JPS63260944A - Polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain a polyolefin composition which can give a molding excellent in resistance to impact clouding, gloss, impact resistance, mechanical strengths and rigidity, by mixing a specified polyolefin composition with a specified phosphate compound. CONSTITUTION:A composition formed by mixing a composition comprising 65-98pts.wt. crystalline alpha-olefin/propylene random copolymer (A), 1-15pts.wt. high-density ethylene polymer (B) and 1-20pts.wt. amorphous ethylene/propylene random copolymer or amorphous ethylene/propylene/nonconjugated diene random copolymer (C) with 0.01-1pt.wt., per 100pts.wt. total of components (A)-(C), phosphate compound of the formula (wherein R1 is sulfur or a 1-4C alkylidene, R2 and R3 are each H or 1-8C alkyl, M is a mono- to tri-valent metal atom, m is 0 or 1 and n is 1-3).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyolefin compositions. More specifically, the present invention relates to a polyolefin composition from which a molded article with excellent impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity can be obtained.

[Prior art] In general, propylene polymers have excellent processability, chemical properties,
Because it has electrical and mechanical properties, it is processed into injection molded products, blow molded products, films, sheets, fibers, etc. and used for various purposes.

However, depending on the specific application, these properties, especially impact resistance, may not be sufficient.
There is a problem in that it is difficult to use for molded products that are subjected to mechanical shock or that are used at low temperatures. Generally, the rigidity and impact resistance of plastic materials are incompatible, and it is often extremely difficult to simultaneously improve and improve the former and the latter. Several proposals have been made regarding improving the impact resistance of propylene polymers. For example, a method in which a propylene polymer is mixed with low density polyethylene, high density polyethylene, or an amorphous ethylene-propylene random copolymer and then melt-kneaded, or a method in which propylene is block copolymerized with ethylene is well known. In particular, ethylene-propylene block copolymers have significantly improved impact resistance compared to propylene homopolymers, but when subjected to impact due to stress, the areas where the stress is concentrated become cloudy or white, reducing the commercial value of molded products. There is a problem of significant damage.

For this reason, in order to improve the impact resistance and impact whitening resistance of propylene polymers,
Publication No. 6, Japanese Patent Publication No. 47-26369, Japanese Patent Application Publication No. 1972
-71478 Publication, Special Publication No. 49-15044,
JP-A-49-99351, JP-A-53-4223
Publication No. 4, JP-A-51141950, JP-A-56
-163137, JP 58185634, JP 58-208337 and JP 60-
No. 112844 discloses a polyolefin composition obtained by blending a propylene polymer with a specific amount of high density polyethylene and an amorphous ethylene-propylene random copolymer, and also improves the impact resistance of the propylene polymer.
To improve impact whitening resistance and rigidity,
No. 23416 discloses that one or more aromatic sulfonic acid compounds and organic carboxylic acid compounds are added to a three-component mixture consisting of a propylene polymer, high-density polyethylene, and an amorphous ethylene-propylene copolymer. Polyolefin compositions containing two or more nucleating agents have been proposed. In addition, in order to bring the crystallization temperature of a propylene polymer closer to the melting point side, JP-A-61-103944 discloses propylene homopolymer, crystalline α-olefin-propylene random copolymer, and crystalline ethylene-propylene. A polyolefin composition containing organo-sodium phosphate has been proposed for a formulation in which high-density polyethylene or an amorphous ethylene-propylene random copolymer is blended with 1ffi or 21 selected from block copolymers. ing.

