichlorohydrin or a derivative of epichlorohydrin (for example, 2-methylepichlorohydrin) is preferable.

condensates of bisphenol or bisphenol derivatives (such as bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol FJ5, and hydrogenated bisphenol S), epoxy oils (e.g. epoxidized soybean oil, epoxidized linseed oil and epoxidized castor oil), epoxidized oleaginous acids, alkyl esters of epoxidized oleaginous acids (e.g. epoxidized octyl stearate, 3,4-epoxycyclohexylmethanol), Fatty acid ester, alkyl ester of 3,4-epoxycyclohexylcarboxylic acid, dialkyl ester of 4゜5-epoxycyclohexane-1,2-dicarboxylic acid, 3,4-epoxy-6-methylcyclohexylmethyl and 3,4- epoxy 6-methylcyclohecane carboxylate, etc.), tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, novolak glycidyl ether,
Polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, P-oxybenzoic acid glycidyl ether-ester, phthalic acid diglycidyl ether,
Tetrahydrophthalate 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-epoxy-6-methylcyclohexylmethyl) ) adipate, vinylcyclohexene dieboxide, dicyclopentadiene oxide, bis(2,3-epoxycyclopentyl) ether and limonene dioxide, in particular condensates of epichlorohydrin and bisphenol A, 2-methylepichlorohydrin and bisphenol. condensate with A,
Triglycidyl isocyanurate and epoxidized soybean oil are preferred; these epoxy compounds can be used alone, but two or more epoxy compounds can also be used in combination. The blending ratio of the epoxy compound 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 30 to 70% 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 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.

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, linoleic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid,
Examples include 12-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 natural to use these fatty acids alone, but it is also possible to use two or more types of fatty acids in combination. 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, the method for blending nm* is to blend fatty acid with surface-untreated magnesium hydroxide, magnesium hydroxide surface-treated with a surface treatment agent other than fatty acids, and other compounds, or to pre-surface magnesium hydroxide with fatty acid. Any method such as blending as treated 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, dripless 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 (e.g. 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 coupling agents (e.g. silane, titanate, boron, aluminate, zircoaluminate, etc.)
The above-mentioned inorganic fillers or organic fillers (for example, wood flour, valves, waste paper, synthetic fibers, natural fibers, etc.) whose surface has been treated with a surface treatment agent such as the following may be used in combination without impairing the object 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 the above-mentioned various additives that are usually added to polyolefin to a polyolefin using a conventional mixing device, such as a conventional mixing device. Mix using a Henschel mixer (trade name), super mixer, ribbon blender, Pan Bali mixer, etc., and mix with a normal single screw extruder, twin screw extruder, Brabender or roll, etc. at a melt mixing temperature of 150°C to 300°C. ℃
, preferably by melt-kneading and pelletizing at 20°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 antioxidative deterioration effects is exhibited, and the heavy metal resistance is extremely excellent. A flame-retardant polyolefin composition is obtained.

In addition, compound A is excellent as a radical linkage M inhibitor in a flame-retardant polyolefin composition containing magnesium hydroxide, because in the coexistence of magnesium hydroxide, compound A is combined with pentaerythritol and a phenolic group-containing aldehyde. 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 phenolic antioxidants having ester or amide groups other than Compound A. Presumed.

Furthermore, Compound B is excellent as a peroxide decomposition agent in a flame-retardant polyolefin composition containing magnesium hydroxide because it is an acetal or dialkyl disulfide of sorbitol and an alkylthioalkanal. fil other than compound B
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 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 rust resistance test. That is, using the obtained pellets, a test piece with a length of 50 m, a medium size of 25 mm, and a thickness of 1 mm was made by injection molding, and this test piece was used to form a copper plate with a length of 25 mm, a medium size of 25 ++ nm, and a thickness of 0.3 aw. Place the specimen in a circulating hot air oven adjusted to a temperature of 150°C or 140°C, and measure the time until the contact area of the test piece completely deteriorates (time until deterioration penetrates). Heavy metal resistance was evaluated based on JIS K7212).

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, the length is 150 m+, the medium is 6.5 am, and the thickness is 3.
A 0 mm combustion test piece was created by injection molding, and the oxygen index was measured using the combustion test piece (JISK7201
Evaluation was made based on the following.

