JP3324620B2 - 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 impact resistance can be obtained. More specifically, the present invention relates to a crystalline polyolefin composition which is obtained by mixing a specific amount of a cyclic phosphorus compound having a specific structure and a specific magnesium compound with a specific amount of a crystalline polyolefin, thereby obtaining a molded article having excellent 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, 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. In particular, the impact resistance is not sufficient, and there is a drawback in that the use of crystalline polyolefin may be restricted in specific applications. Therefore, the present applicant has developed an inorganic filler-containing polyolefin composition having improved tensile elongation and impact resistance without impairing the inherent excellent properties of a molded article obtained from the inorganic filler-containing polyolefin composition, that is, a polyolefin. A specific amount of each of a cyclic phosphorus compound having a specific structure and a metal salt of a fatty acid or a metal salt of an alkyl phosphate having a specific structure is added to a total of 100 parts by weight of the resin 70 to 90 parts by weight and the inorganic filler 30 to 10 parts by weight. The polyolefin resin composition has been previously proposed as JP-A-2-22349.

[0003]

However, although JP-A-2-22349 describes a polyolefin resin composition containing a large amount of an inorganic filler such as talc, the publication discloses talc as an inorganic filler. There is no description or suggestion of further improving the impact resistance of a molded article obtained from the polyolefin resin composition by containing a small amount of.

[0004] The present inventors have intensively studied to obtain a composition which solves the above-mentioned problems relating to a crystalline polyolefin composition, that is, a polyolefin composition having improved impact resistance. As a result, the present inventor has determined that a composition obtained by mixing a specific amount of a cyclic phosphorus compound having a specific structure and a specific magnesium compound with a crystalline polyolefin is a composition that gives a molded article with improved impact resistance. And completed the present invention 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 impact resistance when formed into a molded product.

[0005]

The present invention has the following arrangement. A cyclic phosphorus compound represented by the following general formula (1) (hereinafter referred to as Compound A) is added to 100 parts by weight of the crystalline polyolefin.
That. ) And one or two selected from the following:
A crystalline polyolefin composition comprising 0.01 to 1 part by weight of at least one kind of magnesium compound (hereinafter, referred to as compound B). Magnesium sulfate talc Magnesium phosphinate compound represented by the following general formula (2)

Embedded image

Embedded image (Wherein, Ar _{1 to} Ar ₄ represent an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group, respectively)

The crystalline polyolefin used in the present invention includes ethylene, propylene, butene-1, pentene-1,
Crystalline homopolymers of α-olefins such as 4-methyl-pentene-1, hexene-1, and octene-1, crystalline or low-crystalline random copolymers or crystalline blocks of two or more α-olefins Copolymer, copolymer of the above-mentioned α-olefin and vinyl acetate or acrylate, saponified product of the copolymer, copolymer of these α-olefin and unsaturated silane compound, these α-olefin and Copolymer of unsaturated carboxylic acid or anhydride thereof, reaction product of the copolymer and metal ion compound, crystalline homopolymer of α-olefin, crystalline or low crystalline random copolymer Or 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-mentioned α-olefin, a crystalline or low crystalline run Silane-modified polyolefins obtained by modifying a copolymer or a crystalline block copolymer with an unsaturated silane compound, and the like. These crystalline polyolefins can be used alone, or two or more crystalline polyolefins can be used. They can be used in combination.

Further, the above-mentioned crystalline polyolefin may be replaced with various synthetic rubbers (eg, 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 9,9
10-dihydro-9-oxa-10-phosphaphenanthrene-1
0-oxide, 1-methyl-9,10-dihydro-9-oxa-10-
Phosphafenanthrene-10-oxide, 2-methyl-
9,10-dihydro-9-oxa-10-phosphaphenanthrene
-10-oxide, 6-methyl-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 7-methyl-
9,10-dihydro-9-oxa-10-phosphaphenanthrene
-10-oxide, 8-methyl-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 6,8-dimethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-trimethyl-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-ethyl-9 , 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8 -Diethyl-9,1
0-dihydro-9-oxa-10-phosphaphenanthrene-10
-Oxide, 2,6,8-triethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-i-
Propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 8-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-i-propyl-9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide, 2,6,8-tri-i-propyl-9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide,

