JPH0827321A - Crystalline polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain a crystalline polyolefin compsn. which gives a molding excellent in stiffness and heat resistance by compounding a crystalline polyolefin with a coumarin deriv. and specific phophorus compds. in a specified wt. ratio. CONSTITUTION:This compsn. comprises 100 pts.wt. crystalline polyolefin, 0.001-1pt.wt. coumarin deriv. of formula I (wherein R1 to R6 are each H, halogen, hydroxyl, carboxyl, or a 1-8C hydrocarbon group), 0.001-1 pt.wt. cyclic phosphorus compd. of formula II (wherein R is 1-4C alkylidene, sulfur, or a direct bond; Ar<1> and Ar<2> are each alkylarylene, cycloalkylarylene, arylarylene, or aralkylarylene; and X is fluorine or hydroxyl), and 0.001-1 pt.wt. biphenylylenediphosphoric acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline polyolefin composition capable of obtaining a molded article excellent in rigidity and heat resistance. More specifically, the present invention relates to a crystalline polyolefin composition which is obtained by molding a crystalline polyolefin, a coumarin derivative and a specific phosphorus compound each in a specific amount and is excellent in rigidity and heat resistance.

[0002]

2. Description of the Related Art Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties.
It is used to manufacture various molded products such as hollow molded products, films, sheets, and fibers. However, mechanical properties may not be sufficient depending on various specific uses, and there is a problem that expansion of the specific uses is limited.

In particular, a rigid surface such as rigidity and heat resistant rigidity (hereinafter, rigid surface means rigidity and heat resistant rigidity).
With regard to (1), since it is inferior to polyesters such as polystyrene, ABS resin, polyethylene terephthalate, and polybutylene terephthalate, there is a drawback in that the use of crystalline polyolefin may be limited in specific applications. Therefore, various nucleating agents have been conventionally used for the purpose of improving the rigidity of crystalline polyolefin.

On the other hand, JP-A-6-93188 discloses that the crystallization rate of a crystalline thermoplastic resin, a coumarin derivative and an organic phosphite compound is increased, and mechanical properties such as rigidity and heat resistance are increased. A crystalline resin composition that is excellent in optical properties such as transparency and surface smoothness is described, and as an organic phosphite compound, 2,2'-ethylidene bis (4,6-di-t -Butylphenyl)
Fluorophosphonite, 2,2'-methylenebis (4,6-
Di-t-butylphenyl) octyl phosphite and the like are mentioned.

[0005]

However, although the rigid surface of the molded product obtained from the composition obtained by blending the crystalline polyolefin with various conventionally known nucleating agents is improved to some extent, it is still not sufficiently satisfactory. . Although the molded product obtained from the crystalline polyolefin-based resin composition described in JP-A-6-93188 has improved rigidity, it is still not sufficiently satisfactory, and the organic phosphine described in this publication is not satisfactory. As a phyto compound,
2,2'-ethylidene bis (4,6-di-t-butylphenyl) fluorophosphonite was converted to 2,2'-ethylidene bis (4,6-di-t-butylphenyl) fluorophosphite by 2,2 Crystalline polyolefin resin obtained by substituting 2,2'-methylenebis (4,6-di-t-butylphenyl) acid phosphite for'-methylenebis (4,6-di-t-butylphenyl) octylphosphite. No further mention or suggestion is made to further improve the rigidity of the moldings obtained from the composition.

The present inventor has conducted earnest studies to obtain a crystalline polyolefin composition which gives a molded article having the above-mentioned problems relating to the crystalline polyolefin composition, that is, a rigid surface. As a result, the present inventor has found that a crystalline polyolefin composition comprising a crystalline polyolefin, a coumarin derivative and a specific phosphorus compound each in a specific amount is a composition which gives a molded article having an improved rigidity. The present invention has been completed based on the above.

As is clear from the above description, it is an object of the present invention to provide a crystalline polyolefin composition in which the molded article has an improved rigidity.

[0008]

The present invention has the following constitution. 100 parts by weight of crystalline polyolefin, the following general formula
0.001 to 1 part by weight of a coumarin derivative represented by (1) (hereinafter referred to as compound A), a cyclic phosphorus compound represented by the following general formula (2), and biphenylylene-diphosphonic acid represented by the following general formula (3). One or more compounds (hereinafter, referred to as compound B) 0.
A crystalline polyolefin composition comprising 001 to 1 part by weight.

