JPH04154848A - Inorganic filler-containing polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, capable of providing formed products, excellent in tensile elongation and impact resistance by blending a crystalline polyolefin with prescribed amounts of an inorganic filler and a cyclic phosphorus compound (metallic salt) having a specific structure. CONSTITUTION:The objective composition is obtained by blending (A) 100 pts.wt. composition prepared by blending (i) a crystalline polyolefin with (ii) 10-30wt.% inorganic filter such as talc or asbestos with (B) 0.05-1 pt.wt. cyclic phosphorus compound such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide expressed by formula I and (C) 0.05-1 pt.wt. metallic salt of a cyclic phosphorus compound such as 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide expressed by formula II [Ar1 to Ar4 are (alkyl)arylene, aralkylarylene, etc.; M is Zn or Pb].

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyolefin compositions containing inorganic fillers. More specifically, a crystalline polyolefin containing an inorganic filler, a cyclic phosphorus compound with a specific structure, and a metal salt of a cyclic phosphorus compound with a specific structure in specific amounts is used to produce a product with excellent tensile elongation and impact resistance. The present invention relates to an inorganic filler-containing polyolefin composition from which molded articles can be obtained.

[Prior Art] Polyolefin compositions containing inorganic fillers generally yield molded products with excellent rigidity, heat-resistant rigidity, and dimensional stability.
It is used to manufacture various molded products such as press (stamping) molded products.

However, although inorganic filler-containing polyolefin compositions have the above-mentioned excellent properties, they have the disadvantage that the tensile elongation and impact resistance of molded articles obtained from the compositions are reduced. For this reason, the present applicant has developed an inorganic filler-containing polyolefin composition that has improved tensile elongation and impact resistance without impairing the inherently excellent properties of molded articles obtained from the inorganic filler-containing polyolefin composition, that is, crystalline We have previously proposed a composition in which polyolefin is blended with specific amounts of an inorganic filler, a cyclic phosphorus compound having a specific structure, and a fatty acid metal salt or an alkali earth metal salt having a specific structure (Japanese Patent Application Laid-Open No. 2-22349). Publication No.).

[Problems to be Solved by the Invention] The present inventor was not satisfied with the inorganic filler-containing polyolefin composition proposed in JP-A-2-22349, and conducted further research.

As a result, the present inventor found that a composition obtained by blending a crystalline polyolefin with specific amounts of an inorganic filler, a cyclic phosphorus compound having a specific structure, and a metal salt of a cyclic phosphorus compound having a specific structure has high rigidity and heat-resistant rigidity. They also discovered that the composition provides a molded article with improved tensile elongation and impact resistance without impairing dimensional stability, and based on this knowledge, the present invention was completed.

As is clear from the above description, the object of the present invention is to provide a molded product with improved tensile elongation and impact resistance without impairing the rigidity, heat-resistant rigidity, and dimensional stability of the molded product. An object of the present invention is to provide an inorganic filler-containing polyolefin composition that provides the following.

[! Means to solve one problem] The present invention has the following configuration.

(1) A cyclic phosphorus compound represented by the following general formula [1] (hereinafter referred to as compound A) and the following: An inorganic filler-containing polyolefin composition containing 0.05 to 1 part by weight of a metal salt of a cyclic phosphorus compound represented by general formula [11] (hereinafter referred to as compound B).

(However, in the formula, Ar and ~Ar4 represent an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group, or an aralkylarylene group,
M represents zinc or button, respectively. ) (2) 0.05 to 1 part by weight of Compound A, Compound B, and aliphatic amine are each blended with 100 parts by weight of a composition in which 10 to 30% by weight of an inorganic filler is blended with crystalline polyolefin. Polyolefin composition containing inorganic filler.

(3) Compound A was added to 100 parts by weight of a composition containing 10 to 30% by weight of an inorganic filler in a crystalline polyolefin.
and 0.05 to 1 part by weight of Compound B and 0.05 to 1 part by weight of fluorophosphite represented by the following general formula [m].
．． 001 to 1 part by weight of an inorganic filler-containing polyolefin composition.

(However, in the formula, R is an alkylidene group having 1 to 4 carbon atoms or sulfur, Ar5 and Ar6 are an alkylarylene group or a cycloalkylarylene group, n 1.t
Indicates O or 1, respectively. ) The crystalline polyolefin used in the present invention is ethylene, propylene, butene-
1. Crystalline homopolymers of α-olefins such as pentene-1,4-methyl-pentene-1, hexene-1, octene-1, crystalline or low-crystalline random copolymers of two or more of these α-olefins Polymers or crystalline block copolymers, copolymers of the above-mentioned α-olefins and vinyl acetate or acrylic esters, saponified products of the copolymers, copolymers of these α-olefins and unsaturated silane compounds , copolymers of these α-olefins and unsaturated carboxylic acids or their anhydrides, reaction products of the copolymers and metal ion compounds, crystalline homopolymers of the above-mentioned α-olefins, crystalline or low A modified polyolefin obtained by modifying a crystalline random copolymer or a crystalline block copolymer with an unsaturated carboxylic acid or its derivative, a crystalline homopolymer of the above-mentioned α-olefin, a crystalline or low-crystalline random copolymer, or Examples include silane-modified polyolefins in which a crystalline block copolymer is modified with an unsaturated silane compound, and these crystalline polyolefins can of course be used alone, but two or more types of crystalline polyolefins can be used in combination. You can also do it. In addition, various synthetic rubbers (e.g., amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene terpolymer, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene) are added to the above-mentioned crystalline polyolefin. , chlorinated polypropylene, fluororubber,
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 resins (e.g. polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, fluororesin, Petroleum resins (e.g. C5 petroleum resins, hydrogenated C5 petroleum resins, C9 petroleum resins, hydrogenated C9
petroleum resin, C5-CQ copolymerized petroleum resin, hydrogenated C5-
C9 copolymerized petroleum resin, acid-modified C9 petroleum resin, etc.), D
CPD trees (e.g. cyclopentadiene petroleum resins, hydrogenated cyclopentadiene petroleum resins, cyclopentadiene-C5 copolymer petroleum resins, hydrogenated cyclopentadiene petroleum resins)
C5 copolymerized petroleum resin, cyclopentadiene-C9 copolymerized petroleum resin, hydrogenated cyclopentadiene-〇, copolymerized petroleum resin, cyclopentadiene-c 5-C9 copolymerized petroleum a fat, hydrogenated cyclopentadiene-〇 (DCPD resin with a softening point of 80 to 200℃ such as Ri-C9 copolymerized petroleum resin) etc.)
It is also possible to use a mixture of them. Crystalline propylene homopolymer, crystalline propylene copolymer containing 70% by weight or more of a propylene component, including crystalline ethylene-propylene random copolymer, crystalline propylene-butene-
1 random copolymer, crystalline ethylene-propylene-butene-13 copolymer, crystalline propylene-hexene-
Particularly preferred are buty-243 copolymers and mixtures of two or more thereof.

