JPH11286580A - Flame-retardant polyolefin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of giving a molded product with high resistance to heavy metals. SOLUTION: This flame-retardant polyolefin composition is obtained by incorporating 100 pts.wt. of a composition which is prepared by compounding a polyolefin with 30-70 wt.%, based on the composition, of magnesium hydroxide, with each 0.01-1 pt.wt. of phenolic compound(s) selected from those (1) and (2) described below, a heavy metal deactivator and an epoxy compound. (1) 1,1,3-tris[2,5-dialkyl-4-(3,5-dialkyl-4-hydroxyphenyl propionyloxy) phenyl]butane, and (2) 1,1,3-tris [3,5-dialkyl-4-(3,5-dialkyl-4-hydroxyphenyl propionyloxy) phenyl]butane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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.

[0002]

2. Description of the Related Art In general, various halogen-based flame retardants have been blended with polyolefins as means for making polyolefins 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.

[0003] On the other hand, molded articles molded from a flame-retardant polyolefin composition obtained by mixing magnesium hydroxide and various antioxidants with a polyolefin are used for contact with heavy metals such as copper, brass, iron and nickel. May be used. 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-mentioned flame-retardant polyolefin composition are resistant to heat-induced oxidative deterioration (hereinafter, referred to as resistance) during heavy metal contact. Heavy metal) is significantly reduced. In particular, 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 with the diversification of uses of molded articles obtained from the flame retardant polyolefin composition and the increase in size, The working conditions of the molded product in practical use (heavy metal resistance, electrical insulation, etc.)
The demands on the Internet are also becoming more stringent.

Therefore, in order to improve the heavy metal resistance of a molded article using a flame-retardant polyolefin composition containing magnesium hydroxide, the present inventor has proposed that magnesium hydroxide and a specific phenolic compound be added to the polyolefin. First, a flame-retardant polyolefin composition comprising a heavy metal deactivator and an epoxy compound as essential components, and a specific amount of a thioether-based antioxidant including a specific thioether-based compound and a fatty acid as necessary. Proposals (JP-A-2-214475, JP-A-2-240148, JP-A-3-81352, JP-A-4-36329, JP-A-4
-36330, JP-A-6-41357 and JP-A-9-
No. 20841). On the other hand, JP-A-8-225495, JP-A-10-6356, JP-A-10-6376, JP-A-10-
No. 7850 and Japanese Patent Application Laid-Open No. 10-7917 disclose excellent antioxidative effects in which a hindered phenol compound having a hindered phenyl ester structure is used alone or in combination with a sulfur-based antioxidant. A polyolefin composition has been proposed, and the publication states that a heavy metal deactivator, an epoxy compound, a flame retardant, a filler and the like can be added as additional components.

[0005]

However, Japanese Patent Application Laid-Open No. 8-225495, Japanese Patent Application Laid-Open No. 10-6356, and
10-6376, JP-A-10-7850 and JP-A-10-
When magnesium hydroxide is used as the flame retardant or filler in each publication of 7917, the heavy metal resistance of the flame retardant polyolefin composition obtained by using a heavy metal deactivator and an epoxy compound as essential components is There is no mention or suggestion of further improvement.

The present inventor has disclosed JP-A-2-214475, JP-A-2-240148, JP-A-3-81352, JP-A-4-36329, JP-A-4-36330, and JP-A-4-36330. 6
The present inventors have conducted further studies without satisfaction with the flame-retardant polyolefin compositions proposed in JP-A-41357 and JP-A-9-20841. As a result, the present inventor has proposed a hindered phenolic compound having a specific hindered phenyl ester structure in a flame retardant composition comprising a polyolefin and magnesium hydroxide, a heavy metal deactivator and an epoxy compound,
Furthermore, it has been found that a flame-retardant polyolefin composition having improved heavy metal resistance can be obtained by blending a specific amount of a thioether-based antioxidant or a fatty acid as necessary, and based on this finding, the present invention has been completed. 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.

[0007]

[Means for solving the problems] (1) Polyolefin
One or two phenolic compounds (hereinafter, referred to as Compound A) selected from the following are added to 100 parts by weight of a composition containing 30 to 70% by weight of magnesium hydroxide based on the composition.
That. ), A flame-retardant polyolefin composition comprising 0.01 to 1 part by weight of each of a heavy metal deactivator and an epoxy compound. 1,1,3-tris [2,5-dialkyl-4- (3,5-dialkyl-4-
Hydroxyphenylpropionyloxy) phenyl] butane 1,1,3-tris [3,5-dialkyl-4- (3,5-dialkyl-4-
(Hydroxyphenylpropionyloxy) phenyl] butane (2) Compound A, a thioether-based antioxidant, and a heavy metal-free compound were added to 100 parts by weight of a polyolefin blended with 30 to 70% by weight of magnesium hydroxide based on the composition. A flame-retardant polyolefin composition comprising 0.01 to 1 part by weight of an activator and an epoxy compound. (3) The above-mentioned item 1 or 2, wherein the fatty acid is further compounded in an amount of 0.5 to 5 parts by weight with respect to 100 parts by weight of the composition in which 30 to 70% by weight of magnesium hydroxide is added to the polyolefin. Item 10. The flame-retardant polyolefin composition according to any one of Items 1 to 4.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin used in the present invention is ethylene, propylene, butene-1, pentene-1, 4-
Α- such as methyl-pentene-1, hexene-1, octene-1
Crystalline homopolymer of olefin, two or more of these α-
Olefinic crystalline, low crystalline or amorphous random copolymer or crystalline block copolymer, amorphous ethylene
Polyolefins such as -propylene-non-conjugated diene terpolymer, amorphous ethylene-cyclic alkene copolymer (for example, amorphous ethylene-tetracyclododecene copolymer), the above-mentioned α-olefin and vinyl acetate Or a copolymer with an acrylic acid ester, a saponified product of the copolymer,
Copolymers of these α-olefins and unsaturated silane compounds, copolymers of these α-olefins and unsaturated carboxylic acids or anhydrides, reaction products of the copolymers and metal ion compounds, Examples include modified polyolefins obtained by modifying polyolefins with unsaturated carboxylic acids or derivatives thereof, and silane-modified polyolefins obtained by modifying the above-mentioned polyolefins with unsaturated silane compounds. These polyolefins may be used alone, or two or more kinds may be used. Can be used in combination.

