JP2696558B2 - Flame retardant polyolefin composition - Google Patents

Description

The present invention relates to a flame-retardant polyolefin composition. More specifically, the present invention relates to a flame-retardant polyolefin composition having excellent anti-oxidative deterioration properties of a polyolefin in practical use.

[Prior Art] In general, various halogen-based flame retardants are blended with polyolefin as means for making polyolefin flame-retardant, and are widely used in practice. However, a flame-retardant polyolefin composition containing a halogen-based flame retardant generates a harmful halogen-based gas during combustion. Therefore, a non-halogen-based flame retardant has recently been required as a flame retardant to be used. Among various non-halogen flame retardants, inorganic flame retardants that do not generate harmful combustion gas, especially magnesium hydroxide, are widely used in practice because of their high dehydration decomposition temperature and excellent smoke suppression effect during combustion. . In addition, polyolefins, especially propylene polymers, have tertiary carbon which is susceptible to oxidation in the polymer, and therefore have a disadvantage that they are susceptible to thermal oxidation deterioration during molding and practical use. For this reason, various antioxidants have been widely used for the purpose of preventing thermal oxidation deterioration.

Molded articles made from flame-retardant polyolefin compositions obtained by blending magnesium hydroxide and various antioxidants with polyolefins can be used for applications that come into contact with heavy metals such as copper, brass, iron and nickel. is there. However, since polyolefins are catalytically oxidized and degraded by heavy metal ions contained in the above-mentioned various heavy metals, molded articles using the above-described flame-retardant polyolefin composition have resistance to oxidation and degradation during heavy metal contact (hereinafter referred to as resistance to oxidation). Heavy metal) is significantly reduced.

For this reason, magnesium hydroxide, phenolic antioxidants, and sulfuric antioxidants have been added to polyolefins in order to improve the heavy metal resistance of molded articles using flame-retardant polyolefin compositions containing magnesium hydroxide. (JP-A-52-11238 and JP-A-63-56544), and a composition in which magnesium hydroxide and an epoxy compound are blended with polyolefin (JP-A-59-118). No. 219352, JP-A-63-137963, JP-A-63-159473 and JP-A-63-189462
Publications) have been proposed respectively.

[Problems to be Solved by the Invention] However, in recent years, demands for flame retardancy in applications such as electric and electronic parts or automobile parts have become more and more severe, and molded articles obtained from flame retardant polyolefin compositions have been required. With the diversification of applications and the increase in size, the use conditions of the molded product in practical use (heavy metal resistance, electrical insulation, etc.)
The demands on the Internet are also becoming more stringent. That is, it is necessary to develop a flame-retardant polyolefin composition having more excellent heavy metal resistance than ever before. In order to solve these problems, the above-mentioned Japanese Patent Application Laid-Open No. 52-11238, in which magnesium hydroxide is blended.
JP-A-63-56544, JP-A-59-219352, JP-A-63-137963, JP-A-63-159473 and JP-A-63-189462. The flame-retardant polyolefin compositions are not yet satisfactory enough for heavy metal resistance.

The present inventors have conducted intensive studies to obtain a composition which solves the above-mentioned problems concerning the flame-retardant polyolefin composition containing magnesium hydroxide, that is, a flame-retardant polyolefin composition having improved heavy metal resistance.

As a result, a phenolic compound represented by the following general formula [I] (hereinafter, referred to as compound A) and a pentaerythritol-tetrakis (alkylthioalkanoate) -based compound ( Hereafter, it has been found that a flame-retardant polyolefin composition having improved heavy metal resistance can be obtained by blending a specific amount of each of the compound B, a heavy metal deactivator and an epoxy compound. Was completed.

(Where R ₁ is an alkylidene group having 1 to 4 carbon atoms,
R ₂ represents an alkyl group having 1 to 9 carbon atoms, and R ₃ represents hydrogen or an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or an alkylcyclohexyl group. As is apparent from the above description, an object of the present invention is to provide a flame-retardant polyolefin composition having excellent heavy metal resistance when molded.

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

A phenolic compound represented by the following general formula [I] (hereinafter, referred to as “the compound”) is added to 100 parts by weight of a composition comprising 30 to 70% by weight of polyolefin and 70 to 30% by weight of magnesium hydroxide.
It is called Compound A. ), A pentaerythritol-tetrakis (alkylthioalkanoate) -based compound (hereinafter, referred to as compound B), a heavy metal deactivator, and an epoxy compound in an amount of 0.01 to 1 part by weight, respectively.