[Problems to be solved by the invention] However, the above-mentioned Japanese Patent Publication No. 39-18746, Japanese Patent Publication No. 47-26369, and Japanese Patent Application Laid-Open No. 48-71478
Publication No. 15044, Japanese Patent Publication No. 49-15044, Japanese Patent Publication No. 49-15044
99351, JP 53-42234, JP 54-41950, JP 56-16313
Publication No. 7, JP-A-58-185634, JP-A-5
Publication No. 8-208337 and JP-A-60-11284
The impact resistance and impact whitening resistance of the polyolefin compositions proposed in each publication of Publication No. 4, in which specific amounts of high-density polyethylene and amorphous ethylene-propylene-based random copolymers are blended with the propylene-based polymer, are significantly improved. However, the rigidity of these materials is still not fully satisfactory. In addition, in contrast to the three-component mixture consisting of a propylene polymer, high-density polyethylene, and an amorphous ethylene-propylene copolymer proposed in Japanese Patent Publication No. 45-23416, aromatic sulfonic acid compounds and organic carboxylic acid The impact resistance and impact whitening resistance of the polyolefin composition prepared by adding one or more nucleating agents selected from the compounds are significantly improved as in the above publications, and the effect of improving the wedge stiffness of Japanese punches is shown. Although it is recognized to some extent, it is still not completely satisfactory. In addition, propylene homopolymer, crystalline α-olefin-propylene random copolymer, and crystalline ethylene-propylene random copolymer proposed in JP-A-61-103944
One or two selected from propylene block copolymers
The effect of improving the rigidity of a polyolefin composition containing organic sodium chloride relative to a composition in which high-density polyethylene or an amorphous ethylene-propylene random copolymer is blended as a seed is as follows. Although the blending of the organic sodium phosphate is quite effective, it is not possible to simultaneously satisfy the three requirements of impact resistance, impact whitening resistance, and rigidity. Furthermore, in the above-mentioned JP-A-61-103944, the main components are propylene homopolymer, crystalline α-olefin-propylene random copolymer, and crystalline ethylene-propylene block copolymer, and high-density polyethylene and amorphous There is no description of the presence of a compound containing a polyethylene-propylene random copolymer, and the polyolefin composition simultaneously improves impact resistance, impact whitening resistance, and rigidity. There is no mention of even a statement suggesting that it will be obtained.

The present inventors have conducted extensive research in order to solve the above-mentioned problems regarding the above-mentioned polyolefin composition. the result,
A crystalline α-olefin-propylene random copolymer, a high-density ethylene polymer, an amorphous ethylene-propylene random copolymer, or a component-like ethylene-propylene-nonconjugated diene random copolymer and the following general formula [IF
Phosphny shown in!・Series compounds (hereinafter referred to as compound A
That's what it means. ) was found to be able to solve the above-mentioned problems of polyolefin compositions, and also to provide a composition with excellent gloss and mechanical strength. The present invention was completed based on this.

(However, in the formula, R2 represents sulfur or an alkylidene group having 1 to 4 carbon atoms, R2 and R3 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, and M is monovalent to
m represents a trivalent metal atom, m represents 0 or 1, and n represents an integer of 1 to 3. ) As is clear from the above description, an object of the present invention is to provide an e-fin composition that is excellent in impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity.

[Means for solving problems] The present invention has the following configuration.

(A) 65 to 98 parts by weight of crystalline α-olefin-propylene random copolymer, (B) 1 to 15 parts by weight of high-density ethylene polymer, and (C) amorphous ethylene-propylene random copolymer or parts ethylene-propylene-nonconjugated diene random copolymer 1 to 20 parts by weight of each component, and based on a total of 100 parts by weight of components (A) to (C), a phosphorus compound represented by the following general formula [I] A polyolefin composition containing 0.01 to 1 part by weight of a phate-based compound (hereinafter referred to as compound A).

(However, in the formula, R1 represents sulfur or an alkylidene group having 1 to 4 carbon atoms, R2 and R3 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, and M is a monovalent to
m represents O or 1, and n represents an integer of 1 to 3. ) The crystalline α-olefin-propylene random copolymer which is the component (A) used in the present invention refers to propylene and one α-olefin having 2 to 8 carbon atoms (excluding 3 carbon atoms).
A crystalline random copolymer with a species or two or more species,
Preferred are crystalline ethylene-propylene random copolymer, crystalline ethylene-pro and ton-butene-1 random copolymer, and crystalline propylene-butene-1 random copolymer. The content of α-olefin is preferably 1 to 101% by weight. Also, melt flow rate (MFR;
10 when applying a load of 2.16 kg at 230°C
Discharge amount of molten resin per minute) is usually 0.01-100g/
10 minutes, preferably 0.1 to 50 g/10 minutes.

