JPH10195254A - Flame-retardant polyolefin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant polyolefin composition high in quality, excellent in flame-retardance, useful for injection molding and hollow extrusion molding, capable of improving an unpleasant smell caused by the decomposition of a flame-retardant by the high-temperature heat of a compounding process and a molding process of a flame-retardant polyolefin using an organic halogen based flame retardant. SOLUTION: This composition is obtained by compounding 100 pts.wt. of a polyolefin resin with 2-60 pts.wt. of a halogen based flame retardant, 0.01-2 pts.wt. of a pentaerythritol diphosphite and 0.01-2 pts.wt. of one or more lubricants selected from (1) a fatty acid ester, (2) an aliphatic alcohol, (3) a fatty acid dialkanolamide and (4) an aliphatic dialkanolamine and has 0.1-60g/10 minutes melt flow rate (230 deg.C; 21.18N).

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 composition comprising a crystalline polyolefin, particularly crystalline polypropylene, and a specific halogen-based flame retardant and a lubricant, and a specific amount of pentaerythritol diphosphite.

[0002]

2. Description of the Related Art Non-flammable resins, flame-retardant resins or self-extinguishing resins are used in accordance with required performance for the purpose of preventing ignition, burning or fire caused by electrical troubles. Have been. For this reason, various proposals have been made regarding flame retardancy for olefin resins, particularly polypropylene resins, made from hydrocarbons because of their excellent impact resistance, rigidity, appearance and moldability. In particular, the United States UL standard (UL94) requires a high degree of flame retardancy depending on the product or part as the flame retardancy standard for electric appliances, and products exported to the United States are required to select materials that conform to the UL standard. In addition, the flame retardancy of electric appliances is not limited to the United States, and many countries such as Japan and Western Europe also require a high degree of flame retardancy. In order to meet such a demand, a flame-retardant polyolefin composition having excellent self-extinguishing properties, in which an organic flame retardant and a flame retardant aid are blended with a polyolefin resin, has been developed. The system flame retardant has a problem that it generates halogen-based gas and the like by thermal decomposition in a compound production process or a molding process, causing an unpleasant odor or damaging a molding machine.

On the other hand, as a countermeasure for suppressing decomposition of the flame retardant and preventing discoloration, an organic halogen-based flame retardant is used in an amount of 0.5 to 30 parts by weight and an aliphatic carboxylic acid having a melting point of 60 ° C. or less based on 100 parts by weight of a polyolefin resin. A flame-retardant polyolefin composition comprising 0.01 to 5 parts by weight of an acid and 0.01 to 5 parts by weight of a metal salt of an aliphatic carboxylic acid has a high heat stability, The effect of preventing this is disclosed in Japanese Patent Publication No. 5-51021. However, in this composition, even if the thermal stability is improved, the unpleasant odor due to the aliphatic carboxylic acid blended is strong, and it is still not enough to prevent the unpleasant odor during the compound production process or molding.

[0004]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a molded article having excellent appearance without impairing the flame retardancy and mechanical properties of the flame-retardant polyolefin composition. An object of the present invention is to provide a flame-retardant polyolefin composition in which an unpleasant odor caused by decomposition of a flame retardant at times is improved.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to obtain a flame-retardant polyolefin resin which has achieved the above-mentioned objects. As a result, when a flame retardant polyolefin resin composition is produced by blending an organic halogen-based flame retardant with a polyolefin resin, a flame retardant polyolefin composition comprising a particular phosphorus-based antioxidant and a particular lubricant is blended. Was found to be a composition having excellent thermal stability and extremely low unpleasant odor due to decomposition gas generated by decomposition of the flame retardant during compound production and molding. Based on this finding, the present invention was completed. That is, the present invention includes the following (1) to (5). (1) Per 100 parts by weight of polyolefin resin, 2 to 60 parts by weight of a halogen-based flame retardant, 0.01 to 2 parts by weight of pentaerythritol-di-phosphite as an antioxidant, and 1) to 4 below as a lubricant. ), A melt flow rate (230 ° C .; 21.18) comprising one or more lubricants selected from the group consisting of 0.01 to 1 part by weight.
N, hereinafter referred to as MFR)) of 0.1 to 60 g / 10 min. 1) Fatty acid esters. 2) Aliphatic alcohol. 3) Fatty acid dialkanolamide. 4) Aliphatic dialkanolamine. (2) The halogen-based flame retardant is bis [[3,5-dibromo-4-
(2 ', 3'-dibromopropyloxy)] phenyl] sulfone, 2,2-bis [[3,5-dibromo-4- (2', 3'-dibromopropyloxy)] phenyl] propane, decabromodiphenyl ether , 1,2-bis (2 ', 3', 4 ', 5', 6'-pentabromophenyl) ethane, N, N'-ethylene-bis (tetrabromophthalimide) or a mixture of two or more of these 2. The flame-retardant polyolefin composition according to claim 1. (3) The halogen-based flame retardant is bis [[3,5-dibromo-4-
(2 ', 3'-dibromopropyloxy)] phenyl] sulfone, 2,2-bis [[3,5-dibromo-4- (2', 3'-dibromopropyloxy)] phenyl] propane or a mixture thereof 2. The flame-retardant polyolefin composition according to claim 1, which is a mixture of at least one kind. (4) A flame-retardant polyolefin composition for hollow or extrusion molding, wherein the MFR of the flame-retardant polyolefin composition according to the above (1) to (3) is 0.1 to 4 g / 10 minutes. (5) A flame-retardant polyolefin composition for injection molding, wherein the MFR of the flame-retardant polyolefin composition according to the above (1) to (3) is 3 to 60 g / 10 min.

