JPH02300246A - Crystalline polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain a crystalline polyolefin composition improved in the rigidity, hot rigidity, molding rate, etc., of a molding by mixing a crystalline polyolefin with a specified fluorophosphite compound and potassium salt of an aromatic carboxylic acid in specified amounts. CONSTITUTION:A crystalline polyolefin composition is produced by mixing 100 pts.wt. crystalline polyolefin (A) (e.g. polyethylene) with 0.001-1 pt.wt. fluorophosphite compound (B) of the formula (wherein R is a 1-4C alkylidene or sulfur; Ar1 and Ar2 are each an alkylarylene or a cycloalkylarylene, and n is 0 or 1) and 0.001-1 pt.wt. potassium salt of an aromatic carboxylic acid (C). Examples of component B include 2,2'-bis(4,6-di-t-butylphenyl) fluorophosphite and examples of component C include potassium benzoate and potassium p-t- butylbenzoate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a crystalline polyolefin composition from which a molded article having excellent rigidity and heat-resistant rigidity can be obtained.

More specifically, it relates to a crystalline polyolefin composition in which a molded article with excellent rigidity and heat-resistant rigidity is obtained by blending a fluorophosphite compound having a specific structure and potassium aromatic carboxylate in crystalline polyolefin in specific amounts. .

[Prior Art] Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties, so they can be used for Jt extrusion molded products, blow molded products,
It is used to manufacture various molded products such as films, sheets, and fibers. However, depending on various specific uses, the mechanical properties may not be sufficient, and there is a problem that there is a limit to the expansion of the specific uses. In particular, in terms of rigidity such as rigidity and heat-resistant rigidity (hereinafter, rigidity means rigidity and heat-resistant rigidity), it is inferior to polyesters such as polystyrene, ABS resin, polyethylene terephthalate, and polybutylene terephthalate. However, there are disadvantages in that the applications for which crystalline polyolefins can be used are limited. For this reason,
Various nucleating agents have been used for the purpose of improving the rigidity of crystalline polyolefins. In particular, aromatic carboxylic acid metal salts have a relatively excellent effect on improving rigidity and are widely used.

Further, JP-A-63-227594 discloses a composition in which an aromatic fluoroline compound is blended as an antioxidant with a crystalline polyolefin, and that a nucleating reagent can be used in combination with the composition.

[Problem II1 to be solved by the invention] However, although sodium salts or aluminum salts are excellent in improving stiffness as the aromatic carboxylic acid metal salt, the effect of potassium salts in improving stiffness is still sufficiently satisfactory. In addition, Japanese Patent Application Laid-open No. 1983-227594, which discloses a composition in which an aromatic fluoroline compound is blended with a crystalline polyolefin, discloses that a nucleating reagent, that is, a nucleating agent, is added to the composition. cheap, 6. There is no description that the rigidity of a molded article obtained from a crystalline polyolefin composition is improved by using a potassium aromatic carboxylate such as potassium fragrant in combination, and the rigidity is improved by the combined use. There is no record that suggests this.

The present inventor has conducted extensive research in order to obtain a crystalline polyolefin composition that provides a molded article with improved rigidity, which is the above-mentioned problem M regarding crystalline pyroolefin compositions.

As a result, the inventors discovered that crystalline pyroolefin has a specific l
It has been discovered that a crystalline pyroolefin composition containing specific amounts of a fluorophosphite compound having an Il structure and potassium aromatic carboxylate is a composition that provides a molded article with improved m-property. The present invention was completed based on this knowledge.

As is clear from the above description, one object of the present invention is to provide a crystalline pyroolefin composition which, when formed into a molded article, has improved rigidity.

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

(1) A fluorophosphite compound represented by the following general formula [I] (hereinafter referred to as compound A) and potassium aromatic carboxylate (hereinafter referred to as compound B) are added to 100 parts by weight of the crystalline polyolefin.

), each containing 0.001 to 1 part by weight of a crystalline polyolefin composition.