[0009]

[Chemical 4]

[0010]

Embedded image

[0011]

[Chemical 6]

(In the formula, R _{1 to} R ₆ are hydrogen atom, halogen atom, hydroxyl group, carboxyl group or carbon number 1 to 1)
8 hydrocarbon groups, R is an alkylidene group having 1 to 4 carbon atoms, sulfur or a direct bond, Ar ₁ and Ar ₂ are an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group,
X represents a fluorine atom or a hydroxyl group, respectively. )

The crystalline polyolefin used in the present invention is
Ethylene, propylene, butene-1, pentene-1, 4
-Methyl-pentene-1, hexene-1, octene-1
Such as a crystalline homopolymer of α-olefin, a crystalline or low crystalline random copolymer or a crystalline block copolymer of these two or more α-olefins, the above α-
Copolymer of olefin and vinyl acetate or acrylic ester, saponified product of the copolymer, copolymer of α-olefin and unsaturated silane compound, α-olefin and unsaturated carboxylic acid or anhydride thereof A copolymer, a reaction product of the copolymer and a metal ion compound, a crystalline homopolymer of the above α-olefin, a crystalline or low crystalline random copolymer or a crystalline block copolymer. Modified polyolefin modified with unsaturated carboxylic acid or its derivative, crystalline homopolymer of the above α-olefin, crystalline or low crystalline random copolymer or crystalline block copolymer modified with unsaturated silane compound Examples thereof include silane-modified polyolefins. These crystalline polyolefins can be used alone or in combination with two types. It is also possible to use a mixture of crystalline polyolefin above.

In addition to the above-mentioned crystalline polyolefin, various synthetic rubbers (for example, amorphous 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, etc.) or thermoplastic synthetic resin (for example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate) , Polybutylene terephthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluororesin, petroleum resin (for example, C ₅ petroleum resin, hydrogenated C ₅ petroleum resin, C ₉ petroleum) Resin, hydrogenated C ₉ petroleum resin, C ₅ −
C ₉ copolymerized petroleum resin, hydrogenated C ₅ -C ₉ copolymerized petroleum resin, acid-modified C ₉ petroleum resin, etc., DCPD resin (for example, cyclopentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene- C ₅ copolymerized petroleum resins, hydrogenated cyclopentadiene -C ₅ copolymer petroleum resin, cyclopentadiene -C ₉ copolymer petroleum resin, hydrogenated cyclopentadiene -C ₉ copolymer petroleum resin, cyclopentadiene -C ₅ -C ₉ copolymer Polymerized petroleum resin, hydrogenated cyclopentadiene-
C ₅ -C ₉ copolymer DC softening point 80 to 200 ° C., such as petroleum resin
It is also possible to use a mixture of (PD resin) and the like.

A crystalline propylene homopolymer, a crystalline propylene copolymer containing 70% by weight or more of a propylene component, which is a crystalline ethylene-propylene random copolymer, a crystalline ethylene-propylene block copolymer, or a crystal. Particularly preferred are crystalline propylene-butene-1 random copolymers, crystalline ethylene-propylene-butene-1 terpolymers, crystalline propylene-hexene-butene-1 terpolymers and mixtures of two or more thereof. It is preferably used.