In addition, the high-density ethylene polymer, which is the component (B) used in the present invention, is an ethylene homopolymer or a copolymer of ethylene and one or more α-olefins having 3 to 8 carbon atoms. Yes, density is 0.940-0.975g/
+l" is preferable. Also, melt index (M
r; Load at 190℃! The discharge m) of molten resin for 10 minutes when 2.16 kg is added is usually 0. O1~100
g/10 minutes, preferably 0.1 to 50 g/710 minutes.

5 The amorphous ethylene-propylene random copolymer or amorphous ethylene-propylene-nonconjugated diene random copolymer which is the component (C) used in the present invention has a propylene content of 20 to 60 MM%, and preferably The ethylene-propylene-non-military diene random copolymer preferably has an iodine value of 20 or less.

The blending ratio of each of the above components is component (A) 65 to 98 parts by weight, preferably 75 to 94 parts by weight, component (B) 1 to 15 parts by weight.
parts by weight, preferably 3 to 10 parts by weight and component (C) 1
The amount is 20 parts by weight, preferably 3 to 15 parts by weight, and the total amount of each component (A) to (C) is 100 parts by weight.

Compound A used in the present invention includes sodium-2,
2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate, sodium 1. -2,2'-ethylidene-bis-(4,6-di-L-butylphenyl)phosphate, lithium-2,2'-methylene-bis-
(4,6-di-t-butylphenyl)phosphate,
Lithium-2゜2'-ethylidene-bis-(4,6-di-t-butylphenyl)phosphate, sodium-
2,22-ethylidene-bis-(4-1-propyl-6
-t-butylphenyl)phosphate, lithium-2
, 2'-methylene-bis-(4-methyl-8-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis-(4-ethyl-6-t-butylphenyl) phosphate, calcium -bis-[2,2'-thiobis-(4-methyl-6-t-butylphenyl)phosphate, calcium-bis-[2,2'-thiobis-(4-ethyl-6-1-butylphenyl) ) phosphnitoco, calcium-bis-[2,2'-thiobis-
(4,6-di-monobutylphenyl)phosphate]
, magnesium-bis-[2,2'-thiobis-(4,
G-di-t-butylphenyl) phosphate], magnesium-bis-[2,2'-thiobis-(4-t-octylphenyl) phosphate], sodium-2,
2'-Butylidene-bis-(4,6-di-methylphenyl)phosphate, sodium-2,2'-butylidene-bis-(4,6-di-t-butylphenyl)phosphate, sodium-2, 2'-t-octylmethylene-bis-(4,6-dimethylphenyl)phosphate, sodium-2,2'-t-octylmethylene-
Bis=(4,6-di-t-butylphenyl)phosphate, calcium-bis-[2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate], magnesium-bis -[2,2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate], barium-bis-[2,2'-methylene bis-(
4,6-di-L-butylphenyl) phosphate],
Sodium-2,2'-methylene-bis-(4-methyl-6-1-butylphenyl)phosphate, Sodium-2,2'-methylene-bis-(4-ethyl-et
-butylphenyl) phosphate, sodium (4,
4'-dimethyl-6,6'-di-1-butyl-2,2'
-biphenyl) phosphate, calcium bis-[
(4,4'-dimethyl-6,6'-di-t-butyl-2
,2'-biphenyl)phosphnitoco, sodium-
2,2'-ethylidene bis-(4-8-butyl-6-
L-butylphenyl) phosphate, sodium-2
, 2'-methylene-bis-(4,6-di-methylphenyl) phosphate, sodium-2,21-methylene-bis-(4,6-cy-nitylphenyl) phosphate, potassium-2,2' -ethylidene-bis-(4,6
-di-t-butylphenyl) phosphate, calcium-bis-[2,2'-ethylidene-bis-(4,6-
di-7-butylphenyl) phosphate], magnesium-bis-[2゜2'-ethylidene-bis-(4,6
-di-t-butylphenyl)phosphate], barium-bis-[2,2'-ethylidene-bis-(4,6-
di-t-butylphenyl) phosphate], aluminum tris-[2,2'-methylene-bis-(4,6
-di-t-butylphenyl)phosphate] and aluminumtris-[2,2'-ethylidene-bis-
(4,6-di-t-butylphenyl)phosphate]
Examples include: Particularly preferred is sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate. The blending ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0. .5 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving rigidity, optical R and mechanical strength will not be sufficiently exhibited, and if it is more than 1 part by weight, it is fine.
It is not only impractical, but also uneconomical, since further improvements in the above-mentioned effects cannot be achieved any time soon.

