JPH07118459A - Crystalline polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain a crystalline polyolefin composition capable of producing molded products having excellent rigidity, heat resisting rigidity and impact resistance. CONSTITUTION:A crystalline polyolefin composition is obtained by combining 100 wt.pt. of a crystalline polyolefin with 0.001-1 wt.pt. each of one or two amide compounds selected from the group consisting of (1) Adipic acid dianilide and suberic acid dianilide and one or more compounds selected from the group consisting of (2) Alkylidene-bis-(alkylaryl) fluorophosphite, Thio-bis-(alkylaryl) fluorophosphite or 2, 2'-bis(alkylaryl) fluorophosphite, (3) Diarylamine derivatives, and (4) Radical generating agents.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline polyolefin composition capable of obtaining a molded article excellent in rigidity, heat resistance and impact resistance.

[0002]

2. Description of the Related Art Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties, and are therefore used in the production of various molded products such as injection molded products, hollow molded products, films, sheets and fibers. . However, mechanical properties may not be sufficient depending on various specific uses, and there is a problem that expansion of the specific uses is limited. In particular, it cannot be said that the impact resistance, the heat resistance rigidity and the rigidity are sufficient, and there is a drawback that the use of the crystalline polyolefin may limit the specific application. On the other hand, for the purpose of obtaining a crystalline polypropylene resin composition capable of producing a large amount of β-type crystal structure, a crystalline polypropylene resin composition containing adipic acid dianilide and / or suberic acid dianilide as a β crystal nucleating agent is used. It has been proposed as Japanese Patent Application Laid-Open No. 5-255551, and an antioxidant (phenolic compound,
It is described that a phosphite compound etc.) can be used together.

[0003]

However, although the molded articles obtained from the above-mentioned crystalline polypropylene resin composition are improved in rigidity, heat resistance and impact resistance, they are still not sufficiently satisfactory. Further, in JP-A-5-255551, when a composition containing adipic acid dianilide and / or suberic acid dianilide in a crystalline polyolefin is used in combination with a fluorophosphite or a diarylamine derivative as an antioxidant, There is no description or suggestion that the rigidity, heat resistance and impact resistance of the obtained molded product will be improved.

The present inventor has conducted further studies without being satisfied with the crystalline polypropylene resin composition proposed in JP-A-5-255551. As a result, the inventor has found that a composition obtained by blending crystalline polyolefin with adipic acid dianilide and / or suberic acid dianilide and a specific fluorophosphite, a diarylamine derivative or a radical generator in a specific amount has rigidity,
The present invention has been completed based on this finding based on the finding that it is a composition that gives a molded article with significantly improved heat resistance and impact resistance. As is clear from the above description, it is an object of the present invention to provide a crystalline polyolefin composition capable of obtaining a molded product with significantly improved rigidity, heat resistance and impact resistance when the molded product is formed. .

[0005]

The present invention has the following constitution. (1) With respect to 100 parts by weight of the crystalline polyolefin, one or two kinds of amide compounds selected from the following (hereinafter referred to as compound A) and one or more kinds of compounds selected from the following (see below) , Compound B)
A crystalline polyolefin composition containing 0.001 to 1 part by weight. Adipic acid dianilide and suberic acid dianilide. Alkylidene-bis (alkylaryl) fluorophosphite, thio-bis (alkylaryl) fluorophosphite or 2,2'-bis (alkylaryl) fluorophosphite. Diarylamine derivatives. Radical generator. (2) The crystalline polyolefin composition according to the above item 1, further comprising 0.001 to 1 part by weight of a fatty acid (hereinafter referred to as compound C) with respect to 100 parts by weight of the crystalline polyolefin.

