JPH07133381A - Crystalline polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a molding excellent in rigidity, heat-resistant rigidity and impact resistance by mixing a crystalline polyolefin with a plurality of specified compounds in a specified mixing ratio. CONSTITUTION:00 pts.wt. crystalline polyolefin is mixed with 0.001-1 at least one member selected from among compounds of formulas I and II (R1 is a 1-28C aliphatic, alicyclic or aromatic dicarboxylic acid residue; R2 and R3 are each 3-18C cycloalkyl, cycloalkenyl, 7-18C alkylphenyl, alkenylphenyl, dycloalkylphenyl, biphenyl, alkylcyclohexyl, alkenylcyclohexyl or the like; R4 is a 1-28C aliphatic, alicyclic or aromatic amino acid residue; and R5 and R6 are each R2 or phenyl) and 0.001-1 pt.wt. at least one member selected from among alkylidene-bis(alkylaryl) fluorophosphite, thio-bis(alkylaryl) fluorophosphite, 2,2'-bis(alkylaryl)fluorophosphite, 2,2-bis(alkylaryl) fluorophosphite, a diarylamine deriative, and a free-radical generator to obtain the title composition.

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. Therefore, in order to improve the impact resistance and rigidity of the crystalline polypropylene-based resin, an aliphatic, alicyclic or aromatic dibasic acid-based diamide and / or amino acid-based diamide is added to the β-type crystal structure in a large amount. A crystalline polypropylene-based resin composition containing a β crystal nucleating agent that can be formed is proposed in JP-A-5-262936. In this publication, an antioxidant (phenolic compound, phosphorus-containing compound) is added if necessary. It is described that acid ester compounds, etc.) can be used in combination.

[0003]

However, although the molded article obtained from the above-mentioned crystalline polypropylene resin composition has improved rigidity, heat resistance and impact resistance, it is still not sufficiently satisfactory. Further, in JP-A-5-262936, fluorophosphite is used as an antioxidant in a composition containing a crystalline polyolefin containing an aliphatic, alicyclic or aromatic dibasic acid type diamide and / or an amino acid type diamide. Alternatively, there is no description or suggestion that the combined use of the diarylamine derivative improves the rigidity, heat resistance and impact resistance of the molded article obtained from the composition.

The present inventor has conducted further studies without being satisfied with the crystalline polypropylene resin composition proposed in JP-A-5-262936. As a result, the present inventor has found that the crystalline polyolefin contains an aliphatic, alicyclic or aromatic dibasic acid-based diamide and / or amino acid-based diamide and a specific fluorophosphite, a diarylamine derivative or a radical generator in a specific amount. It was found that the compounded composition is a composition that gives a molded article with improved rigidity, heat resistance and impact resistance,
The present invention has been completed based on this finding. As is clear from the above description, an object of the present invention is to provide a crystalline polyolefin composition in which the molded article has improved rigidity, heat resistance and impact resistance.

[0005]