In the composition of the present invention, component (A) and component (B
) except for various thermoplastic synthetic resins (e.g. ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, propylene homopolymer, propylene and ethylene, butene-1, pentene-1,4-
Crystalline block copolymer with one or more α-olefins such as methyl-pentene-1, hexene-1, octene, polybutene, poly-4-methylpentene-1, α-olefin and V Copolymers with vinyl formate, acrylic esters, etc. or saponified products of the copolymers,
A copolymer of an α-olefin and an unsaturated silane compound,
Copolymers of α-olefins and unsaturated carboxylic acids or their anhydrides, reaction products of the copolymers with metal ion compounds, modified polyolefins obtained by modifying polyolefins with unsaturated carboxylic acids or derivatives thereof, unsaturated polyolefins. silane-modified polyolefin modified with a saturated silane compound, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polycarbonate, polybutylene terephthalate, polyvinyl chloride, fluororesin, etc.), or components Various synthetic rubbers (ex: polybutadiene, polyisoprene, polychloroprene,
Chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer polymers, styrene-propylene-butylene-styrene block copolymers, etc.) can be used in combination without impairing the object of the present invention.

In addition, the composition of the present invention may contain various additives that are normally added to polyolefins, such as phenol-based, dioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, and lubricants. , antistatic agents, antifogging agents, antiblocking agents, dropless agents, pigments, heavy metal deactivators (copper anti-toxic agents), radical generators such as peroxides, dispersants such as metal soaps, or medium Japanese additives, inorganic fillers (e.g. talc,
Mica, clay, wollastonite, zeolite, asbestos, 1 cum 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, metal fiber, etc.) or coupling agents (such as silane, titanate, boron, aluminate, etc.)
The above-mentioned inorganic fillers or organic fillers (for example, wood flour, valves, waste paper, synthetic fibers, natural fibers, etc.) that have been surface-treated with a surface treatment agent such as zircoaluminate (such as zircoaluminate) may be used within a range that does not impair the purpose of the present invention. Can be used together.

The composition of the present invention is prepared by adding predetermined amounts of the compound A and the various additives that are usually added to polyolefins to the components (A), (B), and (C) according to the present invention. Mix using a mixing device such as Hensel Mixer (trade name), Super Mixer, Ribbon Blender, Pan Bali Mixer, etc., and melt and knead with a normal single screw extruder, twin screw extruder, Brabender or roll, etc. at a melt kneading temperature of 170°C. 'C~300℃, preferably 200℃~250℃
It can be obtained by melt-kneading and pelletizing at ℃. 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, the phosphate compound represented by Compound A is generally known to act as a nucleating agent to improve rigidity and 4:1 mechanical strength, as disclosed in JP-A-58-1736. It is being However, by blending Compound A with component (A), component (B), and component (C) having a specific blending ratio according to the present invention, a surprising result that cannot be predicted from the blending of conventionally known nucleating agents can be produced. It has been found that a synergistic effect is exhibited and a composition with significantly superior stiffness, gloss and mechanical strength can be obtained.