(However, in the formula, R represents an alkylidene group having 1 to 4 carbon atoms or sulfur, Ar1 and Ar2 represent an alkylarylene group or a cycloalkylarylene group, and n represents 0 or 1, respectively.) (2) Crystalline polyolefin 100ffi 0.001 to 1 part by weight of each of Compound A and Compound B and 0 part of n aliphatic amine based on the weight of each part.
．． A crystalline polyolefin composition containing 01 to 1ffiffi parts.

(3) A front fin composition further comprising 0.01 to 25 parts by weight of an inorganic filler per 10 parts by weight of M-quality polyolefin.

The crystalline polyolefin used in the present invention is a crystalline homopolymer of α-olefin such as ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1, etc. α−
Crystalline or low-crystalline random copolymers or crystalline block copolymers of olefins, copolymers of the above-mentioned α-olefins and vinyl acetate or acrylic esters, and 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 these copolymers and metal ion compounds, Modified polyolefin 5 obtained by modifying a crystalline homopolymer, crystalline or low-crystalline random copolymer, or crystalline block copolymer of α-olefin with an unsaturated carboxylic acid or a derivative thereof.
Examples include silane-modified polyolefins obtained by modifying crystalline homopolymers of olefins, crystalline or low-crystalline random copolymers, or crystalline block copolymers with unsaturated silane compounds. Although it is possible to use them alone, two or more types of crystalline polyolefins can also be used in combination. Furthermore, in addition to the above-mentioned crystalline polyolefin, various synthetic rubbers (e.g. non-grade ethylene-propylene random copolymer, amorphous 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) or thermoplastic synthetic resins (e.g. polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terebutarate) , polycarbonate, polyvinyl chloride, fluororesin, etc.).
A crystalline propylene copolymer containing at least % by weight, which is a crystalline ethylene-propylene random copolymer, a crystalline propylene-butene-1 random copolymer, or a crystalline ethylene-propylene-butene-13 element copolymer. , a crystalline propylene-hexene-butene-13-element copolymer, and a mixture of two or more thereof are particularly preferably used.

Compound A used in the present invention is 2,2'-bis(
4,6-di-butylphenyl)fluorophosphite, 2,2'-bis(4-methyl-6-t-butylphenyl)fluorophosphite, 2,21-bis(4
-amyl-6-methylphenyl)fluorophosphite, 2,2'-bis(4-s-eicosylphenyl)fluorophosphite, 2,2'-methylene-bis(4-methyl-6-t- butylphenyl)fluorophosphite, 2,2'-methylene-bis(4-ethyl-
6-t-butylphenyl)fluorophosphite, 2
, 2'-methylene bis(4-methyl-6-nonylphenyl)fluorophosphite, 2,2'-methylene-
Bis(4,6-dinonylphenyl)fluorophosphite, 2,2'-methylene-t's(4-methyl-6-
cyclohexylphenyl)fluorophosphite, 2
．． 2'-methylene-bis(4-methyl-8-(1'-methylcyclohexyl)phenyl)fluorophosphite, 2.2"i-propylidene-bis(4-nonylphenyl)fluorophosphite, 2.21-butylidene -bis(4,6-dimethylphenyl)fluorophosphite, 2,2'-methylene-bis(4,6-di-t-
butylphenyl)fluorophosphite, 2.2
'-ethylidene-bis(4-methyl-6-t-butylphenyl)fluorophosphite, 2.2'-ethylidene-bis(4-ethyl-8-t-butylphenyl)fluorophosphite, 2.21-ethylidene - screw (4
-s-butyl-6-t-butylphenyl)fluorophosphite, 2,2'-ethylidene-bis(4,6
- dibutylphenyl) fluorophosphite,
2.22-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, Z,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( Examples include 212'-bis(4,6-di-butylphenyl)fluorophosphite, 2,2'-methylene-bis(4-t-amylphenyl)fluorophosphite, etc.
-Methyl-6-t-butylphenyl)fluorophosphite, 2,2'-methylene-bis(4,6-di-butylphenyl)fluorophosphite, 2,2
'-ethylidene-bis(4-methyl-6-butylphenyl)fluorophosphite 52.2'-ethylidene-bis(4,6-di-butylphenyl)fluorophosphite and 2,2'-thio- Bis(4-methyl-6-t-butylphenyl)fluorophosphite is preferred; these compounds A are disclosed in JP-A No. 63-22759.
It can be obtained by the manufacturing method described in Publication No. 4. That is, according to the reaction formula below, bisphenol, which is a raw material phenol for compound A, is reacted with phosphorus trichloride or phosphorus tribromide to form diarylene monohalophosphite (diarylene monochlorophosphite or diarylene monobromophosphite). ).

