JPH03162427A - Inorganic filler-containing polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having improved tensile elongation and impact resistance, excellent rigidity, dimensional stability, etc., by blending a crystalline polyolefin with an inorganic filler, specific cyclic phosphorus com pound and metallic salt. CONSTITUTION:A crystalline polyolefin is blended with 10-30wt.% inorganic filler to give a composition. 100 pts.wt. of the composition is mixed with 0.05-1 pt.wt. cyclic phosphorus compound shown by the formula (Ar1 and Ar2 are arylene, alkylarylene, cycloalkylarylene, etc.) and 0.01-1 pt.wt. one or two compounds selected from a metallic salt of an aliphatic monocarboxylic acid (metal is potassium, zinc or lead) and a metallic salt of hydroxy higher fatty acid (metal is as shown above). Talc having 2-10mu average particle diameter is used as the inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyolefin composition containing an inorganic filler. More specifically, we have identified inorganic fillers, cyclic phosphorus compounds with specific structures, and specific metal salts in crystalline polyolefins! This article relates to an inorganic filler-containing polyolefin compound that can be blended to produce molded products with excellent tensile elongation and impact resistance. [Prior Art] In general, inorganic filler-containing polyolefin composites can be used to obtain molded products with excellent rigidity, heat-resistant rigidity, and dimensional stability. It is used to manufacture various shaped products such as air-shaped products, pressure-formed products, and press (stamping) shaped products. However, although inorganic filler-containing polyolefin compositions have the above-mentioned excellent properties, they have the following disadvantages: There is a drawback that the tensile elongation and impact resistance of molded products obtained from polyolefin compositions containing inorganic fillers are reduced6. An inorganic filler-containing polyolefin composition that has improved tensile elongation and shock resistance without impairing its properties, that is, a crystalline polyolefin containing an inorganic filler, a cyclic phosphorus compound having a specific structure, and a fatty acid metal salt or an alkyl having a specific structure. We previously proposed a composition containing specific amounts of metal phosphates (Japanese Patent Application No. 326236/1982). In addition, the present inventor has developed a composition in which a specific amount of a cyclic phosphorus compound having a specific W4 structure is blended with a polyolefin composition, that is, a polyolefin, from which a molded article with improved rigidity and impact resistance at low temperatures can be obtained. It was previously proposed in the publication No. 60-181148, and the publication also states that dispersants or neutralizing agents such as metal soaps, and inorganic fillers can be used in combination with the polyolefin compound. [Invention tries to solve! I [] However, although the tensile elongation and temporary impact resistance of the shaped product obtained from the inorganic filler-containing polyolefin composition proposed in the above-mentioned Japanese Patent Application No. 62-326236 are considerably improved, they are still not fully satisfactory. do not have. In addition, the tensile elongation and impact resistance of shaped articles obtained from the inorganic filler-containing polyolefin composition, which is obtained by combining the inorganic filler with the composition proposed in JP-A-60-181146, are also significantly improved. However, it is still not completely satisfactory. Furthermore, although calcium stearate is described as a metal soap in the examples of the publication, by using fatty acid potassium, n-fatty acid zinc, or fatty acid lead in combination with the inorganic filler-containing polyolefin composition, inorganic filler-containing polyolefin can be produced. There is no mention of improving the tensile elongation or impact resistance of a molded article obtained from the composition, nor is there any mention of improving the bow elongation or impact resistance of a molded article obtained from the composition. The present inventor has proposed in Japanese Patent Application No. 62-326236 and Japanese Unexamined Patent Publication No. 60-181148 a composition that solves the above-mentioned problems regarding the inorganic filler-containing polyolefin composite, that is, a molded article. Rigidity of the molded product,
We conducted intensive research to obtain an inorganic filler-containing polyolefin composition that would yield shaped articles with improved tensile elongation and impact resistance without compromising heat-resistant rigidity and dimensional stability. As a result, the present inventors have discovered that a composition formed by blending specific amounts of an inorganic filler, a cyclic phosphorus compound having a specific structure, and a specific metal salt with M crystalline polyolefin can solve the above-mentioned problems. Based on this knowledge, we have completed the present invention. As is clear from the above description, the object of the present invention is to improve the tensile elongation and impact resistance of the molded product without impairing its rigidity, heat-resistant rigidity, and dimensional stability. An object of the present invention is to provide an inorganic filler-containing polyolefin composition from which a product can be obtained. [Means for solving the 1K problem] The present invention has the following structure.

The following general formula [1
] (hereinafter referred to as compound A).

) and 0.05 to 1 part by weight of lm or two or more compounds selected from the following [1] to [2] (hereinafter referred to as compound B).
An inorganic filler-containing polyolefin M-type product containing 0.01 to 1 part by weight of ).