Hereinafter, the present invention will be described specifically. The polyolefin resin used in the flame-retardant polyolefin composition of the present invention refers to propylene homopolymer (homopolypropylene) or propylene-based ethylene,
0.5 to 6% by weight of 1-butene and / or 1-hexene, etc., as a copolymer component, a binary or more polypropylene random copolymer or a copolymer of ethylene and propylene in a propylene chain containing ethylene. 30 ~
70%, preferably 40 to 60% by weight of elastomeric compositional chains (segments) of 5 to 25% by weight, preferably 8 to 15% by weight, said blocks being said to be linked blockwise to propylene chains Α such as ethylene, 1-butene, etc. with polypropylene or propylene as the main component
0.5 to 5% by weight of olefin component, preferably 1 to 3%
80 to 95% by weight of a propylene / α-olefin random copolymer chain portion contained by weight and an α-olefin content of 3% in the α-olefin / propylene copolymer bonded thereto.
A random block copolymer having a chain of an elastomeric composition of 0 to 80% by weight, preferably 40 to 60% by weight, of 5 to 15% by weight can be mentioned. These (co) polymers may be not only one kind but also a mixture of two or more kinds.

The homopolypropylene or the specific polypropylene-based copolymer comprising propylene and α-olefin is used when homopolymerizing propylene or by randomizing propylene as a main monomer and α-olefin as a comonomer or ethylene and propylene. When copolymerizing the elastomeric composition of the block-like, for example, a coordination compound catalyst system such as a Ziegler-Natta catalyst,
It can be obtained by employing a polymerization method such as solution polymerization or gas-phase polymerization under a relatively high hydrogen concentration and a relatively low temperature condition using a known highly active catalyst such as a reduction type or a supported type. The stereoregularity of the polyolefin resin of the present invention is not particularly limited, and any polypropylene that achieves the object of the present invention may be used as long as it is a crystalline polypropylene. Specifically, the isotactic pentad fraction (m) measured by 13 C-NMR (nuclear magnetic resonance spectrum)
mmm) is 0.80 to 0.99, preferably 0.85 to 0.95.
0.99, particularly preferably 0.90 to 0.99 crystalline polypropylene.

Isotactic pentad fraction (mmm
m) is proposed by A. Zambelli et al. (M
acromolecules 6, 925 (1973)) is the isotactic fraction in pentad units in the polypropylene molecular chain measured by 13 C-NMR, and the method for determining the assignment of peaks in the spectrum measurement is described by A. Zamberg (A. Zambel
li) etc. (Macromolecules 8, 687 (1975))
Is determined according to the assigned attribution. Specifically, using a mixed solution of o-dichlorobenzene / bromide benzene = 8/2 weight ratio having a polymer concentration of 20% by weight, 67.20 MHz,
It is determined by measuring at 130 ° C. As the measuring device, for example, a JEOL-GX270 NMR measuring device (manufactured by JEOL Ltd.) is used.

The polyolefin resin used in the present invention has an MFR (230 ° C .; 21.18N) of 0.1 to 60 g / 10 minutes,
Preferably it is 0.3 to 50 g / 10 minutes. For hollow molding and extrusion molding, 0.1 to 4 g / 10 min, preferably 0.3 to 3 g / 10 min is suitable. MFR (230 ° C .;
If 21.18N) is less than 0.1 g / 10 minutes, the shear heat generated during plasticization increases, and the decomposition of the flame retardant and the motor load increase. On the other hand, if it is 4 g / 10 minutes or more, the melt viscosity decreases, and molding becomes extremely difficult. For injection molding, 3 to 50 g / 10 min, preferably 5 to 30 g / 10 min,
More preferably, 8 to 20 g / 10 minutes is suitable. The M
When the FR (230 ° C .; 21.18 N) is less than 3 g / 10 minutes, short molding due to a decrease in fluidity occurs and mass production becomes difficult. Further, when the amount greatly exceeds 60 g / 10 minutes, the mechanical properties are reduced and the flame retardancy is reduced.

The halogen-based flame retardant used in the present invention includes ammonium bromide, ammonium chloride, 2-chlorotetrabromobutane, 2,2-bis [p- (chloroformyloxy) phenyl-3] propane, , 2-Dibromo-3-chloropropane, 1,2,3-tribromopropane, 1,1,2,2-tetrabromoethane, tetrabromobutane, hexabromocyclododecane, hexabromooctane, hexabromobutane, pentabromo Cyclohexane, tribromotrichlorocyclohexane, pentabromochlorocyclohexane, 1,2-dibromo-1,1,2,2-tetrachloroethane, 2,2
-Bis (4-hydroxyethoxy-3,5-dibromophenyl)
Propane, vinyl chloroacetate, 2,4,6-tribromophenyl methacrylate, 2,3,3'-tribromoallylformate, 2,2-dibromopropyl methacrylate, bis (2,3-dibromopropyl) -2, 3-dibromofumarate,
Tribromophenyl acrylate, chloroendic acid, diallyl chloroendate, chloroendic anhydride, bromostyrene, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chloropropanediol, 3-bromo-2,2-bis (bromomethyl) propanol, 2,2-dibromobutene
-1,4-diol, tribromophenol, dibromoneopentyl glycol, tribromoneopentyl alcohol,

