JPH0977954A - Polyolefin resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyolefin resin composition excellent in the balance between the rigidity and the impact resistance of an injection molded article, coatability, moldability, appearance, etc., by compounding a specified propylene/ethylene block copolymer and a specified talc each in a specified amount. SOLUTION: This resin composition consists of 70-95wt.% highly rigid propylene/ ethylene block copolymer comprising a propylene/ethylene block copolymer which is obtained in the presence of a specified catalyst by polymerizing propylene alone in the first polymerization step (A) using two or more polymerizers in series to produce a propylene homopolymer accounting for 60-95wt.% of the total weight of the block copolymer and copolymerizing propylene and ethylene in the second polymerization step (B) using one or more polymerizers to produce a propylene/ethylene copolymer part having an ethylene content of 30-80wt.% and accounting for 5-40wt.% of the total weight of the block copolymer and in which the ratio of the maximum value of MFR's of polymers obtained in the polymerizers in the step A to the minimum value thereof, the isotactic pentad fraction, the Mw/Mn (Q value) and the ratio of MFR of the polymer obtained in the step A to that in the step B are each a specified value; and 5-30wt.% talc with a mean particle diameter of 5μm or smaller.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has an excellent balance between rigidity and impact resistance of an injection-molded product to be obtained, and further has heat resistance and rigidity.
The present invention relates to a polyolefin resin composition having excellent appearance, moldability and paintability.

[0002]

2. Description of the Related Art As a technique for providing a polyolefin resin composition having an excellent balance of rigidity and impact resistance, a highly crystalline propylene-ethylene block copolymer, an amorphous propylene-ethylene random copolymer, and ultrafine particle talc are used. And a resin composition comprising a phosphate compound (Japanese Patent Laid-Open No. 4-270753), a propylene-ethylene block copolymer, an ethylene-propylene copolymer rubber,
Automotive resin composition comprising ethylene-butene copolymer rubber, polyethylene and talc (JP-A-5-29522)
No. 5), a propylene block copolymer, an ethylene / propylene copolymer rubber, an ethylene / propylene / diene copolymer rubber, an ethylene / butene-1 copolymer rubber, and talc. Kaihei 6
No. 100753), crystalline polypropylene, ethylene-butene-1 copolymer rubber, ethylene-propylene copolymer rubber, talc, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, A thermoplastic resin composition comprising a pentaerythritol diphosphite compound, a phenyl benzoate compound and a heterocyclic hindered amine (JP-A-6-128).
No. 450), a reinforced polypropylene resin composition comprising a crystalline ethylene-propylene block polymer, an elastomer and talc (Japanese Patent Laid-Open No. 7-53828).

[0003]

SUMMARY OF THE INVENTION The present invention provides a polyolefin resin composition having excellent balance between rigidity and impact resistance of an injection-molded product to be obtained, and further excellent in heat resistance rigidity, appearance, moldability and paintability. Especially.

[0004]