The crystalline polyolefin used in the present invention includes ethylene, propylene, butene-1, pentene-1,
Crystalline homopolymer of α-olefin such as 4-methyl-pentene-1, hexene-1, octene-1, crystalline or low crystalline random copolymer or crystalline block of two or more α-olefins Copolymers, copolymers of the above α-olefins with vinyl acetate or acrylic acid ester, saponified products of the copolymers, copolymers of these α-olefins with unsaturated silane compounds, and these α-olefins Copolymers with unsaturated carboxylic acids or derivatives thereof, reaction products of the copolymers with metal ion compounds, crystalline homopolymers of the above α-olefins, crystalline or low crystalline random copolymers, or Modified polyolefin obtained by modifying a crystalline block copolymer with an unsaturated carboxylic acid or a derivative thereof, a crystalline homopolymer of the above α-olefin, a crystalline or low crystalline run Examples thereof include silane-modified polyolefins obtained by modifying a copolymer or crystalline block copolymer with an unsaturated silane compound. These crystalline polyolefins can be used alone or two or more crystalline polyolefins can be used. It can also be used as a mixture.

Further, various synthetic rubbers (for example, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene terpolymer, polybutadiene, polyisoprene, polychloroprene) are added to the above-mentioned crystalline polyolefin. , Chlorinated polyethylene, chlorinated polypropylene, fluoro rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene
-Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene
-Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (for example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, Polybutylene terephthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluororesin, petroleum resin (for example, C ₅ petroleum resin, hydrogenated C ₅ petroleum resin, C
_9- based petroleum resin, hydrogenated C _9- based petroleum resin, C ₅ -C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉ copolymerized petroleum resin, acid-modified C _9- based petroleum resin, etc., DCPD resin (eg cyclo Pentadiene petroleum resin, hydrogenated cyclopentadiene 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 copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ -C ₉ copolymerized petroleum resin, etc., having a softening point of 80 to 200 ° C. Can also be used. Crystalline propylene homopolymer, a crystalline propylene copolymer containing 70% by weight or more of a propylene component, crystalline ethylene-propylene random copolymer, crystalline propylene-butene-1 random copolymer,
Crystalline ethylene-propylene-butene-1 terpolymer,
Crystalline propylene-hexene-butene-1 terpolymers and mixtures of two or more thereof are particularly preferably used.

The compound A used in the present invention is adipic acid dianilide and suberic acid dianilide, and the compound A can be used alone or in combination of two kinds. The compounding ratio of the compound A is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the crystalline polyolefin. If the blending ratio is less than 0.001 part by weight, the effect of improving the rigidity, heat resistance and impact resistance will not be fully exerted, and if it exceeds 1 part by weight, the rigidity, heat resistance and impact resistance will not be improved. Not only is it impossible to expect an improvement effect and it is not practical, and it is also uneconomical.

The compound B used in the present invention is 2,
2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-bis (4 -t-Amyl-6-methylphenyl) fluorophosphite, 2,2'-bis (4-s
-Eicosylphenyl) fluorophosphite, 2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-ethyl-6-t
-Butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6-nonylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-dinonylphenyl) fluorophosphite , 2,2'-methylene-bis (4-
Methyl-6-cyclohexylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6- (1'-methylcyclohexyl) phenyl) fluorophosphite,
2,2'-i-Propylidene-bis (4-nonylphenyl) fluorophosphite, 2,2'-butylidene-bis (4,6-dimethylphenyl) fluorophosphite, 2,2'-methylene-
Bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-di-t-amylphenyl) fluorophosphite, 2,2'-ethylidene-bis ( 4-Methyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4-ethyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4- s-Butyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4, 6-di-t-amylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6-t-octylphenyl) fluorophosphite, 2,2'-butylidene-bis (4-methyl- 6- (1'-methylcyclohexyl) phenyl)
Fluorophosphite, 2,2'-methylene-bis (4,6-dimethylphenyl) fluorophosphite, 2,2'-thio-
Bis (4-t-octylphenyl) fluorophosphite, 2,2'-thio-bis (4,6-di-s-amylphenyl) fluorophosphite, 2,2'-thio-bis (4,6- Di-i-octylphenyl) fluorophosphite, 2,2'-thio-bis (5-t-butylphenyl) fluorophosphite, 2,
2'-thio-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4-methyl-6-α-methylbenzylphenyl) fluorophosphite, 2,2 '
-Thio-bis (3-methyl-4,6-di-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4-t-amylphenyl) fluorophosphite,