As the compound A used in the present invention, coumarin, 4-hydroxycoumarin, 7-hydroxycoumarin, 8-hydroxycoumarin, 4-methyl-7-hydroxycoumarin, 5-methyl-7-hydroxycoumarin, 3, 4-dimethyl-7-hydroxycoumarin, 4,
6-dimethyl-7-hydroxycoumarin, 4-methyl-
8-ethyl-7-hydroxycoumarin, 4-propyl-
7-hydroxycoumarin, 3-propyl-4-methyl-
6-ethyl-7-hydroxycoumarin, 3-chloro-4
-Methyl-7-hydroxycoumarin, 4-phenyl-7
-Hydroxycoumarin, 3-phenyl-4-methyl-7
-Hydroxycoumarin, 3-benzyl-4-methyl-7
-Hydroxycoumarin, 4-phenyl-8-methyl-7
-Hydroxycoumarin, 4,7-dimethyl-5-hydroxycoumarin, 3-t-butyl-4,7-dimethyl-5
-Hydroxycoumarin, 4-methyl-7-t-amyl-
5-hydroxycoumarin, 3-chloro-4,7-dimethyl-5-hydroxycoumarin, 4-methyl-6-hydroxycoumarin, 4-phenyl-6-hydroxycoumarin, 3-chloro-4-methyl-7,8- Dihydroxycoumarin, 4-methyl-7,8-dihydroxycoumarin,
4-methyl-6-ethyl 7,8-dihydroxycoumarin, 3-phenyl-4-methyl-7,8-dihydroxycoumarin, 6,7-dihydroxycoumarin, 3-chloro-4-methyl-6,7-dihydroxycoumarin , 4-methyl-5,7-dihydroxycoumarin, 3-chloro-4
-Methyl-5,7-dihydroxycoumarin, coumarin-
Examples thereof include 3-carboxylic acid and coumarin-7-carboxylic acid, and particularly coumarin, 4-hydroxycoumarin, and 4
-Methyl-7-hydroxycoumarin, 3,4-dimethyl-7-hydroxycoumarin, 4-phenyl-7-hydroxycoumarin, 3-chloro-4,7-dimethyl-5-hydroxycoumarin and coumarin-7-carboxylic acid preferable. Not to mention the single use of these compounds A,
It is also possible to use two or more compounds A in combination. The content ratio of the compound A is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the crystalline polyolefin. If the content is less than 0.001 part by weight, the effect of improving the rigidity cannot be fully exerted, and if it exceeds 1 part by weight, not only the effect of improving the rigidity cannot be expected, but it is not practical. It is also uneconomical.

The compound B used in the present invention is
2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-bis (4-methyl-6-
t-Butylphenyl) fluorophosphite, 2,2 '
-Bis (4-t-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-bis (4-methyl-6-cyclohexylphenyl) fluorophosphite, Two
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-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-di-t-amylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4-methyl) -6-t-butylphenyl) fluorophosphite,
2,2'-ethylidene-bis (4-ethyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4-s-butyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4,6-di-t)
-Amylphenyl) 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-i-octylphenyl) fluorophosphite, 2,2′-thio-
Bis (5-t-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-t-butylphenyl) fluorophosphite, 2,2′-thio-bis (4 -T-amylphenyl) fluorophosphite,

2,2'-methylene-bis (4-methyl-6)
-T-butylphenyl) acid phosphite, 2,
2'-methylene-bis (4-ethyl-6-t-butylphenyl) acid phosphite, 2,2'-methylene-bis (4-methyl-6-nonylphenyl) acid phosphite, 2,2'-methylene -Bis (4,6-dinonylphenyl) acid phosphite, 2,2'-methylene-bis (4-methyl-6-cyclohexylphenyl) acid phosphite, 2,2'-methylene-bis {4-
Methyl-6- (1'-methylcyclohexyl) phenyl}
Acid Phosphite, 2,2'-i-propylidene-
Bis (4-nonylphenyl) acid phosphite,
2,2'-butylidene-bis (4,6-dimethylphenyl) acid phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) acid phosphite, 2,2'-methylene -Bis (4,6-di-t-amylphenyl) acid phosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl)
Acid phosphite, 2,2'-ethylidene-bis (4-ethyl-6-t-butylphenyl) acid phosphite, 2,2'-ethylidene-bis (4-s-butyl-6-t-butylphenyl) Acid phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) acid phosphite, 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) acid phosphite Fight, 2,2'-methylene-bis (4-methyl-6-t-octylphenyl) acid phosphite, 2,2'-methylene-bis (4,6-diphenylphenyl) acid phosphite, 2,2 ' -Methylene-bis (4,6-dibenzylphenyl) acid phosphite, 2,2'-ethylidene-bis (4-methyl-6-α)
-Methylbenzylphenyl) fluorophosphite,
2,2'-i-propylidene-bis (4,6-dibenzylphenyl) acid phosphite, 2,2'-butylidene-bis {4-methyl-6- (1'-methylcyclohexyl) phenyl} acid phosphite , 2,2'-methylene-bis (4,6-dimethylphenyl) acid phosphite, 4,4'-biphenylylene-di-phosphonic acid, 4,3'-biphenylylene-di-phosphonic acid and 3,3 Examples thereof include'-biphenylylene-di-phosphonic acid, and particularly 2,2'-ethylidene-bis (4,6-
Di-t-butylphenyl) fluorophosphite,
2,2'-Methylene-bis (4,6-di-t-butylphenyl) acid phosphite and 4,4'-biphenylylene-di-phosphonic acid are preferred.

