JPH1160841A - Polypropylene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene-based resin composition, in which its impact resistance, hardness and surface appearance of molded product to be formed are in excellent balance, by blending a polypropylene-based resin with a novel ethylene-based copolymer having a certain composition ratio, flowability and branching. SOLUTION: This polypropylene-based resin composition mainly consists of (I) 30-95 wt.% of a polypropylene-based resin and (II) 70-5 wt.% of an ethylene-based random copolymer comprising ethylene, a 3-20C α-olefin and a non-conjugated diene. The ethylene-based random copolymer meets the following requirements: (1) an ethylene content of 50-90 wt.% and an ethylene content distribution, as the high ethylene content moiety/low ethylene content moiety ratio, of 1.05-2.5; (2) a melt flow rate(MFR) of 0.02-50 g/10 min (230 deg.C, 2.16 kg); and (3) a viscosity, as the branching index or the 'B' value obtained by gel permeation chromatography(GPC), of 0.5-0.98 with the 'B' value distribution, as the high 'B' value/low 'B' value ratio, of 1.02-1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polypropylene resin composition, and more particularly, to impact resistance,
The present invention relates to a polypropylene resin composition having an excellent balance between hardness and surface appearance.

[0002]

2. Description of the Related Art Polypropylene resins have been widely used in various molded articles and sheets because of their excellent moldability, toughness, water resistance, chemical resistance, etc., low specific gravity and low cost. However, the purpose of use may be limited due to poor impact resistance. In order to improve this problem, many proposals have been made to blend an ethylene-based random copolymer as a rubber component with a polypropylene-based resin. As a method for producing these rubbers, for example, a titanium-based catalyst composed of a titanium compound and an organoaluminum compound or a vanadium-based catalyst composed of a vanadium compound and an organoaluminum compound is used to copolymerize ethylene, α-olefin, and a non-conjugated diene. There are known ways to do this.

On the other hand, as an alternative to the above-mentioned conventional catalyst, a catalyst comprising a transition metal compound and an aluminoxane has been proposed. For example, Japanese Patent Publication No. Hei 4-12283 discloses the following formula (Cp) ₂ MR ¹ X (formula ( ¹ )) Wherein Cp is a cyclopentadienyl group, R ¹ is an alkyl group having 1 to 6 carbon atoms or a halogen atom, M is zirconium or titanium, X is a halogen atom, and a transition metal compound represented by the following formula: R ² ) ₂ AlO [Al (R ² ) O-] _n Al (R ² ) ₂ or [Al (R ² ) O-] _{n + 2} (where n is an integer of 4 to 20, R ² is A method for copolymerizing ethylene and an α-olefin in the presence of a catalyst comprising an aluminoxane represented by a methyl group or an ethyl group) is described. Japanese Patent Publication No. 5-80493 discloses that ethylene and an α-olefin having 3 to 10 carbon atoms are used in the presence of a catalyst comprising a zirconium hydride compound having a group having a conjugated π electron as a ligand and an aluminoxane. A method for copolymerizing a non-conjugated polyene having 5 to 20 carbon atoms is described. However, although the polypropylene-based resin composition containing these copolymers as a rubber component has improved impact resistance, the hardness and surface appearance of molded articles are reduced, and are not practically sufficient. For these improvements, the use of a high-molecular-weight type ethylene-based random copolymer can be considered.
To reduce the fluidity characteristic of polypropylene,
Not practically preferable.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is directed to a novel ethylene copolymer having a fixed composition ratio, fluidity, and branching in a polypropylene resin. Is to provide a polypropylene resin composition having an excellent balance of impact resistance, hardness and appearance of a molded surface.

[0005]

According to the present invention, there are provided (I) 30 to 95% by weight of a polypropylene resin, (II) ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. 70 to 5% by weight of an ethylene random copolymer satisfying the requirements [however, (I) + (II)
= 100% by weight] as a main component. The ethylene content is in the range of 50 to 90% by weight;
The distribution of ethylene content is in the range of 1.05 to 2.5 in the ratio of high ethylene content part / low ethylene content part. Melt flow rate (MFR) (230 ° C, 2.16
kg load) is in the range of 0.02 to 50 g / 10 minutes. Viscosity-gel permeation chromatography (G
PC) the degree of branching index “B” value determined from 0.5 to 0.5
0.98, and the distribution of the “B” value is in the range of 1.02 to 1.5 in the ratio of the high “B” value / low “B” value.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (I) Polypropylene resin The (I) polypropylene resin contained in the composition of the present invention may be a propylene homopolymer or ethylene,
-Copolymers containing α-olefins such as butene, 1-pentene, 1-hexene and 1-octene. The (co) polymer may be a random copolymer, a block copolymer, a blend of a homopolymer obtained by multi-stage polymerization, or a normal blend. The method for obtaining the polypropylene resin (I) is not limited to a polymerization method or a catalyst. Further, the stereoregularity of the propylene unit is not limited at all. (I) Melt flow rate of polypropylene resin (2
30 ° C., 2.16 kg load) is usually 10 to 200 g
/ 10 minutes, preferably 30 to 120 g / 10 minutes.

