JPS62167338A - Flame-retardant polyolefin composition - Google Patents

Abstract

PURPOSE:The titled composition suitable for electrical and electric parts, etc., having improved heat-resistant deterioration in melt blending, thermal stability of molded article, etc., obtained by blending a polyolefin with specific amounts of a specified phenolic compound, epoxy compound etc. CONSTITUTION:100pts.wt. polyolefin is blended with (A) 5-30ptw.wt. halogen flame-retardant (e.g., decabromodiphenyl ether, etc.,) to give a flame-retardant composition, which is blended with (B) 0.01-1pt.wt. phenolic compound {e.g., tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]met hane} shown by formula I (R1 and R2 are H or 1-8C alkyl), (C) 0.01-1pts.wt. phosphonite compound shown by formula II (R3 and R4 are H or 1-8C alkyl) or pentaerythritol diphosphite compound and (D) 0.01-1pts.wt. epoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to flame-retardant polyolefin compositions. More specifically, the present invention relates to a flame-retardant polyolefin composition that is excellent in preventing oxidative deterioration of polyolefin during melt-kneading and in practical use.

[Conventional technology]

Generally, various halogen-based flame retardants are blended into polyolefin for the purpose of making it flame-retardant, but halogen radicals are removed from the halogen-based flame retardant by the heat during melt-kneading during molding. oxidative deterioration of the polyolefin, that is, a decrease in processability and mechanical strength due to cleavage of the molecular chains of the polyolefin, or a decrease in processability due to crosslinking. Further, the problem of coloration occurs due to the oxidation effect of halogen radicals.

In addition, polyolefins, especially polypropylene polymers,
Because the polymer contains tertiary carbon that is easily susceptible to oxidation,
There is a problem with thermal oxidation deterioration resistance in practical use (hereinafter referred to as thermal stability in practical use). In particular, compositions containing halogen-based flame retardants have a problem in that their thermal stability during practical use is significantly reduced by halogen radicals, as described above. For this reason, various antioxidants, metal soaps ( JP-A-49-31749) or epoxy compounds (JP-A-52-119655)
are used alone or in combination.

[Problem that the invention seeks to solve]

However, in recent years, flame-retardant requirements have become increasingly strict in applications such as electrical and electronic products and automobile parts, and as the applications for flame-retardant polyolefins become more diverse and larger, molding is required under a wide range of molding conditions. There is a need for flame retardant polyolefins that can be processed. In addition, the requirements for practical use conditions (heat resistance stability, electrical insulation, etc.) of molded articles obtained from the flame-retardant polyolefin are becoming stricter. In other words, it is necessary to develop flame-retardant polyolefins that are more resistant to thermal oxidative deterioration than conventional ones.

In order to solve these problems, various phenol-based, thioether-based, or phosphorus-based antioxidants have been used singly or in combination, but none of them are fully satisfactory. This is thought to be due to insufficient scavenging action for halogen radicals generated from halogen-based flame retardants. Also, JP-A-49-3174
Although the flame-retardant composition proposed in Publication No. 9@ in combination with a metal soap has a certain degree of coloration prevention effect, it is still not sufficient, and furthermore, it is difficult to mold the composition using the flame-retardant composition. The thermal stability of the molded article during practical use is also unsatisfactory, and almost no synergistic effect is observed when used in combination. In addition, the flame retardant composition proposed in JP-A No. 52-119655, which contains an epoxy compound, has a considerable coloring prevention effect, but the epoxy compound is not used alone or in combination with a metal. When used in combination with soap, the desired effect cannot be obtained unless the epoxy compound is used in a large amount, and conversely, problems arise in that the resulting molded product becomes sticky. Furthermore, when a molded article is made from a composition in which the epoxy compound is used alone or in combination with a metal soap, the thermal stability of the molded article during practical use is also unsatisfactory.

The present inventors have conducted extensive research in order to solve the above-mentioned problems regarding flame-retardant polyolefin compositions containing the above-mentioned halogen-based flame retardants.

As a result, a phenolic compound represented by the following general formula [I] (hereinafter referred to as "compound") and a General formula [I
0.01 to 11 parts of each of a phosphonite compound (hereinafter referred to as compound B) or a pentaerythritol diphosphite compound (hereinafter referred to as compound C) represented by I] and an epoxy compound are blended. It was discovered that the above-mentioned problems of flame-retardant polyolefins can be solved by a composition comprising the following compositions, and the present invention was completed based on this knowledge.

