JP2896626B2 - Crystalline polyolefin composition - Google Patents

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 from which a molded article having excellent rigidity can be obtained. More particularly, the present invention relates to a crystalline polyolefin, a crystalline polyolefin composition capable of obtaining a molded article having excellent rigidity, each comprising a specific amount of biphenylylene-di-phosphonic acid and a specific nitrogen-containing compound.

[0002]

2. Description of the Related Art Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties.
It is used in the production of various molded products such as hollow molded products, films, sheets, and fibers. However, depending on various specific applications, the mechanical properties may not be sufficient, and there is a problem that expansion of the specific applications is limited. Polystyrene, ABS especially for rigidity
Since it is inferior to polyesters such as resin and polyethylene terephthalate and polybutylene terephthalate, there is a drawback that the use of crystalline polyolefin may be restricted in specific applications. For this reason, various nucleating agents have conventionally been used for the purpose of improving the rigidity of the crystalline polyolefin. The present inventors have proposed a crystalline polyolefin composition comprising a crystalline polyolefin and a specific amount of biphenylylene-diphosphonic acid as a composition from which a molded article with improved rigidity can be obtained.
It was previously proposed as -21920.

On the other hand, JP-A-51-52450 discloses specific diphosphonic acid compounds or diphosphinic acid compounds including arylenediphosphonic acid as stabilizers for polyolefins. The publication also discloses that conventional additives such as lubricants and antistatic agents can be used in combination.

[0004]

However, although the rigidity of a molded product obtained from a composition in which various known nucleating agents are blended with a crystalline polyolefin is improved to some extent, it is still not sufficiently satisfactory. JP-A-51-52450 discloses a general formula of a wide range of diphosphonic acid compounds or diphosphinic acid compounds as polyolefin stabilizers. However,
The publication discloses a polyolefin composition in which biphenylylene-di-phosphonic acid is blended as an arylenediphosphonic acid compound, and a fatty acid bisamide as a lubricant or an amine-based antistatic agent or an alkanolamide-based antistatic agent is used as an antistatic agent. There is no description or suggestion of improving the rigidity of the obtained molded article.

[0005] The present inventors have conducted further intensive studies without being satisfied with the crystalline polyolefin composition proposed in Japanese Patent Application No. 5-21920. As a result, the present inventors have found that a crystalline polyolefin, a crystalline polyolefin composition comprising a specific amount of biphenylene-di-phosphonic acid and a specific nitrogen-containing compound, respectively, is a composition that gives a molded article with improved rigidity. The present invention has been completed based on this finding. As is apparent from the above description, an object of the present invention is to provide a crystalline polyolefin composition having an improved rigidity when formed into a molded product.

[0006]

The present invention has the following arrangement. 1) 100 parts by weight of a crystalline polyolefin, biphenylylene-diphosphonic acid (hereinafter referred to as Compound A)
A crystalline polyolefin composition comprising 0.001 to 1 part by weight of each of 0.001 to 1 part by weight and 0.001 to 1 part by weight of one or more compounds selected from the following (1) to (5) (hereinafter, referred to as compound B). (1) Aliphatic amine (2) Fatty acid bisamide (3) Aliphatic amide ethylene oxide adduct (4) Aminotriazine compound (5) Hindered amine compound

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The crystalline polyolefin used in the present invention is:
Crystalline homopolymers of α-olefins such as ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, and the crystallinity of two or more α-olefins Or a low-crystalline random copolymer or a crystalline block copolymer, a copolymer of the above-mentioned α-olefin and vinyl acetate or acrylate, a saponified product of the copolymer, or a mixture of these α-olefins and unsaturated silanes Copolymers with compounds, copolymers of these α-olefins with unsaturated carboxylic acids or anhydrides, reaction products of the copolymers with metal ion compounds, and crystalline α-olefins of the above-mentioned α-olefins. A modified polyolefin obtained by modifying a copolymer, a crystalline or low-crystalline random copolymer or a crystalline block copolymer with an unsaturated carboxylic acid or a derivative thereof; Crystalline homopolymer,
Examples thereof include silane-modified polyolefins in which a crystalline or low-crystalline random copolymer or a crystalline block copolymer is modified with an unsaturated silane compound, and the use of these crystalline polyolefins alone, as well as
Two or more crystalline polyolefins may be used as a mixture.