[Effects] The composition of the present invention is superior to conventional polyolefin compositions in which various nucleating agents are blended with three components consisting of a crystalline propylene polymer, high-density polyethylene, and an amorphous ethylene-propylene random copolymer. Compared to known compositions,
(1) Remarkably excellent rigidity, gloss, and mechanical strength. (2) Excellent impact whitening resistance and impact resistance. (
3) Various applications requiring impact whitening resistance, gloss, impact resistance, mechanical strength and rigidity, especially battery cases,
It can be suitably used for automobile parts such as washer tanks, home appliance parts such as upper and inner lids of washing machines, and vacuum cleaners.

[Example 1] The present invention will be specifically explained using Examples 1 and Comparative Examples below, but the present invention is not limited thereto.

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

1) Impact whitening resistance: Using the obtained pellets,
A test piece with a width of 50 mm and a thickness of 2 cm was made by injection molding, and using the test piece, a 500 g steel ball was placed at 100c+n so that the steel ball hit the center of the test piece.
The test piece is allowed to fall naturally from a height of 100 to cause impact whitening to occur on the test piece. Impact whitening resistance was evaluated by classifying the whitening that occurred into the following four stages.

◎: Hardly any whitening was observed.

O: Slight whitening is observed.

Δ: Significant whitening is observed.

X: Significant whitening is observed.

■) Gloss: Using the obtained pellets, length 50 mm,
A test piece with a width of 50mm and a thickness of 2III111 was created by injection molding, and the gloss rate was measured using this test piece (ASTM
Gloss was evaluated based on D523).

■〉Impact resistance: Length 63.5 using the obtained pellets
A test piece (with a notch) with a width of 13 mm and a thickness of 3.5 mm was prepared by injection molding.
Measurement of Izot impact strength at ℃ (JIS 7!1)
Impact resistance was evaluated based on 0.0).

■) Mechanical strength: length 175 using the obtained pellets
A JISI No. test piece with a width of 10 mm and a thickness of 3.3 mm was prepared by injection molding, and the mechanical strength was evaluated by measuring tensile strength (based on JIS 7113) using the test piece.

■) Stiffness: Length 100II using the obtained pellets
I! l, width 10mm x thickness 4ffim test piece t
i: Produced by injection molding method, rigidity was evaluated by measuring bending elastic modulus (based on JIS K7203) using the test piece.

Examples 1-11, Comparative Examples 1-9 Component (A): Unstabilized powdery crystalline ethylene-propylene random copolymer with MFR 7.0 g/10 minutes; ethylene content 1:2.5 M%; (A)-
[I] ), Component (B) and Component (C) shown in Table 1 below are blended in the proportions shown in Table 1 below, and Components (A) to (C) total of 10
0111 parts by weight, sodium-2,2' as compound A
-methylene-bis-(4,6-di-t-butylphenyl)phosphate and other additives in the Hensel mixer at the mixing ratios listed in Table 1 below.
(trade name), stirred for 3 minutes, and then melted and kneaded at 200° C. in a single-screw extruder with a diameter of 40 mm to pelletize. In addition, as Comparative Examples 1 to 9, component (A) has MFR7,
Og/10 min unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene content 2
．． 5ffi amount%; (A)-[Ico), component (B), component (C) and ? , FEPB were mixed in the proportions shown in Table 1 below,
Further, a predetermined amount of each of the additives listed in Table 1 below was added to a total of 100 parts by weight of components (A) to (C) and EPB, and the mixture was melt-kneaded in accordance with Examples 1 to 11. Obtained pellets.

Test pieces used for impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity tests were obtained by heating the resulting pellets at a resin temperature of 2.
It was prepared by injection molding at 50°C and a mold temperature of 50°C.

Using the obtained test pieces, impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity were evaluated according to the test methods described above. These results are shown in Table 1.