Inorganic fillers used in the present invention include 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.

Examples include carbon fibers, carbon blanks, graphite, and metal fibers, with talc having an average particle size of 2 to 10 μm being particularly preferred. In addition, these inorganic fillers can be used as surface treatment agents such as higher fatty acids, higher fatty acid esters, higher alcohols, higher fatty acid monoamides, higher fatty acid bisamides, silane coupling agents, titanate camping agents, boron coupling agents, and aluminate-based coupling agents. The surface may be previously treated with a known surface treatment agent such as a coupling agent or a zircoaluminate coupling agent.

Not only can these inorganic fillers be used alone, but also two or more types of inorganic fillers can be used in combination.

The blending ratio of the inorganic filler is 10 to 30% by weight based on the composition consisting of the crystalline polyolefin and the inorganic filler.
It is. If the weight is less than 10% by weight, the resulting molded product will have insufficient rigidity, heat-resistant rigidity, and dimensional stability;
If it exceeds 0% by weight, the tensile elongation and impact resistance will decrease, which is not practical.

Compound A used in the present invention includes 9110-dihydro-9-oxa-10-phosphonoaphenanthrene-1
0-oxide, 1-methyl-9,10-dihydro-9
-Oxa-10-phosphonophenanthrene-10-oxide, 2-methyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-methyl-9,10-dihydro -9-oxa-1
0-phosphonoaphenanthrene-10-oxide, 7
-Methyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 8-methyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide ,6. Dimethyl-9゜10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,6.8-trimethyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene -10-oxide, 2-ethyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 6-ethyl-9,
10-dihydro9-oxa-10-phosphonophenanthrene-10-oxide, 8-ethyl-9,10-
Dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6,8-diethyl-9,10-
Dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,6.8- ) diethyl-9
, 10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2-i-propyl-9
, 10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-1-propyl-9
, 10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 8-i-propyl-9
, 10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6. Di-propyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,6.8-
Treatypropyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2-s-butyl-9,10-dihydro-9-oxa-
10-phosphonoaphenanthrene-10-oxide,
6-s-butyl-9,10-dihydro-9-oxa-1
0-phosphonoaphenanthrene-10-oxide, 8
-s-butyl-9゜10-dihydro-9-oxa-10
-Phosnoaphenanthrene-10-oxide, 1,
8-di-S-butyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,6.8-)di-S-butyl-9,10-dihydro-9 -Oxa-10-Phosnoaphenanthrene-10
-oxide, 2-1-butyl-9,10-dihydro-
9-Oxa-10-phosphonophenanthrene-10-
Oxide, 6-t-butyl-9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-1O-oxide, 8-t-butyl-9゜10-dihydro-9-
Oxa-10-phosphonophenanthrene-10-oxide, 1,6-di-butyl-9,10-dihydro-9-oxa-1O-phosphonophenanthrene-10
-oxide, 2,6-di-butyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 2,7-di-butyl-9,1
0-dihydro 9-oxa-10-phospho-phenanthrene-10-oxide, 2,8-di-butyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 6,8 -di-butyl-9.10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,6.8-
Tri-t-butyl-9,10-dihydro-9-oxa-
10-phosphonoaphenanthrene-10-oxide,
2-t-amyl-9゜10-dihydro-9-oxa-1
0-phosphonoaphenanthrene-10-oxide, 6
-t-amyl-9,10-dihydro-9-oxa-10
-Phosphenthrene-10-oxide, 8-
t-amyl-9,10-dihydro-9-oxa-10-
Phosnoaphenanthrene-10-oxide, 6,8
- Di-amyl-9,10-dihydro-9-oxa-
10-phosphonoaphenanthrene-10-oxide,
2,6.8-) diamyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10
-oxide, 2-7-octyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10
-oxide, 6-t-octyl-9,1O-dihydro-9-oxa-10-phosphonoaphenanthrene-10
-oxide, 8-thi-octyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10
-Oxide, 6,8-di-1-octyl-9,10-
Dihydro 9-oxa-10-phosphonoaphenanthrene-10-oxide, 2.6.8-) Dihydro-9,10-dihydro 9-oxa-10-phosphonoaphenanthrene-10-oxide, 2 -Cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene -10-oxide, 8-cyclohexyl-9,10-dihydro-9-oxa-10-
Phosnoaphenanthrene-10-oxide, 6.8
-di-cyclohexyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,6.8-tricyclohexyl-9,10-
Dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-phenyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-
10-oxide, 2-benzyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10
-oxide, 6-benzyl-9,10-dihydro-9
-oxa-10-phosfuphenanthrene-10~oxide, 8-hensyl-9,]]0-dihydro9-
Oxer 10 phosphonoaphenanthrene-10-oxide, 6,8-di-benzyl-9,IO-dihydro-9
-Oxa-10-phosphonoaphenanthrene-10-oxide, 2,6.8-tribenzyl-9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-(α-methylbenzyl)
-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-(α-methylbenzyl) -9,10-dihydro-9-oxa-10
-Phosnoaphenanthrene-10-oxide, 8-
(α-Methylbenzyl)-9°10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 6. Di(α-methylbenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6.8-1-ly(α-methylbenzyl)-9,10- dihydro-9-oxa-10-
Phosphor phenanthrene-10-oxide, 2,6
-di(α,α-dimethylbenzyl) -9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-
10-oxide, 8-butyl-8-methyl-9,
10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-benzyl-8-methyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-cyclohexyl-8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-IO-oxide, 6-benzyl-8-t-butyl-9,10-dihydro- 9-oxa-10-phosphaenanthrene-1
0-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-phosphonophenanthrene-10-
Oxide, 6-benzyl-8-cyclohexyl-9゜10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-t-butyl-8-benzyl-9゜10-dihydro-9- Oxa-10-phosphonoaphenanthrene-10-oxide, 6-cyclohexyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 2,6-di Monobutyru 8-benzyru 9,1
0-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide and 2,6-dicyclohexyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene- Examples include 10-oxide. Particularly preferred is 9.10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide. Not only can these compounds A be used alone, but also two or more kinds of compounds A can be used in combination.