Of these compounds B, 2,2'-alkylidene-bis (substituted aryl) acid phosphite is
For example, it is obtained by reacting phosphorus trichloride with 2,2'-alkylidene bisphenol and then hydrolyzing with water, or by hydrolyzing 2,2'-alkylidene-bis (substituted aryl) alkyl phosphite. Further, biphenylylene-di-phosphonic acid can be prepared as described in, for example, JP-A-47-8772, 4,4 '.
Biphenyl-di-phosphonous acid such as biphenyl-di-phosphonous acid or tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonic acid Knight, Tetrakis (2,4
-Di-t-butylphenyl) -4,3'-biphenylene-
Di-phosphonite or tetrakis (2,4-di-t-butylphenyl) -3,3'-biphenylene-di-
It can be obtained by hydrolyzing and oxidizing phosphonite.

These compounds B may be used alone or in combination of two or more kinds. The content ratio of the compound B is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, relative to 100 parts by weight of the crystalline polyolefin. If the content is less than 0.001 part by weight, the effect of improving the rigidity cannot be fully exerted, and if it exceeds 1 part by weight, not only the effect of improving the rigidity cannot be expected, but it is not practical. It is also uneconomical.

In the composition of the present invention, various additives which are usually added to the crystalline polyolefin, such as phenol type, thioether type and phosphorus type (however, compound B
, Etc.), light stabilizers, heavy metal deactivators (copper damage inhibitors), clarifiers, nucleating agents, lubricants, antistatic agents, antifogging agents, antiblocking agents, non-dripping agents , Radical generating agents such as peroxides, flame retardants, flame retardant aids, pigments, halogen scavengers, dispersants or neutralizing agents such as metallic soaps, organic or inorganic antibacterial agents, inorganic fillers ( For example, talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, magnesium carbonate,
Aluminum hydroxide, magnesium hydroxide, hydrotalcite, basic aluminum-lithium hydroxy carbonate hydrate, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, calcium oxide, zinc sulfide, barium sulfate, magnesium sulfate, silica Calcium acid, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal fiber, etc., coupling agent (for example, silane-based, titanate-based, boron-based, aluminate-based,
The above-mentioned inorganic filler or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with a surface treatment agent such as zircoaluminate type) is used within a range not impairing the object of the present invention. Can be used together.

The composition of the present invention comprises, for example, a crystalline polyolefin and the above-mentioned compound A and compound B and the above-mentioned various additives usually added to the crystalline polyolefin in predetermined amounts in a conventional mixing device such as a Henschel mixer (commercial product). Name), a super mixer, a ribbon blender, a Banbury mixer, etc., and the melt kneading temperature of 150 ℃ ~ 300 ℃, preferably 180 ℃ with a normal single screw extruder, twin screw extruder, Brabender or roll. ~ 270
It can be obtained by melt-kneading and pelletizing at ° C. The obtained composition is used for production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method, and a blow molding method.

[0023]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. 1) Rigidity: Evaluated by a bending test. That is, a test piece having a length of 100 mm, a width of 10 mm, and a thickness of 4 mm was prepared by using the obtained pellet by an injection molding method, and the flexural modulus was measured using the test piece (according to JIS K 7203) to obtain rigidity. Was evaluated. A material having a high rigidity means a material having a large flexural modulus. 2) Heat resistance rigidity: Evaluated by a deflection temperature under load test. That is, using the obtained pellets length 130 mm, width 13 mm,
A test piece with a thickness of 6.5 mm was prepared by an injection molding method, and the heat distortion temperature was measured using the test piece (according to JIS K 7207; 0.4
51 MPa) to evaluate the heat resistance rigidity. A material having high heat resistance and rigidity means a material having a high heat distortion temperature. 3) Impact resistance: evaluated by the Izod impact test. That is, using the obtained pellets length 63.5 mm, width 13 mm,
A test piece having a thickness of 3.5 mm (having a notch) was prepared by an injection molding method, and the test piece was used to measure the Izod impact strength at 23 ° C. (based on JIS K 7110) to evaluate the impact resistance. A material having excellent impact resistance means a material having a high Izod impact strength.