Examples 12 to 22, Comparative Examples 10 to 18 Unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content m4.5% by weight; (A) with MFR 2.0 g/10 min as component (A) )−[
n co), component (B) and component (
C) are respectively blended in the proportions shown in Table 2 below, and the total of components (A) to (C) is 1001.
To each part, predetermined amounts of sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate and other additives as Compound A were listed in Table 2 below. Hensel mixer (product name) with compounding ratio
After stirring and mixing for 3 minutes, the mixture was melt-kneaded at 200° C. using a single-screw extruder with a diameter of 40 mm to form pellets. In addition, as Comparative Examples 1O to 18, component (A) has an MFR of 2.0 g.
/ 10 minutes unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene containing m4.5
Weight %; (A) - [Loco), component (B), component (C) and EPB shown in Table 2 below, respectively.
Blend to the proportions shown in the table, and then add the ingredients (
Predetermined amounts of the additives listed in Table 2 below were added to 1 part of A) to (C) and EPB in total of 100 fftf, and pellets were obtained by melt-kneading according to Examples 12 to 22. .

Test pieces used for impact whitening resistance, gloss, IJ impact resistance, mechanical strength and rigidity tests 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, impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity were evaluated according to the test methods described above. These results are shown in Table 2.

Examples 23 to 33, Comparative Examples 19 to 27 Unstabilized powdery crystalline ethylene-propylene-butene-1 random copolymer with MFR 7.0 g/10 min as component (A) 1 ton 2.5 fft containing ethylene
f1%, butene-1 content 4.5% by weight; (A)-[
[Ico), Component (B) and Component (C) shown in Table 3 below are blended in the proportions shown in Table 3 below, and Components (A) to (C) total of 100
To the parts by weight, predetermined amounts of sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate and other additives as Compound A were listed in Table 3 below. The mixture was put into a Hensel mixer (trade name) at the mixing ratio, stirred and mixed for 3 minutes, and then melt-kneaded at 200°C in a single-screw extruder with a diameter of 40n+n+ to form pellets.

Another comparative example! As 9 to 27, component (A) is MFR7,O
g/10 min unstabilized powdered crystalline ethylene-propylene-butene-1 random copolymer (ethylene content 2.5% by weight, butene-1 content 4.5% by weight
; (A)-[■]), the ingredients shown in Table 3 below (
B), component (C), and EPB were blended in the proportions shown in Table 3 below, and further, component (A)
) ~ (C) and EPB total 100! Predetermined amounts of the additives listed in Table 3 below were added to each part, and the mixture was melt-kneaded in accordance with Examples 23 to 33 to obtain pellets.

Test pieces used for impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity tests were obtained by heating the resulting pellets at a resin temperature of 2.
It was prepared by injection molding at 50°C and a mold temperature of 50°C.

Using the obtained test pieces, impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity were evaluated according to the test methods described above. These results are shown in Table 3.

Examples 34-44, Comparative Examples 28-36 Unstabilized powdery crystalline ethylene-propylene-butene-1 random copolymer (ethylene content 4.0 weight%,
Butene! Content 4.5% by weight; (A)-[:IV
c), component (B) and component (C) shown in Table 4 below.
) were blended in the proportions shown in Table 1 below, and sodium-2,2'-methylene-bis-2,2'-methylene-bis- Predetermined amounts of (4,6-di-t-butylphenyl) phosphate and other additives were added to the
The mixture was put into a Hensel mixer (trade name) at the mixing ratio shown in the table, stirred and mixed for 3 minutes, and then melted and kneaded at 200° C. using an axle extruder with a diameter of 40 mm to form pellets.

In addition, as Comparative Examples 28 to 36, component (A) has a MFR of 7,0
g/10 min unstabilized powdered crystalline ethylene-propylene-butene-1 random copolymer (ethylene content m4.0 wt.%, butene-1 content 4.5 wt.%
; (A)-[■]), the components shown in Table 4 below (B
), component (C) and EPB in the proportions shown in Table 4 below, and component (A).
A total of 100 parts by weight of ~(C) and EPB were blended with predetermined amounts of each of the additives listed in Table 4 below, followed by melting and kneading in Examples 34 to 44 to obtain pellets. .