The compounding ratio of the compound A is 0.05 to 1 part by weight, preferably 0.05 to 0.0 parts by weight, based on 100 parts by weight of a composition containing 10 to 30 weight % of an inorganic filler to a crystalline polyolefin.
．． 5 parts by weight. If the amount is less than 0.05 parts by weight, the effect of improving tensile elongation and impact resistance will not be sufficiently exhibited, and if it is more than 1 part by weight, it will not improve tensile elongation and impact resistance. Not only is it not effective and impractical, but it is also uneconomical.

Compound B used in the present invention is zinc salt and lead salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide.

1-methyl-10-hydroxy-9,10-dihydro-
9-Oxa-10-phosphonophenanthrene-10-
Zinc and lead salts of 2-methyl-10-hydroxy-9゜10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-methyl-10- Hydroxy-9,10-
Zinc and lead salts of dihydro-9-oxa-IO-phosphonophenanthrene-10-oxide, 7-methyl-10-hydroxy-9,1O-dihydro-9-oxa-10-phosphaphenanthrene Zinc and lead salts of 10-oxide, 8-methyl-10-hydroxy-
Zinc and lead salts of 9,10-dihydro-9-oxa-10-phosfuphenanthrene-10-oxide,
6,8-dimethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-
10-Zinc and lead salts of oxides, 2,6.8-
) trimethyl-10-hydroxy-9,10-dihydro-
9-Oxa-10-phosphonophenanthrene-10-
Zinc and lead salts of 2-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 6-nityl-lO-hydroxy -9,10-
Zinc and lead salts of dihydro-9-oxa-10-phosfuphenanthrene-10-oxide, 8-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosfuphenanthrene-10- Zinc and lead salts of oxide, zinc and lead salts of 6,8-diethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,6° 8-triethyl-10-hydroxy-9
, 10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide zinc and lead salts, 2
-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-1
8- Zinc and lead salts of i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6,8-di-propyl-10-hydroxy-
Zinc and lead salts of 9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide,
2,6.8-) Zinc and lead salts of di-1-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 2-s-butyl -10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-
Zinc and lead salts of 10-oxide, 6-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 8- Zinc and lead salts of s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 1,8-di-S-butyl-10-hydroxy- 9,
Zinc and lead salts of 10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,
6.8-) di-S-butyl-10-hydroxy-9,1
Zinc and lead salts of 0-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2-t
-butyl-10-hydroxy-9,10-dihydro-9
-Zinc and lead salts of oxa-10-phosphonophenanthrene-10-oxide, 6-tert-butyl-10-
Hydroxy-9゜10-dihydro-9-oxa-10-
Zinc and lead salts of phosphonophenanthrene-10-oxide, 8-shebutyl-10-hydroxy-9,
Zinc and lead salts of 10-dihydro-9-oxa-10-phosfuphenanthrene-10-oxide, 1,
Zinc and lead salts of 6-di-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2,6-di-L-butyl-10-hydroxy- 9,10-dihydro-
9-Oxa-10-phosphonophenanthrene-10-
Zinc and lead salts of 2,7-di-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphuphenanthrene-10-oxide, 2.8- di-t-butyl-10
-hydroxy-9,10-dihydro-9-oxa-10
- Zinc and lead salts of phosphonophenanthrene-10-oxide, 6,8-di-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphphenanthrene-10-oxide Zinc and lead salts, 2,6.8-) Zinc and lead salts of di-butyl-10-hydroxy-9゜10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 2- Sheaamyl-10-hydroxy-9,10-
Zinc and lead salts of dihydro-9-oxa-10-phosnoaphenanthrene-10-oxide, 6-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosnoaphenanth Zinc and lead salts of rene-10-oxide, zinc and lead salts of 8-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6,8-di-t-amyl-10-hydroxy-
Zinc and lead salts of 9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide,
2,6.8-)di-t-amyl-10-hydroxy-
Zinc and lead salts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
Zinc and lead salts of 2-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-humesphaphenanthrene-10-oxide, 6-octyl-10-hydroxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene - Zinc and lead salts of 0-oxide, 8-tert-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene Zinc and lead salts of aphenanthrene-10-oxide, 6.8-di-1-octyl-10-hydroxy-9.10-dihydro-9-oxa-10-phosphatide, zinc and lead salts of phenanthrene-10-oxide salt,
2,6.8-tri-t-octyl-10-hydroxy-
Zinc and lead salts of 9,1O-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide,
Zinc and lead salts of 2-cyclohexyl-10-hydroxy-9゜10-dihydro-9-oxa-10-phosphaphenanthrene O-oxide, 6-cyclohexyl-10-hydroxy-9,10-dihydro -9-oxa-10-phosphonophenanthrene-10-oxide zinc and lead salts, 8-cyclohexyl-10-
Hydroxy-9,10-dihydro-9-oxa-10-
Zinc and lead salts of phosphonophenanthrene-10-oxide, 6,8-di-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10- Zinc and lead salts of oxides, 2,6.8-) dicyclohexyl-10-
Hydroxy-9,10-dihydro-9-oxa-10-
Zinc and lead salts of phosphonophenanthrene-10-oxide, 6-phenyl-10-hydroxy-9,1
Zinc and lead salts of 0-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2-benzyl-10-hydroxy-9,10-dihydro-9-
Zinc and lead salts of oxa-10-phosphonophenanthrene-10-oxide, zinc salts of 6-benzyl-10-hydroxy-9°10-dihydro-9-oxa-10-phosphophenanthrene-1O-oxide salts and lead salts, 8-benzyl-10-hydroxy-9,10-
Zinc and lead salts of dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6,8-di-benzyl-10-hydroxy-9,10-dihydro-
9-Oxa-10-phosphonophenanthrene-10-
Zinc and lead salts of oxides, 2,6°8-tribenzyl-10-hydroxy-9,10-dihydro-9-
Zinc and lead salts of oxa-10-phosphonophenanthrene-10-oxide, 2-(α-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene -10-oxide zinc and lead salts, 6-(α-methylbenzyl)-
10-hydroxy-9,10-dihydro-9-oxa-
Zinc and lead salts of 10-phosphonophenanthrene-10-oxide, 8-(α-methylbenzyl)-10
-hydroxy-9,10-dihydro-9-oxa-10
-Zinc and lead salts of phosphonophenanthrene-10-oxide, 6,8-di(α-methylbenzyl)-1
0-hydroxy-9,10-dihydro-9-oxa-1
Zinc and lead salts of 0-phosphonophenanthrene-10-oxide, 2,6.8-)su(α-methylbenzyl)-10-hydroxy-9,10-dihydro-9
-Zinc and lead salts of oxa-10-phosphonophenanthrene-10-oxide, 2,6-di(α,α-dimethylbenzyl)-10-hydroxy-9,10-dihydro-9-oxa-10 -Phosnoaphenanthrene-
Zinc and lead salts of 10-oxide, 6-t-butyl-8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10
-zinc and lead salts of oxides, 6-benzyl-8-
Methyl-10-hydroxy-9,10-dihydro-9-
Zinc and lead salts of oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-8-
t-Butyl-10-hydroxy-9,10-dihydro-
9-Oxa-10-phosphonophenanthrene-10-
Oxide zinc and lead salts, 6-benzyl-g-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-
Zinc and lead salts of 10-oxide, 6-(α-methylbenzyl)-8-t-butyl-10-hydroxy-
Zinc and lead salts of 9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide,
Zinc and lead salts of 6-tert-butyl-8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-benzyl-8- Zinc and lead salts of cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 6-butyl-8-benzyl-10-hydroxy- Zinc and lead salts of 9,10-dihydro-9-oxa-10-phosfuphenanthrene-10-oxide, 6-cyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10 -Zinc and lead salts of phosphaphenanthrene-10-oxide, 2,6-dibutyl-8-benzyru]0-
Hydroxy-9,10-dihydro-9-oxa-10-
Zinc and lead salts of phosphonophenanthrene-10-oxide and 2,6-dicyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-
Examples include zinc salts and lead salts of oxa-10-phosfuphenanthrene-10-oxide. Especially 10
-Hydroxy-9,1O-dihydro-9-oxa-1O
-Zinc and lead salts of Phosfabuenanthrene-10-oxide are preferred. Not only can these compounds B be used alone, but also two or more kinds of compounds B can be used in combination. The blending ratio of the compound B is 10 to 10% by weight of the inorganic filler in the crystalline polyolefin.
0.05 to 1 part by weight, preferably 0.05 to 1 part by weight.
05 to 0.5 parts by weight. If the amount is less than 0.05 part by weight, the effect of improving tensile elongation and #impact property will not be sufficiently exhibited, and it may be more than 1 part by weight.