Examples 1 to 8 and Comparative Examples 1 to 9 MFR as crystalline polyolefin (amount of molten resin discharged for 10 minutes when a load of 21.18N at 230 ° C. is applied)
Coumarin as compound A was added to 100 parts by weight of unstabilized powdery crystalline propylene homopolymer at 6.0 g / 10 minutes.
4-hydroxycoumarin, 4-methyl-7-hydroxycoumarin, 3,4-dimethyl-7-hydroxycoumarin, 4-phenyl-7-hydroxycoumarin, 3-chloro-4,7-dimethyl-5-hydroxycoumarin or coumarin -7-carboxylic acid, 2,2'-as compound B
Bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6)
-T-butylphenyl) fluorophosphite, 2,
2'-methylene-bis (4-methyl-6-t-butylphenyl) acid phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) acid phosphite, 2,2 ' -Methylene-bis (4,6-dinonylphenyl) acid phosphite, 4,4'-biphenylylene-di-phosphonic acid, 4,3'-biphenylylene-di-phosphonic acid or 3,3'-biphenylylene- Predetermined amounts of di-phosphonic acid and other additives were added to the Henschel mixer (trade name) at the content ratios shown in Table 1 below, and the mixture was stirred and mixed for 3 minutes.
The mixture was melt-kneaded at 200 ° C. in a twin screw extruder of mm to pelletize.

Further, as Comparative Examples 1 to 9, MFR was 6.0 g / 10.
100 parts by weight of an unstabilized powdery crystalline propylene homopolymer was mixed with a predetermined amount of each of the additives described in Table 2 below, and melt-kneaded according to Examples 1 to 8. Pellets were obtained. Test pieces used for evaluation of rigidity and heat resistance 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, the rigidity and the heat resistance rigidity were evaluated by the above-mentioned test methods. The results are shown in Tables 1 and 2.

Examples 9 to 16 and Comparative Examples 10 to 18 As crystalline polyolefin, MFR 4.0 g / 10 min unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) 100 In parts by weight,
Coumarin, 4-hydroxycoumarin, 4 as compound A
-Methyl-7-hydroxycoumarin, 3,4-dimethyl-7-hydroxycoumarin, 4-phenyl-7-hydroxycoumarin, 3-chloro-4,7-dimethyl-5-hydroxycoumarin or coumarin-7-carboxylic acid,
2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) fluorophosphite as compound B, 2 , 2'-ethylidene-bis (4-
Methyl-6-t-butylphenyl) acid phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) acid phosphite, 2,2'-ethylidene-bis (4,6-) Di-t-amylphenyl) acid phosphite, 4,4'-biphenylylene-di-phosphonic acid, 4,3'-biphenylylene-di-phosphonic acid or 3,3'-biphenylylene-di-phosphonic acid and Predetermined amounts of other additives are shown in Table 3 below.
The mixture was placed in a Henschel mixer (trade name) at the content ratio described in 1 above, stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets.

Further, as Comparative Examples 10 to 18, MFR was 4.0 g / 10.
Unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) 100
A predetermined amount of each of the additives shown in Table 4 described later was mixed in parts by weight, and melt-kneaded in accordance with Examples 9 to 16 to obtain pellets. Test pieces used for evaluation of rigidity, heat resistance and impact resistance were prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. The obtained test pieces were used to evaluate the rigidity, heat resistance and impact resistance by the above-mentioned test methods. The results are shown in Tables 3 and 4.