The resulting diarylene monohalophosphite is treated with a fluorinating reagent (e.g. HF, LiF, NaF, K
F, RbF, CsF, 5bFi, SbF5, Ac F
, I(gF2.CoF3, SF.

Compound A can be obtained by reacting (etc.).

(However, in the formula, R is an alkylidene group having 1 to 4 carbon atoms or sulfur, Arl and Ar2 are an alkylarylene group or a cycloalkylarylene group, X is chlorine or bromine, YF is a fluorinating reagent, and n is O or 1 respectively.) It is natural to use the compound A alone, but it is also possible to use two or more kinds of the compound A in combination.

The blending ratio of the compound A is 100% of the crystalline polyolefin.
0.001 to 1 part by weight, preferably 0.001 to 1 part by weight.
01-0.5. This is the tyu club. If the amount is less than 0.001 part by weight, the effect of improving the rigidity will not be sufficiently exhibited, and although it is possible to add more than 1 part by weight, it is not practical because no further improvement in the rigidity can be expected. It is also uneconomical.

Compound B used in the present invention includes potassium benzoate, potassium 0-toluate, potassium m-toluate,
Potassium p-toluate, Potassium p-t-butylbenzoate, Potassium p-t-amylbenzoate, p-Si-
Potassium octylbenzoate, potassium 0-methoxybenzoate, potassium methoxybenzoate, potassium anisate, potassium phthalate, potassium isophthalate, potassium terephthalate, potassium trimellidate, potassium pyromellitate, potassium pyritate, potassium salicylate, Examples include potassium acetylsalicylate and potassium 3,5-di-butyl-4-hydroxybenzoate.
Particularly preferred are potassium benzoate and potassium pt-butylbenzoate.These compounds B can be used alone, but two or more types of compounds B can also be used in combination.

The compounding ratio of the compound B is 5: 10: Crystalline polyolefin
0.001 to 1 part by weight, preferably 0 parts by weight
．． 01-0.5 parts by weight. If the amount is less than 0.001 part by weight, the effect of improving the rigidity will not be sufficiently exhibited, and although it is possible to add more than 1 part by weight, it is not practical because no further improvement in the rigidity can be expected. It is also uneconomical.

In the composition of the present invention, it is preferable to use an aliphatic amine in combination because it synergistically exhibits the effect of improving the stiffness. As the aliphatic amine, octylamine, laurylamine, myristyl Amine, palmitylamine, stearylamine, oleylamine, cocoaamine, tallowamine, soyamine, N,N-dicocoamine, N,N-citallowamine, N,N-diniumine, N-lauryl-N, N-dimethylamine, N-myristyl-N , N-dimethylamine, N-valmityl-N
, N-dimethylamine 1. N-stearyl-N, N-dimethylamine, N-coco N, N-dimethylamine, N
-Tallow N, N-dimethylamine, N-Soy N, N
-dimethylamine, N-methyl-N, N-dimethylamine, N-methyl-N, N-dicocoamine, N-oleyl-1,3-diaminopropane, N-ta6u1,3
-Diaminopropane.