2,3-dibromopropanol, 2,3,3'-tribromoallyl alcohol, chloropentabromophenyl allyl ether, pentachlorophenoxyglycerin ether, bromophenyl allyl ether, tribromophenol allyl ether, pentabromophenol allyl Ether, pentabromophenyl allyl ether, bromoalkenyl ether, sorbitol-1,6-bis (2 ′,
3'-dibromopropyl) ether, decabromobiphenyl, decabromodiphenylether, decabromodiphenylketone, decabromodiphenylcarbonate, decabromodiphenylsulfide, decabromodiphenyldisulfide, decabromodiphenylsulfone, decabromodiphenylmethane, 1,2-bis (2 ', 3', 4 ', 5', 6'-pentabromophenoxy) ethane, 1,2-bis (2 ', 3', 4 ',
5 ', 6'-pentabromophenyl) ethane, 1,1-bis (2',
3 ', 4', 5 ', 6'-pentabromophenyl) ethane, 2,2-bis (2', 3 ', 4', 5 ', 6'-pentabromophenyl) propane,
Pentadecabromotriphenylamine,

Pentadecabromotriphenylphosphine, hexabromodiphenylether, dibromocresylglycidylether, pentabromoallylether,
1,2-dibromopropyl-tribromophenyl ether,
Decachlorodiphenyl carbonate, decabromodiphenyl carbonate, 2,3,3-tribromoallyl carboxylate, 2,3,5,6,2 ', 3', 5 ', 6'-octachloro-4,4'-di Oxydiphenyl, tetrabromobenzene, α, β-dibromoethylbenzene, 2-bromo-α, β-dibromoethylbenzene, hexabromobenzene, perchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodiene Methanodibenzofuran,

N, N'-ethylene-bis (dibromophthalimide), N, N'-methylene-bis (tetrabromophthalimide), N, N'-ethylene-bis (tetrabromophthalimide), N, N'-ethylidene -Bis (tetrabromophthalimide), N, N '-(1,3-propylene) -bis (tetrabromophthalimide), N, N'-(1,2-propylene) -bis (tetrabromophthalimide), N, N '-(2,2-propylene) -bis (tetrabromophthalimide), N, N'-
(1,4-butylene) -bis (tetrabromophthalimide), N, N '-(1,6-hexamethylene) -bis (tetrabromophthalimide),

N, N '-(1,8-octamethylene) -bis (tetrabromophthalimide), N, N'-(2,5-dimethyl-2,
5-hexamethylene) -bis (tetrabromophthalimide), N, N '-(1,4-phenylene) -bis (tetrabromophthalimide), N, N'-(4,4'-biphenylene) -bis (tetra Bromophthalimide), N, N '-(4,4 "-terphenylene) -bis (tetrabromophthalimide), N,
N′-methylene-bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N′-ethylene-bis (5,6-dibromonorbornan-2,3-dicarboximide), N, N'-ethylidene-bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N '-(1,3-propylene) -bis (5,6-dibromonorbornane-2,3-di Carboximide), N, N'-
(1,2-propylene) -bis (5,6-dibromonorbornane-
2,3-dicarboximide), N, N '-(2,2-propylene)-
Bis (5,6-dibromonorbornane-2,3-dicarboximide),

N, N '-(1,4-butylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N'-
(1,6-hexamethylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N '-(1,8-octamethylene) -bis (5,6-dibromonorbornane- 2,3-dicarboximide), N, N '-(2,5-dimethyl-2,5-hexamethylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N '-(1,4-phenylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N'-
(4,4'-biphenylene) -bis (5,6-dibromonorbornane-2,3-dicarboximide), N, N '-(4,4 "-terphenylene) -bis (5,6-dibromonorbornane) -2,3-dicarboximide),

N, N'-methylene-bis (5,6-dibromo-1,4
-Epoxycyclohexane-2,3-dicarboximide),
N, N'-ethylene-bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N'-ethylidene-bis (5,6-dibromo-1,4- Epoxy cyclohexane
-2,3-dicarboximide), N, N '-(1,3-propylene)
-Bis (5,6-dibromo-1,4-epoxycyclohexane-2,3
-Dicarboximide), N, N '-(1,2-propylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N'-(2 , 2-Propylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N '-(1,4-butylene) -bis (5,6-
Dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N '-(1,6-hexamethylene) -bis (5,6-
Dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N '-(1,8-octamethylene) -bis (5,6-
Dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N '-(2,5-dimethyl-2,5-hexamethylene) -bis (5,6-dibromo-1,4- Epoxy cyclohexane
-2,3-dicarboximide), N, N '-(1,4-phenylene)
-Bis (5,6-dibromo-1,4-epoxycyclohexane-2,3
-Dicarboximide), N, N '-(4,4'-biphenylene)-
Bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-
Dicarboximide),