The present invention has the following constitution. 1) A solid catalyst component (A) containing titanium, magnesium, halogen and a polycarboxylic acid ester as essential components, an organoaluminum compound (B) and a general formula R ⁴ _x R
⁵ _y Si (OR ⁶ ) _z (wherein R ⁴ and R ⁶ are hydrocarbon groups, R
⁵ represents a hydrocarbon group or a hydrocarbon group containing a hetero atom, x + y + z = 4,0 ≦ x ≦ 2,1 ≦ y ≦ 3,1 ≦
z ≦ 3. ) Homopolymerization of propylene was carried out in the polymerization step (I) using a catalyst system in which an organosilicon compound (C) represented by the formula 60-95% by weight of
As the second stage, a polymerization process using one or more polymerization vessels (I
Propylene / ethylene block copolymer obtained by copolymerizing propylene and ethylene in I) to produce a propylene / ethylene copolymer part having an ethylene content of 30 to 80% by weight based on the total weight of 5 to 40% by weight. In, the maximum value (hereinafter referred to as MFR (h)) and the minimum value (MFR) of the melt flow rate of the polymer obtained in each tank of the polymerization step (I)
(Referred to as (l)) has a relationship of 0.1 ≦ Log (MFR (h) / MFR (l)) ≦ 1 (1), and the isotacticity of the propylene polymer obtained in the polymerization step (I) Chick pentad fraction (P) is 0.
96 or more, Mw / Mn (Q value) is 6 or less, and
The melt flow rate of the polymer obtained in the polymerization step (I) (hereinafter referred to as MFR (i)) and the melt flow rate of the polymer obtained in the polymerization step (II) (hereinafter referred to as MFR (ii)) are 3 ≦ Log. (MFR (i) / MFR (ii)) ≦ 7 (2) The crystalline propylene / ethylene block copolymer (a) having a relationship of 70 to 95% by weight and an average particle diameter of 5 μm.
A polyolefin resin composition comprising 5 to 30% by weight of talc (b) of m or less. 2) 92-60% by weight of the crystalline propylene / ethylene block copolymer (a) described in 1 above, 5-30% by weight of talc (b) described in 1 above, and amorphous or low crystalline ethylene.・ Α-olefin copolymer rubber (d) is 3 to 1
A polyolefin resin composition comprising 0% by weight. 3) 91.5 to 57 wt% of the crystalline propylene / ethylene block copolymer (a) described in 1 above, 5 to 30 wt% of talc (ii) described in 1 above, and ethylene described in 2 above. -Α-olefin copolymer rubber (d) is 3 to 10
A polyolefin resin composition containing 0.5% by weight and polyethylene (e) of 0.5 to 3% by weight. 4) 91.5 to 57 wt% of the crystalline propylene / ethylene block copolymer (a) described in 1 above, 5 to 30 wt% of talc (ii) described in 1 above, and ethylene described in 2 above. -Α-olefin copolymer rubber (d) is 3 to 10
% By weight, and the polyethylene (e) described in the above item 3 is 0.5 to
3% by weight, and 0.001% of the organic phosphorus compound (f)
A polyolefin resin composition comprising 0.5 parts by weight.

The present invention will be described in detail below. In the present invention, a solid catalyst component (A) containing at least a magnesium atom, a titanium atom, a halogen atom, and a polyvalent carboxylic acid ester, an organoaluminum compound (B) and an electron donating compound (C) are used as a polymerization catalyst. Although the resulting highly stereoregular catalyst system is used, there is no particular limitation on these catalysts, and it is possible to use a known catalyst system which gives various highly stereoregular polypropylenes. As a method for producing such a solid catalyst component (A),
For example, JP-A-50-108385 and 50-1265.
No. 90, No. 51-20297, No. 51-28189.
No. 51-64586, No. 51-92885, No. 51-136625, No. 52-87489, No. 52.
-100596, 52-147688, 52-
104593, 53-2580, 53-400.
No. 93, No. 53-40094, No. 55-135102
No. 55-135103, No. 55-152710.
No. 56, No. 56-811, No. 56-11908, No. 56
-18606, 58-83006, 58-13
8705, 58-138706, 58-138.
No. 707, No. 58-138708, No. 58-1387.
09, 58-138710, 58-13871.
5, No. 60-23404, No. 61-21109,
61-37802, 61-37803 and 62.
-104810, 62-10481, 62-
No. 104812, No. 62-104813, No. 63-5
It can be manufactured according to the method disclosed in each publication such as 4405.