In addition, various synthetic rubbers (for example, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluorinated rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber)
Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-
Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, ethylene-ethylene-
Butylene-ethylene block copolymer, ethylene-propylene-butylene-ethylene block copolymer, etc. or thermoplastic synthetic resin (for example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate) , polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluorine resin, petroleum resin (e.g. C ₅ petroleum resins, hydrogenated C ₅ petroleum resins, C ₉ petroleum resins, hydrogenated C ₉ petroleum resin, C ₅ -C ₉ copolymer petroleum resin, hydrogenated C ₅ -C ₉ copolymer petroleum resin, acid-modified C ₉
Petroleum resins with a softening point of 80-200 ° C), DC
PD resin (for example, cyclopentadiene-based petroleum resin, hydrogenated cyclopentadiene-based petroleum resin, cyclopentadiene
-C ₅ copolymer petroleum resin, hydrogenated cyclopentadiene -C ₅ copolymer petroleum resin, cyclopentadiene -C ₉ copolymer petroleum resin,
Hydrogenated cyclopentadiene -C ₉ copolymer petroleum resin, cyclopentadiene -C ₅ -C ₉ copolymer petroleum resin, softening point 80 to 200 ° C., such as hydrogenated cyclopentadiene -C ₅ -C ₉ copolymer petroleum resin
DCPD resin) can be used as a mixture.

A crystalline propylene homopolymer, a crystalline propylene copolymer containing at least 70% by weight of a propylene component, comprising a crystalline ethylene-propylene random copolymer, a crystalline ethylene-propylene block copolymer, and a crystalline ethylene-propylene block copolymer. Propylene-butene-1 random copolymer, crystalline ethylene-propylene-butene-1 terpolymer, crystalline propylene-hexene-butene-1 terpolymer and mixtures of two or more of these are especially preferred. It is preferably used.

As the magnesium hydroxide used in the present invention, plate-like and fibrous ones can be used without any limitation. The average particle size of the plate-like magnesium hydroxide is not particularly limited, but is usually 0.1 μm to 10 μm, preferably 0.2 μm.
μm to 2 μm, most preferably 0.5 μm to 1 μm, and the fiber diameter of the fibrous magnesium hydroxide is 0.1 μm to 0.5 μm.
μm and a length of 5 μm to 20 μm are preferred. These magnesium hydroxides are used as surface treatment agents such as metal soaps, higher fatty acid esters, higher alcohols, higher fatty acid monoamides, higher fatty acid bisamides, higher aliphatic phosphoric acids, higher aliphatic metal phosphates, higher aliphatic sulfonic acids, Known metal salts such as aliphatic sulfonic acid metal salts, polyolefin waxes, oxidized polyolefin waxes, silane-based coupling agents, titanate-based coupling agents, boron-based coupling agents, aluminate-based coupling agents, and zirco-aluminate-based coupling agents When the surface treatment is performed in advance with a surface treatment agent, the compatibility and dispersibility of the magnesium hydroxide and the polyolefin are improved, and excellent moldability is obtained. Magnesium hydroxide mug surface-treated with a surface treatment agent because of its improved mechanical strength It is preferable to use Siumu. These magnesium hydroxides can be used alone,
More than one kind of magnesium hydroxide can be used in combination.
The mixing ratio of the magnesium hydroxide is 30 parts with respect to the composition comprising the polyolefin and the magnesium hydroxide in terms of moldability, flame retardancy of the obtained molded article and mechanical strength.
7070% by weight, preferably 50-65% by weight.

The compound A used in the present invention includes 1,1,
3-tris [2-methyl-4- (3-methyl-4-hydroxy-5-t-butylphenylpropionyloxy) -5-t-butylphenyl] butane, 1,1,3-tris [2-methyl- 4- (3,5-di-t-butyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane, 1,1,3-tris [2-methyl-4- (3,5-
Di-t-amyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane, 1,1,3-tris [3-methyl-4- (3-methyl-4-hydroxy-5-t- Butylphenylpropionyloxy) -5-t-butylphenyl] butane, 1,1,3-
Tris [3-methyl-4- (3,5-di-t-butyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane, 1,1,3-tris [3-methyl-4- (3,5-di-t-amyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane, 1,1,3-tris [3,5-di-t-butyl-4- (3 -Methyl-4-hydroxy-5-t-butylphenylpropionyloxy) phenyl] butane, 1,1,3-tris [3,5-di-t-butyl
-4- (3,5-di-t-butyl-4-hydroxyphenylpropionyloxy) phenyl] butane and 1,1,3-tris [3,5-di-t-
Butyl-4- (3,5-di-t-amyl-4-hydroxyphenylpropionyloxy) phenyl] butane. In particular, 1,1,3-tris [2-methyl-4- (3,5-di-t-butyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane and 1,1,3-tris [3-methyl-4- (3,5-di-t-butyl-4-hydroxyphenylpropionyloxy) -5-t-
Butylphenyl] butane is preferred. These compounds A can be used alone, or two or more compounds A can be used in combination. The compounding ratio of the compound A is from 0.05 to 5 parts by weight, preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of a composition in which magnesium hydroxide is added to the polyolefin in an amount of 30 to 70% by weight based on the weight of the composition. 2 parts by weight.

The heavy metal deactivator used in the present invention includes benzotriazole, 2,4,6-triamino-1,3,5-triazine and 3,9-bis [2- (3,5-diamino-2). , 4,6-Triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5]
Undecane, ethylenediamine-tetraacetylic acid, alkali metal salt (Li, Na, K) salt of ethylenediamine-tetraacetylic acid, N, N'-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
-t-butyl-4-hydroxyphenyl) propionyl] hydrazine,

Tris [2-t-butyl-4-thio (2'-methyl-4'-
Hydroxy-5'-t-butylphenyl) -5-methylphenyl]
Phosphite, bis [2-t-butyl-4-thio (2'-methyl-
4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -pentaerythritol-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5) '-
t-butylphenyl) -5-methylphenyl] -1,6-hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2-t-butyl-4-thio (2 ′ -Methyl-4'-hydroxy-5'-t-butylphenyl) -5-
Methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-t-butyl-4-thio
(2'-Methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-salicyloylhydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -di
(Hydroxyethylcarbonyl) hydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2′-methyl-4′-
(Hydroxy-5'-t-butylphenyl) -5-methylphenyl]-
N, N'-bis (hydroxyethyl) oxamide-diphosphite and N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide And oxalic acid-bis
(Benzylidene hydrazide), N, N'-bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyl] hydrazine, tris [2-t-butyl-4-thio (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -5-methylphenyl] phosphite and N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide is preferred. These heavy metal deactivators can be used alone, or two or more heavy metal deactivators can be used in combination. The compounding ratio of the heavy metal deactivator is 0.01 to 1 part by weight, preferably 100 to 100 parts by weight of a composition in which 30 to 70% by weight of magnesium hydroxide is added to the polyolefin from the viewpoint of heavy metal resistance. Is 0.05 to 0.5 parts by weight.