Further, the above-mentioned crystalline polyolefin may be replaced with various synthetic rubbers (for example, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene terpolymer, polybutadiene, polyisoprene, polychloroprene). , 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, fluorine resin, petroleum resin (e.g. C ₅ petroleum resins, hydrogenated C ₅ petroleum resins, C
₉ petroleum resin, hydrogenated C ₉ petroleum resin, C ₅ -C ₉ copolymer petroleum resin, hydrogenated C ₅ -C ₉ copolymer petroleum resin, and an acid-modified C ₉ petroleum resin), DCPD resins (such as cyclopropyl pentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resins, cyclopentadiene -C ₅ copolymer petroleum resin, hydrogenated cyclopentadiene -C ₅ copolymer petroleum resin, cyclopentadiene -C ₉ copolymer petroleum resin, hydrogenated cyclopentadiene - C ₉ copolymer petroleum resin, cyclopentadiene -C ₅ -C ₉ copolymer petroleum resin, softening point 80 to 200 ° C. for DCPD resins such as hydrogenated cyclopentadiene -C ₅ -C ₉ copolymer petroleum resin) and mixed Can also be used. A crystalline propylene homopolymer, a crystalline propylene copolymer containing a propylene component of 70% by weight or more, and a crystalline ethylene-propylene random copolymer, a crystalline propylene-butene-1 random copolymer,
Crystalline ethylene-propylene-butene-1 terpolymer,
Crystalline propylene-hexene-butene-1 terpolymer and mixtures of two or more thereof are particularly preferably used.

The compound A used in the present invention includes 4,4
4'-biphenylylene-di-phosphonic acid, 4,3'-biphenylylene-di-phosphonic acid, 3,3'-biphenylylene-di-
Phosphonic acid and the like can be exemplified, and 4,4′-biphenylylene-di-phosphonic acid is particularly preferable. These compounds A can be used alone, or two or more compounds A can be used in combination. These compounds A are disclosed, for example, in
Oxidizing biphenyl-di-phosphonous acid, such as 4,4'-biphenyl-di-phosphonous acid described in JP-8772, or tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3'-biphenylene-
It can be obtained by hydrolyzing and oxidizing di-phosphonite or tetrakis (2,4-di-t-butylphenyl) -3,3′-biphenylene-di-phosphonite. The content of the compound A is a crystalline polyolefin.
0.001 to 1 part by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight
0.5 parts by weight. If the content is less than 0.001 part by weight, the effect of improving rigidity is not sufficiently exhibited, and even if it exceeds 1 part by weight, a further improvement in rigidity cannot be expected and it is not only practical but also impractical. Economy.

The compound B used in the present invention includes octylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine,
Cocoamine, tallowamine, soyamine, N, N-dicocoamine, N, N-ditarowamine, N, N-disoiamine,
N-lauryl-N, N-dimethylamine, N-myristyl-
N, N-dimethylamine, N-palmityl-N, N-dimethylamine, N-stearyl-N, N-dimethylamine, N-coco-N, N-dimethylamine, N-tallow-N, N-dimethylamine , N-soy-N, N-dimethylamine, N-methyl-
N, N-ditarowamine, N-methyl-N, N-dicocoamine, N-oleyl-1,3-diaminopropane, N-tallow-1,
3-diaminopropane, hexamethylenediamine, N-lauryl-N, N, N-trimethylammonium chloride,
N-palmityl-N, N, N-trimethylammonium chloride, N-stearyl-N, N, N-trimethylammonium chloride, N-docosyl-N, N, N-trimethylammonium chloride, N-coco-N, N, N-trimethylammonium chloride, N-tallow-N, N, N-trimethylammonium chloride, N-soy-N, N, N-N-trimethylammonium chloride, N, N, N-triethyl-
N-benzylammonium chloride, N-lauryl-N,
N-dimethyl-N-benzylammonium chloride, N-
Myristyl-N, N-dimethyl-N-benzylammonium chloride, N-stearyl-N, N-dimethyl-N-benzylammonium chloride, N-coco-N, N-dimethyl-
N-benzylammonium chloride, N, N-dioleyl-N, N-dimethylammonium chloride, N, N-dicoco-N, N-dimethylammonium chloride, N, N-
Ditalow-N, N-dimethylammonium chloride, N,
N-disoi-N, N-dimethylammonium chloride,
N, N-bis (2-hydroxyethyl) -N-lauryl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N-stearyl-N-methylammonium chloride, N, N-bis ( 2-hydroxyethyl) -N-oleyl-N-methylammonium chloride, N, N-bis (2-
(Hydroxyethyl) -N-coco-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-lauryl-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-stearyl- N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-oleyl-N-methylammonium chloride,
N, N-bis (polyoxyethylene) -N-coco-N-methylammonium chloride,