4,4'-Dioctyl-diphenylamine, 4,4 '
-Bis (α, α'-dimethylbenzyl) -diphenylamine, N-phenyl-β-naphthylamine, N, N'-diphenyl-p-phenylenediamine, N, N'-diaryl-p-phenylenediamine, N-phenyl- N'-i-propyl-p-phenylenediamine, N-phenyl-1,3-dimethylbutyl-p-
Phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, N-phenyl-α-naphthylamine, N-o-
Trilyl-β-naphthylamine, 4-i-propoxydiphenylamine, 4,4'-dicumyldiphenylamine, 4,4'-bis (1 ", 1", 3 ", 3" -tetramethyl-butyl) diphenylamine, diphenylamine , 4- (1 ', 1', 3 ', 3'-tetramethyl
-Butyl) diphenylamine, 4,4'-dimethoxy-diphenylamine, 4,4'-bis (α-methylbenzyl) -diphenylamine, 4- (p-toluenesulfonylamino) -diphenylamine, 4-α-methylbenzyl-diphenylamine, 3-methyl-4,4'-dimethoxy-diphenylamine, N,
N'-di-o-tolyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-phenyl-
N'-cyclohexyl-p-phenylenediamine, N-phenyl-N-p-toluenesulfonyl-p-phenylenediamine,
N-o-tolyl-N'-phenyl-p-phenylenediamine, N-
Alkyl-N'-phenyl-p-phenylenediamine, N-sec
-Butyl-N'-phenyl-p-phenylenediamine, N-hexyl-N'-phenyl-p-phenylenediamine, N-phenyl-N '-(1-methylheptyl) -p-phenylenediamine,
N-methyl-N'-phenyl-2-amyl-p-phenylenediamine, 1,3-bis (β-naphthylaminophenoxy) propan-2-ol, dimethyl-bis (4-β-naphthylaminophenoxy) silane, Diethyl-bis (4-β-naphthylaminophenoxy) silane, 2-hydroxy-1,3-bis (4'-phenylamino-phenoxy) propane, bis-β (4-phenylaminophenoxy) ethyl ether, dimethyl-bis (4-phenylaminophenoxy) silane, bis (4-β
-Naphthylaminophenoxy-ethyl) ether, 9,9-dimethyl-9,10-dihydroacridine, 9,9-dimethyl-9,10-
Dihydro-benz (2: 3) acridine,

Benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-
Di (benzoylperoxy) hexane, 2,5-di-methyl-
2,5-di (benzoylperoxy) hexyne-3, t-butyl
-Di-peradipate, t-butylperoxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butylperoxide, dicumyl peroxide, 2, 5-di
-Methyl-2,5-di (t-butylperoxy) hexane, 2,5-
Di-methyl-2,5-di (t-butylperoxy) hexyne-3,
1,3-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
1,1-bis (t-butylperoxy) cyclohexane, 2,2-
Bis (t-butylperoxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-
Butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methylbutyl hydroperoxide, 2,5-di-methyl-2,5-di (hydroperoxy) hexane, trimethylsilyl- Cumyl peroxide, 2,5-di-methyl-2,5-bis (trimethylsilylperoxy) hexane, 2,5-di-methyl-2,5-bis (trimethylsilylperoxy) hexyne-3 and 1,3 Examples thereof include bis (trimethylsilylperoxyisopropyl) benzene.