The epoxy compound used in the present invention is not particularly limited as long as it does not significantly escape or decompose during the melt-kneading process. Epoxy compounds having an epoxy equivalent of about 100 to 1,000 are suitable, and epichlorohydrin or Derivatives of epichlorohydrin (eg 2-
Methyl epichlorohydrin, 2-ethyl epichlorohydrin, 2-propyl epichlorohydrin, etc.) and derivatives of bisphenol or bisphenol (for example, bisphenol A, bisphenol F, bisphenol S,
Hydrogenated bisphenol A, hydrogenated bisphenol F
Epoxidized oils and fats (eg, epoxidized soybean oil, epoxidized linseed oil and epoxidized castor oil), epoxidized oils and fats, and alkyl esters of epoxidized oils and fats (eg, epoxidized Octyl stearate, fatty acid ester of 3,4-epoxycyclohexylmethanol, 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-methylcyclohexanecarboxylate), tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, novolak glycidyl ether, polyalkylene glycol diglycidyl ether, Glycerin triglycidyl ether, pentaerythritol diglycidyl ether, glycidyl ether p-oxybenzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, glycidyl acrylate, dimer dimer Glycidyl ester, glycidyl aniline,
Tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate, epoxidized polybutadiene,
3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, 3,4-
Epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether And condensates of epichlorohydrin and bisphenol A, condensates of 2-methylepichlorohydrin and bisphenol A, triglycidyl isocyanurate, and epoxidized soybean oil. These epoxy compounds may be used alone, or two or more epoxy compounds may be used in combination. The mixing ratio of the epoxy compound is 0.01 to 100 parts by weight of a composition in which magnesium hydroxide is mixed with polyolefin in an amount of 30 to 70% by weight based on the weight of the composition.
To 1 part by weight, preferably 0.05 to 0.5 part by weight.

The thioether antioxidants used in the present invention include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, dicetyl thiodipropionate, and distearyl thiodipropionate. , Dilauryl thiodibutyrate, ditridecyl thiodibutyrate, dimyristyl thiodibutyrate, dicetyl thiodibutyrate, distearyl thiodibutyrate, lauryl stearyl thiodipropionate, lauryl stearyl thiodibutyrate, pentaerythritol-β-lauryl Thiodialkanoate compounds such as thiodipropionate, pentaerythritol-tetrakis (3-octylthiopropionate), pentaerythritol-tetrakis (3-nonylthiopropionate), penta Risuritoru - tetrakis (3
-Decylthiopropionate), pentaerythritol-
Tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-tridecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-palmitylthio) (Propionate), pentaerythritol-tetrakis (3-stearylthiopropionate), pentaerythritol-tetrakis (4-octylthiobutyrate), pentaerythritol-tetrakis (4-
Nonylthiobutyrate), pentaerythritol-tetrakis (4-decylthiobutyrate), pentaerythritol
-Tetrakis (4-lauryl thiobutyrate), pentaerythritol-tetrakis (4-tridecyl thiobutyrate), pentaerythritol-tetrakis (4-myristyl thiobutyrate), pentaerythritol-tetrakis (4
-Palmityl thiobutyrate), pentaerythritol-
Tetrakis (4-stearyl thiobutyrate), pentaerythritol-tetrakis (3-octyl thiobutyrate),
Pentaerythritol-tetrakis (3-nonylthiobutyrate), pentaerythritol-tetrakis (3-decylthiobutyrate), pentaerythritol-tetrakis (3-
Lauryl thiobutyrate), pentaerythritol-tetrakis (3-tridecyl thiobutyrate), pentaerythritol-tetrakis (3-myristyl thiobutyrate), pentaerythritol-tetrakis (3-palmityl thiobutyrate), pentaerythritol- Pentaerythritol such as tetrakis (3-stearyl thiobutyrate)-tetrakis (alkyl thioalkanoate) compounds,

Tetrakis [3- {2- (octyloxycarbonyl) ethylthio} propionyloxymethyl] methane,
Tetrakis [3- {2- (nonyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3-
{2- (decyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (dodecyloxycarbonyl) ethylthio} propionyloxymethyl]
Methane, tetrakis [3- {2- (tridecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3
-{2- (hexadecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, tetrakis [3- {2- (octadecyloxycarbonyl) ethylthio} propionyloxymethyl] methane, 1,3,5-tris [3- {2 -(Octyloxycarbonyl) ethylthio} propionyl] hexahydro-
1,3,5-triazine, 1,3,5-tris [3- {2- (nonyloxycarbonyl) ethylthio} propionyl] hexahydro-1,
3,5-triazine, 1,3,5-tris [3- {2- (decyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,
5-triazine, 1,3,5-tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,
5-triazine, 1,3,5-tris [3- {2- (tridecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,
3,5-triazine, 1,3,5-tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 1,3,5-tris [3- { 2- (hexadecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3,5-triazine, 1,3,5-tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] hexahydro-1,3, 5-triazine, 2,4,6-tris [3- {2- (octyloxycarbonyl) ethylthio} propionyl] -1,
3,5-triazine, 2,4,6-tris [3- {2- (nonyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (Decyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2 , 4,6-Tris [3- {2- (tridecyloxycarbonyl) ethylthio} propionyl]-
1,3,5-triazine, 2,4,6-tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyl] -1,3,5-triazine, 2,4,6-tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] -1,3,5 -Triazine,

Tris [3- {2- (octyloxycarbonyl)
Ethylthio} propionyl] isocyanurate, tris [3
-{2- (nonyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (decyloxycarbonyl) ethylthio} propionyl] isocyanurate,
Tris [3- {2- (dodecyloxycarbonyl) ethylthio}
Propionyl] isocyanurate, tris [3- {2- (tridecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyl] isocyanurate,
Tris [3- {2- (hexadecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyl] isocyanurate, tris [3- {2- (octyloxycarbonyl) ) Ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (nonyloxycarbonyl)
Ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (decyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (dodecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate , Tris [3- {2
-(Tridecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (tetradecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (hexadecyloxycarbonyl) ) Ethylthio} propionyloxyethyl] isocyanurate, tris [3- {2- (octadecyloxycarbonyl) ethylthio} propionyloxyethyl] isocyanurate, bis (4-t-amylphenyl) sulfide, dilauryl disulfide, dimyristyl disulfide, Dialkyl disulfides such as distearyl disulfide, didocosyl disulfide, ditetracosyl disulfide, dihexacosyl disulfide, and dioctacosyl disulfide;