■Aliphatic monocarboxylic acid metal salt (However, the metal represents potassium, zinc, or lead.) ■Hydroxy higher fatty acid metal salt (However, the metal represents potassium, zinc, or lead.) (However, Arl and Ar2 in the formula is an arylene group, an alkylarylene group 5, a cycloalkylarylene group,
Indicates an arylarylene group or an aralkylarylene group, respectively. ) The crystalline polyolefins used in the present invention include ethylene, propylene, butene-1, pentene-1. α such as 4-methyl-pentene-1, hexene-1, octene-1, etc.
-Crystalline homopolymer of olefin, α of two or more of these
-Crystalline or low-crystalline random copolymers or crystalline block copolymers of olefins, copolymers of the above α-olefins and #acid vinyl or acrylic esters, saponified products of these copolymers, these α -Copolymerization of olefin and unsaturated silane compound. Copolymers of these α-olefins and unsaturated carboxylic acids or their anhydrides, reaction products of the copolymers with metal ion compounds, crystalline homopolymers of the above-mentioned α-olefins, crystalline or a modified polyolefin obtained by modifying a low-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 Examples include silane-modified polyolefins obtained by modifying a coalesced or crystalline block copolymer with an unsaturated silane compound.Although it is natural to use these crystalline polyolefins alone, it is possible to use a mixture of two or more crystalline polyolefins. It can also be used as Furthermore, in addition to the above-mentioned crystalline polyolefin, various synthetic rubbers (e.g. non-grade ethylene-propylene random copolymer, non-grade ethylene-propylene-nonconjugated diene terpolymer, polybutadiene, polyisoprene,
Polychloroprene, chlorinated polyethylene, 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 Such)
Or use a mixture of thermoplastic synthetic resins (e.g., polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, fluororesin, etc.) You can also. Crystalline propylene homopolymer, crystalline propylene copolymer containing 70% by weight or more of propylene fraction, including crystalline ethylene-propylene random copolymer, crystalline propylene-butene-1
Random copolymers, crystalline ethylene-propylene-butene-13-element copolymers, crystalline propylene-hexene-butene-13-element copolymers, and mixtures of two or more of these are particularly preferably used. The inorganic fillers used in the present invention include talc, clay, wollastonite, zeolite, kaolin,
bentonite, perlite, diatomaceous earth, asbestos,
Calcium carbonate, aluminum ξ 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, and talc with an average particle size of 2 to 10 μm is particularly preferred. These inorganic fillers are also used as surface treatment agents such as higher fatty acids, higher fatty acid esters, higher alcohols, higher fatty acid monoamides, higher fatty acid bisamides,
The surface may be treated in advance with a known surface treatment agent such as a silane coupling agent, titanate coupling agent, boron coupling agent, aluminate coupling agent, or zircoaluminum coupling agent. ．．
Although it is natural to use these inorganic fillers alone, it is also possible to use two or more types of inorganic fillers 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. If the content is less than 10% by weight, the rigidity, heat-resistant rigidity and dimensional stability of the resulting shaped product will be insufficient, and if it exceeds 30% by weight, the tensile elongation and impact resistance will decrease, which is not practical.

Compound A used in the present invention includes IO-hydroxy-9,10-dihydro-9-oxal IO-7osphaphenanthrene-10-oxide, 1-methyl-IO
-Hydroxy-9.10-dihydro-9-oxa.10
-Phosphaphenanthrene-10-oxide, 2-
Methyl-10-hydroxy-9.10-dihydro-9-
Oxa.IO-phosphaphenanthrene-10-oxide, 6-methyl-10.hydroxy-9,lO-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 7-methyl-lO-hydroxy-
9,10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide, 8-methyl-10-
Hydroxy-9,10-dihydro-9-oxer10-
Phosphaphenanthrene-10-oxide, 6,8
・Dimethyl-10-hydroxy-9.10-dihydro-
9-oxer10-phosphaphenanthrene-10-
oxide, 2,6.8-trimethyl-10-hydroxy-9,10-dihydro-9-oxer 10-7 osphaphenanthrene-10-oxide, 2-ethyl-l
O-hydroxy-9.10-dihydro-9-oxer 1
0.Phosphaphenanthrene-10-oxide, 6
・Ethyl-10-hydroxy-9.10-dihydro-9
-Oxer-10-phosphaphenanthrene-lO-oxide, 8-ethyl-10-hydroxy-9.10-
Dihydro-9-oxa lO-7 osphaphenanthrene-10-oxide, 6,8-diethyl-10-hydroxy-9,10-dihydro-9-oxa-lO-phosphaphenanthrene-10-oxide, 2 ,6.8
-}ethyl-10-hydroxy-9.10-dihydro-9=oxer-10-phosphaphenanthrene-10
-oxide, 2-i-propyl-10-hydroxy-
9.10-dihydro-9-oxer-10-phosphaphenanthrene-10-oxide, 6-i-propyl-1O-hydroxy-9,10-dihydro-9-oxer-10-phosphaphenanthrene-10-oxide,
8-i-propyl-10-hydroxy-9.10-dihydro-9-oxalO-phosphaphenanthrene-
10-oxide, 6,8-di-i-probyl-10-
Hydroxy-9,10-dihydro-9-oxer lO.