(Where R ₁ is an alkylidene group having 1 to 4 carbon atoms,
R ₂ represents an alkyl group having 1 to 9 carbon atoms, and R ₃ represents hydrogen or an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or an alkylcyclohexyl group. The polyolefin used in the present invention is a crystalline homopolymer of α-olefin such as ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, and the like. Crystallinity of the above α-olefin, low crystalline or amorphous random copolymer or crystalline block copolymer, amorphous ethylene-propylene-non-conjugated diene terpolymer, the above α-olefin Copolymers of vinyl acetate or acrylic acid esters, saponified products of the copolymers, copolymers of unsaturated silane compounds with these α-olefins and copolymers of these α-olefins with unsaturated carboxylic acids or anhydrides A copolymer, a reaction product of the copolymer and a metal ion compound, and a modified polymer obtained by modifying the above-mentioned polyolefin with an unsaturated carboxylic acid or a derivative thereof. Examples thereof include olefins and silane-modified polyolefins obtained by modifying the above-mentioned polyolefins with unsaturated silane compounds. These polyolefins can be used alone, or two or more polyolefins can be used in combination. In addition, various synthetic rubbers (for example, polybutadiene, polyisobrene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluorine rubber, 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, fluorine Resin) it can be used as a mixture. Crystalline propylene homopolymer, 70 propylene components
A crystalline propylene copolymer containing at least 1% by weight of a crystalline ethylene-propylene random copolymer, a crystalline ethylene-propylene block copolymer, a crystalline propylene-butene-1 random copolymer, and a crystalline ethylene copolymer. -Propylene-butene-1 terpolymer, crystalline propylene-hexene-butene-1 terpolymer and mixtures of two or more thereof are particularly preferably used.

As the magnesium hydroxide used in the present invention, plate-like and fibrous ones can be used without any limitation. Although the average particle size of the plate-like magnesium hydroxide is not particularly limited, it is usually 0.1 µ to 10 µ, preferably 0.2 µ to 2 µ, most preferably 0.5 µ to 1 µ, and the fibers of fibrous magnesium hydroxide Diameter is 0.1μ ~ 0.5μ, length is 5μ ~
20μ is preferred. In addition, these magnesium hydroxides are surface-treating agents such as higher fatty acids, metal soaps, higher fatty acid esters, higher alcohols, higher fatty acid monoamides, higher fatty acid bisamides, higher fatty acid metal phosphates,
When a surface treatment is performed in advance using a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, a boron coupling agent, an aluminate coupling agent, and a zircoaluminate coupling agent, the Since the compatibility and dispersibility of magnesium hydroxide and polyolefin are improved, excellent moldability is obtained, and the mechanical strength of the molded article when it is made into a molded article is improved.
It is preferable to use magnesium hydroxide surface-treated with a surface treatment agent. Of course, these magnesium hydroxides can be used alone, or two or more magnesium hydroxides can be used in combination. The mixing ratio of the magnesium hydroxide is 30 to 70% by weight, preferably 50 to 65% by weight based on the composition comprising the polyolefin and the magnesium hydroxide.
It is. If the amount is less than 30% by weight, the resulting molded article has insufficient flame retardancy. If the amount exceeds 70% by weight, the moldability becomes difficult and the mechanical strength of the obtained molded article is lowered, which is not practical.