Hexamethylenediamine, N-lauryl-N,N,N-
Trimethylammonium chloride, N-palmityl-N,N,N-)dimethylammonium chloride, N-
Stearyl-N,N,N-)dimethylammonium chloride, N-tocosyl-N,N,N-trimethylammonium chloride, N-coco-N,N,N-trimethylammonium chloride, N-tallow-N,N,N
4-trimethylammonium chloride, N-soy-N, N
, N-) dimethylammonium chloride, N, N, N
-) diethyl-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-
Shitaro N, N-dimethylammonium chloride,
N,N-Cisoee N,N-dimethylammonium chloride, N,N-bis(2- and droxyethyl)-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) lauryl aminobetaine, N, N
-bis(2-hydroxyethyl)tridecylaminobetaine, N,N-bis(2-hydroxyethyl)myristylaminobetaine, N,N-bis(2-hydroxyethyl)pentadecylaminobetaine, N,N-bis( 2-
hydroxyethyl) balmitylaminobetaine, N, N
-bis(2-hydroxyethyl)stearylaminobetaine, N,N-bis(2-hydroxyethyl)oleylaminobetaine, N,N-bis(2-hydroxyethyl)tocosylaminobetaine, N,N-bis(2-hydroxyethyl)tocosylaminobetaine, -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)pentadecylamine, N-(2-hydroxyethyl)palmitylamine, -hydroxyethyl)oleylamine,
N-(2-hydroxyethyl)tocodylamine, N-(
2-hydroxyethyl)oftacosylamine, N-(2
-hydroxyethyl)cocoamine, N-(2-hydroxyethyl)tallowamine, N-methyl-N-(2-hydroxyethyl)laurylamine, Nlthyl-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) -hydroxyethyl)stearylamine, N-methyl-N-(2-hydroxyethyl)oleylamine.

N-Methyl-N-(2-hydroxyethyl)tocodylamine, N-methyl-N-(2-hydroxyethyl)oftacosylamine, N-methyl-N-(2- and droxyethyl)cocoamine, N-methyl-N- (2-hydroxyethyl)tallowamine, N,N-bis(2-hydroxyethyl)laurylamine% N,N-bis(2-hydroxyethyl)tridecylamine, N,N-bis(2-hydroxyethyl)myristylamine , N, N-bis(2
-Hydroxyethyl)pentadecylamine, N,N-bis(2-hydroxyethyl)palmitylamine, N,N
-bis(2-hydroxyethyl)stearylamine, N
, N-bis(2-human[1-xyethyl)oleylamine, N,N-bis(2-hydroxyethyl)tocodylamine, N,N-bis(2-hydroxyethyl)oftacosylamine, N,N-bis(2- N,N-bis(2-hydroxyethyl)n such as N,N-bis(2-hydroxyethyl)tallowamine, N,N-bis(2-hydroxyethyl)cocoamine,
Aliphatic amine, N,N-bis(2-hydroxyethyl)
J+! Mono- or diesters of aliphatic amines with fatty acids such as lauric acid, myristic acid, balmitic acid, stearic acid, oleic acid, polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether,
Polyoxyethylene cocoaminoether, polyoxyethylene cocoaminoether, N, NN l, N l
-tetra(2-hydroxyethyl)-1,3-diaminopropane, N,N,N',Nξtetra(2-hydroxyethyl)-1,6-diaminohexane, N-lauryl-N,N',N' -) Lis(2-hydroxyethyl)-
1,3-diaminopropane, N-stearyl-N,N
'.

N'-tris(2-hydroxyethyl)-1,3-diaminopropane, N-coco-N,N',N'.tris(
2-hydroxyethyl)-1,3-diaminopropane,
N-tallow-N,N',N'-)lis(2-hydroxyethyl)-1,3-diaminopropane, N,N
-Jikoko 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-diaminohexane, N-tallow N, N', N'-
Tris(2-hydroxyethyl)-1,8-diaminohexane, N,N-dicokoN',N'-bis(2-
Hydroxyethyl> -i,a-diaminohexane and N,N-citaro~N',N'-bis(2-hydroxyethyl)-1,6-diaminohexane, etc., and in particular N,N-bis(2-hydroxyethyl) - and droxyethyl) n aliphatic amines are preferred; these aliphatic amines can be used alone, but aliphatic amines of 2$1 or more can also be used in combination. The blending ratio of the aliphatic amine is 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of the crystalline diolefin.

In the composition of the present invention, it is preferable to use an inorganic filler in combination because the effect of improving the rigidity is synergistically exhibited.As the inorganic filler, talc 5
Mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, calcium silicate, aluminum silicate, glass Fiber, potassium titanate, carbon fiber, carbon black.

graphite and metal fibers, as well as coupling agents (e.g. silanes, titanates).