Phosphaphenanthrene-10-oxide, 2,6
．． 8-tri-i-propyl-10-hydroxy-9,
10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide, 2-S-butyl-10-
Hydroxy-9,1O-dihydro-9-oxer-10-
7-osphaphenanthrene-10-oxide, 6-s
-Petyl-10-hydroxy-9,1O-dihydro-9
-Oxar 10-Phosphaphenanthrene-! 0-oxide, 8-s-butyl-ICI-hydroxy-9.
10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide, 1,8-diS-butyl-10-hydroxy-9,10-dihydro 9-oxerlO-phosphaphenanthrene-10- oxide, 2,6.8-triS-butyl-1O-hydroxy-9,1O-dihydro-9-oxerIO-phosphaphenanthrene-10-oxide, 2-t-butyl-10-hydroxy-9.10- dihydro-9-oxer-10-phosphaphenanthrene-10-oxide,
6-t-butyl-10-hydroxy-9,10-dihydro-9-oxa.10-phosphaphenanthrene-1
0-oxide, 8-t-butyl-10-hydroxy-
9.10-dihydro-9-oxer-10-phosphaphenanthrene-10-oxide, l,6-di-butyl-10-hydroxy-9.10-dihydro-9-oxer-10-phosphaphenanthrene- 10-oxide, 2,8-c-t-phthyl-10-hydroxy-9
．． 10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide, 2,7 di-butyl-10-hydroxy-9,10-dihydro-9-oxer 10-phosphaphenanthrene-10 -oxide, 2,8-di-t-butyl-10-hydroxy-9.1
0-dihydro-9-oxer 10-phosphaphenanthrene 10-oxide, 6.8-di-L-butyl-
10-hydroxy-9.10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide,
2.6.8-tri-L-butyl-1O-hydroxy-9
, 10-dihydro-9-oxer IO-phosphaphenanthrene-10-oxide, 2-t-amyl-10
-Hydroxy-9.10-dihydro-9-oxer 10
-Phosphaphenanthrene-10-oxaiF.
at-amyl-10-hydroxy-9,10-dihydro-9-oxer-10-phosphaphenanthrene-1
0-oxide, 8-t. -Amyl-10-hydroxy-9,10-dihydro-9-oxalO-phosphaphenanthrene-10-oxide, 6,8-di-t-amyl-1O-hydroxy-9,IO-dihydro 9-
Oxa-10-phosphaphenanthrene-10-oxide, 2,8.8-triceamyl-10-hydroxy-9.10 dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t -Octyl-10-hydroxy-9,10-dihydro-9-oxer 10-phospaphenanthrene-10-oxide, 8-t-octyl-10-hydroxy-9,10
~dihydro-9.oxer-10-phosphaphenanthrene-10-oxide, 8-t. -Octyl-10・
Hydroxy-9,10-dihydro-9-oxer-10-
Phosphaphenanthrene-lO-oxide, 6,8
~Di-octyl-10-hydroxy-9.10-dihydro-9-oxer-10-phosphaphenanthrene-10-oxide, 2,6.8-tri-L-octyl-1O-hydroxy-9,1O-dihydro- 9-oxer 10-phosphaphenanthrene-10-oxide, 2-cyclohexyl-10-hydroxy-9.10
-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-lO-
Hydroxy-9,10-dihydro-9-oxer10-
Phosphaphenanthrene-10-oxide, 8-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxal lO-phosphaphenanthrene 10
-oxide, 6,8-dihydro-10-hydroxy-9,10-dihydro-9-oxerlO-phosphaphenanthrene-10-oxide, 2,6.
8- Trisic-hexyl-10-hydroxy-9.