2-s-butyl-9,10-dihydro-9-oxa-10-
Phosphafenanthrene-10-oxide, 6-s-butyl
-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-s-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , 1,8-
Di-s-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-s-butyl-9,
10-dihydro-9-oxa-10-phosphaphenanthrene-1
0-oxide, 2-t-butyl-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 6-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-butyl-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 1,
6-di-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-di-t-butyl-9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 2,7-di-t-butyl-9,10-dihydro-9-oxa
-10-phosphaphenanthrene-10-oxide, 2,8-di
-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-butyl-9,10-dihydro-9-oxa-10-phos Faphenanthrene-10-oxide, 2,6,8-tri-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-
Amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-amyl-9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide, 8-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t -Amil-9,
10-dihydro-9-oxa-10-phosphaphenanthrene-1
0-oxide,

2,6,8-tri-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-
t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 8-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-octyl-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-t-octyl-9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 2-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 8-cyclohexyl-9,1
0-dihydro-9-oxa-10-phosphaphenanthrene-10
-Oxide, 6,8-di-cyclohexyl-9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-phenyl -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-benzyl-9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-benzyl-9,10-dihydro-9-oxa-1
0-phosphaphenanthrene-10-oxide, 2,6,8-tri-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2- (α-methyl Benzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,

6- (α-methylbenzyl) -9,10-dihydro-
9-oxa-10-phosphaphenanthrene-10-oxide, 8- (α-methylbenzyl) -9,10-dihydro-9-oxa
-10-phosphaphenanthrene-10-oxide, 6,8-di (α-methylbenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6 , 8-Tri (α-methylbenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-di (α,
α-dimethylbenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8
-Methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-methyl-9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide, 6-cyclohexyl-8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-t-butyl-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 6-
(Α-methylbenzyl) -8-t-butyl-9,10-dihydro-9-
Oxa-10-phosphaphenanthrene-10-oxide,
6-t-butyl-8-cyclohexyl-9,10-dihydro-9-oxa
-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8
-Benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 2,6-di-t-butyl-8-benzyl-
9,10-dihydro-9-oxa-10-phosphaphenanthrene
-10-oxide and 2,6-dicyclohexyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like, and in particular, 9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide is preferred. These compounds A can be used alone, or two or more compounds A can be used in combination. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the crystalline polyolefin. If the compounding ratio is less than 0.01 part by weight, the effect of improving the impact resistance is not sufficiently exhibited, and even if it exceeds 1 part by weight, the effect of further improving the impact resistance cannot be expected and is not practical. It is also uneconomic.

The compound B used in the present invention includes magnesium sulfate, basic magnesium sulfate (magnesium oxysulfate), talc, magnesium-bis (1'-hydroxy-2,2'-biphenylene phosphinate), magnesium- Bis (5-methyl-1'-hydroxy-2,
2'-biphenylene phosphinate), magnesium-bis (6-methyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-)
Methyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-5'-methyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-6'- Methyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-dimethyl-2,2'-biphenylenephosphinate), magnesium-bis (5,4', 6'-trimethyl-1'-hydroxy-2,2'-
Biphenylene phosphinate), magnesium-bis (5-ethyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-ethyl-2,2'-biphenylene Phosphinate), magnesium-bis (1'-hydroxy-6'-ethyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-diethyl-2,2 '-Biphenylene phosphinate), magnesium-bis (5,4', 6'-triethyl-1'-
Hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5-i-propyl-1'-hydroxy-2,2'-
Biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-i-propyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy
-6'-i-propyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-i-
Propyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4 ', 6'-tri-i-propyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5-s-butyl-1′-hydroxy-2,2′-biphenylene phosphinate),

[0013] Magnesium bis (1'-hydroxy-4'-s-
Butyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-6'-s-butyl-2,2'-biphenylene phosphinate), magnesium-bis (6,6'-
Di-s-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5,4 ', 6'-tri-s-butyl-1'-hydroxy-2,2'- Biphenylene phosphinate), magnesium-bis (5-t-butyl-1'-hydroxy-
2,2'-biphenylene phosphinate), magnesium-
Bis (1'-hydroxy-4'-t-butyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-6'-t-butyl-2,2'-biphenylenephosphinate) ), Magnesium-bis (5,6'-di-t-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5,4'-di-t-butyl-1 ') -Hydroxy-2,2'-
Biphenylene phosphinate), magnesium-bis (5,5'-di-t-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (6,4'-di-t-
Butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-
t-butyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4 ', 6'-tri-t-butyl-1'-hydroxy
-2,2'-biphenylene phosphinate), magnesium
-Bis (5-t-amyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-t-amyl-2,2'-biphenylene phosphinate) ), Magnesium-bis (1'-hydroxy-6'-t-amyl
-2,2'-biphenylene phosphinate), magnesium
-Bis (1′-hydroxy-4 ′, 6′-di-t-amyl-2,2′-biphenylene phosphinate), magnesium-bis (5,4 ′,
6'-tri-t-amyl-1'-hydroxy-2,2'-biphenylene phosphinate),