Specific examples of the polyvalent carboxylic acid ester used in the solid component (A) are esters of phthalic acid, maleic acid, substituted malonic acid and the like with an alcohol having 2 or more carbon atoms. In the present invention, there are various magnesium compounds used in the above (A),
A magnesium compound with or without reducing ability is used. Examples of the former include dimethylmagnesium,
Examples thereof include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, ethyl magnesium chloride, propyl magnesium chloride and butyl magnesium chloride. Examples of the latter include magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide, magnesium methoxy chloride, alkoxy magnesium chloride such as ethoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium and butoxy magnesium. Mention may be made of alkoxy magnesium, magnesium laurate, magnesium carboxylates such as magnesium stearate and the like. Of these, particularly preferred compounds are magnesium halide, alkoxy magnesium chloride and alkoxy magnesium. The titanium compound used as the solid catalyst component (A) in the present invention is usually Ti
(OR) _A X _4-A (R is a hydrocarbon group, X is a halogen, 0
The compound represented by ≦ A ≦ 4) is most suitable. Specifically, titanium tetrahalides such as TiCl ₄ and TiBr ₄ , Ti (OCH ₃ ) Cl ₃ and Ti (OC ₂ H ₅ ) C
Trihalogenated alkoxytitanium such as l ₃ , Ti (O
_{CH 3) 2 Cl 2, Ti} ( dihalogenated dialkoxy titanium, such as _{OC 2 H 5) 2 Cl 2} , Ti (OCH 3) 3
Cl, Ti (OC ₂ H ₅ ) ₃ Cl and other monohalogenated trialkoxy titanium, Ti (OCH ₃ ) ₄ , Ti (O
Tetraalkoxytitanium such as C ₂ H ₅ ) ₄ and particularly preferred is TiCl ₄ . In the preparation of the solid catalyst component (A), other electron donors such as alcohol, ether, phenol, silicon compound, aluminum compound and the like are made to coexist as necessary, in addition to the above titanium compound, magnesium compound and polyvalent carboxylic acid ester. be able to.

The organoaluminum compound (B) used in the present invention has a general formula of AlR ² _m R ³ _n X
_{3- (m + n)} (wherein R ² and R ³ represent a hydrocarbon group or an alkoxy group, X represents a halogen, and m and n are 0 ≦ m
An arbitrary number of ≦ 3, 0 ≦ n ≦ 3, and 1.5 ≦ m + n ≦ 3 is shown. ) An organoaluminum compound represented by As a specific example, trimethylaluminum,
Triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, diethyl aluminum chloride, di-n-propyl aluminum monochloride, diethyl aluminum iodide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride , Ethoxydiethylaluminum and the like.
These organoaluminum compounds (B) may be used alone or in 2
More than one kind can be mixed and used.

The electron donor component (C) used in the present invention is represented by the general formula R ⁴ _x R ⁵ _y Si (OR ⁶ ) _z (wherein R ⁴ and R ⁶ are hydrocarbon groups, and R ⁵ is a carbon group). Represents a hydrogen group or a hydrocarbon group containing a hetero atom, x + y + z = 4
0 ≦ x ≦ 2, 1 ≦ y ≦ 3, 1 ≦ z ≦ 3. ) Organosilicon compounds represented by Specific examples thereof include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i. -Propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane,
i-Butyltrimethoxysilane, i-butyltriethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, neopentyltrimethoxysilane, neopentyl Triethoxysilane,
Hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-i-propyldimethoxysilane, di-n- Butyldimethoxysilane, di-i-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-pentyldimethoxysilane, dineopentyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldi Ethoxysilane, cyclohexyltrimethoxysilane,
Cyclohexyltriethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane,
3-isocyanatopropyltriethoxysilane, 2-
(3-Cyclohexenyl) ethyltrimethoxysilane etc. can be illustrated. These organosilicon compounds can be used alone or in admixture of two or more kinds at any ratio. Among these, particularly preferred organosilicon compounds are di-i-propyldimethoxysilane, t-butyltriethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane and cyclohexyltrimethoxysilane. The preferable addition amount of the organosilicon compound (C) is a molar ratio (B) / (C) of 1 to 15 with respect to the organoaluminum compound (B). If the addition amount is small, the improvement of rigidity is insufficient and too large. And the catalytic activity is reduced, which is not practical.