Examples of the inorganic filler surface-treated with a surface treating agent such as boron-based, aluminate-based, zircoaluminate-based, etc., and talc are particularly preferred.

Of course, these inorganic fillers can be used alone, but two or more types of inorganic fillers can also be used in combination. The blending ratio of the M inorganic filler is 0.01 to 25 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 1 to 15 parts by weight based on 100 parts by weight of the crystalline polyolefin.

The composition of the present invention contains various additives that are usually added to crystalline polyolefins, such as antioxidants such as phenol, thioether, and phosphorus (excluding compound A), light stabilizers, heavy metals, etc. Deactivating agent, clarifying agent,
Nucleating agents (excluding compound B), lubricants, antistatic agents, antifogging agents, antiblocking agents, dripless agents, flame retardants, flame retardant aids.

Pigments, radical generators such as peroxides, halogen scavengers, dispersants or neutralizing agents such as metal soaps, or organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) are used in the present invention. They can be used together as long as the purpose is not impaired.

The m-sensitive material of the present invention is prepared by adding predetermined amounts of each of the above-mentioned compounds AJj and B, as well as the above-mentioned various additives that are normally added to crystalline polyolefins, to a crystalline polyolefin using a conventional mixing device such as a Henschel mixer (trade name), a super mixer, etc. Mix using a mixer, ribbon blender, Pan Bali mixer, etc., and mix using a regular single-screw extruder, twin-screw extruder,
Brabender or roll, melting crosstalk temperature 150
It can be obtained by melt-kneading and pelletizing at a temperature of 180 to 270°C, preferably 180 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.

[Function] In the present invention, it is generally known that Compound A acts as a peroxide decomposition agent and Compound B acts as a nucleating agent to improve the rigidity of crystalline polyolefin.6 However, in the present invention In, compound A and compound B
The mechanism of action itself is not clear, but it is presumed to be due to the following mechanism of action. That is, compound B acts as a metal ion donor to the compound, and a coordinate bond or ionic bond is formed between the fluorine atom, which is the element with the highest electronegativity, and the potassium ion of compound B in the molecule of compound A. It is thought that by forming this, the inherent nucleation effect of Compound B is synergistically improved and the rigidity is improved.

[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, the length was 10100n, the width was 10g+,
A test piece with a thickness of 4 nm was created by injection molding, and the bending elastic modulus was sub-determined using the test piece (JIS K 7
Rigidity was evaluated based on 203). A highly rigid material is one that has a large bending modulus.

2) Heat-resistant rigidity: Evaluated by load deflection temperature test. That is, the length is 130 m using the obtained pellets.

A test piece with a width of 13 m and a thickness of 6.5 mm was made by injection molding, and the heat distortion temperature of 1 degree was measured using the test piece (J
Compliant with ISK7207; 4.6k (f/cm2 load)
The heat resistance rigidity was evaluated by A material with high heat resistance and rigidity is one that has a high heat deformation temperature.

Examples 1-11. Comparative Examples 1 to 10 MFR (discharge jk of molten resin for 10 minutes when applying a load of 2.16 kg at 230°C) as crystalline polyolefin 6.0 g/unstabilized powdered crystalline propylene for 10 minutes alone 100 parts by weight of polymer,
Compound A is 2,2'-bis(4,6-di-butylphenyl)fluorophosphite, 2,2'-bis(4-s-eicosylphenyl)fluorophosphite, or 2,2'-ethylidene- Bis(4,6-di-butylphenyl)fluorophosphite, potassium benzoate or potassium pt-butylbenzoate as compound B, and other additives in predetermined amounts in the proportions listed in Table 11 below. The mixture was placed in a Henschel mixer (trade name), stirred and mixed for 3 minutes, and then melt-kneaded at 200° C. in a single-screw extruder with a diameter of 40 to form pellets. In addition, as Comparative Examples 1 to 10, MFR is 6.0 g/1
A predetermined amount of each of the additives listed in Table 1 below was blended with 100 parts by weight of unstabilized powdered crystalline propylene homopolymer 15, and melt-kneaded in accordance with Examples 1 to 11. to obtain pellets.