] (However, in the formula, R, R, 11 and R4 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms.) As is clear from the above description, the purpose of the present invention is to improve flame retardancy. Heat oxidative deterioration resistance during melt kneading of polyolefin compositions (
Hereinafter, it will be referred to as processing stability. ), an object of the present invention is to provide a flame-retardant polyolefin composition which, when formed into a molded article, has an excellent effect of improving thermal stability during practical use of the molded article and coloring caused by the flame retardant used.

[Means for solving problems]

The present invention has the following configuration.

A flame retardant composition consisting of a polyolefin and a halogen flame retardant is added with a phenol compound represented by the following general formula [1] (hereinafter referred to as a compound) and the following general formula [I] per 1001 parts of the polyolefin. It is made by blending 0.01 to 1 part by weight of a phosphonite compound (hereinafter referred to as compound B) or a pentaerythritol diphosphite compound (hereinafter referred to as compound C) represented by [], and an epoxy compound. Flame retardant polyolefin composition.

(However, in the formula, R, R, R and R4 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms.) Polyolefins used in the present invention include ethylene, propylene, butene-1, pentene-1, and Homopolymers of α-olefins such as 1,4-methyl-pentene-1, random copolymers or block copolymers of two or more of these α-olefins, or these α-olefins and vinyl acetate, acrylic esters Copolymers of these α-olefins and unsaturated carboxylic acids or their anhydrides, and reaction products of these copolymers and total ionic compounds may be exemplified. can. Furthermore, a modified polyolefin obtained by graft polymerizing an unsaturated carboxylic acid or a derivative thereof to a polyolefin, or a mixture of the modified polyolefin and an unmodified polyolefin can also be used. In addition, the above polyolefins and synthetic rubbers (e.g. ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, polybutadiene, polyisoprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, styrene- butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (e.g. polystyrene, styrene-acrylonitrile copolymer, acrylonitrile copolymer, etc.) -butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, etc.) may also be used. Propylene polymers such as propylene homopolymer, ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-butene-13 copolymer, propylene-hexene-butene-13 copolymer, etc. is particularly preferred.