Production Example 1 Henschel Mixer (trade name ) and 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 with an average particle size of 0.6 to 0.8 μ as magnesium hydroxide and 2 parts by weight of stearin 1] following general formula [II] as n fatty acid were adjusted to a temperature of 80°C. Place in Henschel mixer (product name) and mix for 5 minutes #
By mixing, surface-treated magnesium hydroxide [II] was obtained.

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 121 parts by weight of n-fatty acid.
] 2 parts by weight of the following general formula [II] was kept at room temperature using a Henschel mixer (trade name; hereinafter, if the temperature of the Henschel mixer is not stated, it indicates that the temperature is room temperature).

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

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 the following general formula [II] in a Henschel mixer (
(trade name) and stirred and mixed for 5 minutes to obtain surface-treated magnesium hydroxide [■].

Examples 1 to 8, Comparative Examples 1 to 15 MFR (discharge amount of molten resin in 10 minutes when applying a load of 2.16 kg at 230"C) 20 g/10 minutes as polyolefin Unstabilized powdered crystals Surface-untreated product 5 with 43% by weight of propylene homopolymer and an average particle size of 0.6 to 0.8μ as magnesium hydroxide.
As compound A, 3,9-bis[2-(3,5-di-t-butyl-4-
hydroxyphenyl)ethyl] -2,4,8,10-
Tetraoxaspiro[5,5]undecane, l.3,2.4-bis(3-laurylthiopropylidene) sorbitol as compound B, l.3,2.4,5.6-tris(3-laurylthio) propylidene) sorbitol or dilauryl disulfide, N as a heavy metal deactivator
, N'-bis[2-(3-(3,S-di-t-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)propionyl]hydrazine or oxalic acid-bis(benzylidene hydrazide), a composite of epichlorohydrin and bisphenol A as an epoxy compound (epoxy equivalent: 700-830)
) or a mixture of a composite of epichlorohydrin and bisphenol A and a composite of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent: 180 to 200)
) and other additives in the mixing ratios listed in Table 1 below into a Henschel mixer (trade name).

After stirring and mixing for 3 minutes, the mixture was melted and mixed at 250° C. using a twin-screw press ratio machine with a diameter of 30 mm to form pellets. Comparative Examples 1 to 15 include 43% by weight of unstabilized powdery crystalline propylene homopolymer with an MFR of 20 g/10 min and an average particle size of 0.6 to 0 as magnesium hydroxide.
．． A total of 100 pieces consisting of 57% by weight of 8μ surface-untreated products.
'1] The following general formula [II1] Mix predetermined amounts of each of the additives listed in Table 1 and melt according to Examples 1 to 8 according to the following general formula [II] Obtained.

The test pieces used for the type copper property test and the flammability test are as follows.

The obtained pellet was heated at a wood temperature of 250°C and a mold temperature of 50°C.
It was prepared by injection molding.

Using the obtained test piece, heavy metal resistance (150°C copper resistance type copper and flame retardance evaluation was carried out using the test method described above. These results were evaluated using the following general formula [Table II1] .

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.
Magnesium hydroxide [I] surface-treated as 59% by weight and magnesium hydroxide, magnesium hydroxide [I
[], magnesium hydroxide [■ or magnesium hydroxide [IV] 70.41% by weight, total 10
1.4 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) were added with 3,9-bis as compound A. [1, Todimethyl-2
-(3-methyl-4-hydroxy-5-t-butylphenyl)ethyl] -2,4,8,10-tetraoxaspiro[5,5-oundecane, 1.3.2 as compound B
・4-bis(2-methyl-3-(2-ethylhexyl)
thiopropylidene) sorbitol, l・3,2・4,5
・6-tris(2-methyl-3-(2-ethylhexyl)thiopropylidene) sorbitol or similistyl disulfide, N,Nξbis[2-(3-(3,5-di-butyl-4) as a heavy metal deactivator -hydroxyphenyl)propionyloxy]ethyl]oxamide, tris[2-t-butyl-4-thio(2'-methyl-
4'-Hydroxy-5'-butylphenyl)-5-
Methylphenylcottosphite, N,N'-bis[3
-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine or oxalin acid-bis(benzylidene hydrazide), as an epoxy compound a combination of epichlorohydrin and bisphenol A (epoxy equivalent: 700 to 830), or A mixture of a composite of epichlorohydrin and bisphenol A, a composite of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent: 180 to 200), and other additives in predetermined amounts at the blending ratios listed in Table 2 below. The mixture was placed in a Henschel mixer (trade name) and stirred and mixed for 3 minutes, and then melt-kneaded at 250°C in a 21 extruder with a diameter of 30Tm to form pellets. Also, Comparative Examples 16 to 30
Unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) with a MFR of 30z/10 min as 30% by weight and an average particle size of 0.6-0 as magnesium hydroxide A total of 100 parts by weight or M
Unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) with FR of 30 g/10 min 29.59% by weight and magnesium hydroxide surface treated as magnesium hydroxide [
II ] 770.41 weight and a total of 101.4
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) are added with predetermined amounts of each of the additives listed in Table 12 below. were blended and melt-kneaded according to Examples 9 to 16 to obtain pellets.