The solid catalyst component (A) is then used in combination with the organoaluminum compound (B) and the aforementioned organosilicon compound (C) as a catalyst for the polymerization of propylene, or more preferably, it is reacted with an α-olefin. Used as a pre-activated catalyst. For pre-activation, 0.3 to 20 mol of organoaluminum (B) is used with respect to 1 mol of titanium in the solid catalyst component (A), 0 to 50 ° C. for 1 minute to 20 hours, and the α-olefin is adjusted to 0. It is desirable to react 1 to 10 mol, preferably 0.3 to 3 mol. The reaction of α-olefin for preactivation can be performed in an aliphatic or aromatic hydrocarbon solvent, or in a liquefied α-olefin such as liquefied propylene or liquefied butene-1 without using a solvent, and vaporized ethylene, propylene or the like. It is also possible to react in phases. Further, the α-olefin polymer or hydrogen obtained in advance can be made to coexist. Furthermore, the organic silane compound (C) can be added in advance in the preliminary activation. The α-olefin used for preactivating is ethylene, propylene, butene-1, hexene-
1, heptene-1, other linear monoolefins, 4
-Methyl-pentene-1, 2-methyl-pentene-1,
Branched chain monoolefins such as 3-methyl-butene-1, styrene and the like. These α-olefins may be used as a mixture of α-olefins to be polymerized. After completion of the preliminary activation, the solvent, the organoaluminum compound and the unreacted α-olefin and the organoaluminum compound can be filtered off, removed by decantation, or dried to be used as a powder or granular material.

The thus-prepared pre-activated catalyst comprises propylene, n-hexane, n-heptane, n
-Slurry polymerization carried out in a hydrocarbon solvent such as octane, benzene or toluene, or bulk polymerization and gas phase polymerization carried out in liquefied propylene. In the case of slurry polymerization, the polymerization temperature is usually 20 to 90 ° C., preferably 50.
It is -80 ° C, and the polymerization pressure is 0 to 5 MPa. In the case of gas phase polymerization, the polymerization temperature is usually 20 to 150.
And the polymerization pressure is 0.2 to 5 MPa.
Hydrogen is usually used for controlling the molecular weight, and MFR of the polymer finally obtained is carried out in the range of 0.1 to 1000.

The amount of polymerization in the polymerization step (I) is 60 to 95% by weight based on the total amount of the propylene / ethylene block copolymer composition finally obtained. If the amount of polymerization is less than the above range, the rigidity of the product will be deteriorated, and if it is too large, the improvement of low temperature impact strength will be insufficient. Polymerization in the polymerization step (I) is performed using two or more polymerization vessels connected in series, and the maximum value (MFR (h)) and the minimum value (MFR) of the melt flow index of the polymer obtained in each tank are
The relationship with (l)) is preferably 0.1 ≦ Log (MFR (h) / MFR (l)) ≦ 1 (1), and more preferably 0.2 ≦ Log (MFR (h) / MFR ( l)) ≦ 0.5 (3). When the MFR ratio is smaller than the range of the above formula (1), the rigidity of the product is deteriorated, and when it is large, the tensile elongation and impact resistance of the propylene / ethylene block copolymer composition finally obtained. It is not preferable because the property deteriorates. The isotactic pentad fraction (P) of the polymer obtained in the polymerization step (I) is 0.96 or more, the weight average molecular weight (Mw) and the number average molecular weight measured by gel permeation chromatography (GPC). Ratio of (Mn) (Q
Value) is 6 or less. When the isotactic pentad fraction (P) is smaller than that of the present invention, the rigidity of the molded article is lowered, and when the Q value is larger than the present invention, the impact resistance of the molded article is unfavorably lowered.