Compound A used in the present invention includes tetrakis[methylene-3-(3'-methyl-4'-hydroxy-
5'-t-butylphenyl)propionate comethane, tetrakis[methylene-3=(3'-ethyl-4'
-Hydroxy-51-t-butylphenyl)propionate comethane, tetrakis[methylene-3-(3'
, 5'-di-t-butyl-4'-hydroxyphenyl)purionate]methane, tetrakis[methylene-3-(3'-methyl-4'-hydroxy-5'-t
-Octylphenyl> Propionate 1 methane, Tetrakis[methylene-3-(3'-t-butyl-4'-hydroxy-5' -1-octylphenyl)propionate comethane, Tetrakis[methylene-3-(2'
-Methyl-4'-hydroxy-5'-1-butylphenyl)propionate comethane, tetrakis methylene-3-(2',5'-di-t-butyl-4'-
hydroxyphenyl)propionate comethane or tetrakis[methylene-3-<2'-t-butyl-4'
-Hydroxy-5'-methylphenyl)propionate comethane and the like can be exemplified. In particular, tetrakisstyrene-3-(3',5'-di-t-butyl-4'
-hydroxyphenyl)propionate comethane is preferred. Compound B includes tetrakis(2-t-butylphenyl)-4,4'-biphenylene-di-7A sphonite, tetrakis(2-t-butyl-4-methylphenyl)-4,4'-biphenylene-di-fi Osphonite, tetrares(2,4-di-t-butylphenyl)-11,4'-biphenylene-diphosphonite or tetrares(2,4-di-t-butylphenyl)-4,4'-biphenylene Examples include phenylenezi phosphonite. In particular, tetrakis (2,4-di-t-
Preferred is (butylphenyl)-4,4'-biphenylene diphosphonite. Compound C includes dialkylpentaerythritol-diphosphite such as distearylpentaerythritol-diphosphite;
or bis(2-t-butylphenyl)-pentaerythritol-shiphosphite, bis(2-t-butyl-
4-Methylphenyl)-bentaerythritol diphosph? bis(2,4-di-t-butylphenyl)
- Pentaerythritol - Siphosphite, bis(2
゜6-di-t-butylphenyl)-pentaerythritol-shiphosphite, bis(2,6-di-t-butyl-4-methylphenyl)-pentaerythritol-shiphosphite, bis(2,6-di-t- butyl-4-ethylphenyl)-pentaerythritol-shiphosphite, bis(2゜6-di-t-butyl-4-s-butylphenyl)-pentaerythritol-shiphosphite, bis(2,6-di-t- Butyl-4-tert-butylphenyl)-pentaerythritol-siphosphite, bis(2,6-di-tert-butyl-4-methoxyphenyl)
- Pentaerythritol - Siphosphite, bis(2
, 6-di-t-butyl-4-ethoxyphenyl)-pentaerythritol-siphosphite, bis(2,6-
di-tert-butyl-4-hydroxymethylphenyl)-pentaerythritol-shifuosphite, bis(2,6
-di-t-butyl-4-methoxymethylphenyl)-pentaerythritol-siphosphite, bis(2,6
-di-t-butyl-3-methylphenyl)-bentaerythritol difuosph? it, bis(2,6-dit)
-butyl-3-ethylphenyl)-pentaerythritol-shiphosphite, bis(2,6-di-t-butyl-3-methoxyphenyl)-pentaerythritol-shiphosphite, bis(2,6-di-t-butyl) -3-
ethoxyphenyl)-pentaerythritol-shifuosphite, bis(2-methyl-6-t-butylphenyl)-pentaerythritol-shifuosphite, bis(
2,4-di-methyl-6-tert-butylphenyl)-pentaerythritol-shiphosphite, bis(2-methyl-4-ethyl-6-1-butylphenyl)-pentaerythritol-shiphosphite or bis(2 Examples include bis(substituted aryl)-pentaerythritol-shiphosphite such as -methyl-4,6-di-t-butylphenyl)-pentaerythritol-shiphosphite. Especially bis(2,4-di-t-butylphenyl)
-Pentaerythritol-shiphosphite is preferred. In addition, epoxy compounds are not particularly limited as long as they do not significantly evaporate or decompose during melt-kneading; soybean oil, epoxidized linseed oil, epoxidized castor oil), epoxidized fatty acids or alkyl esters of epoxidized oils [1 (e.g. epoxidized octyl stearate,
Fatty acid ester of 3,4-epoxycyclohexylmethanol, alkyl ester of 3,4-epoxycyclohexylcarbon, 4,5-epoxycyclohexane-1
．． Examples include 2-dicarboxylic acid dialkyl ester silmethyl or 3,4-epoxy-6-methylcyclohexanecarboxylate. In particular, a combination of epichlorohydrin and bisphenol A,
A condensate of 2-methylebichlorohydrin and bisphenol 8 or epoxidized soybean oil is preferred. The compound Δ, the compound B or the compound C, t3, and the epoxy compound are each blended in a proportion of 0.01 to 1 part by weight, preferably 0, per 100 parts by weight of the polyolefin.

01 to 0.5 vehicle volume part. If the amount of the epoxy compound is less than 1 part by weight, the desired effect will not be fully exhibited, and although it is possible to exceed 1 part by weight, no further improvement in the effect can be expected (if the epoxy compound exceeds 1 part by weight) If it exceeds this, stickiness will result.) It is not only impractical but also uneconomical.

The halogen flame retardants used in the present invention include ammonium bromide, ammonium chloride, 2-chlorotetrabromobutane, 2,2-bis[p-(chloroformyloxy)phenyl-3]propane, and 1.

2-dibromo-3-chloropropane, 1,2,3-tribromopropane, 1,1.2.2-tetrabromoethane, tetrabromobutane, hexabromocyclododecane,
Hexabromooctane, hexabromobutane, pentabromocyclohexane, tribromotrichlorocyclohexane, pentabromochlorocyclohexane, 1,2-dibromo-1,1,2.2-tetrachloroethane, 2.2
-bis(4-hydroxyethoxy-3.5-dibromophenyl)propane, vinyl chloroacetate, 2,4.
6-t-ribromophenyl methacrylate, 2, 3.3
'-tribromoallylformate, 2.

2-dibromopropyl methacrylate, bis(2.