The present invention has the following constitution. (1) Based on 100 parts by weight of crystalline polyolefin, the following
0.001 to 1 of one or two or more amide compounds (hereinafter referred to as compound A) selected from the following and one or two or more compounds selected from the following (hereinafter referred to as compound B) respectively. A crystalline polyolefin composition blended by weight. _{R 2 -NHCO-R 1 -CONH-} R 3 R 5 -CONH-R 4 in -CONH-R ₆ (wherein, R ₁ is an aliphatic saturated or unsaturated 1 to 28 carbon atoms, alicyclic or aromatic the dicarboxylic acid residues of the family, R ₂
And R ₃ are the same or different and are a cycloalkyl group or cycloalkenyl group having 3 to 18 carbon atoms, and 7 to 7 carbon atoms.
18 alkylphenyl group, alkenylphenyl group, cycloalkylphenyl group, biphenyl group, alkylcyclohexyl group, alkenylcyclohexyl group, cycloalkylcyclohexyl group or phenylcyclohexyl group or phenylalkyl group or cyclohexylalkyl group having 7 to 10 carbon atoms, R ₄ is a saturated or unsaturated aliphatic, alicyclic or aromatic amino acid residue having 1 to 28 carbon atoms, R ₅ and R ₆ are the same or different, and a cycloalkyl group having 3 to 18 carbon atoms or Cycloalkenyl group, phenyl group, alkylphenyl group having 7 to 18 carbon atoms,
An alkenylphenyl group, a cycloalkylphenyl group, a biphenyl group, an alkylcyclohexyl group, an alkenylcyclohexyl group, a cycloalkylcyclohexyl group or a phenylcyclohexyl group, or a phenylalkyl group having 7 to 10 carbon atoms or a cyclohexylalkyl group is shown. ) Alkylidene-bis (alkylaryl) fluorophosphite, thio-bis (alkylaryl) fluorophosphite or 2,2'-bis (alkylaryl) fluorophosphite diarylamine derivative Radical generator (2) Crystalline polyolefin 100 weight 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 1 part by weight.

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 their anhydrides, reaction products of the copolymers with metal ion compounds, crystalline homopolymers of the above α-olefins, crystalline or low crystalline random copolymers Alternatively, a 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 amide compounds shown above as the compound A used in the present invention amidate a predetermined aliphatic, alicyclic or aromatic dicarboxylic acid and a predetermined alicyclic or aromatic monoamine. Therefore, it can be easily prepared. As the aliphatic dicarboxylic acid, more specifically, malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid. , Azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid and the like. As an alicyclic dicarboxylic acid,
More specifically, 1,2-cyclohexanedicarboxylic acid, 1,
Examples thereof include 4-cyclohexanedicarboxylic acid and 1,4-cyclohexanediacetic acid. As the aromatic dicarboxylic acid, more specifically, p-phenylenediacetic acid, p-phenylenediethanoic acid, phthalic acid, 4-t-butylphthalic acid, isophthalic acid, 5-t-butylisophthalic acid, terephthalic acid, 1 , 8-Naphthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid , 4,4'-binaphthyldicarboxylic acid, bis (3-
Carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,
3'-sulfonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid,
3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 3,3'-thiodibenzoic acid, 4,4'-thiodibenzoic acid, 4,4 '
-(P-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyldibenzoic acid, 4,4'-terephthaloyldibenzoic acid,
Examples thereof include dithiosalicylic acid.

Specific examples of the alicyclic monoamine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine,
4-methylcyclohexylamine, 2-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-propylcyclohexylamine, 2-isopropylcyclohexylamine, 4-propylcyclohexylamine, 4-isopropylcyclohexylamine, 2-t-butylcyclohexylamine, 4-n-butylcyclohexylamine, 4-i-butylcyclohexylamine, 4-s-butylcyclohexylamine, 4-t-butylcyclohexylamine, 4-n-amylcyclohexylamine, 4-i-amylcyclohexylamine,
4-s-amylcyclohexylamine, 4-t-amylcyclohexylamine, 4-hexylcyclohexylamine, 4-octylcyclohexylamine, 4-nonylcyclohexylamine, 4-decylcyclohexylamine, 4-undecylcyclohexylamine, 4-dodecyl Cyclohexylamine, 4-cyclohexylcyclohexylamine, 4-phenylcyclohexylamine, cycloheptylamine, cyclododecylamine, cyclohexylmethylamine, α-
Examples thereof include cyclohexylethylamine, β-cyclohexylethylamine, α-cyclohexylpropylamine, β-cyclohexylpropylamine and γ-cyclohexylpropylamine. As an aromatic monoamine,
More specifically, aniline, o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-propylaniline, m-propylaniline, p-propylaniline, o-cumidine, m-cumidine, p-cumidine, ot-butylaniline, pn-butylaniline, pi-butylaniline, ps-butylaniline, p-
t-butylaniline, pn-amylaniline, pi-amylaniline, ps-amylaniline, pt-amylaniline, p-
Hexylaniline, p-heptylaniline, p-octylaniline, p-nonylaniline, p-decylaniline, p-undecylaniline, p-dodecylaniline, p-cyclohexylaniline, o-aminodiphenyl, m-aminodiphenyl, p Examples include -aminodiphenyl, p-aminostyrene, benzylamine, α-phenylethylamine, β-phenylethylamine, α-phenylpropylamine, β-phenylpropylamine, γ-phenylpropylamine and the like.