In the polymerization step (II), the polymerization temperature is usually 20 to
It is carried out by copolymerizing ethylene and propylene at 80 ° C., preferably 40 to 70 ° C. and a pressure of 0 to 5 MPa. The method of supplying ethylene and propylene to the polymerization vessel and the polymerization mode are not limited. Hydrogen is usually used to control the molecular weight, and the concentration in the gas phase is 0.1 to 10
Carried out in mol%. The polymerization in the polymerization step (II) is carried out using a one-tank polymerization device or a connected two-tank polymerization device.
The ethylene content in the portion polymerized in the polymerization step (II) is 3
It is 0 to 80% by weight, more preferably 40 to 70% by weight. When the ethylene content is out of the above range, the resulting polymer has poor rigidity and impact resistance, which is not preferable. The polymerization amount in the polymerization step (II) is 5 to 40% by weight based on the total amount of the polymer finally obtained. In addition to ethylene and propylene, other α-olefin, non-conjugated diene and the like may be used together. The relationship between the MFR (i) of the polymer obtained in the polymerization step (I) and the MFR (ii) of the polymer obtained in the polymerization step (II) is 3 ≦ Log (MFR (i) / MFR (ii)) ≦ 7. (2) is preferable, and more preferably 4 ≦ Log (MFR (i) / MFR (ii)) ≦ 6 (4). MFR (i) is the measured value only for the polymer in the polymerization step (I), and MFR (ii) is the MFR after completion of the second stage.
Measured value {MFR (i + ii)}, polymer fraction (W1) in polymerization step (I) and polymer fraction (W in polymerization step (II)
It is a value calculated by the following equations (5) and (6) from 2). LogMFR (T) = W1 × LogMFR (i) + W2 × LogMFR (ii) (5) W1 + W2 = 1 (6) Log (MFR (i) / MFR (ii)) is outside the range of the above formula (2). In the case of, the resulting polymer is inferior in impact resistance and tensile elongation, which is not preferable. The MFR of the finally obtained polymer is preferably in the range of 0.1 to 100, more preferably in the range of 1 to 80. When the MFR is smaller than that of the present invention, moldability is lowered, and when the MFR is larger than the present invention, impact resistance is lowered, which is not preferable.

The talc (b) used in the present invention has an average particle size of 5 μm or less, preferably 2 μm or less in terms of impact resistance, and more preferably a particle size component of more than 10 μm.
The talc content is less than 1% by weight, and particularly preferably 1% by weight in terms of impact resistance.

The amorphous or low crystalline ethylene / α-olefin copolymer rubber (c) used in the present invention is an amorphous or low crystalline ethylene / α-olefin copolymer composed of ethylene and α-olefin. It is rubber. Specific examples of the α-olefin include propylene, 1-butene, 1-hexene and 1-octene, and among them, propylene or 1-octene is preferable. The content of ethylene in the amorphous or low crystalline ethylene / α-olefin copolymer rubber is preferably 40 to 80% by weight, more preferably 45 to 70% by weight, and particularly preferably 50 to 60% by weight. The Mooney viscosity [ML1 + 4 (100 ° C.)] of the amorphous or low crystalline ethylene / α-olefin copolymer rubber is 5 to 6
0 is preferable and 10 to 50 is more preferable. M of the amorphous or low crystalline ethylene / α-olefin copolymer rubber
FR (230 ° C; 21.18N) is 0.1-20g / 1
0 min is preferable, and 0.5 to 10 g / 10 min is more preferable. Specific examples of the amorphous or low crystalline ethylene / α-olefin copolymer include an amorphous ethylene / propylene copolymer rubber and a low crystalline ethylene / 1-octene copolymer rubber.

Examples of polyethylene (e) used in the present invention include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Among them, the rigidity of the propylene resin composition obtained, High-density polyethylene is preferable in terms of impact resistance. The MFR (190 ° C; 21.18N) of the polyethylene is preferably 0.1 to 50 g / 10 min, and 0.5 to 15
g / 10 min is more preferable, and 0.9 to 1.1 g / 1
0 min is particularly preferable. The crystalline melting point of the high-density polyethylene is preferably 131 to 138 ° C., and 136 to 138 ° C., from the viewpoint of rigidity of the resulting propylene resin composition.
Is particularly preferable. The density of the high-density polyethylene is 0.9 in terms of the rigidity of the obtained propylene meter resin composition.
50 to 0.965 g / cm ³ is preferable, and 0.960 to
0.965 g / cm ³ is particularly preferred.