N, N '-(4,4 "-terphenylene) -bis (5,6-dibromo-1,4-epoxycyclohexane-2,3-dicarboximide), N, N'-(4, 4'-biphenylsulfone) -bis (tetrabromophthalimide), N, N '-[4,
4'-bis (3,5-dibromophenyl) sulfone] -bis (tetrabromophthalimide), N, N '-[4,4'-bis (2,3,5,6-tetrabromophenyl) sulfone]- Bis (tetrabromophthalimide), N, N '-(4,4'-biphenylmethane) -bis (tetrabromophthalimide), N,
N '-[4,4'-bis (3,5-dibromophenyl) methane] -bis (tetrabromophthalimide), N, N'-[4,4'-bis (2,3,5,6-tetra Bromophenyl) methane] -bis (tetrabromophthalimide), N, N '-[4,4'-biphenyl
-(1,2-ethane)]-bis (tetrabromophthalimide), N, N '-[4,4'-bis (3,5-dibromophenyl)-
(1,2-ethane)]-bis (tetrabromophthalimide), N, N '-[4,4'-bis (2,3,5,6-tetrabromophenyl)-(1,2-ethane)] -Bis (tetrabromophthalimide), N, N '-[4,4'-biphenyl- (2,2'-propane)]-bis (tetrabromophthalimide), N, N'-
[4,4'-bis (3,5-dibromophenyl)-(2,2'-propane)]-bis (tetrabromophthalimide), N, N'-
[4,4'-bis (2,3,5,6-tetrabromophenyl)-(2,2 '
-Propane)]-bis (tetrabromophthalimide),

Poly (dibromostyrene), poly (tribromostyrene), poly (tetrabromostyrene), poly (pentabromostyrene), 1,4-bis (2 ′, 3 ′, 4 ′, 5 ′, 6 ′)
-Pentabromophenoxy) -2,3,5,6-tetrabromobenzene, 1,4-bis (2 ', 3', 4 ', 5', 6'-pentabromobenzyl) -2,3,5, 6-tetrabromobenzene, 4,4'-bis (2,3,
4,5,6-pentabromophenoxy) -2,2 ', 3,3', 5,5 ', 6,6'
-Octabromodiphenyl ether, 4,4'-bis (2,3,4,
5,6-pentabromobenzyl) -2,2 ', 3,3', 5,5 ', 6,6'-octabromodiphenylmethane,

Tetrabromobisphenol A, tetrabromobisphenol A diethoxylate, bis (2-hydroxyethyl ether) tetrabromobisphenol A, 2,2-bis [[3,5-dibromo-4- (2 ′, 3 ′) -Dibromopropyloxy)] phenyl] propane, 2,2-bis [[3,
5-dibromo-4- (2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] propane, tetrabromobisphenol F, bis [[3,5-dibromo-4- (2', 3'- Dibromopropyloxy)] phenyl] methane, bis [[3,5-dibromo-4- (2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] methane, bis [[3,5-dibromo- Four-
(2 ', 3'-dibromopropyloxy)] phenyl] oxide, bis [[3,5-dibromo-4- (2', 3'-dibromo-2'-
Methylpropyloxy)] phenyl] oxide, bis [[3,5-dibromo-4- (2 ′, 3′-dibromopropyloxy)] phenyl] ketone, bis [[3,5-dibromo-4-
(2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] ketone,

Bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfide, bis [[3,5-dibromo-4- (2', 3'-dibromo- 2'-methylpropyloxy)] phenyl] sulfide, tetrabromobisphenol S, bis [[3,5-dibromo-4- (2 ', 3'-
Dibromopropyloxy)] phenyl] sulfone, bis [[3,5-dibromo-4- (2 ', 3'-dibromo-2'-methylpropyloxy)] phenyl] sulfone, pentabromotoluene, tribromoaniline, acetylene Tetrabromide, 1- (p-tosyl) -3- (2'-bromo-4 ', 4', 4'-trichlorobutyl) urea, 2,3-dibromopropanol ester, tetrabromobisphenol A type epoxy resin, tetra Inorganic and organic halogen-based flame retardants such as bromobisphenol S type epoxy resin, tetrabromobisphenol F type epoxy resin, chlorinated paraffin, chlorinated polyethylene or chlorinated polypropylene can be exemplified,

Bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfone, 2,2-bis [[3,5-dibromo-4- (2', 3 '-Dibromopropyloxy)] phenyl] propane, decabromodiphenyl ether, 1,2-bis (2', 3 ', 4', 5 ', 6'-pentabromophenyl) ethane and N, N'-ethylene -Bis (tetrabromophthalimide) is preferred because it has excellent flame retardancy.
In particular, bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfone and 2,2-bis [[3,5-
Dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] propane is a molded article that exhibits excellent flame retardancy with a relatively small amount and does not impair the excellent gloss of polypropylene. Is preferable since the appearance of the resin becomes good. These flame retardants can be used alone, or two or more flame retardants can be used in combination. The blending ratio of the flame retardant is determined according to the desired flame retardancy (self-extinguishing property), and is not particularly limited, and is usually 2 to 60 parts by weight based on 100 parts by weight of the polyolefin. is there.