Examples 17-24, Comparative Examples 19-27 MFR 7.0 g / 10 min as crystalline polyolefin, an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 90 Wt% and MI (amount of molten resin discharged at a load of 21.18N at 190 ° C for 10 minutes) 15.0 g / 10 minutes unstabilized powder Ziegler-Natta high density ethylene homopolymer 10 weights % In total of 100 parts by weight, and as compound A, coumarin, 4-hydroxycoumarin, 4-methyl-
7-hydroxycoumarin, 3,4-dimethyl-7-hydroxycoumarin, 4-phenyl-7-hydroxycoumarin, 3-chloro-4,7-dimethyl-5-hydroxycoumarin or coumarin-7-carboxylic acid, as compound B 2,2'-Ethylidene-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-thio-
Bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-methylene-bis (4,6-diphenylphenyl) acid phosphite, 2,2'-
i-Propylidene-bis (4,6-dibenzylphenyl) acid phosphite, 2,2'-butylidene-bis {4-methyl-6- (1'-methylcyclohexyl) phenyl} acid phosphite, 4,4 ' -Biphenylylene-di-phosphonic acid, 4,3'-biphenylylene-
Di-phosphonic acid or 3,3'-biphenylylene-
A predetermined amount of each of di-phosphonic acid and other additives was placed in a Henschel mixer (trade name) at the content ratios shown in Table 5 below, and the mixture was stirred and mixed for 3 minutes, and then the caliber was 30 mm.
Was melt-kneaded at 200 ° C. with a twin-screw extruder to produce pellets.

Further, as Comparative Examples 19 to 27, the MFR was 7.0 g / 10.
Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) 90
Unstabilized powdered Ziegler-Natta high density ethylene homopolymer with wt% and MI of 15.0 g / 10 min
A predetermined amount of each of the additives shown in Table 6 described below was mixed with 100 parts by weight of 10% by weight, and the mixture was melt-kneaded according to Examples 17 to 24 to obtain pellets.

The test pieces used for evaluation of rigidity and heat resistance were obtained by pelletizing the pellets at a resin temperature of 250 ° C. and a mold temperature of 50 ° C.
Was prepared by injection molding. Using the obtained test piece, the rigidity and the heat resistance rigidity were evaluated by the above-mentioned test methods. The results are shown in Tables 5 and 6.

The compounds and additives relating to the present invention shown in Tables 1 to 6 are as follows. Compound A [1]: Coumarin Compound A [2]: 4-Hydroxycoumarin Compound A [3]: 4-Methyl-7-hydroxycoumarin Compound A [4]: 3,4-Dimethyl-7-hydroxycoumarin Compound A [ 5]: 4-phenyl-7-hydroxycoumarin Compound A [6]: 3-chloro-4,7-dimethyl-5-
Hydroxycoumarin compound A [7]: coumarin-7-carboxylic acid compound B [1]: 2,2′-bis (4,6-di-t-butylphenyl) fluorophosphite compound B [2]: 2,2 '-Methylene-bis (4-methyl-6-t-butylphenyl) fluorophosphite compound B [3]: 2,2'-methylene-bis (4,6-di-t-butylphenyl) fluorophosphite compound B [4]: 2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) fluorophosphite Compound B [5]: 2,2'-ethylidene-bis (4,6-
Di-t-butylphenyl) fluorophosphite Compound B [6]: 2,2′-thio-bis (4-methyl-6)
-T-butylphenyl) fluorophosphite compound B [7]: 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) acid phosphite compound B [8]: 2,2'-methylene -Bis (4,6-di-t-butylphenyl) acid phosphite compound B [9]: 2,2'-methylene-bis (4,6-dinonylphenyl) acid phosphite compound B [10]: 2 , 2'-Ethylidene-bis (4-methyl-6-t-butylphenyl) acid phosphite Compound B [11]: 2,2'-ethylidene-bis (4,6-
Di-t-butylphenyl) acid phosphite compound B [12]: 2,2'-ethylidene-bis (4,6-
Di-t-amylphenyl) acid phosphite compound B [13]: 2,2'-methylene-bis (4,6-diphenylphenyl) acid phosphite compound B [14]: 2,2'-i-propylidene- Bis (4,6-dibenzylphenyl) acid phosphite compound B [15]: 2,2'-butylidene-bis {4-methyl-6- (1'-methylcyclohexyl) phenyl} acid phosphite compound B [16] ]: 4,4'-biphenylylene-di-phosphonic acid Compound B [17]: 4,3'-biphenylylene-di-phosphonic acid Compound B [18]: 3,3'-biphenylylene-di-phosphonic acid Phenolic antioxidant 1: tetrakis [methylene-3
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 2: 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene phenolic antioxidant 3: tris (3,5-di-t-)
Butyl-4-hydroxybenzyl) isocyanurate Phosphorus antioxidant 1: 2,2'-ethylidene-bis (4
6-di-t-butylphenyl) fluorophosphonite Phosphorus antioxidant 2: 2,2'-methylene-bis (4,6)
-Di-t-butylphenyl) octyl phosphite

[0032]

[Table 1] *: Part by weight of compound and additive based on 100 parts by weight of crystalline polyolefin.