Magnesium-bis (5-t-octyl-1'-hydroxy-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-t-octyl-2,2'- Biphenylene phosphinate), magnesium-bis (1'-hydroxy-6'-t-octyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy
-4 ', 6'-di-t-octyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4', 6'-tri-t-octyl)
-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5-cyclohexyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy- 4'-cyclohexyl-2,2'-
Biphenylene phosphinate), magnesium-bis (1'-hydroxy-6'-cyclohexyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-cyclohexyl- 2,2'-biphenylene phosphinate), magnesium-bis (5,4 ', 6'-tri-cyclohexyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'- Hydroxy-4'-
Phenyl-2,2'-biphenylene phosphinate), magnesium-bis (5-benzyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-
Hydroxy-4'-benzyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-6'-benzyl-2,2'-biphenylenephosphinate), magnesium-bis (1'- Hydroxy-4 ', 6'-di-benzyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4', 6'-tri-benzyl-1'-hydroxy-2,2'-biphenylene Phosphinate), magnesium-bis [5-
(Α-methylbenzyl) -1′-hydroxy-2,2′-biphenylene phosphinate], magnesium-bis [1′-hydroxy-4 ′-(α-methylbenzyl) -2,2′-biphenylene phosphite Nate],

Magnesium-bis [1'-hydroxy-6'-
(Α-methylbenzyl) -2,2′-biphenylene phosphinate], magnesium-bis [1′-hydroxy-4 ′, 6′-
Di (α-methylbenzyl) -2,2′-biphenylene phosphinate], magnesium-bis [5,4 ′, 6′-tri (α-methylbenzyl) -1′-hydroxy-2,2′-biphenylene Phosphinate], magnesium-bis [5,4'-di (α, α-
Dimethylbenzyl) -1'-hydroxy-2,2'-biphenylene phosphinate], magnesium-bis (1'-hydroxy-4'-t-butyl-6'-methyl-2,2'-biphenylene phosphinate ), Magnesium-bis (1'-hydroxy-4'-benzyl-6'-methyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-cyclohexyl-6'-t -Butyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-benzyl)
-6'-t-butyl-2,2'-biphenylene phosphinate),
Magnesium-bis [1′-hydroxy-4 ′-(α-methylbenzyl) -6′-t-butyl-2,2′-biphenylenephosphinate], magnesium-bis (1′-hydroxy-4′-t -Butyl-6'-cyclohexyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-benzyl-6'-cyclohexyl-2,2'-biphenylenephosphinate), magnesium -Bis (1'-hydroxy-4'-t-butyl-6'-benzyl-2,2'-biphenylenephosphinate), magnesium-bis (1'-hydroxy-4'-cyclohexyl-6'-benzyl- 2,2'-biphenylene phosphinate), magnesium-bis (5,4'-di-t-butyl-6'-benzyl-1'-hydroxy-2,2'-biphenylene phosphinate) and magnesium-bis (5,4'-dicyclohexyl
-6'-benzyl-1'-hydroxy-2,2'-biphenylene phosphinate) and the like,

Particularly preferred are magnesium sulfate, basic magnesium sulfate, talc and magnesium-bis (1'-hydroxy-2,2'-biphenylene phosphinate).
These compounds B can be used alone, or two or more compounds B can be used in combination. The compounding ratio of the compound B is 0.01 to 100 parts by weight of the crystalline polyolefin.
To 1 part by weight, preferably 0.05 to 0.5 part by weight. 0.01
If the compounding ratio is less than 10 parts by weight, the effect of improving the impact resistance is not sufficiently exhibited, and the compound B excluding talc may exceed 1 part by weight, but a further improvement in the impact resistance can be expected. Not only impractical but also uneconomical,
When the amount of talc exceeds 1 part by weight, the effect of improving impact resistance is not achieved.

In the composition of the present invention, various additives which are usually added to the crystalline polyolefin, for example, antioxidants such as phenol type, thioether type and phosphorus type (however, excluding compound A), light-stable Agents, heavy metal deactivators (copper damage inhibitors; except for Compound A), clarifying agents,
β crystal nucleating agent, lubricant, antistatic agent, anti-fogging agent, anti-blocking agent, drip-free agent, flame retardant, flame retardant auxiliary, pigment, halogen scavenger, dispersant such as metal soap, or neutralizing agent , Organic and inorganic antibacterial agents, inorganic fillers (such as mica,
Clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, magnesium oxide, zinc oxide, calcium oxide, sulfide Zinc, barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber,
The inorganic filler or the organic filler surface-treated with a surface treating agent such as carbon black, graphite and metal fiber, and a coupling agent (for example, silane-based, titanate-based, boron-based, aluminate-based, and zircoaluminate-based). Fillers (eg, 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.