N, N-bis (2-hydroxyethyl) laurylaminobetaine, N, N-bis (2-hydroxyethyl)
Tridecylaminobetaine, N, N-bis (2-hydroxyethyl) myristylaminobetaine, N, N-bis (2-hydroxyethyl) pentadecylaminobetaine, N, N-
Bis (2-hydroxyethyl) palmitylaminobetaine, N, N-bis (2-hydroxyethyl) stearylaminobetaine, N, N-bis (2-hydroxyethyl) oleylaminobetaine, N, N-bis (2- Hydroxyethyl)
Docosylaminobetaine, N, N-bis (2-hydroxyethyl) octakosylaminobetaine, N, N-bis (2-hydroxyethyl) cocoaminobetaine, N, N-bis (2-
(Hydroxyethyl) tallowaminobetaine, hexamethylenetetramine, triethanolamine, triisopropanolamine, N- (2-hydroxyethyl) laurylamine, N- (2-hydroxyethyl) tridecylamine, N- (2-hydroxyethyl) Myristylamine, N-
(2-hydroxyethyl) pentadecylamine, N- (2-
(Hydroxyethyl) palmitylamine, N- (2-hydroxyethyl) stearylamine, N- (2-hydroxyethyl) oleylamine, N- (2-hydroxyethyl) docosylamine, N- (2-hydroxyethyl) octacosylamine, N- (2-hydroxyethyl) cocoamine, N-
(2-hydroxyethyl) tallowamine, N-methyl-N-
(2-hydroxyethyl) laurylamine, N-methyl-N
-(2-hydroxyethyl) tridecylamine, N-methyl
-N- (2-hydroxyethyl) myristylamine, N-methyl-N- (2-hydroxyethyl) pentadecylamine,
N-methyl-N- (2-hydroxyethyl) palmitylamine, N-methyl-N- (2-hydroxyethyl) stearylamine, N-methyl-N- (2-hydroxyethyl) oleylamine, N-methyl-N -(2-hydroxyethyl) docosylamine, N-methyl-N- (2-hydroxyethyl) octacosylamine, N-methyl-N- (2-hydroxyethyl) cocoamine, N-methyl-N- (2-hydroxyethyl ) Tallowamine,

N, N-bis (2-hydroxyethyl) laurylamine, N, N-bis (2-hydroxyethyl) tridecylamine, N, N-bis (2-hydroxyethyl) myristylamine, N, N- Bis (2-hydroxyethyl) pentadecylamine, N, N-bis (2-hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl) stearylamine, N, N-bis (2-hydroxyethyl ) Oleylamine, N, N-bis (2-hydroxyethyl) docosylamine, N, N-bis (2-hydroxyethyl) octacosylamine, N, N-bis (2-hydroxyethyl) cocoamine, N, N-bis ( N, N-bis (2-hydroxyethyl) aliphatic amines such as 2-hydroxyethyl) tallowamine,
Mono- or diesters of the N, N-bis (2-hydroxyethyl) aliphatic amine with a fatty acid such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, polyoxyethylene laurylamino Ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene coco amino ether, polyoxyethylene tallow amino ether, N, N, N ', N'-tetra (2-hydroxyethyl) -1, 3-diaminopropane, N,
N, N ', N'-tetra (2-hydroxyethyl) -1,6-diaminohexane, N-lauryl-N, N', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-stearyl
-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-coco-N, N', N'-tris (2-hydroxyethyl) -1,3-diaminopropane , N-Taro-N,
N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N, N-dicoco-N', N'-bis (2-hydroxyethyl) -1,3-diaminopropane, N, N-Jitarou-N ',
N'-bis (2-hydroxyethyl) -1,3-diaminopropane, N-coco-N, N ', N'-tris (2-hydroxyethyl) -1,6-diaminohexane, N-tallow-N , N ', N'-Tris (2-hydroxyethyl) -1,6-diaminohexane,
N, N-dicoco-N ', N'-bis (2-hydroxyethyl) -1,
Aliphatic amines such as 6-diaminohexane and N, N-ditarow-N ′, N′-bis (2-hydroxyethyl) -1,6-diaminohexane,

N, N'-methylene-bis-lauric acid amide, N, N'-methylene-bis-myristic acid amide,
N'-methylene-bis-palmitic acid amide, N, N'-methylene-bis-palmitoleic acid amide, N, N'-methylene-
Bis-stearamide, N, N'-methylene-bis-12-hydroxystearic acid amide, N, N'-methylene-bis-oleic acid amide, N, N'-methylene-bis-behenic acid amide, N, N ' -Methylene-bis-erucamide, N, N'-methylene-bis-montanamide, N, N'-ethylene-bis
-Lauric amide, N, N'-ethylene-bis-myristic amide, N, N'-ethylene-bis-palmitic amide, N, N'-ethylene-bis-palmitoleic amide,
N, N'-ethylene-bis-stearamide, N, N'-ethylene-bis-12-hydroxystearic acid amide, N, N'-ethylene-bis-oleic acid amide, N, N'-ethylene-bis
-Behenamide, N, N'-ethylene-bis-erucamide, N, N'-ethylene-bis-montanamide, N, N'-
Hexamethylene-bis-stearamide, N, N'-hexamethylene-bis-oleamide, N, N'-hexamethylene-bis-behenamide, N, N'-distearyloxamidamide, N, N ' -Dioleyl oxalate, N,
N'-distearyl succinamide, N, N'-dioleyl succinamide, N, N'-distearyl adipamide, N, N'-dioleyl adipamide, N, N'-distearyl sebacine Acid amides, fatty acid bisamides such as N, N'-dioleyl sebacic amide,