3-dibromopropyl)-2,3-dibromofumarate, tribromophenyl acrylate, chloroendo acid,
Diallyl chloroendoic acid, anhydrochloroendoic acid, 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, bentab O mophenyl allyl ether, bromo Alkenyl ether, sorbitol-1,6-bis(2,3-dibromopropyl)
Ether, decabromodiphenyl ether, 1゜2-bis(2,3,4,5,6-pentabromophenoxy)ethane, hexabromodiphenyl ether, dibromocresyl glycidyl ether, pentabromoallyl ether, 1,2-dibromopropyl- Tribromophenyl ether, decachlorodiphenyl carbonate, decabromodiphenyl carbonate, 2,3.3-tribromoallylcarboxylate 5', 6'-octachloro-4,4'-dioxydiphenyl, tetrabromobenzene, α, β -dibromoethylbenzene, 2-buOmoα,β-dibuOmoethylbenzene, hexabromobenzene, barchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, tetrabromobisphenol A1 tetra Bromobisphenol A diethoxylate, bis(2-
hydroxyethyl ether) tetrabromobisphenol A1 tetrabromobisphenol A bis(2,3-di-bromopropyl ether), tetrabromodiphenyl sulfone, tetrabromodiphenyl sulfone 7-bis(
2,3-di-bromopropyl ether pentabromotoluene, tribromoaniline, acetylenetetrapromide, 1-(p-tosyl)-3-(2-bromo-4.4.4-trichlorobutyl)urea, 2. 3-
Inorganic and organic halogen flame retardants such as dibromopropanol ester, chlorinated paraffin, chlorinated polyethylene or chlorinated polypropylene. The blending ratio of these halogen flame retardants may be blended depending on the desired flame retardancy, and is not particularly limited, but is usually preferably 5 to 30 parts by weight per 100 parts by weight of the polyolefin.

Additionally, a flame retardant aid may be used in the composition of the present invention. The flame retardant aids include antimony compounds (for example, antimony trioxide, diantimony tetroxide, antimony trichloride, antimony trisulfide, antimony oxychloride, andymonium dichloride perchlorobentane, potassium antimonate, etc.), zirconium oxide, etc. Or a boron compound, etc.

The blending ratio of these flame retardant aids is not limited, but is preferably 20 parts by weight per 100 parts by weight of the halogen flame retardant.
~60 parts by weight. Since the blending of the flame retardant aid acts synergistically in the composition of the present invention to improve flame retardancy,
The amount of flame retardant added can be reduced. Therefore, it is preferable to include the flame retardant aid.

The composition of the present invention contains various additives that are normally added to polyolefins, such as phenolic, thioether, and phosphorus antioxidants, light stabilizers, clarifying agents, nucleating agents, lubricants, and charging agents. Inhibitor, anti-fog agent, anti-blocking agent, anti-drop agent, pigment, heavy metal deactivator (copper inhibitor),
Radical generators such as peroxides, dispersants or neutralizing agents such as metal soaps, and inorganic fillers (e.g. talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide) , barium sulfate, calcium silicate, glass fiber, carbon fiber, etc.) or coupling agents (for example, silane-based, titanate-based, boron-based, aluminate-based,
The above-mentioned inorganic filler or organic filler (for example, wood flour, valve, waste paper, synthetic fiber, natural fiber, etc.) whose surface has been treated with a surface treatment agent such as zircoaluminate (such as zircoaluminate) may be used within the scope of the present invention. Can be used together.

The composition of the present invention is prepared by mixing polyolefin with predetermined amounts of Compound A1, Compound B or Compound C1, an epoxy compound, a halogen flame retardant, a flame retardant aid if necessary, and the above-mentioned various additives that are usually added to polyolefins. Mix using equipment such as Hensel Mixer (trade name), Super Mixer, Ribbon Blender, Pan Bali Mixer, etc., and use a normal single-screw extruder, twin-screw extruder, Brabender or roll, etc. to achieve a melt mixing temperature of 150°C. ~250
It can be obtained by melt-mixing pelletizing at 180°C to 230°C.

The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding.

[For production]

In the present invention, the combination of (1) compound, (2) compound B or compound C, and (3) epoxy compound during melt-kneading of a flame-retardant polyolefin composition formed by blending a halogenated flame retardant, The mechanism of action itself is not clear. However, compound A
The phenolic antioxidant represented by acts as a radical chain inhibitor, and the phosphorus antioxidant consisting of a phosphite-based compound represented by compound B or a phosphite-based compound represented by compound C acts as a peroxide decomposer. However, it is generally known that a combination system of the above-mentioned (1) compound and (2) compound B or compound C is excellent in processing stability of polyolefins. However, when this combination system is applied to the flame-retardant polyolefin composition, processing stability decreases. However, by using the epoxy compound in combination with the combination system, the excellent effects of the combination system in the flame-retardant polyolefin composition are not inhibited, and furthermore, it is impossible to predict from the combination with conventionally known epoxy compounds. It was discovered that a surprising synergistic effect was exhibited.