No further improvement in tensile elongation and impact resistance can be expected, which is not only impractical but also uneconomical.

In the composition of the present invention, it is preferable to use an aliphatic amine in combination because the effect of improving stiffness and impact resistance is exhibited synergistically. Aliphatic amines include octylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, cocoaamine, tallowamine, soyamine, N
, N-dicocoamine, N, N-citaroamine, N, N
-Shisoamine, 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-citallow amine, N-methyl-N , N-dicocoamine, N-
Oleyl-1,3-diaminopropane, N-crow-1
, 3-diaminopropane, hexamethylenediamine, N
-Lauryl-N,N,N-)dimethylammonium chloride, N-palmityl-N,N,N-)dimethylammonium chloride, N-stearyl-N,N
, N-trimethylammonium chloride, N-tocosyl-N.

N,N-) dimethylammonium chloride, N-coco N,N,N-trimethylammonium chloride, N
l1mI-N,N,N-trimethylammonium chloride, N-soy-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-dicoko N,N-dimethylammonium chloride, N,N-citaro-N,N-
Dimethylammonium chloride, N,N-Shisoee 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-hydroxy ethyl) 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)tocosylaminobetaine, N,N-bis(2-hydroxyethyl)octacosylaminobetaine, 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)tocodylamine, N-(2-hydroxyethyl)oftacosylamine, 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) ) tocodylamine, N-methyl-N-(2-hydroxyethyl)oftacosylamine, 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-and-droxyethyl)pentadecylamine, N,N-bis(2-hydroxyethyl)palmitylamine, N,N-bis(2-hydroxyethyl)stearylamine, N,N-bis(2- hydroxyethyl)oleylamine, N,N-bis(2-hydroxyethyl)tocodylamine, N,N-bis(2-hydroxyethyl)
N,N-bis(2-hydroxyethyl) aliphatic amines, such as oftacosylamine, N,N-bis(2-hydroxyethyl)cocoamine, N,N-bis(2-hydroxyethyl)tallowamine, TAN.

N-bis(2-hydroxyethyl) aliphatic amine and lauric acid, myristic acid, palmitic acid, stearic acid,
mono- or diesters with fatty acids such as oleic acid,
Polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene cocoa amino ether, polyoxyethylene cocoa amino ether, N, N, N', N'-tetra(2-hydroxy ethyl)-1゜3-diaminopropane, N, N, N', N''
-tetra(2-hydroxyethyl)-1,6-diamithexane, N-lauryl-N,N',N'-tris(2
-hydroxyethyl)-1,3-diaminopropane, N
-stearyl-N.

N'', N'-) lis(2-hydroxyethyl) -1,
3-diaminopropane, N-coco-N, N', N'-)
Lis(2-hydroxyethyl)-1,3-diaminopropane, N-tallow N,N',N'-tris(2-hydroxyethyl)-1,3-diaminopropane, N,N-
Dicoco N', N'-bis(2-hydroxyethyl)
-1,3-diaminopropane, N,N-citaro-N
',N'-bis(2-hydroxyethyl)-1,3-
Diaminopropane, N-coco-N.

N', N'-)lis(2-hydroxyethyl) -1,
6-diamithexane, N-tallow N, N', N'-
Tris(2-hydroxyethyl)-1,6-diamithexane, N.

N-dicoko N',N'-bis(2-hydroxyethyl)-1,6-diamithexane and N,N-citaro-N',N'-bis(2-hydroxyethyl)
Examples include -1,6-diamithexane, especially N
, N-bis(2-hydroxyethyl)alkylamine is preferred.

Not only can these aliphatic amines be used alone, but also two or more aliphatic amines can be used in combination.