3,9-bis (2-laurylthioethyl) -2,4,8,1
0-tetraoxaspiro [5.5] undecane, 3,9-bis (2-myristylthioethyl) -2,4,8,10-tetraoxaspiro [5.
5] undecane, 3,9-bis (2-stearylthioethyl) -2,
4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis
(2-Laurylthiopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis (2-myristylthiopropyl) -2,4,8,10-tetraoxaspiro [5.5 ] Undecane, 3,
9-bis (2-stearylthiopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2
-{3-Laurylthiopropionyloxy} ethyl] -2,4,8,1
0-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-
Dimethyl-2- {3-myristylthiopropionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane,
3,9-bis [1,1-dimethyl-2- {3-stearylthiopropionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.
5] Undecane, 3,9-bis [1,1-dimethyl-2- {3-laurylthiobutyroyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9- Bis [1,1-dimethyl-2- {3-
Myristylthiobutyroyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {3-stearylthiobutyroyloxy} ethyl] -
2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,2 ・
4-bis (3- (2-ethylhexyl) thiopropylidene) sorbitol, 1,3,2,4-bis (3-n-octylthiopropylidene)
Sorbitol, 1,3,2,4-bis (3-nonylthiopropylidene) sorbitol, 1,3,2,4-bis (3-decylthiopropylidene) sorbitol, 1,3,2,4-bis ( 3-Laurylthiopropylidene) sorbitol, 1,3,2,4-bis (3-tridecylthiopropylidene) sorbitol, 1,3,2,4-bis (3-myristylthiopropylidene) sorbitol, 1. 3,2 ・ 4-bis (3-
Palmitylthiopropylidene) sorbitol, 1,3,2,4-
Bis (3-stearylthiopropylidene) sorbitol, 1.
3,2,4-bis (3-docosylthiopropylidene) sorbitol, 1,3,2,4-bis (3-tetracosylthiopropylidene) sorbitol, 1,3,2,4-bis (3- (Hexacosylthiopropylidene) sorbitol, 1,3,2,4-bis (3-octacosylthiopropylidene) 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-palmitylthiopropylidene) sorbitol, 1,3,2,4-bis (2-methyl-3-stearylthiopropylidene) sorbitol, 1,3,2,4-bis (2-methyl- 3-docosylthiopropylidene) 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-octacosylthiopropylidene) sorbitol, 1,3,2,4-bis (3 -(2-ethylhexyl) thiobutylidene) sorbitol, 1,3,2,4-bis (3
-n-octylthiobutylidene) sorbitol, 1,3,2,4-bis (3-nonylthiobutylidene) sorbitol, 1,3,2,4-bis (3-decylthiobutylidene) sorbitol, 1. 3,2,4-bis (3-laurylthiobutylidene) sorbitol, 1,3,2,4-
Bis (3-tridecylthiobutylidene) sorbitol, 1,3,
2,4-bis (3-myristylthiobutylidene) sorbitol,
1,3,2,4-bis (3-palmitylthiobutylidene) sorbitol, 1,3,2,4-bis (3-stearylthiobutylidene) sorbitol, 1,3,2,4-bis (3 -Docosylthiobutylidene) sorbitol, 1,3,2,4-bis (3-tetracosylthiobutylidene) sorbitol, 1,3,2,4-bis (3-hexacosylthiobutylidene) sorbitol, 1・ 3,2,4-bis (3-octacosylthiobutylidene) 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-pal (Mityl thiobutylidene) sorbitol, 1,3,2,4-bis (4-stearyl thiobutylidene) sorbitol, 1,3,2,4-bis (4-docosylthiobutylidene) sorbitol, 1,3, 2,4-bis (4-tetracosylthiobutylidene) sorbitol, 1,3,2,4-bis (4-hexacosylthiobutylidene) sorbitol, 1,3,2,4-bis (4-octacoxy (Rutiobtylidene) 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, 1,3,2,4,5,6-tris (3-decylthiopropylidene) sorbitol, 1,3,2,4, 5,6-Tris (3-laurylthiopropylidene) sorbitol, 1,3,2,4,5,6-Tris (3-tridecylthiopropylidene) sorbitol, 1,3,2,4,5,6 -Tris (3-myristylthiopropylidene) sorbitol, 1.
3,2,4,5,6-tris (3-palmitylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris (3-stearylthiopropylidene) sorbitol, 1,3,2 4,5,6-tris (3-docosylthiopropylidene) 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-octacosylthiopropylidene) 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-octylthiopropyl) Riden) sorbitol, 1,3,2,4,5,6-tris (2-methyl-3-nonylthiopropylidene) sorbitol, 1,3,2
4,5,6-tris (2-methyl-3-decylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris (2-methyl-3-laurylthiopropylidene) sorbitol, 1. 3,2,4,5,6-tris
(2-methyl-3-tridecylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris (2-methyl-3-myristylthiopropylidene) sorbitol, 1,3,2,4, 5,6-Tris (2-methyl-3-palmitylthiopropylidene) sorbitol, 1,3,
2,4,5,6-tris (2-methyl-3-stearylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris (2-methyl-3-docosylthiopropylidene) sorbitol , 1,3,2,4,5,6-
Tris (2-methyl-3-tetracosylthiopropylidene) sorbitol, 1,3,2,4,5,6-tris (2-methyl-3-hexacosylthiopropylidene) sorbitol, 1,3,2 ・4,5,6-tris (2-methyl-3-octacosylthiopropylidene) sorbitol,

1,3,2,4,5,6-tris (3- (2-ethylhexyl) thiobutylidene) sorbitol, 1,3,2,4,5,6-tris
(3-n-octylthiobutylidene) sorbitol, 1,3,2,4,
5.6-Tris (3-nonylthiobutylidene) sorbitol, 1.
3,2,4,5,6-tris (3-decylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (3-laurylthiobutylidene) sorbitol, 1,3,2 ・4,5,6-tris (3-tridecylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (3-myristylthiobutylidene) sorbitol, 1,3,2,4,5 6-tris (3-palmitylthiobutylidene) sorbitol, 1,3,2
4,5,6-tris (3-stearylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (3-docosylthiobutylidene) sorbitol, 1,3,2,4,5 6-tris (3-tetracosylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (3-hexacosylthiobutylidene) sorbitol, 1,3,2,4,5,6 -
Tris (3-octacosylthiobutylidene) sorbitol,
1,3,2,4,5,6-tris (4- (2-ethylhexyl) thiobutylidene) sorbitol, 1,3,2,4,5,6-tris (4-n-octylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (4-
Nonylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (4-decylthiobutylidene) sorbitol, 1,3,2,4,
5.6-tris (4-laurylthiobutylidene) sorbitol,
1,3,2,4,5,6-tris (4-tridecylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris (4-myristylthiobutylidene) sorbitol, 1.3 , 2,4,5,6-tris (4-palmitylthiobutylidene) sorbitol, 1,3,2,4,5,6-tris
(4-stearylthiobutylidene) sorbitol, 1,3,2,4,
5.6-tris (4-docosylthiobutylidene) 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-octacosylthiobutylidene) sorbitol,

3- (laurylthio) propionylamide, 3-
(Myristylthio) propionylamide, 3- (stearylthio) propionylamide, N, N′-methylene-bis (3-laurylthiopropionyl) amide, N, N′-methylene-bis (3-myristylthiopropionyl) amide, N, N'-methylene-bis (3-stearylthiopropionyl) amide,
N, N'-ethylene-bis (3-laurylthiopropionyl) amide, N, N'-ethylene-bis (3-myristylthiopropionyl) amide, N, N'-ethylene-bis (3-stearylthiopropionyl) amide N, N'-bis (3-laurylthiopropionyl) hydrazide, N, N'-bis (3-myristylthiopropionyl) hydrazide, N, N'-bis (3-stearylthiopropionyl) hydrazide, thioethylene glycol- Bis (β-aminocrotonate), bis [2-methyl-
4- (3-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide, poly [1,4-bis (hydroxymethyl)
Cyclohexane-thiodipropionate],