Furthermore, the reason why the composition of the present invention has an excellent ability to prevent coloration caused by the flame retardant used and excellent thermal stability during practical use is because the epoxy compound used has an extremely excellent ability to capture halogen radicals. it is conceivable that.

〔Example〕

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

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

■) Processing stability: (a) When the polyolefin used is a propylene polymer, measure the melt flow rate (VFR) of the obtained pellet (according to JISK 6758) and
Let it be R. Then, the melting crosstalk is repeated using the obtained pellet, and the MFR of the obtained pellet is measured and taken as the second VFR.

Let the difference between the second VFR and the first VFR be ΔMFR.

Processing stability was evaluated based on the magnitude of the second VFR value and ΔMFR value.

The smaller these values, the better the processing stability during repeated extrusion, in other words, during molding.

(b) When the polyolefin used is an ethyne polymer, the melt index (MI) of the obtained pellet is measured (in accordance with JIS 6160), and this is defined as the first MI. Then, melt-kneading is repeated using the obtained pellet, and the Ml of the resulting pellet is measured, which is defined as the second MI. Let the difference between the second MI and the first MI be ΔMl.

Processing stability was evaluated based on the value of the second MI and the magnitude of the number I revision of ΔMl.

The smaller these values, the better the processing stability during repeated extrusion, in other words, during molding.

I) 13 color resistance: Yl (Yell
Measure ownership index (JIS 7103)
), and the Yl value at this time is defined as the first YI. Then, melt-kneading is repeated using the obtained pellet, and the Y[ of the obtained pellet is measured, which is defined as a second YI. Let the difference between the second YI and the first YI be ΔYl.

The coloring prevention property was evaluated based on the magnitude of the second YI value and the ΔYI value.

The smaller these values are, the better the coloring prevention properties are.

■) Thermal stability in practical use: Evaluated by oven life test. In other words, using the obtained pellet, the length is 50cm.
A test piece with a width of 25g+ and a thickness of 11M1 was prepared by injection molding, and the test piece was placed in a circulating hot air oven adjusted to a temperature of 150°C. time) (JIS K 7
212).

TV) l'i Flammability: UL Subject 94 (Un
derwriters Laboratories T
A flame retardancy test was conducted according to the vertical combustion test method of NC, ). That is, using the obtained pellet, the length is 125ss+
A combustion test piece having a width of 12.5M and a thickness of 1.56a+s was prepared by injection molding, and the combustion test piece was evaluated based on the combustibility classification and the presence or absence of melt dripping.

Examples 1 to 4, Comparative Examples 1 to 4 The polyolefin was a powdered propylene homopolymer with an MFR (6.0 g per 10 minutes of molten resin discharge per 10 minutes when a load of 2.16 kg was applied at 230°C) 1
00 parts by weight, decabromodiphenyl ether as a halogen flame retardant, antimony trioxide as a flame retardant aid, compound A, compound B or compound C, an epoxy compound and other additives listed in Table 1. 8Put in a Hensel mixer (product name), and after mixing, the diameter is 30 m.
The mixture was melt-kneaded and pelletized at 200°C using a twin-screw extruder. Further, as Comparative Examples 1 to 4, 100 parts by weight of a powdered propylene homopolymer having a VFR of 6.0 g/10 minutes was blended with a predetermined amount of each of the additives listed in Table 1, and the same procedure as in Examples 1 to 4 was carried out. and got a beret.

The test pieces used for the oven life test and the flammability test were prepared by injection molding the obtained pellet at a resin temperature of 230°C.

Using the obtained pellets, processing stability and coloring prevention properties were evaluated at a melt-kneading temperature of 230° C. using the test method described above, and oven life tests and flammability tests were performed using the obtained test pieces.

These results are shown in Table 1.

Examples 5 to 8, Comparative Examples 5 to 8 As polyolefin, powdered propylene homopolymer with VFR (discharge n of molten resin in 10 minutes when applying a load of 2.16 kg at 230°C) 6.09/10 minutes 1
001 side contains tetrabromosphenol A bis(2゜3-di-bromopropyl ether) as a halogen flame retardant, antimony dioxide, compound A1 compound B or compound C, epoxy compound and other flame retardant aids. The additives were put into each of the predetermined π Hensel mixers (trade name) listed in Table 2, mixed, and then melt-kneaded at 200° C. using a twin-screw extruder with a diameter of 30 m to pelletize. Further, as Comparative Examples 5 to 8, predetermined amounts of each of the additives listed in Table 2 were blended with 100 parts by weight of a powdered propylene homopolymer having an MFR of 6.0 g/10 minutes, and the same procedure as in Examples 5 to 8 was carried out. Got a beret.