The blending ratio of the aliphatic amine is 0.05 to 1 part by weight, preferably 0.05 parts by weight, based on 100 parts by weight of a composition containing 10 to 30% by weight of an inorganic filler in a crystalline polyolefin.
~0.5 parts by weight.

In the composition of the present invention, by using in combination a fluorophosphite represented by the following formula [m],
It is preferable to use them together because they synergistically exhibit the effect of improving rigidity and impact resistance.

(However, in the formula, R represents an alkylidene group having 1 to 4 carbon atoms or sulfur, Ar5 and Ar6 represent an alkylarylene group or a cycloalkylarylene group, and n represents 0 or 1, respectively.) As the fluorophosphite, 2, 2″-bis(4,6-di-butylphenyl)fluorophosphite, 2,2′-bis(4-methyl-6-t-butylphenyl)fluorophosphite, 2,2′-bis(4- (amyl-6-methylphenyl)fluorophosphite, 2,2'-bis(4-s
-eicosylphenyl)fluorophosphite 2.2
'-methylene-bis(4-methyl-6-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-butylphenyl)fluorophosphite, 2,21-ethylidene-bis(4- Methyl-6
-Sheeptylphenyl) fluorophosphite, 2,
2'-ethylidene-bis(4-ethyl-6-L-butylphenyl)fluorophosphite, 2.2'-ethylidene-bis(4-s-butyl-6-t-butylphenyl)fluorophosphite, 2, 2'-ethylidene-bis(4,6-di-butylphenyl)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-octylphenyl)fluorophosphite, 2,2'-thio- Bis(5-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-butylphenyl)fluorophosphite and 2°2′-thio-bis(4-t- Examples include amyl phenyl) fluorophosphite, particularly 2,2'-bis(
4゜6-di-butylphenyl)fluorophosphite, 2,2'-methylene-bis(4-methyl-6-t)
-butylphenyl)fluorophosphite, 2,2'
-methylene-bis(4,6-di-butylphenyl)
Fluorophosphite, 2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)fluorophosphite, 2,2'-ethylidene-bis(11,6-
Preferred are di-t-butylphenyl)fluorophosphite and 2,2'-thio-bis(4-methyl-6-t-butylphenyl)fluorophosphite. These fluorophosphites can be obtained by the manufacturing method described in JP-A-63-227594.

That is, according to the reaction formula below, diazilene monohalophosphite (diazylene monochlorofusphite or diazilene A fluorinating reagent (e.g. HF,
LiF, NaF, KF, RbF, Cs
F, SbF3, SbF5, AgF, HgF2, C
fluorophosphite can be obtained by reacting F3, SF, etc.).

(However, in the formula, R is an alkylidene group having 1 to 4 carbon atoms or sulfur, Ar5 and Ar6 are an alkylarylene group or a cycloalkylarylene group, X is chlorine or bromine, YF is a fluorinating reagent, and n is ○ or 1, respectively).
It can also be obtained by the manufacturing method described in JP-A-1-135789, which is an improved method of the manufacturing method described in No. 94. That is, when reacting the above-mentioned diazilene monohalophosphite with a fluorinating reagent, a hydrogen halide salt of a pyridine type compound (for example, pyridine hydrochloride, pyridine hydrobromide, pyridine fluoride) is used as a fluorination reaction accelerator. Hydrogen salt, picoline hydrochloride,
Fluorophosphites can also be obtained by reaction in the presence of quinoline hydrochloride, nicotinic hydrochloride, 2-aminopyridine hydrochloride, 2-phenylpyridine hydrochloride, etc.). Not only can the fluorophosphite be used alone, but also two or more fluorophosphites can be used in combination. The blending ratio of the fluorophosphite is 10% to 10% of the inorganic filler to the crystalline polyolefin.
0.0% per 100 parts by weight of the composition containing 30% by weight.
001 to 1 part by weight, preferably 0.01 to 0.5 part by weight.

The composition of the present invention contains various additives normally added to crystalline polyolefins, such as antioxidants such as phenols, thioethers, and phosphorus (excluding compound A), light stabilizers, and heavy metals. Deactivating agents (excluding compound A), clarifying agents, nucleating agents, lubricants, antistatic agents, antifogging agents, anti-blocking agents, anti-drop agents, flame retardants, flame retardant aids, pigments, Radical generators such as oxides, halogen scavengers, dispersants or neutralizing agents such as metal soaps, organic fillers (e.g. wood flour, valves, waste paper, synthetic fibers, natural fibers, etc.) may be used to defeat the purpose of the present invention. Can be used together within the range.

The composition of the present invention includes a crystalline polyolefin, an inorganic filler,
A year-round mixing device such as a Henschel mixer (trade name) for predetermined amounts of Compound A and Compound B and the various additives mentioned above that are usually added to crystalline polyolefins.
, a super mixer, a ribbon blender, a Pan Bali mixer, etc., and a normal single-screw extruder, twin-screw extruder, Brabender or roll, etc., to a melt mixing temperature of 1.
It can be obtained by melt-kneading and pelletizing at 50°C to 300°C, preferably 180°C to 270°C. The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding.

[Effect] Although the mechanism of action of the combined use of Compound A and Compound B in the present invention is not clear, it is presumed to be based on the following mechanism of action. In other words, the zinc ions or lead ions of compound B act on compound A to form a coordinate bond or ionic bond between compound A and compound B, thereby improving tensile elongation and impact resistance. This is thought to work to improve the results.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

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

1) Rigidity: Evaluated by bending test. That is, using the obtained pellets, a test piece with a length of 100 m, a medium size of 10 mm, and a thickness of 4 bars is made by injection molding, and the flexural modulus of elasticity is measured using the test piece (according to JIS K 7203). The rigidity was evaluated by this.

2) Tensile elongation: Evaluated by tensile test. That is, using the obtained pellets, the length was 175 mm, i+]Ovl,
A J ISI test piece with a thickness of 3.3 nwn was prepared by injection molding, and the tensile elongation was measured using the test piece (J ISI
SK7], 1.3).

3) Impact resistance: Evaluated by Izod impact test. That is, using the obtained pellets, the length is 63.5 m and the width]
A test piece (with a notch) of 3nwn and 3.5nn thickness was made by injection molding, and the impact resistance was determined by measuring the Izot impact strength at 23°C (according to JIS K71] 0). evaluated.