Test pieces used for evaluation of rigidity and heat-resistant rigidity 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 piece, rigidity and heat-resistant rigidity were evaluated by the test method described above. These results! ! ! It is shown in Table 1.

Examples 12-22. Comparative Examples 11-20 MFR4,0 as crystalline polyolefin 710
unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight)
2,2'-methylene- as compound A to 100 parts by weight.
Bis(4-methyl-6-t-butylphenyl)fluorophosphite, 2,2'-methylene-bis(4,
6-di-butylphenyl)fluorophosphite or 2,2'-ethylidene-bis(4,6-di-butylphenyl)fluorophosphite, compound B
Add the predetermined amounts of P-hyoctyl benzoate, potassium anisate, and other additives as described below! Henschel mixer at the mixing ratio listed in Table 2.
(product name), stir and mix for 3 minutes, and then
The mixture was melt-kneaded and pelletized at 200° C. using a single-screw extruder. Moreover, as a comparative example It~20, MFR is 4-0
g/10 min of unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene-containing ff1
8.5% by weight) 100 parts by weight were blended with predetermined amounts of each of the additives listed in the fJ2 table below, and Examples 12-
Pellets were obtained by melt cross-fertilization according to 22.

The test pieces used to evaluate stiffness and heat resistance stiffness are as follows.

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 piece, rigidity and heat-resistant rigidity were evaluated by the test method described above. These results are shown in Table 2.

Examples 23 to 33, Comparative Examples 21 to 30 MFR8,0g/1 as crystalline polyolefin
2,2'-methylene-bis(4,6-ditunylphenyl)fluorophosphite, 2,2'-ethylidene- Bis(4-methyl-6-butylphenyl)fluorophosphite or 2,2'-ethylidene-bis(4,6-di-butylphenyl)
butylphenyl) fluorophosphite, potassium salicylate or potassium 3,5-di-L-butyl-4-hydroxybenzoate as compound B, and other additives in the proportions listed in Table 3 below. After stirring and mixing for 3 minutes, the mixture was melted and mixed at 200° C. using a single-screw extruder with a diameter of 40 mm to form pellets. Also, Comparative Examples 21 to 30
100 parts by weight of an unstabilized powdered crystalline propylene homopolymer having an MFR of 8.0 g/10 minutes was blended with a predetermined amount of each of the additives listed in Table 3 below,
Pellets were obtained by melt-kneading according to Examples 23-33.

Test pieces used for evaluation of rigidity and heat-resistant rigidity 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 piece, rigidity and heat-resistant rigidity were evaluated by the test method described above. These results are shown in Table 3.

Examples 34-44, Comparative Examples 31-40 As crystalline polyolefin M F R1.0g/1
0 min unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight)
) 70ffi amount % and MI (discharge amount of molten resin in 10 minutes when applying a load of 2.16 kg at 190°C) Log/unstabilized powdered Ziegler-Natsuta high-density ethylene homopolymer in 10 minutes 30% by weight
2.2' as compound A to a total of 100 parts by weight consisting of
-butylidene-bis(4-methyl-6-(1'-methylcyclohexyl)phenyl)fluorophosphite, 2. 2'-
Thio-bis(4-methyl-6-α-methylbenzylphenyl)fluorophosphite, potassium terephthalate or potassium pyromellitate as compound B, and other additives in prescribed amounts in the proportions listed in Table 4 below. Put it in a Henschel mixer (product name) and mix for 3 minutes, then mix it with a 40mm diameter axle extrusion machine.
The mixture was melted and kneaded at ℃ to form pellets. Also, comparative example 3
Unstabilized powdered crystalline ethylene-7 propylene random copolymer (ethylene content 2.5 wt%) with MFR of 7.0 sections/10 minutes as 1 to 40 (ethylene content 2.5 wt%) and MI of 1Og/10 Unstabilized powdered Ziegler-Natsuta high density ethylene homopolymer 30 minutes
A total of 100 parts by weight consisting of % by weight was blended with a predetermined amount of each of the additives listed in Table 4 below, and Examples 33 to 44 were prepared.
Pellets were obtained by melt mixing according to the following.