As compound A used in the present invention, bis [2-
(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-tert-butylphenyl] isophthalate, bis [2- (3'-tert-butyl-5'-)
Ethyl-2'-hydroxybenzyl) -4-ethyl-6
-T-butylphenyl] isophthalate, bis [2-
(3'-nonyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-nonylphenyl] isophthalate, bis [2- (3 ', 5'-dinonyl-2'-hydroxybenzyl)- 4,6-dinonylphenyl] isophthalate, bis [2- (3'-cyclohexyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-cyclohexylphenyl] isophthalate, bis [2-
(3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxybenzyl) -4-methyl-6
(1′-methylcyclohexyl) phenyl] isophthalate, bis [2- (5′-nonyl-2′-hydroxy (α, α-dimethylbenzyl))-4-nonylphenyl] isophthalate, bis [2- (3 ', 5'-Dimethyl-2'-hydroxy (α-propylbenzyl))-4,6
-Dimethylphenyl] isophthalate, bis [2-
(3 ', 5'-di-tert-butyl-2'-hydroxybenzyl) -4,6-di-tert-butylphenyl] isophthalate, bis [2- (3'-tert-butyl-5'-s) -Butyl-2'-hydroxy (α-methylbenzyl) -4-s-
Butyl-6-t-butylphenyl] isophthalate, bis [2- (3 ', 5'-di-t-butyl-2'-hydroxy (α-methylbenzyl))-4,6-di-t-butyl Phenyl] isophthalate, bis [2- (3'-t-octyl-5'-methyl-2'-hydroxybenzyl) -4
-Methyl-6-t-octylphenyl] isophthalate, bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy (α-propylbenzyl))-4-methyl- 6- (1′-methylcyclohexyl) phenyl] isophthalate, bis [2-
(3 ', 5'-dimethyl-2'-hydroxybenzyl)-
4,6-dimethylphenyl] isophthalate, bis [2-
(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, bis [2- (3'-tert-butyl-5'-)
Ethyl-2'-hydroxybenzyl) -4-ethyl-6
-T-butylphenyl] terephthalate, bis [2-
(3'-nonyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-nonylphenyl] terephthalate, bis [2- (3 ', 5'-dinonyl-2'-hydroxybenzyl) -4 , 6-Dinonylphenyl] terephthalate, bis [2- (3'-cyclohexyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-cyclohexylphenyl] terephthalate, bis [2-
(3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxybenzyl) -4-methyl-6
(1′-methylcyclohexyl) phenyl] terephthalate, bis [2- (5′-nonyl-2′-hydroxy (α, α-dimethylbenzyl))-4-nonylphenyl] terephthalate, bis [2- (3 ′, 5'-dimethyl-2'-hydroxy (α-propylbenzyl))-4,6
-Dimethylphenyl] terephthalate, bis [2-
(3 ', 5'-di-t-butyl-2'-hydroxybenzyl) -4,6-di-t-butylphenyl] terephthalate, bis [2- (3'-t-butyl-5'-methyl-
2'-hydroxy (α-methylbenzyl)) 4-methyl-6-t-butylphenyl] terephthalate, bis [2
-(3'-t-butyl-5'-ethyl-2'-hydroxy (α-methylbenzyl))-4-ethyl-6-t-butylphenyl] terephthalate, bis [2- (3'-t
-Butyl-5'-s-butyl-2'-hydroxy (α-
Methylbenzyl))-4-s-butyl-6-t-butylphenyl] terephthalate, bis [2- (3 ', 5'-di-t-butyl-2'-hydroxy (α-methylbenzyl))-4 , 6-Di-t-butylphenyl] terephthalate, bis [2- (3'-t-octyl-5'-methyl-
2'-hydroxybenzyl) -4-methyl-6-t-octylphenyl] terephthalate, bis [2- (3'-
(1 "-methylcyclohexyl) -5'-methyl-2 '
-Hydroxy (α-propylbenzyl))-4-methyl-6- (1′-methylcyclohexyl) phenyl] terephthalate and bis [2- (3 ′, 5′-dimethyl-
2'-hydroxybenzyl) -4,6-dimethylphenyl] terephthalate and the like, and particularly, bis [2-
(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, bis [2- (3'-tert-butyl-5'-)
Ethyl-2'-hydroxybenzyl) -4-ethyl-6
-T-butylphenyl] terephthalate, bis [2-
(3 ', 5'-di-t-butyl-2'-hydroxybenzyl) -4,6-di-t-butylphenyl] terephthalate and bis [2- (3', 5'-di-t-butyl- 2'-
Hydroxy (α-methylbenzyl))-4,6-di-t-
[Butylphenyl] terephthalate is preferred. The sole specification of compound A is a matter of course.
Can also be used in combination. The compounding ratio of the compound A is 30 to 70% by weight of polyolefin and 70% by weight of magnesium hydroxide.
0.01 to 1 with respect to 100 parts by weight of a composition comprising 30 to 30% by weight.
Parts by weight, preferably 0.05 to 0.5 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving heavy metal resistance is not sufficiently exhibited, and even if it exceeds 1 part by weight, a further improvement effect of heavy metal resistance cannot be expected and it is not practical. Uneconomical and uneconomical.

Compound B used in the present invention includes pentaerythritol-tetrakis (3-octylthiopropionate), pentaerythritol-tetrakis (3-nonylthiopropionate), and pentaerythritol-tetrakis (3-decylthiopropionate). Pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-tridecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3 -Palmitylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), pentaerythritol-tetrakis (4-octylthiobutyrate), pentaerythritol Tetrakis (4-nonylthiobutyrate), pentaerythritol-tetrakis (4-decylthiobutyrate), pentaerythritol-tetrakis (4-laurylthiobutyrate), pentaerythritol-tetrakis (4-tridecylthiobutyrate), Pentaerythritol-tetrakis (4-myristyl thiobutyrate), pentaerythritol-trakis (4-palmityl thiobutyrate), pentaerythritol-tetrakis (4-stearyl thiobutyrate), pentaerythritol-tetrakis (3-octyl thiobutyrate) Pentaerythritol-tetrakis (3-nonylthiobutyrate), pentaerythritol-tetrakis (3-decylthiobutyrate), pentaerythritol-tetrakis (3-laurylthio) Butyrate), pentaerythritol-tetrakis (3-tridecyl thiobutyrate), pentaerythritol-tetrakis (3-myristyl thiobutyrate), pentaerythritol-tetrakis (3-palmityl thiobutyrate) and pentaerythritol-tetrakis (3 -Stearylthiobutyrate), and pentaerythritol-tetrakis (3-laurylthiopropionate) is particularly preferable. These compounds B may be used alone, or two or more compounds B may be used in combination. The compounding ratio of the compound B is 0.01 to 1 part by weight, preferably 0.0 to 1 part by weight based on 100 parts by weight of a composition comprising 30 to 70% by weight of polyolefin and 70 to 30% by weight of magnesium hydroxide.
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 is not sufficiently exhibited, and even if it exceeds 1 part by weight, a further improvement effect of heavy metal resistance cannot be expected and it is not practical. Uneconomical and uneconomical.