10-dihydro-9-oxer 10-phosphaphenanthrene=10-oxide, 6-phenyl-10-hydroxy-9,10-dihydro-9-oxer lO-phosphaphenanthrene-10-oxide, 2-benzyl-10 -Hydroxy-9.10-dihydro-9-oxer-10-phosphaphenanthrene-lO-oxide, 6-benzy-10-hydroxy-9,lO-dihydro-9-oxer-10-phosphaphenanthrene-lO-oxide, 8-benzyl lO-hydroxy-9,10-dihydro-9-oxer lO-phosphaphenanthrene-10-oxide, 6,8-dibenzyl-10-hydroxy-9,10-dihydro-9-oxer10-phospha Phenanthrene-10-oxide, 2,6.8-tribenzyl-10-hydroxy-9.10-dihydro-9-oxal lO-phosphaphephenanthrene-10-oxide, 2-(α-methylbenzyl) -10-hydroxy-9,10-dihydro-
9-OxalO-phosphaphenanthrene-10-
oxide, 6-(α-methylbenzyl)-10-hydroxy-9,10-dihydro-9-oxer-10-phosphaphenanthrene-lO-oxide, 8.(α.
methylbenzyl)-10-hydroxy-9.10-dihydro-9-oxa-10-phosphaphenanthrene-
lO-oxide, 6,8-di(α-methylbenzyl)
-10-hydroxy-9.10-cyhydro-9-oxerIO-phosphaphenanthrene-lO-oxide, 2,6.8-tri(α-methylbenzyl)-lO-hydroxy-9. lO-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide, 2.8-
C(α,α-dimethylbenzyl)-10-hydroxy9. 10-Cyhydro-9-oxer10-phosphaphenanthrene-10-oxide, 6-e-butyl-8-methyl-10-hydroxy-9,10-dihydro-9-oxer10-phosphaphenanthrene-10
-oxide, 6-benzyl 8-methyl-10-hydroxy-9,10-dihydro-9-oxer lO-phosphaphenanthrene-lO-oxide, 6-cyclohexyl-8-t-butyl lO-hydroxy- 9,1
0-dihydro-9-oxer 10-phosphaphenanthrene-1O-oxide, 6-benzyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxer 10-phosphaphenanthrene-10- oxide, 6-(α-methylbenzyl)-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide,
6-tert-butyl-8-cyclohexyl-lO-hydroxy-9,10-dihydro-9-oxerlO-phosphaphenanthrene-10-oxide, 6-benzyl-
8-cyclohexyl-lO-hydroxy-9,10-dihydro-9-oxer10-phosphaphenanthrene-10-oxide,6-t-butyl-8-benzyl-IO-hydroxy-9,to~dihydro-9-oxer10- phosphaphenanthrene-lO-oxide,
6-cyclohexyl-8-benzyl-10-hydroxy-9. 10-dihydro-9-oxerlO-phosphaphenanthrene-10-oxide, 2,6-di-t
-butyl-8-benzyl-10-hydroxy-9.10
-dihydro-9-oxer-10-phosphaphenanthrene-10-oxide and 2,6-dicyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxer-10-phosphaphenanthrene-
Examples include 10-oxide, and 10-hydroxy-9,10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide is particularly preferred. It is natural to use these compounds A alone, but it is also possible to use two or more kinds of compounds A in combination. The blending ratio of the compound A is 10 to 30% by weight of the inorganic filler to the crystalline polyolefin.
A composition containing 0.05 to 100 parts by weight
1 part by weight, preferably 0.605 to 0.5 part by weight. O. If the amount is less than 1 part by weight of OS, the effect of improving tensile elongation and impact resistance will not be sufficiently exhibited, and it may be more than 1 part by weight, but if it is more than 1 part by weight, the effect of improving tensile elongation and impact resistance will not be fully exhibited. Not only is it impractical because it cannot be expected, but it is also uneconomical. Compound B used in the present invention includes potassium acetate, zinc acetate, lead acetate, potassium propionate, zinc brobionate, lead propionate, potassium butyrate, zinc sulfate, lead sulfate, potassium valerate, zinc valerate, Lead grass acid, potassium α-methylbutyrate, zinc α-methylbutyrate, lead α-methylbutyrate, potassium hexanoate, zinc hexanoate, lead hexanoate, potassium sorbate, zinc sorbate, lead sorbate, n-octanoic acid Potassium, n-zinc octoate, n
-Lead octoate, potassium 2-ethylhexanoate, 2-
Ethylhexane ii! ! Zinc, lead 2-ethylhexanoate, potassium nonanoate, zinc nonanoate, lead nonanoate, potassium decanoate, zinc decanoate, lead decanoate, potassium laurate, zinc laurate, lauric acid carrier, ξpotassium listinate, Mainly zinc listate, ξlead listate, potassium palmitate, zinc palmitate, palmitin! 2
Lead, potassium palmitoleate, zinc balmitoleate, lead palmitoleate, potassium stearate, zinc stearate, lead stearate, potassium oleate, zinc oleate, lead oleate, potassium linoleate, zinc linoleate, lead linoleate , potassium linolenate, zinc linolenate, lead linolenate, potassium behenate, zinc behenate, lead behenate, potassium erucate, zinc erucate, lead erucate, potassium lignocerate, zinc lignocerate, lead lignocerate, serotin acid potassium, zinc cerotate, lead cerotate, potassium montanate, zinc montanate, lead montanate, potassium 2-hydroxytetradecanoate, zinc 2-hydroxytetradecanoate,
Lead 2-hydroxytetradecanoate, potassium ibrolate, iprol fen! Lead, lead ibrolate, potassium 2-hydroxyhexadecanoate, zinc 2-hydroxyhexadecanoate, lead 2-hydroxyhexadecanoate, potassium yarapinoleate, zinc yarabinoleate, lead yarapinoleate, potassium yarapinoleate, zinc yarapinoleate, lead yarapinoleate , Potassium Ampretoleate, Zinc Ampretoleate, Ampretol Il Ship, Potassium Alluretate, Zinc Alluretate, Lead Allureate, Potassium 2-Hydroxyoctadecanoate, 2.