The test pieces used for evaluation of rigidity and heat-resistant rigidity were obtained by injection molding the obtained pellets at a resin temperature of 250°C and a mold temperature of 50°C.

Using the obtained test piece, rigidity and heat-resistant rigidity were evaluated by the test method described above. These results are shown in Table 1174.

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

Compound A [1]: 2.2'-bis(4,6-dibutylpuenyl)fluorophosphite compound A [II 2.2'-bis(4-5-eicosylphenyl)fluorophosphite compound A [ml: 2,2'-methylene-bis(4
-Methyl-6-7-butylphenyl)fluorophosphite compound A [rV]: 2,2'-methylene-
Bis(4,6-di-butylphenyl) fluorophosphite compound A [V]: 2,2'-methylene-bis(4,6-ditunylphenyl) fluorophosphite compound A [VI]: 2,2'- Ethylidene-bis(4-methyl-6-t-butylphenyl)fluorophosphite compound A [■]: 2,2'-ethylidene-bis(4
, 6-di-butylphenyl) fluorophosphite compound A [■]: 2,2'-butylidene-bis(
4-Methyl・6-(1′・methylcyclohexyl)phenyl)fluorophosphite compound A [IX]: 2,2′-thio-bis(4-
methyl-e-butylphenyl)fluorophosphite compound A [X]: 2,2'-thio-bis(4
-Methyl-6-α-methylbenzylphenyl) fluorophosphite compound B [1: Potassium benzoate compound B [I[]: ] p-t-t-butyrate potassium compound B [ml: p-t-octyl Potassium benzoate compound B [■] Potassium nianisate compound B
[V]: Potassium salicylate compound B [VI Coni 3
, 5-di-L-butyl-4-hydroxybenzoic acid potassium compound B [■]: Potassium terephthalate compound B [■]
: Bilomelipyripotassium 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-tallow-1,3-diaminopropane aliphatic amine 6: hexamethylenetetramine aliphatic amine 7: N -Tocosyl-N,N,N-1-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 Co-triisoprobanolamine Aliphatic amine +2: N,N-bis(2-hydroxy ethyl)
Cocoamine fatty amine 13: N,N-bis(2-hydroxyethyl)tallowamine fatty amine 14: octadecane a24 (2-hydroxyethyl) octadecyl amino coethyl ester fatty amine 15: (octadecyl imino) diethylene distearate fat Group 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- and droxyethyl) -1,3-diaminopropane aliphatic amine 20: N,N -Jikoko N', N'
-Bis(2-hydroxyethyl) -1,6-cyamitsuhexa 211111 machine filler 1: talc inorganic filler 2: calcium carbonate inorganic filler 3: barium sulfate phenolic antioxidant 1: 2,6-di-butyl P-cresol phenolic antioxidant 2: Tetrakis [methylene 3
- (3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane phenolic antioxidant 3: 1,3.51limethyl-
2,4,6-tris(3,5-di-L-butyl-4-hydroxybenzyl)benzenephenolic antioxidant 4: 1,3. S-Tris (3
, 5-dibutyl-4-hydroxybenzyl) isocyanurate phenolic 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]
Undecanethioether antioxidant 1: dimyristylthiodiprobionate thioether antioxidant 2: distearylthiodipropionate thioether antioxidant 3: pentaerythritol-
Tetrakis(3-laurylthiopropionate) Phosphorous antioxidant 1: Bis(2,4-di-butylphenyl)-pentaerythritol-cyphosphite phosphorus antioxidant 2: Bis(2,6-di-butylphenyl) Shi-butyl-4-methylphenyl)-pentaerythritol-shiphosphite phosphorus-based antioxidant 3: Tetrakis (2,4-di-butyl-4-methylphenyl)-4,4'-biphenylene, diphosphite phosphorus oxidation Inhibitor 4: Tris(2,4-di-butylphenyl)phosphite The Examples and Comparative Examples listed in Table 1 are cases where a crystalline propylene homopolymer was used as the crystalline polyolefin. As can be seen from the $1 table, Examples 1 to 11 are compounds in which Compound A and Compound B are blended into a crystalline propylene homopolymer; (not blended) and Comparative Example 2
(Compound B is blended with the compound and Compound B is not blended), Examples 1 to 11 are significantly superior in terms of rigidity, and Comparative Example 2, in which Compound A is blended with Comparative Example 1, is It can be seen that the combination of A hardly improves the rigidity. Comparing Comparative Examples 3 to 4, in which Compound B was blended and Compound A was not blended, and Examples 1 to 11, the rigidity of Comparative Examples 3 to 4 was improved to some extent compared to Comparative Examples 1 to 2. Comparative Examples 5 to 8 and Examples 1 to 11, in which a phosphorus antioxidant (a phosphite compound or a phosphite compound) other than Compound A was added to Comparative Example 3, were compared. As a result, the rigidity of Comparative Examples 5 to 8 is comparable to that of Comparative Example 3, which is still not sufficient, and even if a phosphorus-based antioxidant other than Compound A is used in combination with Compound B, the rigidity is hardly improved. I understand. Furthermore, Comparative Example 9 in which R aliphatic amine was blended and Compound A and Compound B were not blended, and Examples 1 to
When compared with Comparative Example 11, it can be seen that Comparative Example 9, like Comparative Example 2, is not improved in terms of rigidity. Furthermore, when comparing Comparative Example 10, which is a combination of Comparative Example 3 and Comparative Example 9, that is, Comparative Example 10 in which an aliphatic amine was used in combination with Compound B, and Examples 1 to 11, the rigidity of Comparative Example 10 is improved compared to Comparative Example 3. Although efforts are being made, it is still not sufficient.