The test pieces used for the oven life test and the flammability test were prepared by injection molding the obtained pellets at a resin temperature of 200'C.

Using the obtained pellets, processing stability and anti-coloring properties were evaluated at a melt-kneading temperature of 200° C. using the test method described above, and oven life tests and flammability tests were performed using the obtained test pieces. The results are shown in Table 2.

Examples 9 to 12, Comparative Examples 9 to 12 As the polyolefin, VFR (discharge of molten resin in 10 minutes when adding 9 to load 2.16 at 230°C > 6.0y/10 minutes powdered propylene alone) To 1 part of polymer 100EIiff, tetrabutmodiphenylsulfone bis(2,3-di-bromopropyl ether) as a halogen flame retardant, antimony trioxide, compound A, compound B or compound C, and epoxy as a flame retardant aid. Predetermined amounts of the compounds and other additives listed in Table 3 were put into a Hensel mixer (trade name), mixed, and then melt-kneaded at 200°C using a twin-screw extruder with a diameter of 30M to pelletize.Also, comparative examples. As 9 to 12, MFR is 6.0g/
To 1011 parts of powdered propylene homopolymer for 10 min.
Predetermined amounts of each of the additives listed in the table were blended, and Examples 9-
A beret was obtained in the same manner as in 12.

The test pieces used for the oven life test and the flammability test were manufactured by WJ by injection molding the obtained pellet at a resin temperature of 200°C.

Using the obtained pellets, processing stability and anti-coloring properties were evaluated at a melt-kneading temperature of 200° C. using the test method described above, and oven life tests and flammability tests were performed using the obtained test pieces. The results are shown in Table 3.

Examples 13 to 16, Comparative Examples 13 to 16 As polyolefin, powdered propylene homopolymer with VFR (discharge of molten resin for 10 minutes ff1 when applying a load of 2.16 Ky at 230°C) 6.0 g/10 minutes 100 parts by weight, dodecachlorododecahydrodimethanodibenzocyclooctene as a halogen flame retardant, antimony trioxide, compound A1 compound B as a flame retardant aid
Alternatively, compound C, an epoxy compound, and other additives are put into a Hensel mixer (trade name) in the respective predetermined amounts listed in Table 4, and after mixing, a twin screw extruder with a diameter of 30a* is used to
The mixture was melt-kneaded and pelletized at 0°C. Also, Comparative Example 13~
As No. 16, predetermined amounts of each of the additives listed in Table 4 were blended with 100 parts by weight of a powdered propylene homopolymer having a VFR of 6.0 g/10 minutes, and pellets were obtained in the same manner as in Examples 13 to 16. .

The test pieces used for the oven life test and the flammability test were prepared by injection molding the obtained pellet at a resin temperature of 230°C.

Using the obtained pellets, processing stability and anti-coloring properties were evaluated at a melt crosstalk temperature of 230° C. using the test method described above, and oven life tests and flammability tests were performed using the obtained test pieces. The results are shown in Table 4.

Examples 17-20. Comparative Examples 17 to 20 As polyolefin, powdered ethylene-propylene block copolymer (ethylene content 8.5 type car%) 100
In the heavy M part, decabromodiphenyl ether as a halogen-based flame retardant, antimony trioxide as a flame retardant aid, Compound A, Compound B or Compound C1, an epoxy compound and other additives are added in the respective prescribed amounts listed in Table 5. The mixture was placed in a Hensel mixer (trade name), mixed, and then melt-kneaded at 200° C. in a twin-screw extruder with a diameter of 3 ONR to pelletize.

Further, as Comparative Examples 17 to 20, a powdered ethylene-propylene block copolymer (ethylene content: 8.5 wt ω%) with a VFR of 4.0 g/10 min was added to 100 parts of heavy oil with prescribed additives listed in Table 5. A pellet was obtained in the same manner as in Examples 17-20.

The test pieces used for the oven life test and the flammability test were prepared by injection molding the obtained pellet at a resin temperature of 230°C.