The antioxidants pentaerythritol-di-phosphite to be incorporated in the flame-retardant polyolefin composition of the present invention include di-stearyl-pentaerythritol-di-phosphite and bis (2,6-di-t-t-phosphite). -Butyl-
4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, diisodecyl-pentaerythritol-di-phosphite, and the like,
The mixing ratio of these pentaerythritol-di-phosphites is 0.01 to 2 parts by weight, preferably 0.05 to 1.0 part by weight, more preferably 0.05 to 100 parts by weight of the polyolefin resin. -0.5 parts by weight, and these can be used alone or in combination of two or more. If the amount is less than 0.01 part by weight, the effect of improving the unpleasant odor is small, and if the amount is much more than 2 parts by weight, the effect of improving the odor caused by the decomposition of the flame retardant reaches saturation, which increases the cost and is not economical.

The fatty acid ester used as a specific lubricant in the composition of the present invention includes glycerin monopalmitate, glycerin monostearate, glycerin monooleate, glycerin monolaurate, butyl laurate, butyl stearate, and decyl laurate. Rate, decyl stearate, lauryl stearate, stearyl stearate and the like. Examples of the aliphatic alcohol include decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and the like. Examples of the fatty acid dialkanolamide include behenic acid diethanolamide, oleic acid diethanolamide, stearic acid diethanolamide, myristic acid diethanolamide, lauric acid diethanolamide, capric acid diethanolamide, caprylic acid diethanolamide, and the like. Examples of the dialkanolamine include lubricants such as behenyldiethanolamine, oleyldiethanolamine, stearyldiethanolamine, myristyldiethanolamine, lauryldiethanolamine, decyldiethanolamine, octyldiethanolamine, and hexyldiethanolamine. Particularly, glycerin monolaurate, lauryl alcohol and lauric acid diethanolamide are preferred. The mixing ratio of these fatty acid ester, aliphatic alcohol, fatty acid dialkanolamide and aliphatic dialkanolamine is 0.01 to 2 parts by weight, preferably 0.03 part by weight, per 100 parts by weight of the polyolefin resin.
To 1 part by weight, more preferably 0.05 to 0.5 part by weight. These may be used alone or in combination of two or more. If the compounding ratio is less than 0.01 part by weight, the effect of improving the unpleasant odor is small, and if it exceeds 2 parts by weight, the effect of improving the unpleasant odor is saturated and the cost is increased. Further, even if the amount exceeds 2 parts by weight, the surging phenomenon in the granulation process lowers the productivity, and furthermore, the bleeding phenomenon occurs on the surface of the molded product, and the flame retardancy is lowered.

Further, a flame retardant auxiliary can be used in the composition of the present invention. Examples of the flame retardant aid include antimony compounds (for example, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, antimony trichloride, antimony trisulfide, antimony oxychloride,
Antimony dichloride perchloropentane and potassium antimonate, etc., boron compounds (eg, zinc metaborate, zinc tetraborate, zinc borate and basic zinc borate), zirconium oxide, tin oxide and molybdenum oxide Can be exemplified, particularly antimony trioxide,
Antimony tetroxide, antimony pentoxide, antimony trichloride, antimony trisulfide and zinc borate are preferred. These flame retardants can be used alone, or two or more flame retardants can be used in combination. The blending ratio of these flame retardants is not particularly limited, but is preferably 20 to 60 parts by weight based on 100 parts by weight of the halogen-based flame retardant. Since the compounding of the flame retardant aid acts synergistically with the halogen-based flame retardant in the composition of the present invention to increase the flame retardancy, the compounding amount of the halogen-based flame retardant can be reduced. Therefore, it is preferable to add the flame retardant auxiliary.

In addition, 2.6-di-tert-butyl-P-cresol, tetrakis [methylene (3,5-di-tert-), which is used as a stabilizer for polyolefin, is used in the composition of the present invention.
Butyl-4-hydroxyhydrocinnamate)] methane,
Phenolic antioxidants such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Thio-based antioxidants, such as distearyl-ββ'-thiodipropionate, dimyristyl-ββ'-thiodipropionate, dilaurilu ββ'-thiodipropionate, calcium stearate, hydrotalcite (trade name) : Kyowa Chemical Industry Co., Ltd.), 2-hydroxy-4-n-octoxybenzophenone, 2- (2′hydroxy-3 ′, 5 ′)
UV absorbers such as -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole,

N-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-butylphenyl-3 ′, 5′-di-tert-butyl-4′-hydroxybenzoate,
Bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, dimethyl succinate 2- (4-hydroxy-2,2,
6,6-tetramethyl-1-peripyridyl) ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl]
[(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]}, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1, Light-fastening agents such as 3,5-triazine condensates,

Further, inorganic fillers such as talc, calcium carbonate, potassium titanate whisker, glass fiber, mica, magnesium hydroxide, silica, zeolite, sericite and the like can be blended. They may be used alone or in combination as long as they do not impair. The talc has a specific surface area of 17,000 cm 2 /
talc having an average particle size of 20 μm or less, preferably 5 μm or less, more preferably 2 μm or less, and having a particle size component exceeding 10 μm of 5% by weight or less and 1% by weight or less in terms of impact resistance. As the calcium carbonate, those having a specific surface area of 8,000 cm 2 / g or more, an average particle diameter of 3 μm or less, and a particle diameter component exceeding 10 μm of 5% by weight or less are preferable. As the potassium titanate whisker, an average fiber diameter is preferable. 0.2-1.5 μm and average fiber length 10-5
Whiskers of 0 μm are preferred. As the mica, mica having an average flake diameter of 200 to 40 μm and an aspect ratio of 30 to 70 is preferable.
Glass fibers with an average fiber system of 4 to 13 μm and a fiber length of 3 to 6 mm are preferred. The magnesium hydroxide has an average particle diameter of 0.5 to 2 μm, the zeolite has an average particle diameter of 10 to 20 μm, and the sericite has an average particle diameter of 3 to 20 μm.
Those having a thickness of 10 μm and those having a silica of 1 to 15 μm are preferred. Further, the filler can be either an untreated filler or a filler which has been silane-treated to increase the reinforcing effect.