Hydroxyoctadecane ril zinc, lead 2-hydroxyoctadecanoate, potassium 12-hydroxyoctadecanoate, zinc 12-hydroxyoctadecanoate, lead 12-hydroxyoctadecanoate, potassium l8-hydroxyoctadecanoate, zinc 18-hydroxyoctadecanoate, l8-hydroxy Lead octadecanoate. 9.10-
Potassium dihydroxyoctadecanoate, 9,1O-zinc dihydroxyoctadecanoate. 9.10 ~ Lead dihydroxyoctadecanoate, potassium ricinoleate, zinc ricinoleate, lead ricinoleate, potassium camrolenate,
Cam Loren! 2 Zinc, lead camrolenate, potassium lycanate, zinc lycanate, lead lycanate, potassium ferronate,
Zinc ferronate, lead ferronate, potassium cerebronate: Examples include zinc cerebronate and lead cerebrate, particularly potassium stearate. stearin M zinc,
Stearin W1 button, potassium 12-hydroxyoctadecanoate, zinc 12-hydroxyoctadecanoate and 1
Lead 2-hydroxyoctadecanoate is preferred. It is natural to use these compounds B alone, but if two or more kinds of compound B
Can also be used together. The compounding ratio of the compound B is 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of a combination of crystalline polyolefin and 10 to 30% by weight of an inorganic filler. It is 1 part heavy. 0.0
If the amount is less than 1 part 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 the nail tensile elongation and impact resistance. Not only is it not effective and impractical, but it is also uneconomical. 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 agent (excluding compound A), clarifying agent, nucleating agent (excluding compound A)
(excluding compound (excluding compound B), dispersants or neutralizing agents such as metal soaps (excluding compound B), and organic fillers (e.g., wood flour, pulp, waste paper, composite IIi.I! male, natural fibers, etc.). They can be used together as long as the purpose is not compromised. The composition of the present invention includes a crystalline polyolefin, an inorganic filler,
Predetermined amounts of each of Compound A and Compound B and the various additives mentioned above which are usually added to crystalline polyolefins are mixed in a conventional mixing device such as Henschel ξ Kisser (trade name).
, a super kiln mixer ribbon blender, a Banbury mixer, etc., and a normal single-screw extruder, twin-screw extruder, Brabender or roll, etc., to a melt mixing temperature of 15
It can be obtained by melt-kneading and pelletizing at 0°C to 300°C, preferably 180°C to 270°C. The obtained assembly or material is used to manufacture the desired preformed article by various molding methods such as injection molding, extrusion molding, blow molding, etc. [Function] In the present invention. What kind of action does the combination of compound A and compound B have? Its action a! Although the lateral force itself is not clear, it is presumed to be due to the following mechanism of action. In other words, the metal ions of compound B act on compound A to form a coordinate bond or ionic bond between compound A and compound B in some way, thereby improving tensile elongation and impact resistance. It is thought that [
Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation method used in the Examples and Comparative Examples was as follows. 1) Rigidity: Evaluated by bending test. That is, using the obtained pellet, the length is loomm and the width is 10 rtea.
．． A test piece with a thickness of 4 m was made using the injection molding method, and the stiffness was evaluated by measuring the flexural modulus of the test piece (according to JISK 7203). 2) Tensile elongation:
It was evaluated using a tensile test. That is, using the obtained pellets, a length of 175 m and a width of 10 m. J with thickness 3.3mm
An ISI test piece was prepared using the injection molding method, and the tensile elongation was measured using the test piece (according to JISK7113) IF
I appreciated it. 3) Impact resistance: Evaluated by Izod impact test. That is, using the obtained pellet, the length is 63
．． A test piece (with a notch) measuring 5 m long, 13 m wide, and 3.5 mm thick was made by injection molding, and the test piece was heated to 23°C using the injection molding method.