1- [β- (octylthio) ethyl] -3- (octylthio) cyclohexane, 1- [β- (octylthio) ethyl]
-4- (octylthio) cyclohexane, 1- [β- (2-ethylhexylthio) ethyl] -3- (2-ethylhexylthio) cyclohexane, 1- [β- (2-ethylhexylthio) ethyl] -4- (2
-Ethylhexylthio) cyclohexane, 1- [β- (nonylthio) ethyl] -3- (nonylthio) cyclohexane, 1- [β-
(Nonylthio) ethyl] -4- (nonylthio) cyclohexane,
1- [β- (dodecylthio) ethyl] -3- (dodecylthio) cyclohexane, 1- [β- (dodecylthio) ethyl] -4- (dodecylthio) cyclohexane, 1- [β- (tetradecylthio) ethyl] -3 -(Tetradecylthio) cyclohexane, 1- [β- (tetradecylthio) ethyl] -4- (tetradecylthio) cyclohexane, 1- [β- (hexadecylthio) ethyl] -3- (hexadecylthio) cyclohexane, 1- [β- (hexadecylthio) ethyl] -4- (hexadecylthio) cyclohexane, 1-
[β- (octadecylthio) ethyl] -3- (octadecylthio)
Cyclohexane, 1- [β- (octadecylthio) ethyl] -4-
(Octadecylthio) cyclohexane, 1- [β- (docosylthio) ethyl] -3- (docosylthio) cyclohexane, 1- [β
-(Docosylthio) ethyl] -4- (docosylthio) cyclohexane, 1- [β- (octacosylthio) ethyl] -3- (octacosylthio) cyclohexane, 1- [β- (octacosylthio)
1- such as ethyl] -4- (octakosylthio) cyclohexane
[β- (alkylthio) ethyl] -3- (alkylthio) cyclohexane, 1- [β- (alkylthio) ethyl] -4- (alkylthio) cyclohexane, 2,4-bis (octylthio) -6- (4-hydroxy- 3,5-di-t-butylanilino) -1,3,5-triazine and 2,4-bis [(octylthio) methyl] -o-cresol. Especially dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), distearyl disulfide, 3,9-bis (2-lauryl thioethyl) -2,4, 8,10-tetraoxaspiro [5.5] undecane, 1- [β- (octadecylthio) ethyl] -3- (octadecylthio) cyclohexane and 1- [β- (octadecylthio) ethyl] -4- (octadecylthio) Cyclohexane is preferred. These thioether-based antioxidants can be used alone, or two or more thioether-based antioxidants can be used in combination. The mixing ratio of the thioether-based antioxidant is 0.01 to 1 part by weight, preferably 100 to 100 parts by weight of a composition in which magnesium hydroxide is mixed with polyolefin in an amount of 30 to 70% by weight based on heavy metal resistance. Is 0.05 to 0.5 parts by weight.

The fatty acid used in the present invention is acetic acid,
Propionic acid, n-butyric acid, i-butyric acid, n-valeric acid, i-valeric acid,
n-hexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid,
Oleic acid, linoleic acid, linolenic acid, arachinic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, mericinic acid, 12-hydroxyoctadecanoic acid,
Examples include ricinoleic acid and cerebronic acid.
Preferred are ethylhexanoic, lauric, myristic, palmitic, stearic, oleic, behenic, erucic, montanic and 12-hydroxyoctadecanoic acids. These fatty acids can be used alone,
More than one fatty acid can be used in combination. The proportion of the fatty acid is 0.5 to 5 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of a composition in which 30 to 70% by weight of magnesium hydroxide is added to the polyolefin with respect to the composition from the viewpoint of heavy metal resistance.
3 parts by weight. In addition, the method of compounding the fatty acid is to mix the fatty acid with untreated magnesium hydroxide or magnesium hydroxide surface-treated with a surface treating agent other than the fatty acid and other compounds, or to previously surface-treat magnesium hydroxide with the fatty acid. Any method may be used, such as a method of mixing as magnesium hydroxide.

In the composition of the present invention, various additives usually added to the polyolefin, for example, phenol-based (except for compound A), phosphorus-based antioxidants, light stabilizers, transparentizers, etc. Agents, nucleating agents, lubricants (excluding fatty acids), antistatic agents, antifogging agents, antiblocking agents, drip-free agents, radical generators such as peroxides, flame retardants (however, Excluding.), Flame retardant aids, pigments, halogen scavengers, dispersants or neutralizers such as metallic soaps, organic and inorganic antibacterial agents, inorganic fillers (eg, talc, mica, clay, wool) Lastnite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, aluminum hydroxide, hydrotalcite, basic aluminum lithium hydroxy -Carbonate hydrate, silicon dioxide, titanium dioxide, zinc oxide, calcium oxide, magnesium oxide, zinc sulfide, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, The inorganic filler or the organic filler surface-treated with a surface treatment agent such as graphite and metal fiber, and a coupling agent (for example, silane-based, titanate-based, boron-based, aluminate-based, and zircoaluminate-based). (For example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used in combination as long as the object of the present invention is not impaired.

The composition of the present invention comprises a polyolefin containing magnesium hydroxide, compound A, a heavy metal deactivator and an epoxy compound, magnesium hydroxide, compound A, a thioether antioxidant, a heavy metal deactivator and an epoxy compound, Magnesium hydroxide, compound A, heavy metal deactivator, epoxy compound and fatty acid or magnesium hydroxide, compound A, thioether-based antioxidant, heavy metal deactivator, epoxy compound and fatty acid and the above-mentioned usually added to polyolefin A predetermined amount of each of the various additives is mixed using a usual mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, or the like, and is then mixed with a normal single-screw extruder, twin-screw extruder, Brabender Or with a roll, etc., melt-kneading temperature 150 ℃ ~ 300 ℃, preferably Can be at 200 ° C. to 250 DEG ° C. obtained by melt-kneading pelletized. 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.

[0028]

EXAMPLES The present invention will be described below in more detail 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 pellet, length 50mm, width 25mm, thickness 1mm
Circulating hot air adjusted to a temperature of 150 ° C or 140 ° C by making a test piece by injection molding, making a contact with a copper plate 25 mm long, 25 mm wide and 0.3 mm thick using the test piece and fixing it with a clip. 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 (in accordance with 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 test piece for combustion 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 (according to JIS K 7201). ).