The test pieces used in the copper-drunkness 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 evaluated for heavy metal resistance (150° C. copper resistance type copper and flame retardance) according to the test method described above. These results are shown in Table J12.

Examples 17-24. Comparative Examples 31 to 45 Unstabilized powdery crystalline ethylene-propylene-butene-13 copolymer (ethylene content 2.5% by weight, butene-1 content) Amount 4.5% by weight ) 50% by weight and magnesium hydroxide as average grains! A total of 100 parts by weight, including 50% by weight of 0.8-0.8μ surface-untreated products.

As compound A, 3,9-bis(3,5-di-t-octyl-4-hydroxyphenyl)-2,4,8,10-
Tetraoxaspiro[5,5]undecane, 1,3,2,4-bis(3-stearylthiobutylidene) sorbitol as compound B, 1,3,2,4,5,6-tris(3-stearylthio butylidene) sorbitol or distearyl disulfide, N,N'-bis[2-[3.(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]oxamide as a heavy metal deactivator, Tris[2-t-butyl-4-thio(
2'-methyl-41-hydroxy-5'-t-butylphenyl)-5-methylphenyl]phosphite, N,
N'-bisC3-(3,5-di-t-butyl-4-hydroxyphenyl)probionylcohydrazine or oxalic acid-bis(benzylidenehydrazide)
, as an epoxy compound triglycidyl isocyanurate (epoxy equivalent 100-1) following general formula [II0] or epoxidized soybean oil (epoxy equivalent 220-240
) and other additives in the mixing ratios listed in Table 13 below in a Henschel mixer (trade name), stirred and mixed for 3 minutes, and then heated at 250°C in a twin-screw extruder with a diameter of 30 mm. It was melt-kneaded and pelletized. Moreover, as Comparative Examples 31 to 45, unstabilized powder crystalline ethylene-propylene-
Butene-13 element copolymer (contains ethylene! 2.5% by weight)
, 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. Blend the prescribed amounts of each of the additives listed in
Pellets were obtained by melt-kneading according to Examples 17-24.

The specimens are suitable for type copper resistance test and flammability test.

The obtained pellets were heated to a temperature of 50°C and a mold temperature of 50".
Prepared by injection molding.

The obtained test pieces were used to evaluate heavy metal resistance (140°C hot copper rust resistance and flame retardance) according to the test method described above.The results are shown in Table jI3.