The organophosphorus compound (f) used in the present invention includes sodium-bis (4-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-t).
-Butylphenyl) phosphate, sodium-2,2'-
Ethylidene-bis (4,6-di-t-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-2,2'-ethylidene-bis (4-i-propyl-6-t-
Butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-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-t-Butylphenyl) phosphate], calcium-
Bis [2,2'-thiobis (4,6-di-t-butylphenyl) phosphate], Magnesium-bis [2,2'-thiobis (4,
6-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-di-methylphenyl) 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-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate ,
Sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl ) Phosphate, calcium-bis [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4- s-Butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4, 6-Di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-
Di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-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 Aluminum-Tris [2,
2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and the like. Especially sodium-2,2'-
Methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

If desired, the high-rigidity propylene / ethylene block copolymer composition of the present invention may be added with an antioxidant, an antistatic agent, a colorant (pigment), a slip agent, and a slip agent so long as the object of the present invention is not impaired. One or more kinds of various additives such as an agent, a release agent, a flame retardant, an ultraviolet absorber, a weather resistance agent, a plasticizer and a radical generator can be blended.

As the method (blending method) for producing the polyolefin resin composition of the present invention, a commonly used method for blending powdery or granular substances can be applied. For example, a predetermined amount of each component used in the present invention and a stabilizer and a colorant are mixed by stirring with a ribbon blender, a tumbler mixer, a Hensell mixer (trade name), a super mixer, etc. to obtain the polyolefin resin composition. The method can be exemplified, and if necessary, the polyolefin-based resin composition is melted at a melting temperature of 150 with a roll, a Banbury mixer, a Labo Plastomill, a single-screw or twin-screw kneading extruder.
A method for obtaining a polyolefin-based resin composition on pellets by melt-kneading and pelletizing at a temperature of 300 to 300 ° C., preferably 180 to 250 ° C. can also be exemplified. The polyolefin resin composition of the present invention thus obtained can be used for the production of various molded products by various molding methods such as injection molding, extrusion molding, vacuum molding, and pressure molding, and among them, molding by injection molding is possible. The manufacture of goods is preferred.

[0019]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The analysis of various physical properties and the measuring method according to the examples described later are shown below. (1) MFR-1; ASTM D-1238 (unit: g
/ 10 min). 230 ° C, 21.18N load. (2) MFR-2; ASTM D-1238 (unit: g
/ 10 min). 190 ° C, 21.18N load. (3) Isotactic pentad fraction (P); mac
romolecules 8 687 (1975). It is the isotactic fraction in pentad units in the polypropylene molecular chain using ¹³ C-NMR. (4) Average molecular weight (Mn, Mw); The sample was dissolved in ortho-dichlorobenzene at 135 ° C.
0C type GPC (Gel Permeation Ch)
It was measured by romatograph). Column used T
SK GEL GMH6-HT (5) Ethylene content; by infrared absorption spectroscopy.
(Unit: wt%) Polymerization ratio (W1, W) between the polymerization step (I) and the polymerization step (II)
2); Make a copolymer in which the reaction amount ratio of ethylene / propylene is changed in advance, use this as a standard sample, and make a calibration curve by infrared absorption spectrum to obtain the reaction amount ratio of ethylene / propylene in the polymerization step (II). Furthermore, it was calculated from the ethylene content in the total polymer. (Weight / weight) (6) Flexural modulus, flexural strength; conforms to JIS K7203 (unit: MPa). (7) Tensile strength; JIS K7113 (unit: MPa)
Complies with. (8) Tensile elongation according to JIS K7113 (unit:%). (9) Izod impact strength; conforms to JIS K7110 (unit: J / m ² ). (10) Heat distortion temperature; JIS K7207 (unit: ° C)
Complies with. (11) Rockwell hardness; conforms to JIS K 7202 (unit: R scale). (12) Gloss; conforms to JIS K 7105 (unit:%). (13) Peeling strength of coating film: Melt resin temperature of 230 using an injection molding machine (M150A manufactured by Meiki Seisakusho) with a mold clamping force of 150 t.
Test piece (150 mm x 25 mm x 3 mm) is injection-molded at ℃, mold water temperature of 40 ℃, injection speed of 35 mm / sec, and a primer (PRIMAC 1500 made by NOF CORPORATION) is applied at a film thickness of 15 μm for 10 minutes. After leaving it to stand, a top coat (R-255, manufactured by Nippon Bee Chemical Co., Ltd.) was applied thereon with a film thickness of 20 μm, left to stand for 10 minutes, and then dried at 80 ° C. for 30 minutes to give a test piece for evaluation of coatability. Create a test piece and coating 1
The maximum stress at the time of peeling was determined at an angle of 80 degrees.
(Unit: g / cm)