[0019]

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. Impact resistance: Evaluated by Izod impact test. That is, using the obtained pellets, length 63.5 mm, width 13 mm, thickness
A 3.5 mm test piece (with a notch) 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 6, Comparative Examples 1 to 9 MFR (discharge rate of molten resin for 10 minutes when a load of 2.16 kg at 230 ° C. is applied) as a crystalline polyolefin 6.
Compound A was added to 100 parts by weight of an unstabilized powdery crystalline propylene homopolymer of 0 g / 10 min as 9,10-dihydro
-9-oxa-10-phosphaphenanthrene-10-oxide or 2,6,8-tri-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , Compound B as magnesium sulfate, talc, magnesium
Bis (1'-hydroxy-2,2'-biphenylenephosphinate) or magnesium-bis (5,4 ', 6'-tri-t-butyl-1'-hydroxy-2,2'-biphenylenephosphinate ) And other additives are placed in a Henschel mixer (trade name) at the mixing ratios shown in Table 1 below and mixed with stirring for 3 minutes, and then at 200 ° C. with a twin-screw extruder having a diameter of 30 mm. The mixture was pelletized by melt kneading. Further, as Comparative Examples 1 to 9, a predetermined amount of each of the additives described in Table 1 described below was blended with 100 parts by weight of an unstabilized powdery crystalline propylene homopolymer having an MFR of 6.0 g / 10 minutes,
Pellets were obtained by melt-kneading according to Examples 1-6. A test piece used for evaluation of impact resistance was prepared by injection molding the obtained pellet at a resin temperature of 250 ° C and a mold temperature of 50 ° C. Using the obtained test pieces, impact resistance was evaluated by the test method described above. The results are shown in Table 1.

Examples 7 to 12, Comparative Examples 10 to 18 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,
Compound A as 2-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 6-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, basic magnesium sulfate, talc, magnesium-bis (5-
Cyclohexyl-1'-hydroxy-2,2'-biphenylene phosphinate) or magnesium-bis (1'-hydroxy-4'-phenyl-2,2'-biphenylene phosphinate) and other additives The quantified amount was placed in a Henschel mixer (trade name) at the compounding ratio shown in Table 2 below, and the mixture was stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. with a twin-screw extruder having a diameter of 30 mm to pelletize. As Comparative Examples 10 to 18, 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content: 8.5% by weight) having an MFR of 4.0 g / 10 min.
A predetermined amount of each of the additives listed in the table was blended, and
Pellets were obtained by a melt-kneading treatment according to 1212. A test piece used for evaluation of impact resistance was prepared by injection molding the obtained pellet at a resin temperature of 250 ° C and a mold temperature of 50 ° C.
Using the obtained test pieces, impact resistance was evaluated by the test method described above. The results are shown in Table 3.

Examples 13 to 18, Comparative Examples 19 to 27 Powdered crystalline ethylene-propylene random copolymer (ethylene content: 2.5% by weight) 90 as an unstabilized crystalline polyolefin having an MFR of 7.0 g / 10 min. 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) % As the compound A, 2-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 6- (α-methylbenzyl) -8- t-butyl-9,10-dihydro-9-oxa-10-
Phosphafenanthrene-10-oxide, basic magnesium sulfate, talc, magnesium as compound B
Bis (5-benzyl-1'-hydroxy-2,2'-biphenylene phosphinate) or magnesium-bis [1'-hydroxy-4 '-(α-methylbenzyl) -6'-t-butyl-2, 2'-
Biphenylene phosphinate] and other additives were placed in a Henschel mixer (trade name) at the mixing ratios shown in Table 3 below, and mixed by stirring for 3 minutes, followed by a twin-screw extruder having a diameter of 30 mm. The mixture was melt-kneaded at 200 ° C. and pelletized. In addition, MFRs as Comparative Examples 19 to 27
7.0g / 10min unstabilized powdered crystalline ethylene
-Total of 90% by weight of a propylene random copolymer (2.5% by weight of ethylene content) and 10% by weight of an unstabilized powdered Ziegler-Natta high-density ethylene homopolymer having an MI of 15.0 g / 10 minutes 100 parts by weight
A predetermined amount of each of the additives described in the table was blended, and Example 13 was added.
The pellets were obtained by melt-kneading in accordance with Nos. A test piece used for evaluation of impact resistance was prepared by injection molding the obtained pellet at a resin temperature of 250 ° C and a mold temperature of 50 ° C.
Using the obtained test pieces, impact resistance was evaluated by the test method described above. The results are shown in Table 3.