N, N-bis (2-hydroxyethyl) lauramide, N, N-bis (2-hydroxyethyl) tridecylamide, N, N-bis (2-hydroxyethyl) myristylamide, N, N- Bis (2-hydroxyethyl) pentadecylamide, N, N-bis (2-hydroxyethyl) palmitylamide, N, N-bis (2-hydroxyethyl) stearylamide, N, N-bis (2-hydroxyethyl ) Oleylamide, N, N-bis (2-hydroxyethyl) docosylamide, N, N-bis (2-hydroxyethyl) octacosylamide, N, N-bis (2-hydroxyethyl) cocoamide, N, N- Bis (2-hydroxyethyl) tallowamide,
Aliphatic amide ethylene oxide adducts such as polyoxyethylene lauryl amide ether, polyoxyethylene stearyl amide ether, polyoxyethylene oleyl amide ether, polyoxyethylene cocoamide ether, and polyoxyethylene tallow amide ether;

2,4,6-triamino-1,3,5-triazine, 2,4
-Diamino-6-methyl-1,3,5-triazine, 2,4-diamino-
6-phenyl-1,3,5-triazine, 1,4-bis (3,5-diamino-2,4,6-triazinyl) butane, 3,9-bis [2- (3,5-
Diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10
Aminotriazine compounds such as -tetraoxaspiro [5.5] undecane,

4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2 , 6,6-Tetramethylpiperidine, 1- (4-t-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6, 6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 1-benzyl-2,2,6,6-tetramethyl-4-piperidylmalate, bis (2, 2,6,6-tetramethyl-4-piperidyl)
Succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4
-Piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) fumarate, bis (1,2,3 , 6-Tetramethyl-2,6-diethyl-4-piperidyl) sebacate,
Bis (1-allyl-2,2,6,6-tetramethyl-4-piperidyl)
Phthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone) , 2-methyl-2-
(2,2,6,6-tetramethyl-4-piperidyl) imino-N-
(2,2,6,6-tetramethyl-4-piperidyl) propionamide, 2-methyl-2- (1,2,2,6,6-pentamethyl-4-piperidyl) imino-N- (1,2 , 2,6,6-pentamethyl-4-piperidyl) propionamide, 1-propargyl-4-β-cyanoethyloxy-2,2,6,6-tetramethylpiperidine, 1-acetyl-2,2,6,6 -Tetramethyl-4-piperidyl-acetate, trimellitic acid-tris (2,2,6,6-tetramethyl-4-
Piperidyl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) dibutylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) dibenzyl-malonate, bis (1,2,3,6-tetramethyl-2) ,
6-diethyl-4-piperidyl) dibenzyl-malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-
Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate,

Bis (2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3-dicarboxylate, bis (1,2,2,6,6 -Pentamethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3
-Dicarboxylate, bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.5]
Undecane-3,3-dicarboxylate, 1,3-bis [2,2'-
[Bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-dioxacyclohexane-5,5-dicarboxylate]],
Bis (2,2,6,6-tetramethyl-4-piperidyl) -2- [1-methylethyl] -1,3-dioxacyclohexane-5,5-dicarboxylate]], 1,2-bis [2,2 '-[bis (2,2,6,6-
Tetramethyl-4-piperidyl) -2-methyl-1,3-dioxacyclohexane-5,5-dicarboxylate]], bis (2,2,6,6-tetramethyl-4-piperidyl) -2- [2- (3,5-
Di-t-butyl-4-hydroxyphenyl)] ethyl-2-methyl-1,3-dioxacyclohexane-5,5-dicarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) -1,5-
Dioxaspiro [5.11] heptadecane-3,3-dicarboxylate, hexane-1 ', 6'-bis-4-carbamoyloxy
-1-n-butyl-2,2,6,6-tetramethylpiperidine), toluene-2 ', 4'-bis (4-carbamoyloxy-1-n-butyl-
2,2,6,6-tetramethylpiperidine), dimethyl-bis (2,2,6,6-tetramethylpiperidine-4-oxy) -silane, phenyl-tris (2,2,6,6-tetramethyl Piperidine-4-oxy) -silane, tris (1-propyl-2,2,6,6-
Tetramethyl-4-piperidyl) -phosphite, tris (1-propyl-2,2,6,6-tetramethyl-4-piperidyl)-
Phosphate, phenyl- [bis (1,2,2,6,6-pentamethyl-4-piperidyl)]-phosphonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2 , 3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4
-Piperidyl) 1,2,3,4-butanetetracarbonamide,
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)
1,2,3,4-butanetetracarbonamide,