In addition, metal deactivators (copper damage inhibitors), antistatic agents, coloring agents and fatty acids for dispersing them, polyethylene wax, polypropylene wax, montanic acid wax, calcium stearate, magnesium stearate, A dispersant such as stearyl phosphate, a crystal nucleating agent, polyethylene, an olefin-based elastomer and the like can be blended within a range not to impair the object of the present invention.

The flame-retardant polyolefin composition of the present invention can be obtained by mixing the above components.
For mixing these components, a conventional mixing device such as a mixer with a high-speed stirrer such as a Henschel mixer (trade name) or a super mixer (trade name), a ribbon blender, or a tumbler mixer may be used. When melt kneading is required, pelletization can be performed by pelletizing with a usual single screw extruder or twin screw extruder. The kneading temperature is generally 190 to 220 ° C. in the case of the flame-retardant polyolefin composition of the present invention. However, the resin temperature during kneading should be 1 to suppress the decomposition of the flame retardant.
The temperature is preferably set to about 90 to 210 ° C.

As a method for obtaining a molded article using the flame-retardant polyolefin composition of the present invention, a molding temperature in consideration of the decomposition temperature of the flame retardant is selected so as not to impair the flame retardancy. is important. Generally 180-2
Set the temperature to 10 ° C. In the composition used for the injection molding method, the MFR is 3 to 50 g / 10 min, preferably 5 to 30 g / 10 min, more preferably 8 to 20 g / min.
10 minutes. In the case of a composition used for an extrusion molding method, when forming a hollow molded article or sheet, MF is used.
R is 0.1 to 4 g / 10 min, preferably 0.3 to 3 g / 1
0 minutes.

[0031]

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 to these specific examples. The following methods were used to evaluate the characteristics used in the following examples and comparative examples. (1) Crystal melting point (abbreviation: Tm): A 10 mg sample was measured from a room temperature (23 ° C.) at a heating rate of 20 ° C./min under a nitrogen atmosphere using a scanning differential calorimeter (abbreviation: DSC). It is expressed as the peak temperature of the endothermic curve (unit: ° C) accompanying the melting of. (2) Density: Measured based on JIS K7112 (1980) test condition D method (density gradient tube method) (unit: g / cm)
3). (4) MFR: Test condition 14 of JIS K7210 (2
30 ° C; 21.18N) (unit: g / 10min). (5) Mooney viscosity: JIS-K6300 ML1 + 4
(100 ° C). (6) Rigidity: Flexural modulus was measured according to the test method of JIS K7203. Specimen dimensions (100 × 10 × 4mm),
Bending speed 1.5 mm / min. (7) Izod impact strength: JISK- (8) Odor: 500 cc of test piece (50 × 50 × 2 mm)
50g each in a wide-mouth glass container with a sealed stopper
After heating in an oven for 30 minutes, the stopper is removed, and the odor is evaluated with the nose by fanning the inside of the container by hand. The odor generated by the thermal decomposition of the flame retardant during the compounding or molding process can be confirmed by reheating. Five odor evaluators. G: Everyone does not feel particularly uncomfortable. F: One or two out of five persons feel a slight unpleasant odor. P: Everyone feels some unpleasant odor. B: Everyone feels unpleasant odor. (9) Gloss: Measured based on JIS K7105 (1981) test conditions (60-degree specular gloss) (unit:
%). Test piece: mirror-finished surface of 50 × 50 × 2 mm injection-molded at 200 ° C. (10) Flame retardancy: 125 × 1 prepared by injection molding
Using a 2.5 × 0.8 mm test piece, a test is performed in accordance with the UL94 vertical fire test method, which is a UL standard in the United States, to evaluate the flame retardancy (class).

The polyolefin resin, lubricant, antioxidant, flame retardant, flame retardant auxiliary, elastomer and inorganic filler used in the following Examples and Comparative Examples are abbreviated as follows. [Polyolefin resin] PP: MFR composed of propylene homopolymer = 7.9 g
/ 10 min, crystal melting point (Tm) = 165 ° C, molecular weight distribution (M
(w / Mn) = 4.6, density = 0.901 g / cm 3 homopolypropylene. PP: ethylene-propylene copolymer part having an ethylene content of 47% by weight and a propylene content of 53% by weight 8.
MFR composed of 7% by weight and 91.3% by weight of a propylene homopolymer part = 15.5 g / 10 min, and the crystal melting point (T
m) = 163 ° C., molecular weight distribution (Mw / Mn) = 7.2,
Block polypropylene with a density = 0.901 g / cm3. PP: MFR = 0.61 g / 10 min containing propylene as a main component and 2.1 wt% of ethylene at random weight;
Crystal melting point (Tm) = 150 ° C., molecular weight distribution (Mw / M
n) = 7.6, density = 0.899 g / cm3 random
polypropylene. PP: ethylene-propylene copolymer part having an ethylene content of 59% by weight and a propylene content of 41% by weight 8.
MFR composed of 7% by weight and 87.3% by weight of propylene homopolymer part = 0.5 g / 10 min, crystal melting point (Tm)
= 163 ° C, molecular weight distribution (Mw / Mn) = 7.2, density = 0.901 g / cm 3 block polypropylene. PP: ethylene / propylene copolymer part 1 having an ethylene content of 56% by weight and a propylene content of 44% by weight
MFR consisting of 2.5% by weight and 87.5% by weight of propylene homopolymer part: 87 g / 10min, crystal melting point (Tm)
= 163 ° C, molecular weight distribution (Mw / Mn) = 5.2, density = 0.901 g / cm3 block polypropylene.