[0033]

[Table 2]

The examples and comparative examples shown in Tables 1 and 2 are:
This is the case where a crystalline propylene homopolymer is used as the crystalline polyolefin. As can be seen from Tables 1 and 2, Examples 1 to 8 are Compound A and Compound B related to the present invention.
It is found that Examples 1 to 8 and Comparative Example 1 (which do not contain Compound A and Compound B) have significantly excellent rigidity in Examples 1 to 8. . Comparative Example 2 containing only Compound A and Examples 1 to 1
As compared with Comparative Example 2, the effect of improving the rigidity of Comparative Example 2 is slightly recognized as compared with Comparative Example 1. Further, comparing Comparative Examples 3 to 5 and Examples 1 to 8 containing the compound B [1] or the phosphorus-based antioxidants 1 and 2 respectively, the effect of improving the rigidity of Comparative Examples 3 to 5 was compared. It turns out that there is almost no. Similarly, comparing Comparative Examples 6 to 7 and Examples 1 to 8 containing only Compound B [7] or Compound B [16], Comparative Examples 6 to
Although the effect of improving the rigidity of No. 7 is recognized to some extent, it is still not sufficiently satisfactory.

Further, Comparative Examples 8 to 9 and Example 1 in which the compound B in Examples 1 to 8 was replaced by the organic phosphite compound described in JP-A-6-93188, that is, the phosphorus type antioxidants 1 and 2. Comparing 8 to 8, Comparative Examples 8 to 9
The effect of improving the rigid surface of the composition is about the same as in Comparative Examples 6 to 7, and the composition obtained by using the compound A in combination with the phosphorus antioxidants 1 and 2, that is, the composition described in JP-A-6-93188, is the present invention. It can be seen that the effect of improving the rigid surface is not observed. Therefore, it is apparent that the comparative examples that do not simultaneously satisfy the inclusion of the two components of the compound A and the compound B according to the present invention do not exhibit the effects of the present invention. That is, it can be said that the rigid surface obtained in the present invention is a unique effect that can be seen only when the compound A and the compound B are contained in the crystalline polyolefin.

[0036]

[Table 3] *: Weight of compound and additive to 100 parts by weight of crystalline polyolefin

[0037]

[Table 4]

Tables 3 and 4 use crystalline ethylene-propylene block copolymers as the crystalline polyolefin, and the same effects as above were confirmed for these. In addition, in each of the examples of the composition of the present invention in Table 3, the inclusion of the compound A did not cause a decrease in impact resistance due to the improvement of the rigidity surface, and the impact resistance was higher than that of each comparative example. It was confirmed that there was no difference.

[0039]

[Table 5] *: Part by weight of compound and additive to 100 parts by weight of crystalline polyolefin

[0040]

[Table 6]

Tables 5 and 6 use a mixture of a crystalline ethylene-propylene random copolymer and a high-density ethylene homopolymer as the crystalline polyolefin.
The effects similar to those described above were also confirmed for these.

[0042]

EFFECTS OF THE INVENTION The composition of the present invention (1) is extremely excellent in the rigidity of the molded product when it is formed into a molded product. (2) Not only can the thickness of the molded product be reduced, which contributes to resource saving, but the cooling rate during molding is also faster, so the molding rate per unit time can be increased, which also improves productivity. Can contribute.

Claims (1)

[Claims] 1. A crystalline polyolefin (100 parts by weight), 0.001 to 1 part by weight of a coumarin derivative represented by the following general formula (1), a cyclic phosphorus compound represented by the following general formula (2) and a general formula (3) below. A crystalline polyolefin composition comprising 0.001 to 1 part by weight of one or more compounds selected from biphenylylene-diphosphonic acid. Embedded image Embedded image Embedded image (In the formula, R _{1 to} R ₆ are a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group or a hydrocarbon group having 1 to 8 carbon atoms, and R is an alkylidene group having 1 to 4 carbon atoms, sulfur or a direct bond, Ar ₁ and Ar ₂ represent an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group, and X represents a fluorine atom or a hydroxyl group.)