2-Dibutylamino-4,6-bis (9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.
5] -3-undecylmethoxy) -s-triazine, 2-dibutylamino-4,6-bis (9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] -3-undecylmethoxy) -s-triazine, tetrakis (9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.
5] -3-undecylmethyl) -1,2,3,4-butanetetracarboxylate, tetrakis (9-aza-3-ethyl-8,8,9,1
0,10-pentamethyl-1,5-dioxaspiro [5.5] -3-undecylmethyl) -1,2,3,4-butanetetracarboxylate, tridecyltris (2,2,6,6-tetramethyl- 4-piperidyl) 1,2,3,4-butanetetracarboxylate, tridecyl tris (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, Di (tridecyl) bis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, di (tridecyl) bis (1,2,2,6, 6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 2,2,4,4-
Tetramethyl-7-oxa-3,20-diazaspiro [5,1,11,
2] heneicosan-21-one, 3,9-bis [1,1-dimethyl-
2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,
4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butyl] Carbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.
5] undecane, poly (2,2,6,6-tetramethyl-4-piperidyl acrylate), poly (1,2,2,6,6-pentamethyl-4)
-Piperidyl acrylate), poly (2,2,6,6-tetramethyl-4-piperidyl methacrylate), poly (1,2,2,6,6
-Pentamethyl-4-piperidyl methacrylate), poly [[bis (2,2,6,6-tetramethyl-4-piperidyl) itaconate] [vinyl butyl ether]], poly [[bis (1,2,2,6, 6-pentamethyl-4-piperidyl) itaconate] [vinyl butyl ether]], poly [[bis (2,2,
6,6-tetramethyl-4-piperidyl) itaconate] [vinyl octyl ether]], poly [[bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) itaconate] [vinyl octyl ether]], dimethyl succinate-2- (4-
Hydroxy-2,2,6,6-tetramethylpiperidyl) ethanol condensate,

Poly [hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [ethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[1,3,5-triazine-2,4-diyl] [(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6- (diethylimino)-
1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,
6,6-tetramethyl-4-piperidyl) imino]], poly [[6-[(2-ethylhexyl) imino] -1,3,5-triazine-2,4-diyl] [(2,2,6 , 6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-[(1,1,3,3
-Tetramethylbutyl) imino] -1,3,5-triazine-2,4
-Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6- (Cyclohexylimino) -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6- Tetramethyl-4-piperidyl) imino]], poly [[6-morpholino-1,3,5-triazine-2,
4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]], poly [[6- (butoxyimino) -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexa Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-[(1,1,3,3-tetramethylbutyl)
Oxy] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [oxy [6-[(1-piperidyl) -1,3,5 -
Triazine-2,4-diyloxy-1,2-ethanediyl]
[(2,2,6,6-tetramethyl-3-oxo-1,4-piperidyl)
-1,2-ethanediyl] [(3,3,5,5-tetramethyl-2-oxo-1,4-piperidyl) -1,2-ethanediyl]], poly [oxy [6-[(1,1 , 3,3-Tetramethylbutyl) imino]-
1,3,5-triazine-2,4-diyloxy-1,2-ethanediyl] [(2,2,6,6-tetramethyl-3-oxo-1,4-piperidyl) -1,2-ethanediyl] [(3,3,5,5-tetramethyl-2-
Oxo-1,4-piperidyl) -1,2-ethanediyl]], poly [[6-[(ethylacetyl) imino] -1,3,5-triazine-2,4-diyl] [(2,2, 6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl
-4-piperidyl) imino]], poly [[6-[(2,2,6,6-
Tetramethyl-4-piperidyl) butylimino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2 , 6,6-tetramethyl-4-piperidyl) imino]],