Examples 25-32, Comparative Examples 46-60 Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 55 with MFR 7.0 g/10 min as polyolefin
Weight%, MI (discharge amount of molten resin in 10 minutes when applying a load of 2.161@ at 190°C) 20g/
10% by weight of unstabilized powdered Ziegler-Natsuta high-density ethylene homopolymer for 10 minutes, unstabilized powdered amorphous ethylene-propylene random copolymer with Mooney viscosity MLI÷4 (100°C) 25 To a total of 100 parts by weight consisting of 5% by weight of polymer (propylene content 25%) and 30% by weight of surface untreated magnesium hydroxide with an average particle size of 0.6 to 0.8μ, 3% of compound A was added. 9-bis[3-(3-t-butyl-4-hydroxyphenyl)butyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 1 as compound B
・3,2,4-bis(4-ophtacosylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris(4
-oftacosylthiobutylidene) sorbitol or dioctacosyl disulfide, N,N'-bis[2-(3-(3,5-di-t-
Butyl-4-hydroxyphenyl)propionyloxy]ethyl]oxamide, tris[2-t-butyl-4-
Thio(2ξmethyl-4'-hydroxy-5ξ7-butylphenyl)-5-methylphenylcottosphite, N
, N'-bis[3-(3,5-di-t-phthyl-4-hydroxyphenyl)propionyl]hydrazine or oxalic acid-bis(benzylidene hydrazide), triglycidyl isocyanurate as an epoxy compound (epoxy equivalent: 100 to 1 ] Following general formula [II0)
Or epoxidized soybean oil (epoxy equivalent: 220-24
0) and other additives in the mixing ratios listed in Table 3 below in a Henschel mixer (trade name), stirred and mixed for 3 minutes, and heated to 250°C using a twin-screw extruder with a diameter of 30 m. The mixture was melt-mixed and pelletized. Comparative Example 46-6° is an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) with an MFR of 7-1 f/10 min.
5% by weight, 10% by weight of unstabilized powdered Ziegler-Natsuta high density ethylene homopolymer with MI of 20g/10min, Mooney viscosity M L 1+4 (100°C
) is 25 unstabilized powdered amorphous ethylene-
A total of 100 parts by weight consisting of 5% by weight of propylene random copolymer (propylene content 125%) and 30% by weight of a surface-untreated magnesium hydroxide product with an average particle size of 0.6 to 0.8μ is added to Table 14 below. A predetermined amount of each of the additives described in 1. was blended and melt-kneaded according to Examples 25 to 32 to obtain pellets.

The test pieces used for the mold copper property test and the flammability test were made by injection molding the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C to obtain msI! Shita.

The obtained test pieces were used to evaluate heavy metal resistance (140°C copper resistance type copper and flame retardance) according to the test method described above. The results are shown in Table 4.

j1] The compounds and additives related to the present invention shown in the following general formula [Table II to Table 4 are as follows.