Examples 1 to 12, Comparative Examples 1 to 9 As a crystalline polyolefin, MFR (discharge m of molten resin for 10 minutes when applying a load of 2.16 kg at 230°C) 6.0 g/unstabilized for 10 minutes To a total of 100 parts by weight consisting of 80% by weight of a powdered crystalline propylene homopolymer and 20% by weight of talc with an average particle size of 6 to 8μ as an inorganic filler, 9°10- as Compound A was added.
Dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 2,6,8-tri-butyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide or 2 -Cyclohexyl-9゜10-dihydro-9-oxa-10-phosphaphenanthrene O-oxide, 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene as compound B Zinc salt of -10-oxide, 2,6.8-) so-t-butyl-10-
Hydroxy-9,10-dihydro-9-oxa-10-
Zinc salt of phosphonophenanthrene-10-oxide or 2-cyclohexyl-10-hydroxy-9,
Predetermined amounts of each of the zinc salt of 10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide and other additives were added to a Henschel mixer (trade name) at the mixing ratios listed in Table 1 below. After stirring and mixing for 3 minutes, the mixture was heated to 250℃ using a twin-screw extruder with a diameter of 30IIITl.
The mixture was melt-kneaded and pelletized. Also, comparative example 1~
Total 1 consisting of 80% by weight of unstabilized powdered crystalline propylene homopolymer and 20% by weight of talc with an average particle size of 6 to 8 μm, with an MFR of 6.0 g/10 min.
00 parts by weight were blended with predetermined amounts of each of the additives listed in Table 1 below, and subjected to melt mixing treatment according to Examples 1 to 12 to obtain pellets.

The test pieces used for evaluation of rigidity, tensile elongation, and impact resistance were obtained by heating the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C.
tIIl was manufactured by injection molding.

Using the obtained test pieces, rigidity, tensile elongation, and impact resistance were evaluated according to the test method described above.

These results are shown in Table 1.

Examples 13-24, Comparative Examples 10-18 M F R4,0g710 as crystalline polyolefin
unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight)
9.10-dihydro-9-oxa-10-phosphonoaphenanthrene-10- as compound A was added to a total of 100 parts by weight consisting of 70% by weight and 30% by weight of talc with an average particle size of 6 to 8μ as an inorganic filler. Oxide, 2,6.8
-) Dibutyl-9,10-dihydro-9-oxa-O-phosphaphenanthrene-10-oxide or 6-phenyl-9,10-dihydro-9-oxa-10-phosphonophenanthrene- 10-oxide, 6-phenyl-10-hydroxy- as compound B
Zinc salt of 9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide, 2-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene -10-oxide zinc salt or 6-(α-methylbenzyl)-8-
Butyl-10-hydroxy-9,10-dihydro-
9-Oxa-]]O-phosphafluorene-10
Predetermined amounts of zinc salt of oxide and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 2 below, stirred and mixed for 3 minutes, and then
The mixture was melt-kneaded and pelletized at 250° C. using a 0-dish twin-screw extruder. In addition, as Comparative Examples 10 to 18, MF
Unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) with R of 4.0 g/10 min 70% by weight and average particle size 6-8μ
A total of 100 parts by weight consisting of 30% by weight of talc was blended with predetermined amounts of each of the additives listed in Table 2 below, and melt-kneaded according to Examples 13 to 24 to obtain pellets.

The test pieces used for evaluation of rigidity, tensile elongation, and impact resistance were the obtained pellets at a resin temperature of 250°C, a mold temperature of 5.
Prepared by injection molding at 0°C.

Using the obtained test pieces, rigidity, tensile elongation, and impact resistance were evaluated according to the test method described above.

These results are shown in Table 2.

Examples 25-36, Comparative Examples 19-27 M F R1.0g/1 as crystalline polyolefin
0 min unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene content 2,5% by weight
) 70% by weight, MI (load 2.16k at 190°C
Discharge amount of 78 molten resin in 10 minutes when adding g) 1
0g710min unstabilized powdered Ziegler
A total of 100 parts by weight of 20% by weight of Natsuta-based high-density ethylene homopolymer and 10% by weight of talc with an average particle size of 6 to 8μ as an inorganic filler was added with 9°10-
dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, 2,6.8-) di-butyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide or 2-benzyl-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide, as compound B 10-hydroxy-9゜]]0-dihydro-9-oxa-10-phosphaphenanthrene- Lead salt of 10-oxide, 2,6,8-tri-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide lead salt or 2-cyclohexyl -10-Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide lead salt and other additives were mixed in the prescribed amounts in the proportions listed in Table 3 below. After putting it in Henschel mixer (trade name) and stirring for 3 minutes,
The mixture was melt-kneaded and pelletized at 250°C using a twin-screw extruder with a diameter of 30 mm. Also, as Comparative Examples 19 to 27, M
Unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene content 2.5 wt%) with FR 7.0+:/10 min 70 wt%, MI 10 g/
A total of 100 parts by weight of 20% by weight of a powdered Ziegler-Natsuta high-density ethylene homopolymer that has not been stabilized for 10 minutes and 10% by weight of talc with an average particle size of 6 to 8 μm was added to a total of 100 parts by weight as described in Table 3 below. Predetermined amounts of each additive were blended and melt-kneaded according to Examples 25 to 36 to obtain pellets.

The test pieces used for evaluation of rigidity, tensile elongation, and impact resistance were obtained by heating the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C.
Prepared by injection molding at °C.

Using the obtained test piece, rigidity, tensile elongation, and #impact strength were evaluated by the test method described above.

These results are shown in Table 3.

Examples 37-48, Comparative Examples 28-36 MFR8,0g/1 as crystalline polyolefin
80% by weight of unstabilized powdered crystalline propylene homopolymer of 0 min, average particle size 2-3μ as inorganic filler
9,10-dihydro-9-oxa-10- as compound A was added to a total of 100 parts by weight consisting of 5% by weight of talc and 15% by weight of barium sulfate with an average particle size of 0.4 to 0.6μ.
Phosfuphenanthrene-10-oxide, 2,6
゜8-tri-L-butyl-9.10-dihydro-9-oxa-10-phosphonanthrene-10-oxide or 6-(α-methylbenzyl) -g-t-
butyl-9,10-dihydro-9-oxa-]]0-phosphaphenanthrene-10 oxide, as compound B 6-phenyl-10-hydroxy-9,10-dihydro-9-oxa-1O-phosphono Aphenanthrene
Lead salt of 10-oxide, 2-benzyl-10-hydroxy-9,10-dihydro-9-oxa-IO-phosphaphenanthrene-10-oxide or 6-(α-methylbenzyl)-8- t-butyl-10
-hydroxy-9,10-dihydro-9-oxa-10
- Predetermined amounts of the lead salt of phosphonophenanthrene-10-oxide and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 4 below, and after stirring and mixing for 3 minutes, The mixture was melt mixed at 250° C. and pelletized using a twin-screw extruder with a diameter of 30 Iwl.