1,6,11-tris [｛4,6-bis (N-butyl-
N- (2,2,6,6-tetramethyl-4-piperidyl) amino)-
1,3,5-triazin-2-yl {amino] undecane, 1,6,1
1-tris [｛4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazine
-2-yl @ amino] undecane, 1,6,11-tris [@ 4,6-
Bis (N-octyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl} amino]
Undecane, 1,6,11-tris [｛4,6-bis (N-octyl
-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl {amino] undecane,
1,5,8,12-tetrakis [4,6-bis (N- (2,2,6,6-tetramethyl-4-piperidyl) -butylamino) -1,3,5-triazin-2-yl ] -1,5,8,12-Tetraazadodecane, 1,5,8,1
2-tetrakis [4,6-bis (N- (1,2,2,6,6-pentamethyl-4-piperidyl) -butylamino) -1,3,5-triazine-
2-yl] -1,5,8,12-tetraazadodecane and other hindered amine compounds, and in particular, N, N-bis (2-hydroxyethyl) aliphatic amine, N, N′-ethylene-bis-
Stearoamide, N, N-bis (2-hydroxyethyl) aliphatic amide, 2,4,6-triamino-1,3,5-triazine, bis (2,2,6,6-tetramethyl-4-piperidyl) Sebacate, poly [[6-[(1,1,3,3-tetramethylbutyl) imino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl 4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-morpholino-1,3,5-triazine-2,
4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]] and 1,5,8,12-tetrakis [4,6-bis (N- (1,2,2,6,6-pentamethyl-4-piperidyl) -butylamino) -1,3, 5-triazin-2-yl] -1,5,
8,12-Tetraazadodecane is preferred. These compounds B
Can be used alone, or two or more compounds B can be used in combination. The content ratio of the compound B 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 content is less than 0.001 part by weight, the effect of improving rigidity is not sufficiently exhibited.
Although it is possible to exceed the weight part, no further improvement in rigidity can be expected, which is not only practical but also uneconomical.

In the composition of the present invention, various additives usually added to the crystalline polyolefin, such as antioxidants such as phenol-based, thioether-based and phosphorus-based (excluding compound A), light-stable Agent (however, compound B
), Heavy metal deactivator (copper damage inhibitor; excluding compound B), clarifier, nucleating agent (compound A)
), A lubricant (however, except for compound B), an antistatic agent (however, except for compound B), an antifogging agent, an antiblocking agent, a drip-free agent, a radical generator such as a peroxide, a flame retardant, Flame retardant aids, pigments, halogen scavengers (excluding compound B), dispersants or neutralizers (excluding compound B) such as metallic soaps, organic and inorganic antibacterial agents, inorganic Fillers (for example, talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide , Zinc sulfide, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black , Graphite and metal fibers, etc., and the above-mentioned inorganic or organic filler surface-treated with a surface treatment agent such as a coupling agent (for example, silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based, etc.). (For example, wood flour, pulp, waste paper,
Synthetic fibers, natural fibers, etc.) can be used in combination as long as the object of the present invention is not impaired.

The composition of the present invention can be prepared, for example, by adding a predetermined amount of each of the compounds A and B to the crystalline polyolefin and the above-mentioned various additives which are usually added to the crystalline polyolefin by using a conventional mixing apparatus such as a Henschel mixer (commercially available). Name), super-mixer, ribbon blender, Banbury mixer, etc., and melt-kneading temperature of 150 ° C. to 300 ° C., preferably 180 ° C. using a usual single screw extruder, twin screw extruder, Brabender or roll, etc. ~ 270
It can be obtained by melt-kneading pelletizing at ° C. The obtained composition is used for production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method, and a blow molding method.

[0023]

EXAMPLES The present invention will now be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The evaluation method used in the examples and comparative examples was based on the following method. 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 injection molding using the obtained pellets, and the flexural modulus was measured using the test piece (in accordance with JIS K 7203). Was evaluated. A highly rigid material is one having a large flexural modulus. 2) Impact resistance: evaluated by an Izod impact test. That is, using the obtained pellets, length 63.5 mm, width 13 mm,
A test piece (with a notch) having a thickness of 3.5 mm was prepared by an injection molding method, and the Izod impact strength at 23 ° C. was measured using the test piece (based on JIS K 7110) to evaluate the impact resistance. A material having excellent impact resistance means a material having a large Izod impact strength.

Examples 1 to 9 and Comparative Examples 1 to 7 MFR as crystalline polyolefin (discharge rate of molten resin for 10 minutes when a load of 2.16 kg at 230 ° C. is applied) 6.
100 parts by weight of an unstabilized powdery crystalline propylene homopolymer of 0 g / 10 minutes was added as compound A with 4,4′-biphenylylene-diphosphonic acid and 4,3′-biphenylylene-di-
Phosphonic acid or 3,3'-biphenylylene-di-phosphonic acid, compound B as laurylamine, N, N-dicocoamine, N-stearyl-N, N-dimethylamine, hexamethylenediamine, N-tallow-1, 3-diaminopropane, hexamethylenetetramine, N-docosyl-N, N, N
-Trimethylammonium chloride, N, N, N-triethyl-N-benzylammonium chloride or N, N
A predetermined amount of each of N-bis (2-hydroxyethyl) -N-oleyl-N-methylammonium chloride and other additives is put into a Henschel mixer (trade name) at a content ratio shown in Table 1 below for 3 minutes. After stirring and mixing, the mixture was melt-kneaded at 200 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. As Comparative Examples 1 to 7, the MFR was 6.0 g / 10
A predetermined amount of each of the additives described in Table 1 described below was blended with 100 parts by weight of a powdery crystalline propylene homopolymer that had not been stabilized for one minute, and melt-kneaded according to Examples 1 to 9. A pellet was obtained. A test piece used for evaluation of rigidity was prepared by injection molding the obtained pellet at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The rigidity was evaluated by the test method using the obtained test pieces. Table 1 shows these results.
It was shown to.