Therefore, two of compound A and compound B related to the present invention are
It is clear that comparisons that do not simultaneously satisfy the composition of the components do not exhibit the effects of the present invention. That is, it can be said that the rigidity obtained in the present invention is a unique effect that can only be seen when Compound A and Compound B are used together in the present invention. Furthermore, in the compositions of Examples 1 to 6, Examples 7 to 11 in which various aliphatic amines were used in combination were those of Examples 1 to 6.
It can be seen that the excellent stiffness improving effect of Compound A and Compound B is not inhibited compared to Compound 6, and a remarkable synergistic effect is observed by the combined use of aliphatic amine.

Tables 2 to 4 show crystalline ethylene-propylene block copolymers, crystalline propylene homopolymers, crystalline ethylene-propylene random copolymers, and Ziegler-Natsuta high-density ethylene homopolymers as crystalline polyolefins, respectively. The same effects as those described above were confirmed for these as well.

[Effects of the Invention] Compared to conventionally known crystalline polyolefin compositions containing potassium aromatic carboxylate and having improved rigidity, the composition of the present invention has the following advantages: It has outstanding rigidity. (2) Not only can the molded product be made thinner, contributing to resource conservation, but also the cooling rate during molding is faster, which increases the molding speed per unit time, contributing to improved productivity. can.

that's all

Claims (3)

[Claims] (1) For 100 parts by weight of crystalline polyolefin, add a fluorophosphite compound represented by the following general formula [I] (hereinafter referred to as compound A) and potassium aromatic carboxylate (hereinafter referred to as compound B). A crystalline polyolefin composition containing 0.001 to 1 part by weight of each. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, R is an alkylidene group having 1 to 4 carbon atoms or sulfur, Ar_1 and Ar_2 are an alkylarylene group or a cycloalkylarylene group, and n is 0.
or 1 respectively. ) (2) A crystalline polyolefin composition comprising 0.001 to 1 part by weight of each of Compound A and Compound B and 0.01 to 1 part by weight of an aliphatic amine to 100 parts by weight of crystalline polyolefin. (3) The crystalline polyolefin composition according to claim (1) or claim (2), further comprising 0.01 to 25 parts by weight of an inorganic filler per 100 parts by weight of the crystalline polyolefin.