Using the obtained pellets, processing stability and coloring prevention properties were evaluated at a melt-kneading temperature of 230° C. using the test method described above, and oven life tests and flammability tests were performed using the obtained test pieces. The results are shown in Table 5.

Examples 21-24, Comparative Examples 21-24 As polyolefin, M I (discharge amount of molten resin in 10 minutes when applying load 2.1611:g at 190°C)5. To 100 parts by weight of powdered Degla-Natsuta ethylene homopolymer of OLj/10 minutes, decabromodiphenyl ether as a halogen flame retardant, antimony trioxide, compound A, compound B or compound C, and epoxy as a flame retardant aid. The compounds and other additives were added in predetermined amounts listed in Table 6 into Hensel Miki 4-No (trade name), mixed, and then melt-kneaded at 200° C. using a 30# twin-screw extruder to pelletize. Moreover, as Comparative Examples 21 to 24, MI5. Predetermined amounts of each of the additives listed in Table 6 were blended into 100 parts of a powdered Ziegler-Natsuta ethylene homopolymer of Og/10 min, and pellets were obtained in the same manner as in Examples 21-24.

The test piece used for the flammability test was prepared by injection molding the obtained pellet at a resin temperature of 230°C.

Using the obtained pellets, processing stability and coloring prevention properties were evaluated at a melt crosstalk temperature of 230° C. using the above-mentioned test method, and the obtained test pieces were evaluated in a flammability test. The results are shown in Table 6.

The compounds and additives according to the present invention shown in Tables 1 to 6 are as follows.

Compound A (phenolic compound): Tetrakis[methylene-3-(3',5'-di-t-butyl-4'
-Hydroxyphenyl)propionate comethane compound B ()A sphonite compound); Tetrakis [
2,4-di-t-butylphenyl)-4゜41-biphenylene-di7osphonite compound C (pentaerythritol-diphosphophite compound); bis(2,4
-di-t-butylphenyl)-bentaerythritol-diphosphite epoxy compound [■]; Mixture of a condensate of epichlorohydrin and bisphenol A and a condensate of 2-methylepichlorohydrin and bisphenol A (trade name MA
RKEP-17 manufactured by Niadeka Argus Chemical Co., Ltd.) Epoxy compound [■]: Eboxidized soybean oil (product name A
DK CIZER0-130P manufactured by Niadeka Argus Chemical Co., Ltd.) Halogen flame retardant [■]; Decabromodiphenyl ether halogen flame retardant [■]; Tetrabromo-sphenol A bis (2,3-di-bromopropyl ether) Flame retardant [■]: Tetrabromodiphenylsulfone bis(2,3-di-bromopropyl ether) Halogen-based flame retardant [■]: Dodetori Hydrodimethanodibenzocyclooctene Flame retardant aid; Antimony trioxide Phenol compound; 2,6-di-t-butyl-p-cresol phosphite compound (triarylphosphite); Tris(2,4-di-t-butylphenyl)phosphite thioether compound; Distearylthiodipro Pionate Ca-8t Calcium Nistearate [Effects] The present invention will be explained in detail with reference to each example.

The Examples and Comparative Examples shown in Table 1 are cases where propylene homopolymer was used as the polyolefin, decabromodiphenyl ether was used as the halogen flame retardant, and antimony trioxide was used as the flame retardant aid. As can be seen from Table 1, Examples 1 to 4 used Compound A1, Compound B, or Compound C1 and an epoxy compound according to the present invention, and Examples 1 to 4 and Comparative Example 1 (conventionally known Comparing the combinations of antioxidants, Examples 1 to 4
is processing stability, coloration prevention property, and thermal stability during practical use (
It can be seen that both oven life) are excellent. In particular, as is clear from the value of ΔYl, which represents the coloring prevention property, Comparative Example 1, which does not use an epoxy compound, is significantly inferior in coloring prevention property. Furthermore, when Comparative Example 2 using only an epoxy compound is compared with Examples 1 to 4, Comparative Example 2 has considerably improved discoloration prevention properties, but is still not sufficient, and has poor processing stability and thermal stability during practical use. It can be seen that almost no effect is observed. Comparative Example 3 (Comparative Example 1
Comparing the combination of Comparative Example 2 and Examples 1 to 4, it can be seen that Comparative Example 3 is inferior in all respects.