Examples 10-18, Comparative Examples 8-14 As crystalline polyolefin, an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) having an MFR of 4.0 g / 10 min. Weight parts,
As compound A, 4,4'-biphenylylene-di-phosphonic acid, 4,3'-biphenylylene-di-phosphonic acid or
3,3′-biphenylylene-diphosphonic acid, N, N-bis (2-hydroxyethyl) stearylaminobetaine, triisopropanolamine, N, N-bis (2-hydroxyethyl) cocoamine as compound B, N-bis (2-hydroxyethyl) tallowamine, 2-octadecanoic acid
[(2-hydroxyethyl) octadecylamino] ethyl ester, (octadecylimino) diethylene distearate, polyoxyethylene lauryl amino ether (ethylene oxide 10 mol adduct), polyoxyethylene stearyl amino ether (ethylene oxide 30
Mol adduct) or N, N, N ', N'-tetra (2-hydroxyethyl) -1,3-diaminopropane and other additives in the amounts specified in Henschel in the proportions shown in Table 2 below. The mixture was placed in a mixer (trade name), 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, MFR
Is blended with 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) of 4.0 g / 10 min. Then, a melt-kneading treatment was performed according to Examples 10 to 18 to obtain pellets. Test pieces used for evaluation of 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 rigidity and the impact resistance were evaluated by the test method using the obtained test pieces. Table 2 shows the results.

Examples 19 to 27 and Comparative Examples 15 to 21 As crystalline polyolefin, an unstabilized powdery crystalline ethylene-propylene random copolymer having an MFR of 7.0 g / 10 min (ethylene content 2.5% by weight) 90 10% by weight of unstabilized powdered Ziegler-Natta-based high-density ethylene homopolymer of 15.0 g / 10 min by weight% and MI (discharge rate of molten resin for 10 minutes when a load of 2.16 kg at 190 ° C. is applied) % Of 4,4′-biphenylylene-di-phosphonic acid, 4,3′-biphenylylene-di-phosphonic acid or 3,3′-biphenylylene-di-phosphonic acid as the compound A N-tallow-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N, N-dicoco-N', N'-bis (2-hydroxyethyl ) -1,6-Diaminohexane, N, N'-ethylene-bis-stearoa N, N-bis (2-hydroxyethyl) cocoamide, 2,4,6-triamino-1,3,5-triazine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Poly [[6-[(1,1,3,3-tetramethylbutyl)
Imino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-morpholino-1,3,5-triazine-2,
4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]] or 1,5,8,12-tetrakis [4,6-bis (N- (1,2,2,6,6-pentamethyl-4-piperidyl) -butylamino) -1,3, 5-triazin-2-yl] -1,5,
A predetermined amount of each of 8,12-tetraazadodecane and other additives is placed in a Henschel mixer (trade name) at a content ratio shown in Table 3 below, and mixed by stirring for 3 minutes. Then, a twin-screw extruder having a diameter of 30 mm is used. At 200 ° C. to form pellets. As Comparative Examples 15 to 21, the MFR was 7.0 g / 10
Of powdered crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 90% not stabilized
Unstabilized powdered Ziegler-Natta high density ethylene homopolymer with weight% and MI of 15.0 g / 10 min
A predetermined amount of each of the additives described in Table 3 described below was blended with 100 parts by weight of 10% by weight in total, and the mixture was melt-kneaded according to Examples 19 to 21 to obtain pellets. The test piece used for the evaluation of the rigidity, the obtained pellets resin temperature 250 ℃,
It was prepared by injection molding at a mold temperature of 50 ° C. The rigidity was evaluated by the test method using the obtained test pieces.
Table 3 shows the results.