Test pieces used for impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity tests were obtained by heating the resulting pellets at a resin temperature of 2.
It was prepared by injection molding at 50°C and a mold temperature of 50°C.

Using the obtained test pieces, impact whitening resistance, gloss, impact resistance, mechanical strength, and rigidity were evaluated according to the test methods described above. These results are shown in Table 4.

Ingredients (A) to (A) related to the present invention shown in Tables 1 to 4
C) and compound A and EPB and additives are as follows.

Component (A) (A)-[I1; Crystalline ethylene-propylene random copolymer (MFR7.0g/10 minutes; ethylene content 2.5% by weight) (A)-[■]; Crystalline ethylene-propylene Random copolymer (MFR2, Og/10 minutes; ethylene content 4.5% by weight) (A)-[ml; Crystalline ethylene-propylene-butene-based J1 copolymer (MFR?.Og/10 minutes) : Ethylene content 2.5% by weight, butene-1 content @4
．． 5% by weight) (A)-[IV]; Crystalline ethylene-propylene-butene-1 random copolymer (MFR?,
Og/10 minutes; ethylene content 4.0% by weight, butene-1 content 4.5M%) EPB; Crystalline ethylene-propylene block copolymer (MFR4.0g/1
0 minutes; ethylene-containing In 8.5% by weight) Component (B) (B)-[I1; Ziegler-Natsuta-based high-density ethylene homopolymer (formerly 5.0 g/10 minutes; density 0.98
38/c+n')-(B)-[n]; Ziegler-Natsuta high-density ethylene-propylene copolymer (Ml 5.Og/10 minutes;
Density 0.9503/cm'; 3.0 methyl branches/1000 carbons) (B)-[I11]; Ziegler-Natsuta high-density ethylene-butene-1 copolymer (
Old 5.0g/10 minutes; Density 0.9483/cm'
:0.0111 ethyl branches/1000 carbons) component (
C) (C)-[I]; Amorphous ethylene-propylene random copolymer (Mooney viscosity ML1+4 (100°C) 63
; Propylene content: 4123% by weight; Product name, manufactured by Japan Synthetic Rubber Co., Ltd. [JSRT7961] (C)-[I]]; Amorphous ethylene-propylene random copolymer (Mooney viscosity MLI + 4 (100°C) 4
0; propylene content 1149% by weight; trade name manufactured by Japan Synthetic Rubber Co., Ltd. [JSREPII Co.] (C)-[ml; amorphous ethylene-propylene-ethylidene norbornene random copolymer (Mooney viscosity MLI+4 (100°C) 82; propylene Contains fi26
Weight%; Iodine value! 5.0; Manufactured by Japan Synthetic Rubber Co., Ltd. Product □ Name [JSREP57P]) Compound A; Sodium-2,2'-methylene bis-
(4゜6-di-t-butylphenyl)phosphate (
Manufactured by Adeka Argus Chemical Co., Ltd. Product name [MARKNA-1]
10FI) Nucleating agent 1; Aluminum p-t-butylbenzoate nucleating agent 2: l.3,244-dibenzylidene sorbitol Nucleating agent 3; Sodium-bis=(4-t-butylphenyl) phosphate (Adeka・Manufactured by Argus Chemical Co., Ltd. Product name [MARK NA-10UF] Phenolic antioxidant 1; 2,6-di-t-butyl-p-cresol Phenolic antioxidant 2; Tetrakis [methylene-
3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane phosphorus antioxidant 1; bis(2,4-di-t-butylphenyl)-pentaerythritol rouzi Phosphyrin-based antioxidant 2; Tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite Ca-3t; Calcium stearate Examples listed in Table 1 and In the comparative example, a crystalline ethylene-propylene random copolymer was used as component (A), and those listed in Table 1 were used as other components. As can be seen from Table 1, in Example 1-If, compound A was added to components (A) to (C) within the range of the blending ratio of the present invention.
Examples 1 to 3 and Comparative Examples 1 to 3 (
When compared with a product in which no nucleating agent is used for components (A) to (C) within the range of the blending ratio of the present invention, the impact resistance and impact whitening resistance are at the same level. It can be seen that Comparative Examples 1 to 3 are inferior to Examples 1 to 3 in gloss, mechanical strength, and rigidity. In addition, compound A is added to components (A) to (C) within the range of the blending ratio of the present invention.
Comparing Examples 1 to 3 with Comparative Examples 4 to 6, in which a nucleating agent consisting of a compound other than the above was blended, Comparative Examples 4 to 6 did not have sufficient improvement effects on gloss, mechanical strength, and rigidity, and 1 to 3 have significantly superior mechanical strength and rigidity,
It can be seen that the use of Compound A produces a remarkable synergistic effect on υn. In other words, the mechanical strength and rigidity obtained in the present invention are unique effects that are observed when components (A) to (C) are used in compounds within the range of blending ratios limited in the present invention. It can be said. Furthermore, the polyolefin composition described in the above-mentioned Japanese Patent Application Laid-Open No. 61-103944, that is, the component (A), component (B), component (C), and EPB which are outside the blending ratio range of the present invention.
Comparing Examples 1 to 3 with Comparative Examples 7 to 9 in which organic sodium phosphate, that is, Compound A was blended with one or two selected from It can be seen that Examples 1 to 3 are superior in all of these points, while they are inferior in any one of properties, mechanical strength, and rigidity. Moreover, it can be seen that the same effects as Examples 1 to 3 were obtained in Examples 4 to 11 in which the component (B) and component (C) used in Examples 1 to 3 were changed, respectively.