As the heavy metal deactivator used in the present invention, benzotriazole, 2,4,6-triamino-1,3,5-triazine, 3,9-bis [2- (3,5-diamino-2,4, 6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, ethylenediamine-tetraacetylic acid, alkali metal salt of ethylenediamine-tetraacetylic acid (Li, Na, K ) Salt, N, N'p disalicylidene-ethylenediamine, N, N "-disalicylidene-1,2-propylenediamine, N, N'-disalicylidene-
N'-methyl-dipropylenetriamine, 3-salicyloylamino-1,2,4-triazole, decamethylenedicarboxylic acid-bis (N'-salicyloylhydrazide), nickel-bis (1-phenyl- 3-methyl-4-decanoyl-5-pyrazolate), 2-ethoxy-2'-ethyloxanilide, 5-t-butyl-2-
Ethoxy-2'-ethyloxanilide, N, N-diethyl-N ', N'-diphenyloxamide, N, N'-diethyl-N, N'-diphenyloxamide, oxalic acid-bis (benzylidene hydrazide ), Thiodipropionic acid-bis (benzylidene hydrazide), isophthalic acid-bis (2-phenoxypropionyl hydrazide), bis (salicyloyl hydrazine),
N-salicylidene-N'-salicyloylhydrazone, N,
N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris [2-
t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite, bis [2-t-butyl-4-thio (2'- Methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -pentaerythritol-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy) -5'-
t-butylphenyl) -5-methylphenyl] -1,6-
Hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -phosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-t-butyl-4
-Thio (2'-methyl-4'-hydroxy-5'-t-
Butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-salicyloylhydrazide-diphosphite, tetrakis [2
-Tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide-
Diphosphite, tetrakis [2-t-butyl-4-
Thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] -N, N'-bis (hydroxyethyl) oxamide-diphosphite,
And N, N'-bis [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide and the like, particularly oxalic acid-bis (benzylidene hydrazide) N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris [2-t-butyl-4-thio (2'-methyl-4'- Hydroxy-5 '
-T-butylphenyl) -5-methylphenyl] phosphite and N, N'-bis [2- [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide is preferred. Of course, these heavy metal deactivators may be used alone, or two or more heavy metal deactivators may be used in combination. The compounding ratio of the heavy metal deactivator is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of a composition comprising 30 to 70% by weight of polyolefin and 70 to 30% by weight of magnesium hydroxide. is there. If the amount is less than 0.01 part by weight, the effect of improving heavy metal resistance is not sufficiently exhibited, and even if it exceeds 1 part by weight, a further improvement effect of heavy metal resistance cannot be expected and it is not practical. Uneconomical and uneconomical.

The epoxy compound used in the present invention is not particularly limited as long as it does not significantly escape or decompose during melt kneading, and the epoxy equivalent is 100 to 1,0.
About 00 is preferred, and epichlorohydrin or epichlorohydrin derivatives (for example, 2-methyl epichlorohydrin, 2-ethyl epichlorohydrin and 2-propyl epichlorohydrin, etc.) and bisphenol or bisphenol derivatives (for example, bisphenol A, bisphenol F, bisphenol S, hydrogen) Condensates with added bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, etc., epoxidized oils (eg, epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, etc.), epoxidized oils and fats, epoxidized oils and fats Alkyl esters of acids (eg epoxidized octyl stearate, fatty acid esters of 3,4-epoxycyclohexylmethanol, 3,4-epoxycyclohexyl carboxylate) Alkyl esters of phosphate, 4, 5
-Epoxycyclohexane-1,2-dicarboxylic acid dialkyl ester, 3,4-epoxy-6-methylcyclohexylmethyl and 3,4-epoxy-6-methylcyclohexanecarboxylate, etc.), tetrahydroxyphenylmethanetetraglycidyl 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 ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid glycidyl ester, dimer acid dimer acid Glycidyl ester,
Glycidylaniline, tetraglycidyldiaminodiphenylmethane, triglycidylisocyanurate, 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 diepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether and limonene Examples include dioxide and the like. In particular, a condensate of epichlorohydrin and bisphenol A, a condensate of 2-methylepichlorohydrin and bisphenol A, triglycidyl isocyanurate and Epoxidized soybean oil are preferred. These epoxy compounds may be used alone, or two or more epoxy compounds may be used in combination. The compounding ratio of the epoxy compound is polyolefin 30.
The amount 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 comprising 70 to 30% by weight of magnesium hydroxide and 70 to 30% by weight of magnesium hydroxide. If the amount is less than 0.01 part by weight, the effect of improving heavy metal resistance is not sufficiently exhibited, and even if it exceeds 1 part by weight, a further improvement effect of heavy metal resistance cannot be expected and it is not practical. Uneconomical and uneconomical.