Measurement of Izod impact strength (JISK7110
The impact resistance was evaluated based on the following criteria. Example 1
~13, Comparative Examples 1 to 6 MFR as crystalline polyolefin (discharge amount of molten resin per 10 minutes when applying a load of 2.16 kg at 230°C) 8.0 g/unstabilized powdered crystals for 10 minutes 10-hydroxy-9.10-dihydro-9-oxer IO- as compound A was added to a total of 100 parts by weight consisting of 80% by weight of propylene homopolymer and 20% by weight of talc with an average particle size of 6 to 8μ as an inorganic filler. Phosphaphenanthrene-lO-oxide, 2,6.8-
}-tert-butyl-lO-hydroxy-9,lO-dihydro-9-oxa-10-phosphine-
10-oxide or 2-cyclohexyl-1O-
Hydroxy-9,IO-dihydro-9-oxer10-
Phosphaphenanthrene-10-oxide, potassium acetate as compound B,! Add the prescribed amounts of each of zinc I acid, lead acetate, potassium stearate, zinc stearin W1 or lead stearate and other additives to the amounts described below.
Henschel Tomokisa (product name) with the combination ratio listed in the table.
After stirring and mixing for 3 minutes, the mixture was subjected to melt mtx kneading at 250°C using a twin-screw extruder with a diameter of 30 mm to form pellets. In addition, as Comparative Examples 1 to 9, MFR was 6.0 g/1
80% by weight of unstabilized powdered crystalline propylene homopolymer of 0 minutes and talc 20 with an average particle size of 6-8μ
Predetermined amounts of each of the additives listed in Table 1 below were blended into a total of 100 parts by weight consisting of 100 parts by weight, and pellets were obtained by melt mixing according to Examples 1 to 13. The test pieces used for evaluation of tensile elongation and impact resistance were manufactured by injection molding the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C. Using the obtained test pieces, tensile elongation and temporary impact resistance were evaluated using the test method described above. These results are shown in Table 1. Examples 14 to 26, Comparative Examples 10 to 18 M F R 4.0 g/as crystalline polyolefin
10 minutes unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) 701% and as inorganic filler average particle size 6-8
10-hydroxy-9,to-dihydro-
9-oxerIO-phosphaphenanthrene-10-
Oxide, 2,6, tert-butyl-10-hydroxy-9,10-dihydro-9-oxal lO-phosphaphenanthrene-10-oxide or 6-
Phenyl-10-hydroxy-9,1O-dihydro-9
-oxerlO-phosphaphenanthrene-10-oxide, compound B as potassium 2-ethylhexanoate, 2-ethylhexane N & zinc, 2-ethylhexane m lead, potassium stearate, zinc stearate or lead stearate and Predetermined amounts of each of the other additives were added to a Henschel mixer (trade name) at the mixing ratios listed in Table 2 below, and after stirring and mixing for 3 minutes,
It was subjected to fs melt cross-mixing treatment at 250°C using a twin-screw extruder (ii) and pelletized. In addition, as Comparative Examples 10 to 18, unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) with an MFR of 4.0/10 minutes and an average of 70% by weight were used. A total of 100 parts by weight consisting of 30% by weight of talc with a particle size of 6 to 8μ, and the second
Example 1
Pellets were obtained by melt-kneading according to 4-26. The test pieces used for evaluation of tensile elongation and rlJ @ impact resistance are:
The obtained pellets were heated at a resin temperature of 250°C and a mold temperature of 50°C.
It was prepared by injection molding. Using the obtained test pieces, tensile elongation and impact resistance were evaluated according to the test method described above. Table 2 shows these results. Examples 27-39, Comparative Examples 19-27 MFR 7.0g/as crystalline polyolefin
70% by weight of unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) for 10 minutes. MI (Discharge amount of molten resin during 10 minutes of ringing with a load of 2.16- at 190°C) Log/10 minutes of unstabilized powdered Ziegler-Natta high-density ethylene homopolymer 20% by weight and 10% by weight of talc with an average particle size of 6 to 8μ as an inorganic filler, and 10% of compound A as an inorganic filler.
-Hydroxy-9.10-dihydro-9-oxer 10
-Phosphaphenanthrene-10-oxide.