Production Example 1 100 parts by weight of an untreated surface having an average particle diameter of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of lauric acid as a fatty acid were put in a Henschel mixer (trade name) adjusted to a temperature of 50 ° C. The mixture was stirred and mixed for 5 minutes to obtain surface-treated magnesium hydroxide [1]. Production Example 2 100 parts by weight of an untreated surface having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of stearic acid as a fatty acid were put into a Henschel mixer (trade name) adjusted to a temperature of 80 ° C. The mixture was stirred and mixed for 2 minutes to obtain surface-treated magnesium hydroxide [2]. Production Example 3 100 parts by weight of an untreated surface having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of oleic acid as a fatty acid were kept at room temperature by a Henschel mixer (trade name; Unless otherwise indicated, it indicates that the temperature is room temperature.) And stirred and mixed for 5 minutes to obtain surface-treated magnesium hydroxide [3]. Production Example 4 100 parts by weight of an untreated surface having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of linoleic acid as a fatty acid were put into a Henschel mixer (trade name) and mixed by stirring for 5 minutes to perform surface treatment. Thus, magnesium hydroxide [4] was obtained. Production Example 5 100 parts by weight of an untreated surface having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 2 parts by weight of behenic acid as a fatty acid were put into a Henschel mixer (trade name) adjusted to a temperature of 90 ° C. The resulting mixture was stirred and mixed for 5 minutes to obtain surface-treated magnesium hydroxide [5].

Examples 1 to 11 and Comparative Examples 1 to 12 Melt flow rate as a polyolefin (discharge rate of molten resin for 10 minutes when a load of 21.18 N at 230 ° C. is applied; hereinafter abbreviated as MFR) 20 g / 10 43% by weight of powdered crystalline propylene homopolymer not stabilized
And a total of 100 parts by weight of magnesium hydroxide and 57% by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm, and 1,1,3-tris [2-methyl-4- (3-methyl -4-hydroxy-5-t-butylphenylpropionyloxy) -5-t
-Butylphenyl] butane, N, as a heavy metal deactivator
N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2
-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite, N,
N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl)
Propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), a condensate of epichlorohydrin with bisphenol A (epoxy equivalent: 700 to 830) or a condensate of epichlorohydrin with bisphenol A as an epoxy compound, 2-methylepichlorohydrin and bisphenol A Mixture of condensates (epoxy equivalent 180
~ 200), dimyristylthiodipropionate, pentaerythritol-tetrakis (3-laurylthiopropionate), distearyl disulfide, 3,9-bis (2-laurylthioethyl) -2,
4,8,10-tetraoxaspiro [5.5] undecane, 1- [β-
(Dodecylthio) ethyl] -3- (dodecylthio) cyclohexane or 1- [β- (dodecylthio) ethyl] -4- (dodecylthio)
A predetermined amount of each of cyclohexane and other additives is placed in a Henschel mixer (trade name) at the mixing ratio shown in Table 1 below, and stirred and mixed for 3 minutes, and then melted at 250 ° C. with a twin-screw extruder having a diameter of 30 mm. The mixture was kneaded and pelletized.
Further, as Comparative Examples 1 to 12, 43% by weight of an unstabilized powdery crystalline propylene homopolymer having an MFR of 20 g / 10 min
A predetermined amount of each of the additives described in Table 1 described below was blended in a total of 100 parts by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide and 57% by weight. Pellets were obtained by a melt-kneading treatment according to.
The test piece used for the copper resistance test and the flammability test was prepared by injection molding the obtained pellet 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 by the test method described above. The results are shown in Table 1.

Examples 12 to 22, Comparative Examples 13 to 24 50% by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) as a polyolefin having an MFR of 30 g / 10 minutes and water Compound 1, as a compound A, 1,1,3-tris [2-methyl-4- (3,5-diene) was added to a total of 100 parts by weight of 50% by weight of a surface-untreated product having an average particle size of 0.6 to 0.8 μm as magnesium oxide. -t-butyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane, N, N'-bis [2- [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl-4-
Thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl)-
5-methylphenyl] phosphite, N, N'-bis [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), triglycidyl isocyanurate (epoxy equivalent 100-110) or epoxidized soybean oil (epoxy equivalent 220 To 240), thioether-based antioxidants such as dimyristylthiodipropionate, pentaerythritol-tetrakis (3-laurylthiopropionate), distearyl disulfide, and 3,9-bis (2
-Laurylthioethyl) -2,4,8,10-tetraoxaspiro
[5.5] Undecane, 1- [β- (dodecylthio) ethyl] -3- (dodecylthio) cyclohexane or 1- [β- (dodecylthio)
Ethyl] -4- (dodecylthio) cyclohexane and other additives were placed in a Henschel mixer (trade name) at the mixing ratio shown in Table 2 below and mixed under stirring for 3 minutes, and then mixed with a biaxial shaft having a diameter of 30 mm. The mixture was melt-kneaded at 250 ° C. in an extruder and pelletized. MF as Comparative Examples 13 to 24
An unstabilized powdery crystalline ethylene-propylene block copolymer having an R of 30 g / 10 min (ethylene content 8.5
Wt.) 50 wt.% And 50 wt.% Of an untreated surface having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide.
A predetermined amount of each of the additives described in Table 2 described below was blended into 00 parts by weight, and the mixture was melt-kneaded according to Examples 12 to 22 to obtain pellets. The test piece used for the copper resistance test and the flammability test was prepared by applying the obtained pellet to a resin temperature of 250 ° C and a mold temperature of 50 ° C.
It was prepared by injection molding at ℃. Using the obtained test pieces, heavy metal resistance (copper resistance at 150 ° C.) and flame retardancy were evaluated by the test method described above. Table 2 shows the results.