In the composition of the present invention, various additives usually added to the polyolefin, for example, phenol-based (however,
Thioethers (excluding compound A)
), Phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, lubricants, antistatic agents, antifogging agents, antiblocking agents, drip-free agents, flame retardants (but magnesium hydroxide ), A radical generator such as a flame retardant aid, a pigment, a peroxide, a dispersant or a neutralizing agent such as a metal soap, an inorganic filler (for example, talc, mica, clay, wollastonite, zeolite, asbestos) , Calcium carbonate, aluminum hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate,
Calcium silicate, aluminum silicate, glass fiber,
Surface-treated with a surface treating agent such as potassium titanate, carbonated fiber, carbon black, graphite, metal fiber, etc. or a coupling agent (eg, silane-based, titanate-based, boron-based, aluminate-based, zirco-aluminate-based). In addition, the above-mentioned inorganic or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used in combination within a range not to impair the object of the present invention.

The composition of the present invention is prepared by adding magnesium hydroxide, compound A, compound B, a heavy metal deactivator and an epoxy compound to a polyolefin and a predetermined amount of each of the above-mentioned various additives which are usually added to a polyolefin in a usual mixing apparatus such as a Henschel mixer. (Trade name), mixed using a super mixer, a ribbon blender, a Banbury mixer, etc., and melt-kneaded at a temperature of 150 ° C. to 300 ° C., preferably with a normal single screw extruder, twin screw extruder, Brabender or roll, etc. It can be obtained by melt-kneading pelletizing at 200 ° C to 250 ° C. The obtained composition is used for production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method, and a blow molding method.

[Action] In the present invention, compound A is a radical chain inhibitor, compound B is a peroxide decomposer, a heavy metal deactivator is a deactivator for the catalytic oxidative degradation of polyolefin by heavy metal ions, and It is generally known that epoxy compounds each act as an adsorption inhibitor. However, the use of a compound A, a compound B, a heavy metal deactivator and an epoxy compound according to the present invention in combination with a flame-retardant polyolefin composition containing magnesium hydroxide has a conventionally known effect of preventing oxidation deterioration. A surprising synergistic effect, which cannot be predicted at all from the compounding, is obtained, and a flame-retardant polyolefin composition having remarkably heavy metal resistance is obtained.

Compound A is excellent as a radical chain inhibitor in a flame retardant polyolefin composition containing magnesium hydroxide because the compound A is an ester of phenol and an aromatic carboxylic acid, that is, an aromatic ester. From the above, it is presumed that Compound A is less susceptible to alkali hydrolysis in the presence of magnesium hydroxide than phenolic antioxidants having an aliphatic ester group or an aliphatic amide group other than Compound A.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The evaluation method used in the examples and comparative examples was based on the following method.

1) Heavy metal resistance: evaluated by a copper resistance test. That is, using the obtained pellets, length 50 mm, width 25 mm, thickness 1 mm
A test piece was prepared by injection molding, and the test piece was used to contact a copper plate 25 mm long, 25 mm wide and 0.3 mm thick, fixed with clips, and circulated hot air adjusted to a temperature of 150 ° C or 140 ° C. The test piece was placed in an oven, and the time until the copper plate contact portion of the test piece completely deteriorated (the time until the deterioration penetrated) was measured (based on JIS K 7212) to evaluate heavy metal resistance.

2) Flame retardancy: A flame retardancy test was performed according to a combustion test method for a polymer material by an oxygen index method. That is, a flame-retardant test piece having a length of 150 mm, a width of 6.5 mm and a thickness of 3.0 mm was prepared by injection molding using the obtained pellets, and the oxygen index was measured using the test piece for combustion (JIS K 7201). Compliance).

Examples 1 to 7, Comparative Examples 1 to 14 MFR as polyolefin (load 2.16 kg at 230 ° C)
Of melted resin in 10 minutes when water is added) 20 g / 10 min unstabilized powdery crystalline propylene homopolymer
43% by weight and average particle size 0.6 as magnesium hydroxide
Bis [2- (5'-nonyl-2 ') as compound A was added to a total of 100 parts by weight of .about.0.8 .mu.
-Hydroxy (α, α-dimethylbenzyl))-4-nonylphenyl] isophthalate or bis [2-
(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, compound B as pentaerythritol
Tetrakis (3-laurylthiopropionate) or pentaerythritol-tetrakis (3-stearylthiopropionate), N, N 'as a heavy metal deactivator
-Bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl-4-thio (2'-methyl-4 '-Hydroxy-5'-tert-butylphenyl)-
5-methylphenyl] phosphite, N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), epoxy compound Condensates of epichlorohydrin and bisphenol A (epoxy equivalents 700 to 830) or mixtures of condensates of epichlorohydrin and bisphenol A and condensates of 2-methyl epichlorohydrin and bisphenol A (epoxy equivalents 180 to 200) and other additives Are placed in a Henschel mixer (trade name) at the mixing ratio shown in Table 1 below, and stirred and mixed for 3 minutes.
The mixture was melt-kneaded at 250 ° C. with a twin-screw extruder having a diameter of 30 mm and pelletized. Further, as Comparative Examples 1 to 14, the MFR was 43% by weight of an unstabilized powdery crystalline propylene homopolymer of 20 g / 10 min, and the average particle diameter was 0.3 as magnesium hydroxide.
A predetermined amount of each of the additives described in Table 1 described below was blended into a total of 100 parts by weight of 6 to 0.8 μm of an untreated surface product of 57% by weight, and melt kneading was performed according to Examples 1 to 7. Thus, a pellet was obtained.