Further, the amide compound shown above as the compound A used in the present invention is obtained by amidating a predetermined aliphatic, alicyclic or aromatic amino acid with a predetermined monocarboxylic acid or monoamine. It can be easily prepared. As the aliphatic amino acid, more specifically, aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-aminoacrylic acid, α-aminobutyric acid,
β-aminobutyric acid, γ-aminobutyric acid, α-amino-α-methylbutyric acid, γ-amino-α-methylbutyric acid, α-amino-i-butyric acid,
β-amino-i-butyric acid, α-amino-n-valeric acid, δ-amino-n-
Valeric acid, β-aminocrotonic acid, α-amino-β-methylvaleric acid, α-amino-i-valeric acid, 2-amino-4-pentenoic acid, α-amino-n-caproic acid, 6-aminocaproic acid ,
Examples include α-amino-i-caproic acid, 7-aminoheptanoic acid, α-amino-n-caprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. It As the alicyclic amino acid, more specifically, 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2- Amino-2-norbornanecarboxylic acid and the like are exemplified. As the aromatic amino acid, more specifically, α-aminophenylacetic acid, α-amino-β-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-amino-3-phenylpropionic acid, α-
Aminocinnamic acid, 2-amino-4-phenylbutyric acid, 4-amino-3-
Phenyl butyric acid, anthranilic acid, m-aminobenzoic acid, p-
Aminobenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 2-
Amino-3-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino-3-methoxybenzoic acid, 3- Amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3-methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o-aminophenylacetic acid, m-aminophenyl Acetic acid, p-aminophenylacetic acid, 4- (4-aminophenyl) butyric acid, 4-aminomethylbenzoic acid, 4-aminomethylphenylacetic acid, o-aminocinnamic acid, m-aminocinnamic acid, p-aminocinnamic acid, p-aminohippuric acid, 2-amino-1-naphthoic acid, 3-amino-1-naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1
-Naphthoic acid, 6-amino-1-naphthoic acid, 7-amino-1-naphthoic acid, 8-amino-1-naphthoic acid, 1-amino-2-naphthoic acid, 3-amino-2-naphthoic acid, 4 -Amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-2-naphthoic acid,
Examples thereof include 7-amino-2-naphthoic acid and 8-amino-2-naphthoic acid.

As the alicyclic monocarboxylic acid, more specifically, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid,
3-methylcyclopentanecarboxylic acid, 1-phenylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid Acid, 4-propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid,
4-phenylcyclohexanecarboxylic acid, 1-phenylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-
Examples thereof include butylcyclohexenecarboxylic acid, cycloheptanecarboxylic acid, 1-cycloheptenecarboxylic acid, 1-methylcycloheptanecarboxylic acid, 4-methylcycloheptanecarboxylic acid and cyclohexylacetic acid. As the aromatic monocarboxylic acid, more specifically, benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, p-
Ethylbenzoic acid, p-propylbenzoic acid, pn-butylbenzoic acid, pi-butylbenzoic acid, ps-butylbenzoic acid, pt-
Butylbenzoic acid, pn-amylbenzoic acid, pi-amylbenzoic acid, ps-amylbenzoic acid, pt-amylbenzoic acid, p-hexylbenzoic acid, o-phenylbenzoic acid, p-phenylbenzoic acid, p-cyclohexylbenzoic acid Examples thereof include acids, phenylacetic acid, phenylpropionic acid, phenylbutyric acid and the like. The monoamine which is a raw material of the amide compound shown above is the same as the monoamine which is a raw material of the amide compound shown above. These compounds A may 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.