Particularly, 2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-
Methyl-6-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl)
Fluorophosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) fluorophosphite,
2,2'-Ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4-methyl-6-t
-Butylphenyl) fluorophosphite, 4,4'-bis (α, α'-dimethylbenzyl) -diphenylamine, 2,5-
Di-methyl-2,5-di (t-butylperoxy) hexane, 2,
5-di-methyl-2,5-di (benzoylperoxy) hexyne
-3 and 1,3-bis (t-butylperoxyisopropyl)
Benzene is preferred. These compounds B may be used alone or in combination of two or more kinds. The compounding ratio of the compound B is 10
0.001 to 1 part by weight, preferably 0.01 to 0, relative to 0 part by weight.
5 parts by weight. Rigidity at a blending ratio of less than 0.001 parts by weight,
The effects of improving heat resistance and impact resistance are not fully exerted, and the amount may exceed 1 part by weight, but further improvement in rigidity, heat resistance and impact resistance cannot be expected, and it is not practical. It is also uneconomical.

In the crystalline polyolefin composition of the present invention, the combined use of compound C synergistically exhibits the effect of improving rigidity, heat resistance and impact resistance, and therefore it is preferably used in combination. Compound C includes 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, arachidic acid, behenic acid, erucic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, 12-hydroxyoctadecanoic acid,
Examples include ricinoleic acid and cerebronic acid.
2-Ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, montanic acid and 12-hydroxyoctadecanoic acid are preferred. Further, acid components such as hydrogen chloride remaining as a catalyst residue in the crystalline polyolefin as the above-mentioned various fatty acids, and a fatty acid metal salt blended as a neutralizing agent in the crystalline polyolefin (for example, fatty acid calcium, fatty acid zinc, fatty acid magnesium, Fatty acid sodium, fatty acid lithium, etc.) or a basic inorganic compound fatty acid surface-treated product (for example, hydrotalcite fatty acid surface-treated product, magnesium hydroxide fatty acid surface-treated product, zeolite fatty acid surface-treated product, etc.) Fatty acids produced by the neutralization reaction are also included in the compound C of the present invention. These compounds C may be used alone or in combination of two or more kinds. The compounding ratio of the compound C is 0.001 to 100 parts by weight of the crystalline polyolefin.
It is 1 part by weight, preferably 0.01 to 0.5 part by weight.

In the composition of the present invention, various additives usually added to crystalline polyolefins such as phenol-based, thioether-based, phosphorus-based antioxidants (except compound B), photostability, etc. Agent, heavy metal deactivator (copper damage inhibitor), clarifying agent, nucleating agent (however, compound A
), Lubricants (excluding compound C), antistatic agents, antifogging agents, antiblocking agents, non-dripping agents, flame retardants,
Flame retardant aids, pigments, halogen scavengers, dispersants or neutralizers for metal soaps, organic or inorganic antibacterial agents, inorganic fillers (eg talc, mica, clay, wollastonite, zeolite) , Kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, calcium oxide, zinc sulfide, barium sulfate,
Calcium silicate, aluminum silicate, glass fiber,
Surface treatment with surface treatment agents such as potassium titanate, carbon fibers, carbon black, graphite and metal fibers), coupling agents (eg silane, titanate, boron, aluminate, zircoaluminate, etc.) Further, the above-mentioned inorganic filler or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used together within the range not impairing the object of the present invention.

The composition of the present invention comprises, for example, a crystalline polyolefin containing the above-mentioned compound A and compound B and the above-mentioned various additives usually added to the crystalline polyolefin in predetermined amounts in a conventional mixing device such as a Henschel mixer (commercial product). Name), a super mixer, a ribbon blender, a Banbury mixer, etc., and the melt kneading temperature of 150 ℃ ~ 300 ℃, preferably 180 ℃ with a normal single screw extruder, twin screw extruder, Brabender or roll. ~ 270
It can be obtained by melt-kneading and pelletizing at ° C. The obtained composition is used for producing a desired molded article by various molding methods such as an injection molding method, an extrusion molding method and a blow molding method.