Test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C.

Using the obtained test pieces, heavy metal resistance (copper resistance at 150 ° C.) and flame retardancy were evaluated according to the test methods described above. The results are shown in Table 1.

Examples 8-14, Comparative Examples 15-28 As polyolefin, 30% by weight of unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) of 30 g / 10 minutes MFR and magnesium hydroxide Untreated surface with an average particle size of 0.6 to 0.8μ
Compound A, bis [2- (5'-nonyl-2'-hydroxy (α, α)
-Dimethylbenzyl))-4-nonylphenyl] isophthalate or bis [2- (3'-tert-butyl-5 ')
-Methyl-2'-hydroxybenzyl) -4-methyl-
6-t-butylphenyl] terephthalate, compound B as pentaerythritol-tetrakis (3-laurylthiopropionate) or pentaerythritol-
Tetrakis (3-stearylthiopropionate), N, N'-bis [2- [3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5 ')
-T-butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), a condensate of epichlorohydrin with bisphenol A as an epoxy compound (epoxy equivalent 700 to 830)
Alternatively, a predetermined amount of each of a mixture of a condensate of epichlorohydrin and bisphenol A, a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent: 180 to 200), and other additives is set in a mixing ratio described in Table 2 below. Into a Henschel mixer (trade name), and stirred and mixed for 3 minutes. Then, the mixture was melt-kneaded at 250 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. Comparative Examples 15 to 28
30% by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) having an MFR of 30 g / 10 minutes and magnesium hydroxide having an average particle size of 0.6 to 0.8 μm. A prescribed amount of each of the additives shown in Table 2 described below was blended in a total of 100 parts by weight consisting of 70% by weight of the processed product, and the mixture was melt-kneaded according to Examples 8 to 14 to obtain pellets.

Test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C.

Using the obtained test pieces, heavy metal resistance (copper resistance at 150 ° C.) and flame retardancy were evaluated according to the test methods described above. Table 2 shows the results.

Examples 15 to 21, Comparative Examples 29 to 42 Powdered crystalline ethylene-propylene-butene-13 not stabilized as MFR 7.0 g / 10 min as polyolefin
A total of 50% by weight of the original copolymer (2.5% by weight of ethylene content, 4.5% by weight of butene-1 content) and 50% by weight of an untreated product having an average particle size of 0.6 to 0.8μ as magnesium hydroxide In part, bis [2-
(3 ', 5'-di-t-butyl-2'-hydroxy (α-
Methylbenzyl))-4,6-di-t-butylphenyl]
Terephthalate or bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy (α-propylbenzyl))-4-methyl-6
(1'-methylcyclohexyl) phenyl] terephthalate, compound B as pentaerythritol-tetrakis (4-octylthiobutyrate) or pentaerythritol-tetrakis (3-stearylthiobutyrate), and N, N 'as heavy metal deactivator -Bis [2- [3
-(3,5-di-t-butyl-4-hydroxyphenyl)
[Proponyloxy] ethyl] oxamide, tris [2
-Tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5- t-butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), triglycidyl isocyanurate (epoxy equivalents 100 to 110) or epoxidized soybean oil (epoxy equivalents 220 to 240) as an epoxy compound and A predetermined amount of each of the other additives is added to a Henschel mixer (trade name) at a mixing ratio shown in Table 3 below, and the mixture is stirred and mixed for 3 minutes. Then, the mixture is melt-kneaded at 250 ° C. by a twin-screw extruder having a diameter of 30 mm. Processed and pelletized. Also as Comparative Examples 29 to 42
50% by weight of an unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymer (ethylene content 2.5% by weight, butene-1 content 4.5% by weight) having an MFR of 7.0 g / 10 minutes and Average particle size 0.6-0.8μ as magnesium hydroxide
A predetermined amount of each of the additives described in Table 3 described below is blended with a total of 100 parts by weight of 50% by weight of the untreated surface of
Pellets were obtained by melt-kneading according to Examples 15-21.

Test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C.

Using the test pieces obtained, heavy metal resistance (140 ° C. copper resistance) and flame retardancy were evaluated by the above-described test methods. The results are shown in Table 3.