Comparative Example 4 (compound B or compound C according to the present invention)
Comparing Examples 1 to 4 with other phosphorus antioxidants, compound A, and combination systems with epoxy compounds), it was found that Comparative Example 4 was inferior in all respects, which was noticeable in the composition of the present invention. A synergistic effect is observed.

Furthermore, it was confirmed that the flame retardant composition of the present invention has flame retardancy equivalent to that of conventionally known flame retardant compositions.

Tables 2 to 4 show propylene homopolymer as the polyolefin, tetrabromobisphenol A bis(2,3-di-bromopropyl ether) and tetrabromodiphenyl sulfonbis(2,3-di-bromopropyl ether) as the halogen flame retardant, respectively.
, 3-di-bromopropyl ether) and dodecachlorododecahydrodimethanodibenzocyclooctene, and the same effects as described above were confirmed for these as well. In addition, Tables 5 and 6 show polyolefins such as ethylene-propylene block copolymer and Ziegler block copolymer, respectively.
This is a single type combination of Natsuta-based ethylene using decabromodiphenyl ether as a halogen-based flame retardant.
The same effects as described above were confirmed for these as well.

This shows that the flame-retardant composition of the present invention is superior in all respects to flame-retardant compositions containing conventionally known additives alone or in combination. A remarkable effect was confirmed.

That is, the flame-retardant polyolefin composition of the present invention is significantly superior in processing stability and discoloration resistance during molding processing, without reducing flame retardancy, compared to conventional flame-retardant polyolefin compositions. .

Moreover, the thermal stability of molded articles made from the flame-retardant polyolefin composition of the present invention during practical use is extremely excellent. Good thermal stability indicates that there is no oxidative deterioration due to heat, and also indicates that there is no decrease in electrical insulation properties due to oxidative deterioration. Therefore, the flame retardant polyolefin composition of the present invention is required to have flame retardancy. It can be suitably used for various molded products such as electrical/electronic products and automobile parts.

Applicant's agent Hiroshi Fujimoto
8 February 19, 1986

Claims (1)

[Scope of Claims] 1. A phenolic compound represented by the following general formula [I] (
Hereinafter, it will be referred to as compound A. ), a phosphonite compound represented by the following general formula [II] (hereinafter referred to as compound B) or a pentaerythritol diphosphite compound (hereinafter referred to as compound C), and an epoxy compound at 0.01% each. ~1 part by weight of a flame-retardant polyolefin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼［I］ ▲There are mathematical formulas, chemical formulas, tables, etc.▼［II］ 2. In the general formulas [I] and [II], R_1, R_
2. The flame-retardant polyolefin composition according to claim 1, wherein R_3 and R_4 are a methyl group or a t-butyl group. 3. Compound A is tetrakis[methylene-3-(3',5
'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, compound B is tetrakis(2,4-
di-t-butylphenyl)-4,4'biphenylene-di-phosphonite, compound C is bis(2,4-di-t
-butylphenyl)-pentaerythritol diphosphite. The flame retardant polyolefin composition of claim 1. 4. A patent claim in which the epoxy compound is one or more compounds selected from a condensate of epichlorohydrin or an epichlorohydrin derivative and bisphenol or a bisphenol derivative, an epoxidized oil or fat, an epoxidized oil or fatty acid, or an alkyl ester of an epoxidized oil or fatty acid. A flame-retardant polyolefin composition according to item 1 of the range. 5. The flame-retardant polyolefin composition according to claim 1, wherein the epoxy compound is a condensate of epichlorohydrin or its derivative and bisphenol A, or epoxidized soybean oil. 6. Halogenated flame retardants include decabromodiphenyl ether, barchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, dodecachlorooctahydrodimethanodibenzofuran, tetrabromobisphenol A, tetrabromodiphenyl sulfone,
Tetrabromobisphenol A bis(2,3-di-bromopropyl ether) or tetrabromodiphenylsulfone bis(2,3-di-bromopropyl ether)
The flame-retardant polyolefin composition according to claim 1, which is one or more selected from: 7. Claim 1 comprising 5 to 30 parts by weight of a halogen flame retardant per 100 parts by weight of polyolefin
Flame-retardant polyolefin composition. 8. The flame-retardant polyolefin composition according to claim 1, which contains 20 to 60 parts by weight of a flame retardant aid per 100 parts by weight of the halogenated flame retardant. 9. The flame-retardant polyolefin composition according to claim 8, wherein the flame-retardant auxiliary agent is one or more selected from antimony trioxide, diantimony tetroxide, antimony trichloride, and antimony trisulfide.