[0016]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. 1) Rigidity: Evaluated by a bending test. That is, a test piece having a length of 100 mm, a width of 10 mm and a thickness of 4 mm was prepared by using the obtained pellet by an injection molding method, and the flexural modulus was measured by using the test piece (according to JIS K 7203) to obtain rigidity. Was evaluated. A material having a high rigidity means a material having a large flexural modulus. 2) Heat resistance rigidity: Evaluated by a deflection temperature under load test. That is, using the obtained pellets length 130 mm, width 13 mm,
A test piece having a thickness of 6.5 mm was prepared by an injection molding method, and the heat distortion temperature was measured using the test piece (according to JIS K 7207;
4.6 kgf / cm ² load) to evaluate the heat resistance rigidity. A material having high heat resistance and rigidity means a material having a high heat distortion temperature. 3) Impact resistance: evaluated by the Izod impact test. That is, using the obtained pellets length 63.5 mm, width 13 mm,
A 3.5 mm-thick test piece (having a notch) was prepared by an injection molding method, and the test piece was used to measure the Izod impact strength at 23 ° C. (according to JIS K 7110) to evaluate the impact resistance. A material having excellent impact resistance means a material having a high Izod impact strength.

Examples 1-10, Comparative Examples 1-7 MFR as a crystalline polyolefin (amount of molten resin discharged for 10 minutes when a load of 2.16 kg at 230 ° C. is applied) 6.
To 100 parts by weight of unstabilized powdery crystalline propylene homopolymer of 0 g / 10 minutes, as compound A, adipic acid dianilide or suberic acid dianilide, and as compound B,
2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 4,4 ' -Bis (α,
α'-Dimethylbenzyl) -diphenylamine or 2,5
-Di-methyl-2,5-di (t-butylperoxy) hexane and other additives were added to the Henschel Mixer (trade name) at the prescribed amounts shown in Table 1 below, and 3
After stirring and mixing for 2 minutes, 200 ° C with a twin-screw extruder with a diameter of 30 mm
Was melt-kneaded and pelletized. Comparative Examples 1 to 1
No. 7 was added to 100 parts by weight of powdered crystalline propylene homopolymer having an MFR of 6.0 g / 10 min, which is not stabilized.
Each of the additives described in Example 1 is blended in a predetermined amount, and
Melt-kneading treatment was performed according to 10 to obtain pellets. rigidity,
Test pieces used for evaluation of heat resistance rigidity and impact resistance were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. The results are shown in Table 1.

Examples 11 to 20 and Comparative Examples 8 to 14 As crystalline polyolefin, MFR 4.0 g / 10 minutes of unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) 100 In parts by weight,
Compound A is adipic acid dianilide or suberic acid dianilide, and compound B is 2,2'-methylene-bis (4,6-
Di-t-butylphenyl) fluorophosphite, 2,2'-
Ethylidene-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 4,4'-bis (α, α'-dimethylbenzyl) -diphenylamine or 2,5-di-methyl-2,5-
Predetermined amounts of di (benzoylperoxy) hexyne-3 and other additives were added to the Henschel mixer (trade name) at the compounding ratios shown in Table 2 below, and the mixture was stirred and mixed for 3 minutes, and then a twin-screw with a diameter of 30 mm was used. It was melt-kneaded at 200 ° C. in an extruder and pelletized. Also, as Comparative Examples 8 to 14, MF
Unstabilized powdery crystalline ethylene-propylene block copolymer with an R of 4.0 g / 10 min (ethylene content 8.5
100% by weight of each of the additives shown in Table 2 described below was added, and the mixture was melt-kneaded in accordance with Examples 11 to 20 to obtain pellets. Test pieces used for evaluation of rigidity, heat resistance and impact resistance were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. The results are shown in Table 3.