In addition, as Comparative Examples 28 to 36, MFR is 8.0 g/10
A total of 80% by weight of unstabilized powdered crystalline propylene homopolymer, 5% by weight of talc with an average particle size of 2-3μ and 15% by weight of barium sulfate with an average particle size of 0.4-0.6μ. Predetermined amounts of each of the additives listed in Table 4 below were added to 100 parts by weight, and the mixture was subjected to melt mixing treatment according to Examples 37 to 48 to obtain pellets.

The test pieces used for evaluation of rigidity, tensile elongation, and #WJ impact resistance were obtained by heating the obtained pellets at a resin temperature of 250°C and a mold temperature of 5°C.
Prepared by injection molding at 0°C.

Using the obtained test pieces, rigidity, tensile elongation, and impact resistance were evaluated according to the test method described above.

These results are shown in Table 4.

The compounds and additives related to the present invention shown in Tables 1 to 4 are as follows.

Compound A [Ico:9,10-dihydro-9-oxa-
10-Phosphaphenanthrene-10-oxide compound A [11]: 2,6.8-tri-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound A[mco: 2-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Compound A[IV]: 6-phenyl-9,10-dihydro-9- Oxa-10-phosphonoaphenanthrene-10
-Oxide compound A [V]: 2-benzyl-9,10-dihydro-
9-oxa-10-phosphaphenanthrene-1O-
Oxide compound A [VI co: 6-(α-methylbenzyl)
-8-t-butyl-9,10-dihydro-9-oxa-
IO-phosphaphenanthrene-10-oxide Compound B [I Co: lO-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Zinc Salt Compound B [II Co: Zinc salt of 2,6.8-tri-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide Compound B [ml: 2-cyclohexyl-10-
Hydroxy-9,10-dihydro-9-oxa-10-
Zinc salt of phosphonophenanthrene-10-oxide Compound B[]]V]: Zinc salt of 6-phenyl-10-hydroxy 9°10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide Compound B [toco: 2-benzyl-10-hydroxy-
Zinc salt of 9°lO-dihydro-9-oxa-1O-phosphonophenanthrene-10-oxide Compound B [VI]: 6-(α-methylbenzyl) -8
-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10
- Zinc salt of oxide compound B [■: 10-hydroxy-9,10-dihydro-9-oxa-10-phosphonoaphenanthrene-
10-oxide lead salt compound B [■ Co: 2,6. Mortley T-butyl 1
0-hydroxy-9,10-dihydro-9-oxa-1
0-Phosphaphenanthrene-10-oxide lead salt compound B [IX]: 2-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10- Oxide lead salt compound B [X co: 6-phenyl-10-hydroxy-9゜10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide lead salt compound B [XI]: 2- benzyl-10-hydroxy-
9゜10-dihydro-9-oxa-10-phosphonoaphenanthrene-10-oxide lead salt compound B [XII: 6-(α-methylbenzyl)
-8-t-Butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphonophenanthrene-10-oxide lead salt Aliphatic amine 1 Nilaurylamine Aliphatic amine 2: N,N -Dicocoamine aliphatic amine 3
:N-stearyl-N,N-dimethylamine aliphatic amine 4: hexamethylenediamine aliphatic amine 5: N-crow-1,3-diaminopropane aliphatic amine 6: hexamethylenetetramine aliphatic amine 7: N -Tocosyl-N,N,N-trimethylammonium chloride aliphatic amine 8: N,N,N-)liethyl-N-benzylammonium chloride aliphatic amine 9: N,N-bis(2-hydroxyethyl)-N-oleyl -N-methylammonium chloride Aliphatic amine 10: N,N-bis(2-hydroxyethyl) stearyl aminobetaine Aliphatic amine 11 Nitriisopropanolamine Aliphatic amine 12: N,N-bis(2-hydroxyethyl)cocoamine Fat Group amine 13: N,N-bis(2-hydroxyethyl)tallowamine Aliphatic amine 14: Octadecanoic acid 2-[(2-hydroxyethyl)octadecylamino]ethyl ester Aliphatic amine 15: (octadecylimino)diethylene distearate Amine 16: Polyoxyethylene lauryl amino ether Aliphatic amine 17: Polyoxyethylene stearyl amino ether Aliphatic amine 18: N,N,N',N'-tetra(2
-hydroxyethyl) -1,3-diaminopropane aliphatic amine 19: N-tallow N,N',N'-)lis(2-hydroxyethyl) -1,3-diaminopropane aliphatic amine 20: N,N -Jikoko N', N'
-bis(2-hydroxyethyl)-1,6-diamithexane fluorophosphite 1: 2,2'-bis(4,6-di-butylphenyl)fluorophosphite fluorophosphite 2: 2.2' -Bis(4-s-eicosylphenyl)fluorophosphite Fluorophosphite 3: 2,2'-methylene-bis(4-methyl-6-t-butylphenyl)fluorophosphite Fluorophosphite 4: 2,2 '-methylene-
Bis(11,6-di-butylphenyl)fluorophosphite Fluorophosphite 5: 2,2'-methylene-
Bis(4,8-dinonylphenyl)fluorophosphite Fluorophosphite 6: 2,2'-ethylidene-bis(4-methyl-6-t-butylphenyl)fluorophosphite Fluorophosphite 7: 2,2' -ethylidene-bis(4,6-di-butylphenyl)fluorophosphite Fluorophosphite 8: 2,2'-butylidene-bis(4-methyl-6-(1'-methylcyclohexyl)phenyl)fluorophosphite Fluorophosphite 9: 2,2'-thio-bis(4-methyl-6-sheepylphenyl) fluorophosphite Fluorophosphite 10: 2,2'-thio-bis(4-methyl-6-α-methyl benzylphenyl) fluorophosphite phenolic antioxidant 1: 2,6-di-t-butyl-p-cresol phenolic antioxidant 2: tetrakis[methylene-3
-(3',5'-di-butyl-4'-hydroxyphenyl)propionate comethane phenolic antioxidant 3: 1,3,5-tris(
3,5-di-butyl-4-hydroxybenzyl) isocyanurate phenolic antioxidant 4: 1,3. Trimethyl-2,4,6-tris (3,5-di-butyl-4-
Hydroxybenzyl)benzenephenolic antioxidant 5: 3,9-bis[1,1
-dimethyl-2-(β-(3-L-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl]-2.4,8.10-tetraoxaspiro[5,5
Condecane thioether antioxidant 1: Dimyristylthiodiprobionate Thioether antioxidant 2 Distearylthiodipropionate Thioether antioxidant 3: Pentaerythritol-
Tetrakis(3-laurylthiopropionate) Phosphorus antioxidant 1: Bis(2,6-di-butyl-4-methylphenyl)-pentaerythritol-Shiphosphite Phosphorus antioxidant 2: Bis(2, 4-di-t-butylphenyl)-pentaerythritol-siphosphite phosphorus antioxidant 3: Tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene-diphosphionite cyclic Metal salts of phosphorus compounds 1:10-hydroxy-9,1
Lithium salt of 0-dihydro-9-oxa-1O-phosphaphenanthrene-10-oxide [manufactured by Sangen Kagaku ■; metal salt of CA-Li cocyclic phosphorus compound 2:10-hydroxy-9,1
Sodium salt of 0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide [Tangen Kagaku I
+llO ; CA-Na cocyclic phosphorus compound metal salt 3:10-hydroxy-9,]
] 〇-dihydro-9-oxer-10-potassium salt of sulfphenanthrene-10-oxide [manufactured by Sangen Kagaku ■; metal salt of cocyclic phosphorus compound in CA-4:10-hydroxy-9,1
0-dihydro-9-oxa-1O-phosphaphenanthrene-1O-oxide magnesium salt [Sanko Kagaku Kyoku Co., Ltd.; CA-Mg] Zinc salt 1 Nishin-P-phenolsulfonate Zinc salt 2 Nishin-n-butyl- Dithiocarbamate Table 1 The Examples and Comparative Examples described here are cases where a crystalline propylene homopolymer is used as the crystalline polyolefin and talc is used as the inorganic filler.