Tables 2 to 4 use a crystalline ethylene-propylene random copolymer and a crystalline ethylene-propylene-butene-1 random copolymer as component (A), respectively, and these are the same as above. The effect was confirmed.

This indicates that the composition of the present invention contains a nucleating agent in a specific blending ratio of each component of the conventionally known propylene polymer, high-density polyethylene, and amorphous ethylene-propylene random copolymer. It was found that the composition of the present invention is superior in impact whitening resistance, gloss, impact resistance, mechanical strength and rigidity, especially in terms of mechanical strength and rigidity, compared to the composition of the present invention. A remarkable effect was confirmed.

Procedural amendment 8 (voluntary) Kunio Ogawa, Commissioner of the Patent Office1, Indication of the case 1988, Samurai Patent Application No. 966402, Name of the invention Polyolefin composition 8, Relationship with the person making the amendment Patent application 3-6-32 Nakanoshima, Kita-ku, Osaka-shi, Osaka (530)
(207) Chisso Corporation Representative Sadao Nogi 4, Agent 2-8-1 Shinjuku, Shinjuku-ku, Tokyo (160) 5, Subject of amendment "Detailed description of the invention" column 6, Amendment "Table 1" on page 26, line 15 of the description of contents is amended to "Table 4."

that's all

Claims (3)

[Claims] (1) (A) 65 to 98 parts by weight of crystalline α-olefin-propylene random copolymer, (B) 1 to 15 parts by weight of high-density ethylene polymer, and (C) amorphous ethylene-propylene random copolymer The combined or amorphous ethylene-propylene-nonconjugated diene random copolymer consists of 1 to 20 parts by weight of each component, and the following general formula [I] The phosphate compound shown by (hereinafter referred to as compound A) is 0.01
A polyolefin composition containing ~1 part by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (However, in the formula, R_1 is sulfur or an alkylidene group having 1 to 4 carbon atoms, and R_2 and R_3 are each hydrogen or the same or different alkyl group having 1 to 8 carbon atoms. group, M is a monovalent to trivalent metal atom, m is 0 or 1, n is 1 to
Indicates an integer of 3. ) (2) In the general formula [I], R_1 is a methylene group,
The polyolefin composition according to claim (1), wherein the alkyl groups represented by R_2 and R_3 are t-butyl groups. (3) The polyolefin composition according to claim (1), which contains sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate as compound A. thing.