2,6.8-}-butyl-10-hydroxy-9
, 10-dihydro-9-oxa.10-phosphabenthrene-10.oxide or 2-benzyl-10-hydroxy-9.10-dihydro-9-oxa.10-phosphaphenanthrene-10-oxide,
As compound B, predetermined amounts of potassium stearate, zinc stearate, lead stearate, potassium 12-hydroxyoctadecanoate, zinc 12-hydroxyoctadecanoate, or lead 12-hydroxyoctadecanoate and other additives were added to jl! described below. The mixture proportions listed in Table 3 were added to a Henschel mixer (trade name), stirred and mixed for 3 minutes, and then melted at 250°C using a twin-screw extruder with a diameter of 30 m. It was kneaded and made into pellets. Also, comparative example 19~
27 is an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5 weight) with an MFR of 7.0 g/10 minutes, 70% by weight. MI is 1
0g/10min unstabilized powdered Ziegler-Natta high density ethylene homopolymer 20% by weight and 10% talc with early average particle size 6-8μ.
Predetermined amounts of each of the additives listed in Table 3 below were added to 0 parts by weight, and pellets were obtained by melt-kneading according to Examples 27-39. The test pieces used for the evaluation of tensile elongation and shock resistance were prepared by injection molding the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C. Using the obtained test pieces, tensile elongation and shock resistance were evaluated using the test method described above. These results are shown in Table 3. Examples 40 to 52, Comparative Examples 28 to 36 M F R 8.0 g/ as crystalline polyolefin
10 minutes of unstabilized powdered crystalline propylene homopolymer 801 (% by weight, as inorganic filler, average particle size 2~
5% by weight of 3μ talc and average particle size 0.4-0.6μ
To a total of 100 parts by weight consisting of 15% by weight of barium sulfate, 10-hydroxy-9,10-dihydro9-oxa-10-phosphaphenanthrene-IO was added as compound 8.
-oxide, 2,6.8- }-butyl-10
-Hydroxy-9,10-dihydro-9-oxer 10
-7 Osphaphenanthrene-10-oxide or 6-(α-methylbenzyl)-g-t-butyl-1
0-Hydroxy-9.10-dihydro-9-oxal
O-phosphafluorenethrene-10-oxide,
As compound B, potassium montanate, zinc montanate,
Predetermined amounts of lead montanate, potassium ricinoleate, zinc ricinoleate or lead ricinoleate and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 114 below, and mixed by stirring for 3 minutes. Thereafter, it was melted and mixed at 250°C in a twin-screw extruder with a diameter of 30 m to form pellets. Also, as Comparative Examples 28 to 36, MF
80% by weight of unstabilized powdered crystalline propylene homopolymer with R of 8.0g/10min, average particle size 2-3μ
A total of 100 parts by weight of 5% by weight of talc and 15% by weight of barium sulfate with an average particle size of 0.4 to 0.6μ was blended with predetermined amounts of each of the additives listed in Table 4 below. Peleft was obtained by melting and kneading according to 52. The test pieces used for the evaluation of tensile elongation and *W impact resistance were obtained by injection molding the obtained bar left at a resin temperature of 250°C and a mold temperature of 50°C to a mW of 4t. Using the obtained test pieces, tensile elongation and impact resistance were evaluated using the test method described above. These results are shown in Table 1!4. The compounds and additives related to the present invention shown in Tables 11 to 14 are as follows. Compound ACI: 10-
Hydroxy-9.10-dihydro-9-oxer10-
Phosphaphenanthrene-10-oxide compound A [■1: 2,6.8-tri-t-butyl-10-hydroxy-9.10-dihydro-9-oxer 10-phosphaphenanthrene-10-oxide compound A [ m]: 2-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxer10-buosphaphenanthrene-lO-oxide compound A CIV]: 6-phenyl-lO-hydroxy-9,lO-dihydro-9- Oxer lO-phosphaphenanthrene-lO1 oxide compound A [V co:2-benzyl-10-hydroxy-9
,lO-dihydro-9-oxer-10-phosphaphenanthrene-lO-oxide Compound A [VI]: 8-(α-methylbenzyl)-8-t-butyl-10-hydroxy-9,IO-dihydro-
9-Oxa-10-phosphaenanthrene-10-
Oxide compound B [1]: #acid potassium compound B [II]: Zinc acetate compound B [:III]: ! l'Acid lead compound B [
[V]: Potassium 2-ethylhexanoate compound B
[V]: Zinc 2-ethylhexanoate compound B [V
I]: Lead 2-ethylhexanoate compound B [■]: Potassium stearate compound B [■]: Zinc stearate compound B []X]: Lead stearate compound B [X
] : Montanic acid potassium compound BCXII: Montan W! Zinc compound B [X■]: Lead montanate compound B [Xm]: Potassium 12-hydroxyoctadecanoate compound B [XIV]: 12-hydroxyoctadecane W1 Zinc compound B [XV]: Lead 12-hydroxyoctadecanoate compound B [ XVI]: Potassium ricinoleate compound B [X■]: Zinc ricinoleate compound B [X■]: Lead ricinoleate phenolic antioxidant 1: 2,6-di-t-butyl-P-cresol phenolic antioxidant 2 : Tetrakis [methylene-3