Examples 23-33, Comparative Examples 25-36 Unstabilized powdered crystalline ethylene-propylene-butene-13 with a MFR of 7.0 g / 10 min as polyolefin
Copolymer (ethylene content 2.5% by weight, butene-1 content
Magnesium hydroxide [1], magnesium hydroxide [2], magnesium hydroxide [3], magnesium hydroxide [4] or magnesium hydroxide [5] surface-treated with 29.59% by weight) and a fatty acid as magnesium hydroxide. ]
101.4 parts by weight consisting of 70.41% by weight (crystalline ethylene-propylene-butene-1 excluding fatty acids used for the surface treatment)
Compound A as 1,1,3-tris [3-methyl-4- (3,5-di-t-butyl) in 100 parts by weight of the terpolymer and the untreated surface of magnesium hydroxide in total -4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane, N, N'-bis [2- [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl-4-thio (2 ′
-Methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidenehydrazide), a condensate of epichlorohydrin with bisphenol A (epoxy equivalent: 700 to 830) or a condensate of epichlorohydrin with bisphenol A as an epoxy compound
Mixture of condensates of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent: 180-200), dimyristyl thiodipropionate as thioether antioxidant, pentaerythritol-tetrakis (3-lauryl thiopropionate), distearyl Disulfide, 3,9-
Bis (2-laurylthioethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1- [β- (dodecylthio) ethyl] -3
A predetermined amount of each of-(dodecylthio) cyclohexane or 1- [β- (dodecylthio) ethyl] -4- (dodecylthio) cyclohexane and other additives was added to a Henschel mixer (trade name) in the mixing ratio shown in Table 3 below. The mixture was stirred and mixed for 3 minutes, and then melt-kneaded at 250 ° C. with a twin-screw extruder having a diameter of 30 mm to form a pellet. As Comparative Examples 25 to 36, an unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymer having an MFR of 7.0 g / 10 min (ethylene content 2.5% by weight, butene-1 content 4.5 101.4 parts by weight consisting of 29.59% by weight) and 70.41% by weight of magnesium hydroxide [2] surface-treated with a fatty acid as magnesium hydroxide (crystalline ethylene-propylene-butene-1 excluding the fatty acid used for the surface treatment). 100 parts by weight of the terpolymer and the untreated surface of magnesium hydroxide in total) or an unstabilized powdery crystalline ethylene-propylene-butene-1 having an MFR of 7.0 g / 10 min. 30% by weight combined (ethylene content 2.5% by weight, butene-1 content 4.5% by weight) and average particle size as magnesium hydroxide
0.6-0.8μm untreated surface 70% by weight total 100
A prescribed amount of each of the additives described in Table 3 described below was blended in parts by weight, and the mixture was melt-kneaded according to Examples 23 to 33 to obtain pellets. The test piece used for the copper resistance test and the flammability test was obtained by molding the obtained pellet at a resin temperature of 250 ° C and a mold temperature of 50 ° C
Was prepared by injection molding. Using the obtained test pieces, heavy metal resistance (140 ° C. copper resistance) and flame retardancy were evaluated by the test method described above. Table 3 shows the results.

Examples 34-44, Comparative Examples 37-48 55% by weight of unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) as a polyolefin having an MFR of 7.0 g / 10 minutes , Melt index (when a load of 21.18 N at 190 ° C is applied
Discharge amount of molten resin for 10 minutes; hereinafter abbreviated as MI. ) 20
g / 10 min unstabilized powdered Ziegler-Natta type high density ethylene homopolymer 10% by weight, Mooney viscosity ML1 + 4 (100 ° C) 25, unstabilized powdered amorphous ethylene-propylene A total of 100 parts by weight consisting of 5% by weight of a random copolymer (propylene content 25% by weight) and 30% by weight of an untreated surface having an average particle diameter of 0.6 to 0.8 μm as magnesium hydroxide, and 1,1 as a compound A , 3-Tris [3,5-di
-t-butyl-4- (3,5-di-t-amyl-4-hydroxyphenylpropionyloxy) phenyl] butane, N, N'-bis [2- [3- (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] phosphite, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine or oxalic acid-bis (benzylidene hydrazide), epoxy compound As triglycidyl isocyanurate (epoxy equivalent 100 to 110) or epoxidized soybean oil (epoxy equivalent 22
0-240), thioether-based antioxidants such as dimyristylthiodipropionate, pentaerythritol-tetrakis (3-laurylthiopropionate), distearyl disulfide, and 3,9-bis (2-laurylthioethyl) -2 ,
4,8,10-tetraoxaspiro [5.5] undecane, 1- [β-
(Dodecylthio) ethyl] -3- (dodecylthio) cyclohexane or 1- [β- (dodecylthio) ethyl] -4- (dodecylthio)
A predetermined amount of each of cyclohexane, acetic acid, 2-ethylhexanoic acid, erucic acid, montanic acid or 12-hydroxyoctadecanoic acid as a fatty acid and other additives is added to a Henschel mixer (trade name) in a mixing ratio shown in Table 4 below. After stirring and mixing for 3 minutes, use a twin screw extruder with a diameter of 30 mm.
The mixture was melt-kneaded at 250 ° C. and pelletized. As Comparative Examples 37 to 48, an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content: 2.5% by weight) having an MFR of 7.0 g / 10 minutes was 55% by weight, and MI was 20 g / 10%.
10% by weight of unstabilized powdered Ziegler-Natta high density ethylene homopolymer, Mooney viscosity ML1 +
4 (100 ° C.) 25 unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content 25
% By weight) and 30% by weight of an untreated surface having an average particle size of 0.6 to 0.8 μm as magnesium hydroxide.
A predetermined amount of each of the additives described in Table 4 described below was blended into 00 parts by weight, and the mixture was melt-kneaded according to Examples 34 to 44 to obtain pellets. The test piece used for the copper resistance test and the flammability test was prepared by applying the obtained pellet to a resin temperature of 250 ° C and a mold temperature of 50 ° C.
It was prepared by injection molding at ℃. Using the obtained test pieces, heavy metal resistance (140 ° C. copper resistance) and flame retardancy were evaluated by the test method described above. Table 4 shows the results.

The compounds and additives according to the present invention shown in Tables 1 to 4 are as follows. Magnesium hydroxide [0]: untreated surface with an average particle size of 0.6 to 0.8 μm Magnesium hydroxide [1]: lauric acid (fatty acid [3]) in 100 parts by weight of an untreated surface with an average particle size of 0.6 to 0.8 μm 2
Surface treated product treated with parts by weight Magnesium hydroxide [2]: Stearic acid (fatty acid [4]) is added to 100 parts by weight of untreated surface having an average particle size of 0.6 to 0.8 μm
Surface treated product treated with 2 parts by weight Magnesium hydroxide [3]: Oleic acid (fatty acid [5]) 2 added to 100 parts by weight of untreated surface having an average particle size of 0.6 to 0.8 μm
Surface treated product treated with parts by weight Magnesium hydroxide [4]: Linoleic acid (fatty acid [6]) 2 in 100 parts by weight of untreated surface having an average particle size of 0.6 to 0.8 μm
Surface treated product treated with parts by weight Magnesium hydroxide [5]: Surface treated product treated with 2 parts by weight of behenic acid (fatty acid [7]) to 100 parts by weight of untreated surface with an average particle size of 0.6 to 0.8 μm Compound A [1]: 1,1,3-tris [2-methyl-4- (3-methyl-
4-hydroxy-5-t-butylphenylpropionyloxy)
-5-t-butylphenyl] butane Compound A [2]: 1,1,3-tris [2-methyl-4- (3,5-di-t-
(Butyl-4-hydroxyphenylpropionyloxy) -5-t
-Butylphenyl] butane Compound A [3]: 1,1,3-tris [3-methyl-4- (3,5-di-t-
(Butyl-4-hydroxyphenylpropionyloxy) -5-t
-Butylphenyl] butane Compound A [4]: 1,1,3-tris [3,5-di-t-butyl-4- (3,
5-di-t-amyl-4-hydroxyphenylpropionyloxy) phenyl] butane