The compounds and additives according to the present invention shown in Tables 1 to 3 are as follows. Compound A [1]: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Compound A [2]: 2,6,8-tri-t-butyl-9,10-dihydro -
9-oxa-10-phosphaphenanthrene-10-oxide Compound A [3]: 2-cyclohexyl-9,10-dihydro-9-
Oxa-10-phosphaphenanthrene-10-oxide Compound A [4]: 6-phenyl-9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide Compound A [5]: 2-benzyl-9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide Compound A [6]: 6- (α-methylbenzyl) -8-t-butyl
-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Compound B [1]: Magnesium sulfate Compound B [2]: Basic magnesium sulfate (MgSO ₄ .5)
MgO · 8H ₂ O) Compound B [3]: Talc (average particle size 2～3Myu) Compound B [4]: Magnesium - bis (1'-hydroxy -
2,2′-biphenylene phosphinate) Compound B [5]: magnesium-bis (5,4 ′, 6′-tri-t-)
Butyl-1'-hydroxy-2,2'-biphenylene phosphinate) Compound B [6]: magnesium-bis (5-cyclohexyl-1'-hydroxy-2,2'-biphenylene phosphinate) Compound B [7 ]: Magnesium-bis (1'-hydroxy-
4'-phenyl-2,2'-biphenylene phosphinate) Compound B [8]: magnesium-bis (5-benzyl-1'-)
Hydroxy-2,2'-biphenylene phosphinate) Compound B [9]: magnesium-bis [1'-hydroxy-
4 '-(α-methylbenzyl) -6'-t-butyl-2,2'-biphenylene phosphinate]

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: bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite phosphorus antioxidant 2: bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite magnesium compound 1: magnesium hydroxide magnesium compound 2: magnesium carbonate magnesium compound 3: hydrotalcite (Mg _4.5 A
l ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O [Kyowa Chemical Industry Co.
HT-4A])

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

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 6 contain the compounds A and B according to the present invention, and Examples 1 to 6 and Comparative Example 1 (Compound A)
And those without compound B), it can be seen that Examples 1 to 6 are significantly superior in impact resistance. Comparing Comparative Examples 2 to 4 and Examples 1 to 6 in which only the compound B was blended, it can be seen that the impact resistances of Comparative Examples 2 to 4 are almost the same as Comparative Example 1 and are hardly improved. Comparing Comparative Example 5 containing only compound A with Examples 1 to 6, it is clear from Comparative Example 1 that the impact resistance of Comparative Example 5 is hardly improved. Comparative Example 6 in which magnesium compounds 1 to 3 other than compound B were blended instead of compound B of examples 1 to 6, respectively.
Comparing Examples 1 to 6 with Comparative Examples 6 to 8, the impact resistance of Comparative Examples 6 to 8 was improved but not sufficiently satisfactory. It can be seen that the effect of improving the impact resistance is remarkable. Then, when comparing Comparative Example 9 in which Compound B is used in combination with Compound A in a proportion exceeding the blending ratio of the present invention and Examples 1 to 6, Comparative Example 9 shows that Compound A and Compound B are blended. It can be seen that the effect of improving the impact resistance was hardly recognized. Therefore, it is clear that Comparative Examples which do not simultaneously satisfy the specific amounts of 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, the impact resistance obtained in the present invention is:
It can be said that this is a unique effect that can be seen only when compound A and compound B are respectively compounded in a specific amount to the crystalline polyolefin.

Tables 2 and 3 show the use of a mixture of a crystalline ethylene-propylene block copolymer, a crystalline ethylene-propylene random copolymer and a high-density ethylene homopolymer, respectively, as crystalline polyolefins. In these cases, the same effects as described above were confirmed.

[0030]

The composition of the present invention, when formed into a molded product, has remarkably excellent impact resistance.

Claims (1)

(57) [Claims] 1 to 100 parts by weight of a crystalline polyolefin, 0.01 to 1 part by weight of a cyclic phosphorus compound represented by the following general formula (1) and one or more magnesium compounds selected from the following: A crystalline polyolefin composition which is blended. Magnesium sulfate talc Magnesium phosphinate compound represented by the following general formula (2) Embedded image (Wherein, Ar _{1 to} Ar ₄ represent an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group, respectively)