The components used in the compositions of Examples and Comparative Examples are abbreviated as shown below. PP-1: MFR-1 is 23 g / 10 min, isotactic pentad fraction P is 0.996, and Q value is 5.
A crystalline propylene-ethylene copolymer comprising 0 propylene homopolymer and ethylene-propylene copolymer. Other properties of this crystalline propylene-ethylene copolymer are listed in Table 1. PP-2: MFR-1 is 23 g / 10 min, isotactic pentad fraction P is 0.955, and Q value is 5.
7. A crystalline propylene-ethylene copolymer comprising the propylene homopolymerization part of 7 and an ethylene-propylene copolymerization part. Other properties of this crystalline propylene-ethylene copolymer are listed in Table 1. PP-3: MFR-1 is 23 g / 10 min, isotactic pentad fraction P is 0.987, and Q value is 9.
A crystalline propylene-ethylene copolymer comprising 0 propylene homopolymer and ethylene-propylene copolymer. Other properties of this crystalline propylene-ethylene copolymer are listed in Table 1. Talc-1: Talc having an average particle diameter of 1.3 μm EPR-1: Ethylene-propylene copolymer rubber having an ethylene content of 54% by weight and a Mooney viscosity ML _{1 + 4} (100 ° C.) of 65. EPR-2: Ethylene-octene copolymer rubber having an ethylene content of 76% by weight and a Mooney viscosity ML _{1 + 4} (100 ° C.) of 31. PE-1: High-density polyethylene with MFR-2 of 1.0 g / 10 min, a crystal melting point of 137 ° C., and a density of 0.963 g / cm ³ . Nucleating agent-1: Sodium-2,2 @ -methylenebis (4,6-di-
t-Butylphenyl) phosphate (Asahi Denka Kogyo Co., Ltd., trade name [ADEKA STAB NA-11UF])

(Examples 1-5, Comparative Examples 1-2) PP-
1, PP-2, PP-3, talc-1, EPR-1, E
PR-2, PE-1 and / or nucleating agent-1 are shown in Table 2 below.
Parts by weight, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite 0.0
6 parts by weight, 0.03 parts by weight of calcium stearate,
0.2 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and tris (3,5-di-t-butyl-4-
(Hydroxybenzyl) isocyanurate 0.1 part by weight is mixed and mixed at room temperature for 10 minutes with a high-speed stirring mixer (Note. Henschel mixer, trade name), and the mixture is used with an extrusion granulator having a screw diameter of 40 mm. Granulation was carried out at a cylinder setting temperature of 200 ° C. to obtain a pelletized composition.
The composition is set in an injection molding machine at a cylinder temperature of 230 ° C.,
A JIS type test piece was prepared at a mold temperature of 50 ° C., and the physical property values were measured after being left for 72 hours in a room at a humidity of 50% and a room temperature of 23 ° C. The results are shown in Table 2 below. Further, the peeling strength of the coating film was evaluated using the composition, and the results are shown in Table 2. As is clear from Table 2, Examples 1 to 5 are simultaneously excellent in flexural modulus, Izod impact strength, heat deformation temperature, Rockwell hardness, and coating peeling strength, but Comparative Examples 1 and 2 each have flexural modulus. , Izod impact strength remains a problem.