In particular, 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 the compound C synergistically improves the rigidity, heat resistance and impact resistance, so that it is preferable to use the compound C together. 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 compounds A and 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.

[0019]

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.
N, N'-dicyclohexyl terephthalamide, N, N'-dicyclohexyl-1,4-cyclohexanedicarboxamide as compound A was added to 100 parts by weight of unstabilized powdery crystalline propylene homopolymer at 0 g / 10 min. Or N,
N'-dicyclohexyl-2,6-naphthalene dicarboxamide, 2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite as compound B, 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) ) A predetermined amount of each of hexane and other additives is put into a Henschel mixer (trade name) at a compounding ratio shown in Table 1 below, and the mixture is stirred and mixed for 3 minutes, and then a diameter of 30 mm.
Was melt-kneaded at 200 ° C. with a twin-screw extruder to produce pellets. Further, as Comparative Examples 1 to 7, powdery crystalline propylene homopolymers having an MFR of 6.0 g / 10 min and not being stabilized 10
A predetermined amount of each of the additives shown in Table 1 below was mixed with 0 parts by weight, and melt-kneaded according to Examples 1 to 10 to obtain pellets. The test pieces used for evaluation of rigidity, heat resistance and impact resistance are obtained by pelletizing the pellets at a resin temperature of 250 ° C,
It was prepared by injection molding at 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,
N, N'-dicyclohexyl-4,4'-biphenyldicarboxamide, N, N'-bis (p-methylphenyl) hexanediamide or N, N'-bis (p-ethylphenyl) hexanediamide as compound A, 2,2'-methylene-bis (4,6-di-t-butylphenyl) fluorophosphite and 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) fluorophosphite as compound B , 4,4'-bis (α, α'-dimethylbenzyl) -diphenylamine or 2,5-di-methyl-2,5-di (benzoylperoxy) hexyne-3 and other additives Table 2 below
The mixture was placed in a Henschel mixer (trade name) at the blending ratio described in 3), stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 8 to 14, 100 parts by weight of powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) having an MFR of 4.0 g / 10 min and not being stabilized are shown in Table 2 below. A predetermined amount of each additive is blended, and Example 1 is used.
Melt-kneading processing was performed according to 1 to 20 to obtain pellets.
For the test pieces used to evaluate rigidity, heat resistance and impact resistance, the pellets obtained were resin temperature 250 ℃, mold temperature 50 ℃
Was prepared by injection molding. 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 2.

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 %, N, N′-bis (4-cyclohexylphenyl) hexanediamide, p- (N-cyclohexanecarbonylamino) benzoic acid cyclohexylamide or δ- (N-benzoylamino) as compound A. -n-valeric acid anilide, as compound B 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 other additives in prescribed amounts Put in a Henschel mixer (trade name) in the mixing ratio shown in Table 3 of the above, stir and mix for 3 minutes, and then use a twin-screw extruder with a diameter of 30 mm.
The mixture was melt-kneaded at 200 ° C. 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 minutes and not stabilized and MI
15.0 g / 10 min of unstabilized powdered Ziegler-Natta high density ethylene homopolymer (10% by weight) in total 100 parts by weight and the respective prescribed amounts of the additives shown in Table 3 below. Then, the melt-kneading process was performed 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]: N, N'-dicyclohexylterephthalamide Compound A [2]: N, N'-dicyclohexyl-1,4-cyclohexanedicarboxamide Compound A [3]: N, N'-dicyclohexyl-2, 6-naphthalenedicarboxyamide compound A [4]: N, N'-dicyclohexyl-4,4'-biphenyldicarboxamide compound A [5]: N, N'-bis (p-methylphenyl) hexanediamide compound A [6]: N, N'-bis (p-ethylphenyl) hexanediamide Compound A [7]: N, N'-bis (4-cyclohexylphenyl) hexanediamide Compound A [8]: p- (N-cyclohexane Carbonylamino) benzoic acid cyclohexylamide Compound A [9]: δ- (N-benzoylamino) -n-valeric acid anilide Compound B [1]: 2,2′-bis (4,6-di-t-butylphenyl) ) Fluorophos Aito 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