Examples 21-30, Comparative Examples 15-21 Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) as MFR 7.0 g / 10 min as crystalline polyolefin 90 Wt% and MI (amount of molten resin discharged at a load of 2.16 kg at 190 ° C. for 10 minutes) 15.0 g / 10 minutes unstabilized powdered Ziegler-Natta high density ethylene homopolymer 10 weights %, Adipic acid dianilide or suberic acid dianilide as the compound A and 2,2′-ethylidene-bis (4,6-di-t-
Butylphenyl) fluorophosphite, 2,2'-thio-
Bis (4-methyl-6-t-butylphenyl) fluorophosphite, 4,4'-bis (α, α'-dimethylbenzyl) -diphenylamine or 1,3-bis (t-butylperoxyisopropyl) benzene and The predetermined amount of each of the other additives was put in a Henschel mixer (trade name) at a blending ratio shown in Table 3 below, and the mixture was stirred and mixed for 3 minutes, and then the caliber was measured.
The mixture was melt-kneaded at 200 ° C. with a 30 mm twin-screw extruder and pelletized. Further, as Comparative Examples 15 to 21, 90% by weight of powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) having an MFR of 7.0 g / 10 min and an MI of 15.0 g / 10 min. Unstabilized powdered Ziegler-Natta high density ethylene homopolymer 10
A predetermined amount of each of the additives shown in Table 3 below was added to 100 parts by weight in total, and melt-kneaded according to Examples 21 to 30 to obtain pellets. Test pieces used for evaluation of rigidity, heat resistance and impact resistance were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. The results are shown in Table 3.

The compounds and additives relating to the present invention shown in Tables 1 to 3 are as follows. Compound A [1]: adipic acid dianilide Compound A [2]: suberic acid dianilide Compound B [1]: 2,2′-bis (4,6-di-t-butylphenyl) fluorophosphite Compound B [2] : 2,2'-methylene-bis (4-methyl-6-t-
Butylphenyl) fluorophosphite compound B [3]: 2,2'-methylene-bis (4,6-di-t-butylphenyl) fluorophosphite compound B [4]: 2,2'-ethylidene-bis ( 4-methyl-6-t
-Butylphenyl) fluorophosphite compound B [5]: 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite compound B [6]: 2,2'-thio-bis (4-Methyl-6-t-butylphenyl) fluorophosphite Compound B [7]: 4,4'-bis (α, α'-dimethylbenzyl) -diphenylamine Compound B [8]: 2,5-di- Methyl-2,5-di (t-butylperoxy) hexane Compound B [9]: 2,5-di-methyl-2,5-di (benzoylperoxy) hexyne-3 Compound B [10]: 1, 3-bis (t-butylperoxyisopropyl) benzene compound C [1]: 2-ethylhexanoic acid compound C [2]: stearic acid compound C [3]: oleic acid compound C [4]: behenic acid compound C [ 5]: montanic acid compound C [6]: 12-hydroxyoctadecanoic acid phenolic antioxidant 1 2,6-di -t- butyl--p- cresol phenolic antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 3: 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene Phosphorus antioxidant 1: 2,2'-methylene-bis (4,6-di-t-
Butylphenyl) octylphosphite phosphorus-based antioxidant 2: bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite phosphorus-based antioxidant 3: bis (2,6-di-t- Butyl-4-methylphenyl) -pentaerythritol-diphosphite Aliphatic amine: N, N-bis (2-hydroxyethyl) tallowamine