The compounds and additives according to the present invention shown in Tables 1 to 3 are as follows. Compound A [1]: 4,4'-biphenylylene-di-phosphonic acid Compound A [2]: 4,3'-biphenylylene-di-phosphonic acid Compound A [3]: 3,3'-biphenylylene-di -Phosphonic acid Compound B [1]: Laurylamine Compound B [2]: N, N-dicocoamine Compound B [3]: N-stearyl-N, N-dimethylamine Compound B [4]: Hexamethylenediamine Compound B [5]: N-tallow-1,3-diaminopropane Compound B [6]: Hexamethylenetetramine Compound B [7]: N-docosyl-N, N, N-trimethylammonium chloride Compound B [8]: N, N, N-triethyl-N-benzylammonium chloride Compound B [9]: N, N-bis (2-hydroxyethyl)-
N-oleyl-N-methylammonium chloride Compound B [10]: N, N-bis (2-hydroxyethyl) stearylaminobetaine Compound B [11]: Triisopropanolamine Compound B [12]: N, N-bis ( 2-hydroxyethyl) cocoamine Compound B [13]: N, N-bis (2-hydroxyethyl) tallowamine Compound B [14]: 2-[(2-hydroxyethyl) octadecylamino] ethyl octadecanoate Compound B [15 ]: (Octadecyl imino) diethylene distearate Compound B [16]: Polyoxyethylene lauryl amino ether (ethylene oxide 10 mol adduct) Compound B [17]: Polyoxyethylene stearyl amino ether (ethylene oxide 30 mol adduct) Compound B [18]: N, N, N ', N'-tetra (2-hydroxyethyl) -1,3-diamine Propane Compound B [19]: N-tallow-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane Compound B [20]: N, N-dicoco-N', N '-Bis (2-hydroxyethyl) -1,6-diaminohexane

Compound B [21]: N, N'-ethylene-bis-
Stearoamide Compound B [22]: N, N-bis (2-hydroxyethyl) cocoamide Compound B [23]: 2,4,6-Triamino-1,3,5-triazine Compound B [24]: Bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate Compound B [25]: poly [[6-[(1,1,3,3-tetramethylbutyl) imino] -1,3,5-triazine- 2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino]] Compound B [26]: Poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] Compound B [27]: 1,5,8,12-tetrakis [4,6-bis (N-
(1,2,2,6,6-pentamethyl-4-piperidyl) -butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane Phenolic antioxidant Agent 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: bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 2: bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite Ca-St: calcium stearate nitrogen-containing compound 1: tris (3,5-di-t-butyl-) 4-hydroxybenzyl) isocyanurate nitrogen-containing compound 2: N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide nitrogen-containing Compound 3: 3-salicyloylamino-1,2,4-triazole Nitrogen-containing compound 4: 2- (2'-hydroxy-3'-t-butyl-5 '
-Methylphenyl) -5-chlorobenzotriazole Nitrogen-containing compound 5: Oleic acid amide

[0029]

[Table 1]

The examples and comparative examples shown in Table 1 are cases where a crystalline propylene homopolymer is used as the crystalline polyolefin. As can be seen from Table 1, Examples 1 to
9 contains Compound A and Compound B according to the present invention, and when Examples 1 to 9 are compared with Comparative Example 1 (containing no Compound A and Compound B), Examples 1 to 9 Shows that the rigidity is remarkably excellent. Further, Comparative Example 2 in which the inventor of the present invention previously proposed as Japanese Patent Application No. 5-21920, ie, Compound A alone, was used.
In comparison with Examples 1 to 9, it can be seen that Examples 1 to 9 have a remarkable synergistic effect of improving rigidity by the combined use of Compound B. Further, in Examples 1 to 9, compound B
In comparison with Comparative Examples 3 to 7 and Examples 1 to 9 in which nitrogen-containing compounds 1 to 5 were respectively contained instead of Comparative Examples 3, Comparative Examples 3 to 7 were clearly included as compared with Comparative Example 2. It can be seen that the rigidity improving effect of the combined use of the nitrogen compounds 1 to 5 is hardly recognized. Therefore, it is clear that Comparative Examples not simultaneously satisfying the two components of Compound A and 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 obtained in the present invention is a unique effect that can be seen only when the compound A and the compound B are contained in the crystalline polyolefin.

[0031]

[Table 2]

Table 2 shows the results obtained by using a crystalline ethylene-propylene block copolymer as the crystalline polyolefin, and the same effects as described above were confirmed for these. In addition, in each of the examples of the composition of the present invention shown in Table 2, the compound A and the compound B did not show a decrease in the impact resistance due to the improvement in rigidity. The gender was confirmed to be comparable.

[0033]

[Table 3]

Table 3 shows the results obtained by using a mixture of a crystalline ethylene-propylene random copolymer and a high-density ethylene homopolymer as the crystalline polyolefin, and the same effects as described above were confirmed for these.

[0035]

The composition of the present invention (1) when formed into a molded article, has extremely excellent rigidity. (2) The molded product can be made thinner, which not only contributes to resource saving, but also increases the cooling rate during molding, so that the molding speed per unit time can be increased, contributing to improved productivity. it can.

Claims (1)

(57) [Claims] 1. 100 parts by weight of a crystalline polyolefin, and 0.001 of biphenylylene-di-phosphonic acid represented by the following chemical formula 1.
A crystalline polyolefin composition comprising 0.001 to 1 part by weight and 0.001 to 1 part by weight of one or more compounds selected from the following (1) to (5). (1) Aliphatic amine (2) Fatty acid bisamide (3) Aliphatic amide ethylene oxide adduct (4) Aminotriazine compound (5) Hindered amine compound