- (3',5'-di-t-butyl 4'-hydroxyphenyl)propionate]methanephenol antioxidant 3: 1,3,5-tris(3
．． 5-di-t-butyl-4-hydroxybenzyl) isocyanurate phenolic antioxidant 4: 1,3.5-trimethyl-2,4.8-}lis(3,5-di-butyl-4)
-hydroxybenzyl)benzenephenolic antioxidant 5: 3.9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)probionyloxy}ethylco-2 .4,8.10-tetraoxasubi [5,5 undecane thioether antioxidant 1: dimyristylthiodibrobionate thioether antioxidant 2: distearylthiodipropionate thioether antioxidant 3: Pentaerys Litho-rutetrakis (3-laurylthiopiobionate) Phosphorus antioxidant 1: Bis(2,6-di-t-butyl-4-methylphenyl)-pentaerythritol-diphosphite Phosphorus antioxidant 2: Bis(2 , 4-di-t-butylphenyl)-pentaerythritol-diphosphite phosphorus antioxidant 3: Tetrakis(2,4-di-L-butylphenyl)-4.4'-biphenylene-diphosphonite Na - St: Sodium stearate Mg-
St: Magnesium stearate Ca-St: Calcium stearate Sr-St: Strontium stearate B
a-S t: Barium stearate Al! -St
: Aluminum Stearate 9J11 The Examples and Comparative Examples listed in Table are cases where a crystalline propylene homopolymer was used as the crystalline polyolefin and talc was used as the inorganic filler. As can be seen from the construction table, Examples 1 to 13
is a mixture of crystalline propylene homopolymer with talc, Compound A, and Compound B. Comparing Examples 1 to 13 with Comparative Example (without Compound A and Compound B), it is found that It can be seen that Examples 1 to 13 are excellent in tensile elongation and impact resistance. Comparative Example 2 in which Compound A is not blended and Compound B is not blended (a composition in which an inorganic filler is used in combination with the polyolefin composition related to JP-A-F@60-181146 previously proposed by the present inventor) and Examples Comparing Samples Nos. 1 to 13, Comparative Example 2 shows a considerable improvement in tensile elongation and impact resistance compared to Comparative Example 1, but it is still not sufficient. Comparing Comparative Example 3, which contains Compound B but does not contain Compound A, and Examples 1 to 13, it is clear that Comparative Example 3 has better tensile elongation and #IgE impact resistance than Comparative Example 1. It can be seen that almost no improvement effect is observed. Furthermore, Example 1~
Comparing Comparative Examples 4 to 9 in which a fatty acid metal salt other than Compound B was blended in place of Compound B in Example 13, it was found that the tensile elongation and '#i of Comparative Examples 4 to 9 were
The impact strength is almost the same as that of Comparative Example 2, and it can be seen that fatty acid metal salts other than Compound B hardly improve the tensile elongation and impact resistance. Therefore, it is clear that the comparative examples 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 #I impact strength obtained in the present invention are unique effects that can only be seen when Compound A and Compound B are used together in a composition containing an M-grade polyolefin and an inorganic filler. It can be said.

Tables 2 and 3 show a mixture of a crystalline ethylene-propylene block copolymer or a crystalline ethylene-propylene random copolymer and a Ziegler-Natta high-density ethylene homopolymer as the crystalline polyolefin, and an inorganic filler, respectively. The same effects as those described above were confirmed for these 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 kumikaimono of the present invention has (1) extremely excellent tensile elongation and impact resistance without impairing the rigidity, heat-resistant rigidity, and dimensional stability of the molded product when it is made into a ji-shaped product. ing. (2)
Due to its outstanding tensile elongation and impact resistance, it is suitable for various types of molded products such as injection molded products, extruded molded products, vacuum formed products, pressure molded products, and press (stamping) molded products. It can be used. that's all

Claims (1)

[Claims] (1) A cyclic phosphorus compound represented by the following general formula [I] (hereinafter, compound A
That's what it means. ) and 0.05 to 1 part by weight of the following [1] to [
2] one or more compounds selected from
It is called compound B. ) is blended in an amount of 0.01 to 1 part by weight. [1] Aliphatic monocarboxylic acid metal salt (however, metal indicates potassium, zinc or lead) [2] Hydroxy higher fatty acid metal salt (however, metal indicates potassium, zinc or lead) ▲Mathematical formula, chemical formula , tables, etc. ▼ [ I ] (However, in the formula, Ar_1 and Ar_2 represent an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group, or an aralkylarylene group, respectively.)