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

The examples and comparative examples shown in Table 1 are the cases where a crystalline propylene homopolymer was used as the crystalline polyolefin. As can be seen from Table 1, Examples 1 to 1
10 is a mixture of the compound A and the compound B according to the present invention, and comparing Examples 1 to 10 and Comparative Example 1 (one in which the compound A and the compound B are not mixed), Examples 1 to 10 are compared. It can be seen that is extremely excellent in rigidity, heat resistance and impact resistance. Comparing Comparative Examples 2 to 4 in which only Compound B is mixed with Examples 1 to 10, Comparative Examples 2 to 4
It is understood that the rigidity, heat resistance and impact resistance of Comparative Example 1 are almost the same as those of Comparative Example 1 and are hardly improved. Further, comparing Comparative Example 5 in which only Compound A is blended with Examples 1 to 10, the rigidity, heat resistance and impact resistance of Comparative Example 5 are improved as is apparent from Comparative Example 1. I'm still not completely satisfied. Further, instead of the compound B of Examples 1 to 10, Comparative Examples 6 to 7 and Examples in which an alkylidene-bis (alkylaryl) alkylphosphite other than the compound B, that is, a phosphorus-based antioxidant 1 or an aliphatic amine was blended, respectively. Compared to 1-10,
Comparative Examples 6 to 7 have the same results as Comparative Example 5, and even if the compound A is used in combination with the phosphorus antioxidant 1 or the aliphatic amine, the effect of improving rigidity, heat resistance and impact resistance is hardly recognized. I understand. Therefore, it is apparent that the comparative examples that do not simultaneously satisfy the combination of the two components of the compound A and the compound B according to the present invention do not exhibit the effects of the present invention. That is, it can be said that the rigidity, the heat resistance and the impact resistance obtained in the present invention are unique effects that can be observed only when the compound A and the compound B are blended with the crystalline polyolefin. Further, in the compositions of Examples 1 to 7, Examples 8 to 10 in which the compound C was used in combination are
Superior rigidity of Compound A and Compound B compared to ~ 7,
It can be seen that a remarkable synergistic effect by the combined use of the compound C is recognized without impairing the effects of improving the heat resistance and the impact resistance.

Tables 2 to 3 use a mixture of a crystalline ethylene-propylene block copolymer, a crystalline ethylene-propylene random copolymer and a high density ethylene homopolymer as the crystalline polyolefin, respectively. The effects similar to those described above were also confirmed for these.

[0026]

EFFECT OF THE INVENTION The composition of the present invention is a composition which, when formed into a molded product, gives a molded product having extremely excellent rigidity, heat resistance and impact resistance.

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[Procedure amendment]

[Submission date] January 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

In the composition of the present invention, various additives usually added to the crystalline propylene polymer, such as phenol-based, thioether-based and phosphorus-based antioxidants,
Light stabilizer, heavy metal deactivator (copper damage inhibitor), clarifier, nucleating agent (excluding compound A), lubricant, antistatic agent, antifogging agent, antiblocking agent, non-dripping agent, Radical generators such as organic peroxides, flame retardants, flame retardant aids, pigments, halogen scavengers, dispersants or neutralizers for metallic soaps, organic or inorganic antibacterial agents, inorganic fillers ( For example, talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, basic aluminum-lithium-hydroxy-carbonate-
Hydrate, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, calcium oxide, zinc sulfide, barium sulfate, calcium silicate, aluminum silicate,
Such as glass fiber, potassium titanate, magnesium oxysulfate, carbon fiber, carbon black, graphite and metal fiber), coupling agent (for example, silane, titanate, boron, aluminate, zircoaluminate, etc.) The above-mentioned inorganic filler or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with the surface-treating agent can be used together within the range not impairing the object of the present invention.

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Claims (2)

[Claims] 1. 0.001 to 1 part by weight of one or two kinds of amide compounds selected from the following and one or more kinds of compounds selected from the following to 100 parts by weight of the crystalline polyolefin. A crystalline polyolefin composition blended. Adipic acid dianilide and suberic acid dianilide. Alkylidene-bis (alkylaryl) fluorophosphite, thio-bis (alkylaryl) fluorophosphite or 2,2'-bis (alkylaryl) fluorophosphite. Diarylamine derivatives. Radical generator. 2. The crystalline polyolefin composition according to claim 1, wherein 0.001 to 1 part by weight of a fatty acid is further added to 100 parts by weight of the crystalline polyolefin.