Examples 22 to 28, Comparative Examples 43 to 56 Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 55% by weight of MFR 7.0 g / 10 minutes as a polyolefin, MI ( Discharge rate of molten resin for 10 minutes when a load of 2.16 kg at 190 ° C is applied) 20 g / 10 minutes of unstabilized powdered Ziegler-Natta type high-density ethylene homopolymer 10% by weight, Mooney viscosity ML1 + 4 ( 5% by weight of an unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content 25% by weight) of 25% and an untreated surface having an average particle size of 0.6 to 0.8μ as magnesium hydroxide Compound A, bis [2-
(3 ', 5'-di-t-butyl-2'-hydroxy (α-
Methylbenzyl))-4,6-di-t-butylphenyl]
Terephthalate or bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy (α-propylbenzyl))-4-methyl-6
(1'-methylcyclohexyl) phenyl] terephthalate, compound B as pentaerythritol-tetrakis (4-octylthiobutyrate) or pentaerythritol-tetrakis (3-stearylthiobutyrate), and N, N 'as heavy metal deactivator -Bis [2- [3
-(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] ethyl] oxamide, tris [2
-Tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5- Di-t
-Butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), triglycidyl isocyanurate (epoxy equivalent 100 to 110) or epoxidized soybean oil (epoxy equivalent 220 to 240) as an epoxy compound and A predetermined amount of each of the other additives is added to a Henschel mixer (trade name) at a mixing ratio shown in Table 4 below, and the mixture is stirred and mixed for 3 minutes, and then melt-kneaded at 250 ° C. by a twin-screw extruder having a diameter of 30 mm. Processed and pelletized. As Comparative Examples 43 to 56, 55% by weight of an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content: 2.5% by weight) having an MFR of 7.0 g / 10 minutes, MI (load: 2.16 at 190 ° C.) kg
Of molten resin for 10 minutes when water is added) 20 g / 10 minutes of unstabilized powdered Ziegler-Natta high-density ethylene homopolymer 10% by weight, Mooney viscosity ML1 + 4 (1
00 ° C) 25 unstabilized powdered amorphous ethylene-
Average particle size as propylene random copolymer (propylene content 25% by weight) 5% by weight and magnesium hydroxide
A total of 100 consisting of 30% by weight of 0.6-0.8μ untreated surface
A prescribed amount of each of the additives described in Table 4 described below was blended in parts by weight, and the mixture was melt-kneaded according to Examples 22 to 28 to obtain pellets.

Test pieces used for the copper resistance test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C.

Using the test pieces obtained, heavy metal resistance (140 ° C. copper resistance) and flame retardancy were evaluated by the above-described test methods. The results are shown in Table 4.

The compounds and additives according to the present invention shown in Tables 1 to 4 are as follows.