Heavy metal deactivator [1]: N, N'-bis [2
-[3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide Heavy metal deactivator [2]: tris [2-t-butyl-4-thio (2'- Methyl-4'-hydroxy-5'-t-butylphenyl) -5-
Methylphenyl] phosphite heavy metal deactivator [3]: N, N'-bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyl] hydrazine heavy metal deactivator [4]: oxalic acid-bis (benzylidenehydrazide) epoxy compound [1]: condensate of epichlorohydrin and bisphenol A (epoxy equivalent 700 to 830; Asahi ARALITE AER 6003 manufactured by Ciba Co., Ltd.) Epoxy compound [2]: a mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (epoxy equivalent 18
ADK CIZER E manufactured by Asahi Denka Kogyo Co., Ltd.
P-17) Epoxy compound [3]: triglycidyl isocyanurate (epoxy equivalent 100-110) Epoxy compound [4]: epoxidized soybean oil (epoxy equivalent 220-240; ADK CIZER manufactured by Asahi Denka Kogyo KK)
O-130P)

Thioether antioxidant [1]: dimyristylthiodipropionate Thioether antioxidant [2]: pentaerythritol-tetrakis (3-laurylthiopropionate) thioether antioxidant [3]: di Stearyl disulfide thioether antioxidant [4]: 3,9-bis (2-laurylthioethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane thioether antioxidant [5]: 1- [β- (dodecylthio) ethyl] -3- (dodecylthio) cyclohexane thioether antioxidant [6]: 1- [β- (dodecylthio) ethyl] -4- (dodecylthio) cyclohexane fatty acid [1]: acetic acid fatty acid [2] ]: 2-ethylhexanoic acid fatty acid [3]: lauric acid fatty acid [4]: stearic acid fatty acid [5]: oleic acid fatty acid [6]: linoleic acid fatty acid [7]: base Phosphate fatty [8]: erucic fatty acid [9]: montanate fatty [10]: 12-hydroxy octadecanoic acid

Phenolic antioxidant: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene phosphorus antioxidant 1: bis ( 2,4-di-t-butylphenyl)-
Pentaerythritol-diphosphite phosphorus antioxidant 2: bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 3: tetrakis (2,4- Di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite Higher fatty acid ester: butyl stearate Higher alcohol: stearyl alcohol Higher fatty acid monoamide: Stearamide Higher aliphatic amine: N, N-bis ( 2-Hydroxyethyl) tallow amine Ca-St: calcium stearate carbon black: carbon # 45 manufactured by Mitsubishi Chemical Corporation

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

The examples and comparative examples shown in Table 1 are the cases where a crystalline propylene homopolymer was used as the polyolefin and an untreated product was used as the magnesium hydroxide. As can be seen from Table 1, Examples 1 to 11 are obtained by blending magnesium hydroxide (untreated surface), compound A, heavy metal deactivator and epoxy compound with a crystalline propylene homopolymer. 1 to 11 and Comparative Examples 1 to 3 (Compound A
(Alone or in combination with a heavy metal deactivator or epoxy compound), Examples 1 to 11 are remarkably excellent in heavy metal resistance. Similarly, Examples 1 to 11
When compared with Comparative Examples 4 to 6 (in which a phenolic antioxidant is used alone or in combination with a heavy metal deactivator or an epoxy compound), Examples 1 to 11 are remarkably excellent in heavy metal resistance. You can see that. In addition, Examples 1 to 11 and Comparative Examples 7 to 12 (Examples 1 to 5 using a phenolic antioxidant instead of compound A or further using a thioether-based antioxidant in combination; In comparison with the compositions proposed in JP-A-2-214475 and JP-A-9-20841, Examples 1 to 5 were compared.
It can be seen that the heavy metal resistance of No. 11 is further improved as compared with Comparative Examples 7 to 12. Further, it can be seen that Examples 6 to 11, in which the thioether-based antioxidant is used in combination with the compositions of Examples 1 to 5, have improved heavy metal resistance compared to Examples 1 to 5. Therefore, it is clear that each comparative example which does not simultaneously satisfy the compounding of the three components of the compound A, the heavy metal deactivator and the epoxy compound according to the present invention does not exhibit the effects of the present invention. That is, the heavy metal resistance obtained in the present invention is:
It can be said that this is a unique effect first seen when the compound A, the heavy metal deactivator and the epoxy compound are used in combination with the flame-retardant polyolefin composition containing magnesium hydroxide. Further, the flame retardant composition according to the present invention comprising the compound A, the heavy metal deactivator and the epoxy compound has flame retardancy comparable to that of a conventionally known flame retardant composition. It was confirmed that.

Table 2 shows the results obtained by using a crystalline ethylene-propylene block copolymer as the polyolefin and an untreated product as the magnesium hydroxide. The same effects as described above were confirmed for these. Table 3 shows the results obtained by using a crystalline ethylene-propylene-butene-1 terpolymer as a polyolefin and a surface-treated product treated with a fatty acid as magnesium hydroxide, and Table 4 shows the results obtained by using a crystalline ethylene-propylene random copolymer as a polyolefin. A mixture of a polymer, a Ziegler-Natta high-density ethylene homopolymer and a non-crystalline ethylene-propylene random copolymer, and further mixed with a fatty acid using a surface-untreated product as magnesium hydroxide. The same effect as described above and the effect of improving heavy metal resistance by using a fatty acid in combination were confirmed.

[0044]

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 heavy metal resistance is remarkably excellent, there is no decrease in the electrical insulation due to the oxidative deterioration of the polyolefin. Therefore, applications requiring flame retardancy and heavy metal resistance in various molding fields (for example, deflection yokes, It can be suitably used for electric and electronic functional parts such as CRT sockets and connectors, automotive parts such as a distributor cap, a car heater case and a car air-conditioner case, and insulating materials such as a wire covering material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5:15 5:09)

Claims (3)

[Claims] 1. One or two phenolic compounds selected from the following (1) or (2), based on 100 parts by weight of a composition obtained by mixing 30 to 70% by weight of magnesium hydroxide with a polyolefin, based on the composition. , A compound A), a heavy metal deactivator and an epoxy compound each in an amount of 0.01 to 1 part by weight. 1,1,3-tris [2,5-dialkyl-4- (3,5-dialkyl-4-
Hydroxyphenylpropionyloxy) phenyl] butane 1,1,3-tris [3,5-dialkyl-4- (3,5-dialkyl-4-
Hydroxyphenylpropionyloxy) phenyl] butane 2. Compound A, a thioether-based antioxidant, a heavy metal deactivator and an epoxy compound per 100 parts by weight of a composition obtained by mixing magnesium hydroxide with polyolefin in an amount of 30 to 70% by weight based on the composition. A flame-retardant polyolefin composition comprising 0.01 to 1 part by weight of each. 3. The composition according to claim 1, further comprising 0.5 to 5 parts by weight of a fatty acid based on 100 parts by weight of a composition in which 30 to 70% by weight of magnesium hydroxide is added to the polyolefin. The flame-retardant polyolefin composition according to claim 1.