As can be seen from Table 1, Examples 1 to 12 contain talc, compound A and compound B in crystalline propylene 1/1 homopolymer.
Examples 1 to 12 are different from Comparative Examples 1 (in which Compound A and Compound B are not blended) and Comparative Examples 2 to 3 (in which Compound A or Compound B is blended alone). A closer look reveals that Examples 1 to 12 are excellent in tensile elongation and WJfm impact resistance.

In addition, in Example 2, a zinc salt or a lead salt of a cyclic phosphorus compound according to the present invention, that is, a cyclic phosphorus compound in which zinc or button of compound B was replaced with another metal, was blended in place of compound B. Comparing Examples 1 to 12 with Comparative Examples 4 to 7 and Comparative Examples 8 to 9 in which a zinc salt other than Compound B was blended in place of Compound B, it was found that the tensile elongation and #Impact resistance is at the same level as Comparative Example 2 and is still not sufficient. Even if compound A is used in combination with a metal salt of a cyclic phosphorus compound other than compound B or a zinc salt other than compound B, the tensile elongation and impact resistance are It turns out that there is almost no improvement. Therefore, it is clear that comparisons that do not simultaneously satisfy the two-component combination of compound A and compound B related to the present invention do not exhibit the effects of the present invention. That is, the tensile elongation and impact resistance obtained in the present invention are unique effects that are observed when Compound A and Compound B are used together in an inorganic filler-containing polyolefin composition formed by blending an inorganic filler. It can be said. Furthermore, in the compositions of Examples 1 to 4, Examples 5 to 9 in which various aliphatic amines were used in combination or Examples 10 to 12 in which fluorophosphite was used in combination were those in Example 1.
-4, the excellent tensile elongation and impact resistance improvement effects of Compound A and Compound B are not inhibited, and the combined use of aliphatic amine or fluorophosphite provides a remarkable synergistic improvement in stiffness and impact resistance. It can be seen that the effect is recognized.

Tables 2 and 3 show a mixture of a crystalline ethylene-propylene block copolymer or a crystalline ethylene-propylene random copolymer and a Ziegler-Natsuta high-density ethylene homopolymer as the crystalline polyolefin, and an inorganic filler, respectively. The same effects as mentioned above were confirmed with these products as well. Furthermore, Table 4 shows the results using a crystalline propylene homopolymer as the crystalline polyolefin and a mixture of talc and barium sulfate as the inorganic filler, and the same effects as described above were confirmed for these as well.

[Effects of the Invention] The composition of the present invention has the following properties: (1) without impairing the rigidity, heat-resistant rigidity, and dimensional stability of the molded product when formed into a molded product;
Excellent tensile elongation and impact resistance. (2) It has extremely excellent tensile elongation and #gi impact resistance, making it suitable for various molded products such as injection molded products, extrusion molded products, vacuum molded products, pressure molded products, and press (stamping) molded products. It can be used for.

that's all

Claims (3)

[Claims] (1) A cyclic phosphorus compound represented by the following general formula [I] (hereinafter, compound A
That's what it means. ) and a metal salt of a cyclic phosphorus compound represented by the following general formula [II] (hereinafter referred to as compound B) in an amount of 0.05 to 1 part by weight, respectively. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, in the formula, Ar_1 to Ar_4 are arylene groups, alkylarylene groups, cycloalkylarylene groups, arylarylene groups or an aralkylarylene group, and M represents zinc or lead, respectively.) (2) Compound A was added to 100 parts by weight of a composition containing 10 to 30% by weight of an inorganic filler in a crystalline polyolefin.
, Compound B and aliphatic amine each from 0.05 to 1
An inorganic filler-containing polyolefin composition containing parts by weight. (3) Compound A was added to 100 parts by weight of a composition containing 10 to 30% by weight of an inorganic filler in a crystalline polyolefin.
An inorganic filler-containing polyolefin composition comprising 0.05 to 1 part by weight of Compound B and 0.001 to 1 part by weight of fluorophosphite represented by the following general formula [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] (However, in the formula, R is an alkylidene group having 1 to 4 carbon atoms or sulfur, Ar_5 and Ar_6 are an alkylarylene group or a cycloalkylarylene group, and n is 0.
or 1 respectively. )