Magnesium hydroxide [0]: Average particle size 0.6-0.8μ
Surface-untreated product magnesium hydroxide [1] Following general formula [II: Surface-treated product hydroxide obtained by surface-treating 100 parts by weight of surface-untreated product with an average particle size of 0.6 to 0.8μ with 2 parts by weight of lauric acid. Magnesium [1] General formula [II] below: Average particle size 0.6-0
．． Surface-treated magnesium hydroxide [■
]: Surface-treated magnesium hydroxide product obtained by surface-treating 100 parts by weight of an untreated product with an average particle size of 0.6 to 0.8 μm and 2 parts by weight of oleic acid [■]: Average particle size of 0.6 to 0.8 μm
Compound A[I]: 3.9-bis[2-(3,5-di-t)
-butyl-4-hydroxyphenyl)ethyl] -2,
4,8,10-tetraoxaspiro[5,5]undeline compound A [II]: 3,9-bis[1,1-dimethyl-2-(3-methyl-4-hydroxy-5-t-
butylphenyl)ethyl]-2.4,8.10-tetraoxaspiro[5,5]undecane compound A[mconi-3,9-bis(3,5-di-octyl-4-hydroxyphenyl)-2, 4,8,10
-Tetraoxaspiro[5,5]undecane Compound A [rVconi3.9-bis[3-(3-t-butyl-4-hydroxyphenyl)butyl] -2,4,8
, 10-tetraoxaspiro[5,5]underin compound B [I]: 1,3,2,4-bis(3-laurylthiopropylidene) sorbitol compound B [I[coni1,3,2, 4-bis(2-methyl-3-(2-ethylhexyl)thiopropylidene)sorbitol compound B [I[I]: 1.3,2.4-bis(3
-stearylthiobutylidene) sorbitol compound B [IV]: 1.3,2.4-bis(4-
ophtacosylthiobutylidene) sorbitol compound B [Vconi 1,3,2,4,5,6-tris(3
-Laurylthiopropylidene) Sorbitol Compound B [VI Coni 1,3,2,4,5,6-tris(2-methyl-3-(2-ethylhexyl)thiopropylidene)Sorbitol Compound B [■Coni 1,3,2・4,5・6-tris(3
-stearylthiobutylidene) sorbitol compound B [■]: 1,3,2,4,5,6-tris(4
-ophtacosylthiobutylidene) sorbitol compound B [IX]: dilauryl disulfide compound B [X]: cimilistyl disulfide compound B
[XI Conidistearyl disulfide compound B [X
Uco: Dioctacosyl disulfide heavy metal deactivator [
I]:N,N''-bis[2-(3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxy]ethyl cooxamide heavy metal deactivator [II]:) Lis[2- t-butyl-
4.thio(2ξmethyl-41-hydroxy-5'-t-
butylphenyl)-5-methylphenylcotiosphite heavy metal deactivator [1] The following general formula [II1]:
N,N'-bis[3-(3,5"di-t-butyl-4-
Hydroxyphenyl)propionylcohydrazine Heavy metal deactivator [IV] Nioxalic acid-
Bis(benzylidene hydrazide) Epoxy compound [I]: Condensate of epichlorohydrin and bisphenol A (epoxy equivalent 700-830; C
Made by IBA-GEIGY AG ARA-LDITE
GT 7004) Epoxy compound [■]: Mixture of a condensate of shrimp chlorohydrin and bisphenol A and a mixture of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 180-200; Adeka Argus Chemical-If MA
RK EP-17) Epoxy compound [m]: )
Liglycidyl isocyanurate (epoxy equivalent 100-
1] The following general formula [II0; CI BA -GEIG
Y AGli ARALDITE PT epoxy compound [IV]: Epoxidized soybean oil (epoxy equivalent 2
20-240; Adeka Argus Chemical eessADK
CI ZER0-130P) Fat Ill: Acetic acid m fatty acid 2: 2-ethylhexanoic acid fatty acid 3: Lauric acid fatty acid 4 Nistearic acid fatty acid 5 Nioleic acid fat W16: Linoleic acid fat 17: Behenic acid MI Fatty acid: Erucic acid fat I ! 9: Montanic acid fat *1o: 12-hydroxyoctadecanoic acid phosphorus antioxidant 1: Bis(2,6-di-butyl-4-methylphenyl)-pentaerythritol-cyphosphite phosphorus antioxidant 2: Bis (2,4-di-butylphenyl)-pentaerythritol-siphosphite phosphorus antioxidant 3: Tetrakis (2,4-di-butylphenyl)-4,4'-biphenylene-diphosphonite phenol Antioxidant 1: 2,6-di-t-butyl-
p-cresol phenolic antioxidant 2: Tetrakis C methylene-3
-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane phenolic antioxidant 3:2,2-bis[4-[2-
<3.5-Dibutyl-4-hydroxyphenylpropionyloxy)ethoxy]phenyl]propane Phenolic antioxidant 4: Tris(4-t-butyl-3
-Hydroxy-2,6-cyphthylbenzyl)isocyanurate phenolic antioxidant 5: Tris[3-(3,5-
di-t-butyl-4-hydroxyphenyl)propionyloxyethyl coisocyanurate phenolic antioxidant 6: 1,1.3-)lis(5
-t-butyl-4-hydroxy-2-methylphenyl)
-Butanephenolic antioxidant 7: bis[3,3-bis(4'
-Hydroxy-3″-t-butylphenyl) ptyric acid coethylene glycol ester phenolic antioxidant 8:2,2-thio diethylenebis[3-(3
,5-di-t-butyl-4-hydroxyphenyl)propionate-tocophenolic antioxidant 9: 1,3.5-)listyl-2,4,6-tris(3,5-di-t-butyl) -4-
Hydroxybenzyl)benzenephenolic antioxidant 10: bisr2- (3'-
t-Butyl-5'-methyl-2'-hydroxybenzyl)-4-methyl-6-t-butylphenylcoterephthalate thioni-thyl antioxidant 1 Nidimyristylthiodipropionate thioether antioxidant 2 :Pentaerythritol-
Tetrakis(3-laurylthiopropionate) Thioether antioxidant 3: N,N'・bis(3-
laurylthiopropionyl) hydrazide carbon black: Carbon #45 C manufactured by Mitsubishi Kasei ■
a-8t Calcium nystearate 31] The following general formula [Examples and comparative examples shown in Table II are cases where a crystalline propylene homopolymer was used as the polyolefin and a surface-untreated product was used as the magnesium hydroxide. As can be seen from Table 1, Examples 1 to 8 are crystalline propylene homopolymer blended with magnesium hydroxide (surface-untreated product), compound A, compound B, a heavy metal deactivator, and an epoxy compound. and Examples 1 to 8
When comparing Comparative Examples 1 to 7 (in which phenolic antioxidants 2 to 8 other than Compound A were blended in place of Compound A in Examples 1 to 4), Examples 1 to 8 were heavy metal resistant. It can be seen that in the coexistence of magnesium hydroxide, phenolic antioxidants 2 to 8 other than Compound A do not sufficiently exhibit radical chain inhibiting action, that is, antioxidant effect. In addition, Examples 1 to 8 and Comparative Examples 8 to 10 (
Comparing Examples 1 to 4, in which thioether antioxidants 1 to 3 other than Compound B were blended in place of Compound B, Comparative Examples 8 to 10 had the same heavy metal resistance as Comparative Examples 1 to 7. Although it is improved, it is still not sufficient, and it can be seen that thioether antioxidants 1 to 3 other than Compound B do not sufficiently exhibit peroxide decomposition action, that is, antioxidant effect, in the coexistence of magnesium hydroxide. Also 1
In the flame-retardant polyolefin compositions related to Japanese Patent Application No. 1-35792 and Japanese Patent Application No. 1-62845 previously proposed by the present inventors, that is, Examples 1 to 4, the phenolic antioxidant 9 was used instead of Compound A. and Comparative Example 1 in which thioether antioxidant 1 was blended in place of compound B, or phenolic antioxidant 10 was blended in place of compound A, and thioether antioxidant 2 was blended in place of compound B] Comparing the following general formula [II-12 and Examples 1-8, Comparative Example 1] The following general formula [
Although the heavy metal resistance of II to 12 is improved compared to Comparative Examples 1 to 7, it 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 Comparative Example 15 which contains a Compound A, Compound B and an epoxy compound but does not contain a heavy metal deactivator.
Comparing Examples 1 to 8, Comparative Examples 13 to 15
The resistance to heavy metals is still not sufficient.