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[Table 1]

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[Table 2]

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EFFECT OF THE INVENTION The polyolefin resin composition of the present invention has an excellent balance of rigidity and impact resistance of the obtained injection-molded product, and further exhibits excellent heat rigidity, appearance, paintability and moldability. , It is extremely useful for automobile interior materials (instrument panels, door trims, pillars, high mount stop lamps, etc.) and automobile exterior materials (bumpers, side moldings, splash guards, air dams, etc.).

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 23:16 23:08)

Claims (4)

[Claims] 1. A solid catalyst component (A) containing titanium, magnesium, halogen and a polycarboxylic acid ester as essential components, an organoaluminum compound (B) and a general formula R ⁴ _x R ⁵ _y Si (OR ⁶ ) _z. (In the formula, R ⁴ and R ⁶ are hydrocarbon groups, R ⁵ is a hydrocarbon group or a hydrocarbon group containing a hetero atom, and x + y + z = 4,0 ≦ x ≦ 2,1 ≦ y ≦
3, 1 ≦ z ≦ 3. 2) is used as the first step by using a catalyst system in which an organosilicon compound (C) represented by
Propylene homopolymerization was carried out in a polymerization step (I) using a tank or more polymerization vessels in series to produce 60 to 95% by weight of the total weight, and as a second step, polymerization using one or more vessel polymerization machines. A propylene / ethylene block copolymer produced by copolymerizing propylene and ethylene in step (II) to produce a propylene / ethylene copolymer part having an ethylene content of 30 to 80% by weight based on the total weight of 5 to 40% by weight. In the polymer, the maximum value (hereinafter referred to as MFR (h)) and the minimum value (MF) of the melt flow rate of the polymer obtained in each tank of the polymerization step (I)
R (l)) has a relationship of 0.1 ≦ Log (MFR (h) / MFR (l)) ≦ 1 (1) and the iso of the propylene polymer obtained in the polymerization step (I). The tactic pentad fraction (P) is 0.
96 or more, Mw / Mn (Q value) is 6 or less, and
The melt flow rate of the polymer obtained in the polymerization step (I) (hereinafter referred to as MFR (i)) and the melt flow rate of the polymer obtained in the polymerization step (II) (hereinafter referred to as MFR (ii)) are 3 ≦. Log (MFR (i) / MFR (ii)) ≦ 7 (2) The high-rigidity propylene / ethylene block copolymer (a) having a relationship of 70 to 95% by weight and an average particle diameter of 5 μm.
A polyolefin resin composition comprising 5 to 30% by weight of talc (b) of m or less. 2. The crystalline propylene / ethylene block copolymer (a) according to claim 1 is 92 to 60% by weight, the talc (b) according to claim 1 is 5 to 30% by weight, and it is amorphous or low. Crystalline ethylene / α-olefin copolymer rubber (d)
Of 3 to 10% by weight. 3. The crystalline propylene / ethylene block copolymer (a) according to claim 1 is 91.5 to 57% by weight, and the talc (b) according to claim 1 is 5 to 30% by weight.
A polyolefin resin composition comprising 3 to 10% by weight of the ethylene / α-olefin copolymer rubber (d) and 0.5 to 3% by weight of polyethylene (e). 4. 100 parts by weight of the polyolefin resin composition according to any one of claims 1 to 3 and 0.0 of the organic phosphorus compound (f).
A polyolefin resin composition comprising 01 to 0.5 parts by weight.