[Flame retardant] Bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] sulfone. 2,2-bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] propane. 1,2-bis (2 ', 3', 4 ', 5', 6'-pentabromophenyl)
Ethane. Decabromodiphenyl ether. N, N'-ethylene-bis (tetrabromophthalimide). [Flame retardant aid] Antimony trioxide: specific gravity 5.2, average particle size 3.5 μm.

[Lubricant] Glycerin monolaurate. Cetyl alcohol. Lauric acid diethanolamide. Stearyl diethanolamine. Lauric acid.

[Antioxidant]: di-stearyl-pentaerythritol-di-phosphite. : Bis (2,6-di-tert-butyl-4-methylphenyl)
Pentaerythritol-silo-phosphite. : Tris (2,4-di-t-butylphenyl) phosphite. [Elastomer] EPM: Ethylene propylene elastomer [ML1 +
4 (100 ° C.)] = 22, MFR (230 ° C .; 21.18N) = 3.
8 g / 10 min, propylene content = 22% by weight.

[Nucleating agent] Sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate

[Inorganic Filler] Talc: specific surface area 44,000 cm 2 / g, average particle size 1.6 μm, component having a particle size of 10 μm or more 0.5% by weight, Mg
33.1% by weight of O component, 62.5% by weight of SiO2 component,
Other 0.45% by weight.

Examples 1 to 13 and Comparative Examples 1 to 4 The polyolefin resin, flame retardant, flame retardant aid, lubricant and antioxidant shown in Table 1 below were put into a Henschel mixer in the proportions shown in Table 1 below. After mixing, temperature 210 ° C
The mixture was melted, kneaded and extruded, and the strand was cooled and cut to obtain a pellet-shaped composition. As Comparative Examples 1 to 4, the polyolefin resin, the flame retardant, the flame retardant aid, the lubricant and the antioxidant shown in Table 1 were put into a Henschel mixer at the compounding ratio shown in Table 1, and the results were based on Examples 1 to 13. Then, the mixture was melted, kneaded, and extruded to obtain a pellet-shaped composition. Using the compositions obtained in the Examples and Comparative Examples, M
Measurement of FR and preparation of a predetermined test piece by injection molding method, flexural modulus (rigidity), Izod impact strength, odor,
Gloss and flame retardancy (UL94) were measured and the results are shown in Table 1. As is clear from Table 1, the flame-retardant polyolefin compositions obtained in each of the examples have extremely excellent thermal stability, little decomposition odor during the compound production process and molding, and excellent self-extinguishing flammability. It can be seen that the unpleasant odor caused by the decomposition of the flame retardant is also significantly improved. On the other hand, Comparative Example 1 and Comparative Example 2 were inferior in odor because neither the antioxidant of the present invention nor the lubricant of the present invention was blended, and Comparative Example 3 used an antioxidant outside the present invention. However, the odor is inferior as in Comparative Examples 1 and 2. In Comparative Example 4, the MFR of the polyolefin resin was high, and the MFR of the obtained flame-retardant polyolefin composition was extremely high. When the blending amount of the flame retardant was equal to that in the examples, flaming drip was generated and the combustibility was lowered. You can see that.

Examples 14 to 19, Comparative Examples 5 and 6 Polyolefin resins, flame retardants, flame retardant aids, lubricants, antioxidants, elastomers, nucleating agents, inorganic fillers and the like shown in Table 2 below were used. The mixture was placed in a Henschel mixer at the blending ratio described in 2, mixed according to Examples 1 to 13, then melted, kneaded, and extruded at a temperature of 210 ° C., and the strand was cooled and cut to obtain a pellet-shaped composition. Was. Also,
As Comparative Examples 5 and 6, polyolefin resins described in Table 2;
Flame retardants, flame retardant aids, lubricants, antioxidants and elastomers
Was placed in a Henschel mixer at the blending ratio shown in Table 2, mixed, melted, kneaded and extruded according to Examples 1 to 13, to obtain a pellet-shaped composition. Using the compositions obtained in the Examples and Comparative Examples, MFR was measured and predetermined test pieces were prepared by an injection molding method, and the flexural modulus (rigidity), Izod impact strength, odor, gloss and flame retardancy were obtained. Sex (U
L94) was measured, and the results are shown in Table 2. Table 2
As is clear from Examples 14, 15 and 15, the impact resistance is remarkably improved in the case where the elastomer is blended. Also,
In Examples 16 and 17, impact resistance and rigidity were improved by blending an elastomer and a nucleating agent. In Examples 18 and 19, both the impact resistance and the rigidity were improved by blending an elastomer and an inorganic filler.
Moreover, all of the compositions of Examples 14 to 19 have extremely good odor and flame retardancy. On the other hand, in Comparative Example 5, a lubricant other than the present invention was used, and a decrease in odor was observed. In Comparative Example 6, the amount of the lubricant of the present invention was increased, and it can be seen that the productivity was reduced due to the surging phenomenon in the compound production process, and further, the flaming drip was generated in the flammability, and the flame retardancy was reduced.