Therefore, it is clear that comparisons that do not simultaneously satisfy the four component formulations of compound A, compound B, heavy metal deactivator, and epoxy compound related to the present invention do not exhibit the effects of the present invention. Namely.

The heavy metal resistance obtained in the present invention is achieved by adding compound A to a flame-retardant polyolefin composition containing magnesium hydroxide.
This can be said to be a unique effect that can only be seen when Compound B, a heavy metal deactivator, and an epoxy compound are used together. Furthermore, in Examples 5 to 8, in which various fatty acids were used in combination in Examples 1 to 4, compared to Examples 1 to 4, compound A
It can be seen that the excellent effects of improving heavy metal resistance of Compound B, the heavy metal deactivator, and the epoxy compound are not inhibited, and a remarkable synergistic effect is observed by 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 it was.

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 or crystalline ethylene-propylene random copolymer, Ziegler-Natsuta high-density ethylene homopolymer, and non-produced 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 conventional flame-retardant polyolefin ready-made products containing magnesium hydroxide and having improved heavy metal resistance, the composition of the present invention has (1) lower resistance when formed into molded products; The molded product has excellent resistance to heavy metals. (2) Because it has extremely high resistance to heavy metals, there is no reduction in electrical insulation properties caused by oxidative deterioration of polyolefins, so it is used in applications that require flame retardancy and heavy metal resistance in various molding fields (e.g. deflection yokes, It can be suitably used for electrical 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 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 2 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] Dialkyl disulfide compounds ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, , where R_1 represents an alkyl group having 1 to 8 carbon atoms.
_2 is hydrogen or an alkyl group having 1 to 8 carbon atoms, R_
3 is an alkylene group having 2 to 4 carbon atoms, and R_4 is an alkylene group having 8 carbon atoms.
~28 alkyl group, R_5 is an alkylene group having 2 or 3 carbon atoms, R_6 and R_7 are hydrogen or both form a 5-membered ring>CH-R_7-S-R_6 group,
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.