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[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. Examples 1 to 10 and comparative example 1 (compound A
It is understood that Examples 1 to 10 are remarkably excellent in rigidity, heat resistance rigidity and impact resistance. Comparing Comparative Examples 2 to 4 and Examples 1 to 10 in which only the compound B is blended, the rigidity, heat resistance and impact resistance of Comparative Examples 2 to 4 are the same as those of Comparative Example 1 and are hardly improved. I understand. In addition, Comparative Example 5 and Examples 1 to 10 in which only Compound A was blended
In comparison with Comparative Example 5, the rigidity, heat resistance and impact resistance of Comparative Example 5 are improved, as is clear from Comparative Example 1, but still not fully satisfactory. Further, in place of the compound B of Examples 1 to 10, Comparative Examples 6 to 7 and Examples in which an alkylidene-bis (alkylaryl) alkyl phosphite other than the compound B, that is, the phosphorus-based antioxidant 1 or the aliphatic amine was blended, respectively. Comparing Nos. 1 to 10, Comparative Examples 6 to 7 show the same results as Comparative Example 5, and even if the compound A is used in combination with the phosphorus-based antioxidant 1 or the aliphatic amine, rigidity, heat resistance and impact resistance are obtained. It can be seen that the effect of improving sex is hardly recognized. 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. In addition, in the compositions of Examples 1 to 7, Example 8 in which compound C was used in combination
Compared with Examples 1 to 7, Nos. 10 to 10 did not impair the excellent rigidity, heat resistance and impact resistance improving effects of Compound A and Compound B, and a remarkable synergistic effect by the combined use of Compound C was observed. Shows.

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 crystalline polyolefins, respectively. The effects similar to those described above were also confirmed for these.

[0029]

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

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[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, 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.

Claims (2)

[Claims] 1. One or two or more amide compounds selected from the following and one or two selected from the following with respect to 100 parts by weight of the crystalline polyolefin.
A crystalline polyolefin composition comprising 0.001 to 1 part by weight of each of at least one compound. _{R 2 -NHCO-R 1 -CONH-} R 3 R 5 -CONH-R 4 in -CONH-R ₆ (wherein, R ₁ is an aliphatic saturated or unsaturated 1 to 28 carbon atoms, alicyclic or aromatic the dicarboxylic acid residues of the family, R ₂
And R ₃ are the same or different and are a cycloalkyl group or cycloalkenyl group having 3 to 18 carbon atoms, and 7 to 7 carbon atoms.
18 alkylphenyl group, alkenylphenyl group, cycloalkylphenyl group, biphenyl group, alkylcyclohexyl group, alkenylcyclohexyl group, cycloalkylcyclohexyl group or phenylcyclohexyl group or phenylalkyl group or cyclohexylalkyl group having 7 to 10 carbon atoms, R ₄ is a saturated or unsaturated aliphatic, alicyclic or aromatic amino acid residue having 1 to 28 carbon atoms, R ₅ and R ₆ are the same or different, and a cycloalkyl group having 3 to 18 carbon atoms or Cycloalkenyl group, phenyl group, alkylphenyl group having 7 to 18 carbon atoms,
An alkenylphenyl group, a cycloalkylphenyl group, a biphenyl group, an alkylcyclohexyl group, an alkenylcyclohexyl group, a cycloalkylcyclohexyl group or a phenylcyclohexyl group, or a phenylalkyl group having 7 to 10 carbon atoms or a cyclohexylalkyl group is shown. ) Alkylidene-bis (alkylaryl) fluorophosphite, thio-bis (alkylaryl) fluorophosphite or 2,2'-bis (alkylaryl) fluorophosphite diarylamine derivative 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.