Examples 20 to 27 and Comparative Examples 7 to 10 Polyolefin resins, flame retardants, flame retardant aids, lubricants, antioxidants, and inorganic fillers shown in Table 3 below are blended in the proportions shown in Table 3. And put in a Henschel mixer.
In accordance with No. 13, after mixing, melt at a temperature of 210 ℃,
After kneading and extruding, the strand was cooled and cut to obtain a pellet-shaped composition. In addition, as Comparative Examples 7 to 10, the polyolefin resin, the flame retardant, the flame retardant auxiliary, the lubricant, and the antioxidant shown in Table 3 were put into a Henschel mixer at the compounding ratio shown in Table 2, and the results were based on Examples 1 to 13. Then, the mixture was melted, kneaded, and extruded to obtain a pellet-shaped composition. Using the compositions obtained in the Examples and Comparative Examples, MFR was measured and predetermined test pieces were prepared by an injection molding method, and the flexural modulus (rigidity), Izod impact strength, odor, gloss and flame retardancy were obtained. The properties (UL94) were measured and the results are shown in Table 3. As is clear from Table 3, Examples 20 to 27 show the flame-retardant polyolefin compositions for extrusion molding for hollow molding and sheeting of the present invention. Example 20 uses a random polypropylene as the polyolefin resin and has a slightly lower rigidity, but is effective as a material for extrusion molding that requires flexibility. Examples 21 to 27 are compositions using block polypropylene, which are compositions that are effective for molding a flame-retardant case and a shield plate, etc., which require impact resistance. Moreover, the compositions of Examples 20 to 27 all have low odor and good flame retardancy. Comparative Example 7
Comparative Example 7 is a composition not containing the lubricant of the present invention, Comparative Example 8 is a composition not containing the antioxidant of the present invention, and Comparative Example 9 is a composition not containing the antioxidant of the present invention. Comparative Example 10 is a composition not containing both a lubricant and an antioxidant. In Comparative Example 10, a lubricant other than the present invention was used. It is understood that the odor, which is the purpose of the above, is inferior.

[0041]

The flame-retardant polyolefin composition of the present invention is formed by decomposition of the flame retardant as compared with the conventional flame-retardant polyolefin composition by using a specific antioxidant and a lubricant as the halogen-based flame retardant. It is a composition that can significantly reduce the generation of decomposition gas and the like, and can significantly improve the unpleasant odor during compounding and molding. Therefore, it has a low odor as a molded product and can be suitably used for molding injection molded products and extruded molded products, and can be suitably used for various uses such as home electric appliances and industrial products.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/10 C08K 5/10 5/17 5/17 5/20 5/20 5/42 5/42 5/524 5/524 // B29K 23:00 B29L 31:34

Claims (5)

[Claims] 1. A halogenated flame retardant of 2 to 60 parts by weight and pentaerythritol diphosphite as an antioxidant in an amount of 0.0 to 100 parts by weight of a polyolefin resin.
1 to 2 parts by weight and 1 selected from the following 1) to 4)
Melt flow rate (230 ° C .; 21.18) comprising at least one kind or two or more kinds of lubricants in a proportion of 0.01 to 2 parts by weight.
N) is a flame-retardant polyolefin composition of 0.1 to 60 g / 10 min. 1) Fatty acid esters. 2) Aliphatic alcohol. 3) Fatty acid dialkanolamide. 4) Aliphatic dialkanolamine. 2. The halogen-based flame retardant is bis [[3,5-dibromo-4- (2 ′, 3′-dibromopropyloxy)] phenyl].
Sulfone, 2,2-bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] propane, decabromodiphenyl ether, 1,2-bis (2', 3 ', 4 ', 5', 6'-
The flame-retardant polyolefin composition according to claim 1, which is pentabromophenyl) ethane, N, N'-ethylene-bis (tetrabromophthalimide) or a mixture of two or more thereof. 3. The halogen-based flame retardant is bis [[3,5-dibromo-4- (2 ′, 3′-dibromopropyloxy)] phenyl].
The flame retardant according to claim 1, which is sulfone, 2,2-bis [[3,5-dibromo-4- (2 ', 3'-dibromopropyloxy)] phenyl] propane or a mixture of two or more thereof. Polyolefin composition. 4. The flame retardant polyolefin composition according to claim 1 or 2, wherein the melt flow rate is 0.1 to 0.1.
A flame-retardant polyolefin composition for blow molding or extrusion molding having a weight of 4 g / 10 minutes. 5. The flame retardant polyolefin composition according to claim 1, wherein the melt flow rate is from 3 to 60.
g / 10 minutes, a flame-retardant polyolefin composition for injection molding.