Compound A [I]: bis [2- (5′-nonyl-2′-hydroxy (α, α-dimethylbenzyl))-4-nonylphenyl] isophthalate Compound A [II]: bis [2- (3 ′ -T-butyl-5 '
-Methyl-2'-hydroxybenzyl) -4-methyl-
6-t-butylphenyl] terephthalate Compound A [III]: bis [2- (3 ', 5'-di-t-butyl-2'-hydroxy (α-methylbenzyl))-4,
6-di-t-butylfehir] terephthalate Compound A [IV]: bis [2- (3 '-(1 "-methylcyclohexyl) -5'-methyl-2'-hydroxy (α
-Propylbenzyl))-4-methyl-6- (1'-methylcyclohexyl) phenyl] terephthalate Compound B [I]: pentaerythritol-tetrakis (3-laurylthiopropionate) Compound B [II]: pentaerythritol- Tetrakis (3-stearylthiopropionate) Compound B [III]: pentaerythritol-tetrakis (4-octylthiobutyrate) Compound B [IV]: Pentaerythritol-tetrakis (3-stearylthiobutyrate) Heavy metal inactivation Agent [I]: N, N'-bis [2- [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide heavy metal deactivator [II]: tris [2-t-butyl-4
-Thio (2'-methyl-4'-hydroxy-5'-t-
Butylphenyl) -5-methylphenyl] phosphite heavy metal deactivator [III]: N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine Activator [IV]: Oxalic acid-bis (benzylidene hydrazide) Epoxy compound [I]: Condensation product of epichlorohydrin and bisphenol A (epoxy equivalent 700-830; CIBA-GEI
ARA-LDITE GT 7004 manufactured by GY AG) Epoxy compound [II]: a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent
180-200; MARK EP-1 manufactured by Adeka Argus Chemical Co., Ltd.
7) Epoxy compound [III]: triglycidyl isocyanurate (epoxy equivalent: 100 to 110; ARALDI manufactured by CIBA-GEIGY AG)
TE PT 810) Epoxy compound [IV]: Epoxidized soybean oil (epoxy equivalent 220-240; ADK CIZER manufactured by Adeka Argus Chemical Co., Ltd.)
O-130P) Thioether antioxidant 1: dimyristyl thiodipropionate Thioether antioxidant 2: distearyl thiodipropionate Phosphorus antioxidant 1: bis (2,6-di-t-butyl-4) −
Methylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 2: bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 3: tetrakis (2,4- Di-tert-butylphenyl) -4,4'-biphenylene-diphosphonite Phenolic antioxidant 1: 2,6-di-tert-butyl-p-
Cresol phenolic antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 3: 2,2-bis [4- [2- (3,5
-Di-t-butyl-4-hydroxyphenylpropionyloxy) ethoxy] phenyl] propane phenolic antioxidant 4: 1,3,5-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) isocyanurate phenolic antioxidant 5: 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate phenolic antioxidant 6 : 1,3,5-tris [(3,5-di-
t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate phenolic antioxidant 7: 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane phenolic oxidation Inhibitor 8: bis [3,3-bis (4'-hydroxy-3'-tert-butylphenyl) butylic acid] ethylene glycol ester phenolic antioxidant 9: 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Carbon black: carbon # 45 manufactured by Mitsubishi Chemical Corporation Ca-St: calcium stearate The examples and comparative examples described in Table 1 are cases where a crystalline propylene homopolymer is used as the polyolefin. As can be seen from Table 1, Examples 1 to 7 were obtained by adding magnesium hydroxide, compound A,
Examples 1 to 7 and Comparative Examples 1 to 8 (compounds containing a phenolic antioxidant other than compound A instead of compound A) containing compound B, a heavy metal deactivator and an epoxy compound. In comparison, Examples 1 to 7 are excellent in heavy metal resistance, and that phenolic antioxidants other than compound A in the presence of magnesium hydroxide do not sufficiently exhibit a radical chain inhibiting action, that is, an antioxidant effect. I understand. When comparing Comparative Examples 9 to 11 and Examples 1 to 7 in which compound B, a heavy metal deactivator or an epoxy compound were used in combination with compound A, respectively, Comparative Examples 9 to
It turns out that the heavy metal resistance of 11 is considerably inferior. Comparative Example 12 containing Compound A, Compound B and a heavy metal deactivator and not containing an epoxy compound, and Compound A,
When comparing Comparative Example 13 in which the compound B and the epoxy compound were blended and the heavy metal deactivator was not blended with Examples 1 to 7, the heavy metal resistance of Comparative Examples 12 to 13 was improved as compared with Comparative Examples 9 to 11. What is done is still not enough. Example 2
Comparing Comparative Example 14 in which thioether-based antioxidant 1 was blended in place of Compound B of Example 1 with Examples 1 to 7, the effect of improving the heavy metal resistance of Comparative Example 14 was considerably recognized, but still sufficiently satisfactory. Not something. Therefore, it is clear that Comparative Examples which do not simultaneously satisfy the compounding of 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 is obtained when the compound A, the compound B, the heavy metal deactivator and the epoxy compound are used in combination with the flame-retardant polyolefin composition containing magnesium hydroxide in the present invention. It can be said that this is a unique effect that can be seen for the first time.

Further, the flame retardant composition according to the present invention comprising the compound A, the compound B, the heavy metal deactivator and the epoxy compound has a flame retardancy which is not inferior to that of a conventionally known flame retardant composition. Was confirmed.

Tables 2 to 4 show, as polyolefins, crystalline ethylene-propylene block copolymer, crystalline ethylene-propylene-butene-1 terpolymer or crystalline ethylene-propylene random copolymer, Ziegler-Natta, respectively. A mixture of a system high-density ethylene homopolymer and an amorphous ethylene-propylene random copolymer was used, and the same effects as described above were confirmed for these.

[Effects of the Invention] The composition of the present invention has the following advantages when compared to a conventionally known flame-retardant polyolefin composition having improved heavy metal resistance obtained by blending magnesium hydroxide: The heavy metal resistance of the molded product is remarkably excellent. (2) Since the resistance to heavy metals is remarkably excellent, there is no decrease in electrical insulation due to oxidative deterioration of polyolefin, and therefore, applications requiring flame retardancy and heavy metal resistance in various molding fields (for example, deflection yokes, Electrical and electronic equipment parts such as CRT sockets and connectors, distributor caps,
It can be suitably used for automotive parts such as car heater cases and car air conditioner cases, and insulating materials such as wire covering materials.

Claims (1)

(57) [Claims] 1. A phenolic compound represented by the following general formula [I] (hereinafter referred to as compound A) based on 100 parts by weight of a composition comprising 30 to 70% by weight of a polyolefin and 70 to 30% by weight of magnesium hydroxide. ), A pentaerythritol-tetrakis (alkylthioalkanoate) -based compound (hereinafter, referred to as compound B), a heavy metal deactivator, and an epoxy compound in an amount of 0.01 to 1 part by weight, respectively. (Where R ₁ is an alkylidene group having 1 to 4 carbon atoms,
R ₂ represents an alkyl group having 1 to 9 carbon atoms, and R ₃ represents hydrogen or an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or an alkylcyclohexyl group. )