(II) Ethylene random copolymer The component (II) used in the present invention is ethylene, having 3 carbon atoms.
It is an ethylene-based random copolymer consisting of α-olefins of 20 to 20 and a non-conjugated polyene, and satisfying the following requirements. Here, as the α-olefin having 3 to 20 carbon atoms (hereinafter also referred to as “α-olefin”) constituting the ethylene-based random copolymer (II), specifically, propylene, 1-butene, -Pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 5-methyl-1-hexene, 1
-Octene, 5-ethyl-1-hexene, 1-decene,
Examples thereof include 1-dodecene, and propylene, 1-butene, 1-hexene, and 1-octene are preferably used. These α-olefins can be used alone or in combination of two or more.

The (II) non-conjugated polyene constituting the ethylene-based random copolymer includes a non-conjugated polyene compound having two or more types of polymerization-reactive groups equivalent in polymerization reactivity, and aromatic compounds such as divinylbenzene. A divinyl compound, an aliphatic divinyl compound and the like can be mentioned. Examples of the non-conjugated polyene compound having two polymerization reactive groups equivalent in polymerization reactivity include 1,4-pentadiene, 1,5-hexadiene, 1,6-pentadiene, 1,7-octadiene, 8-nonadiene, 1,9-decadiene, 1,1
0-undecadiene, 1,11-dodecadiene, 1,1
2-tridecadiene, 1,13-tetradecadiene,
3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 1,4,7-octatriene, 5-methyl-1,8-nonadiene, 1,5,9
-Decatriene, 1,20-heneicosadien, 5-
(5-hexenyl) -2-norbornene, 5- (2-propenyl) -2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 4-vinylcyclohexene, ), (Chem. 3) and the like.

[0009]

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Of these, 5-vinylnorbornene, 2,5-norbornadiene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene,
1,9-decadiene is preferred. Further, the non-conjugated polyene constituting the (II) ethylene-based random copolymer includes a non-conjugated polyene having a polymerization reactive group having unequal polymerization reactivity. This non-conjugated polyene includes 1,4-hexadiene, 2-methyl-
1,5-hexadiene, 1,9-octadecadiene, 6
-Methyl-1,5-heptadiene, 7-methyl-1,6
-Octadiene, 11-ethyl-1,11-tridecadiene and the like, and alicyclic compounds such as dicyclopentadiene, tricyclopentadiene, 5-ethylidene-2-
Norbornene, propenylnorbornene, methyltetrahydroindene, isopropenylidenenorbornene, alkenyl-substituted norbornene having an internal double bond in the alkenyl group, unsaturated derivatives of bicyclo (2,2,2) octane, and the like, preferably 5 -Ethylidene-2-norbornene, cyclopentadiene, 1,4-hexadiene. These non-conjugated polyenes
They can be used alone or as a mixture of two or more.

The (II) ethylene random copolymer used in the present invention must satisfy the following requirements. Ethylene content; The ethylene content in the (II) ethylene random copolymer of the present invention is 50 to 90% by weight, preferably 60 to 85% by weight. If it is less than 50% by weight, the polypropylene resin composition will be significantly softened,
On the other hand, if it exceeds 90% by weight, the effect of modifying the impact resistance of the polypropylene resin becomes poor. The distribution of ethylene content is 1.05 to 2.5, preferably 1.08 to 2.0, in the ratio of high ethylene content part / low ethylene content part.
Range. If it is less than 1.05, an ethylene-based random copolymer having uniform crystallinity is obtained, and a crystalline portion and an amorphous portion cannot be obtained in a well-balanced manner, and a polypropylene-based resin composition having an excellent rigidity / impact resistance balance is obtained. I can't get it. On the other hand, if it exceeds 2.5, a copolymer having both ethylene crystals and propylene crystals is obtained, and a polypropylene-based resin composition having an excellent rigidity / impact resistance balance cannot be obtained. For adjusting the ethylene content, a blending method of mixing a plurality of random copolymers having different ethylene contents at a specific ratio, a method of mixing and polymerizing a plurality of polymerization catalysts having different activities for ethylene, and the like are used.
However, the present invention is not limited to these as long as the effects of the present invention can be obtained.

Here, the distribution of ethylene content (ratio of high ethylene content part / low ethylene content part) is defined as follows. (1) After dissolving 5 g of the copolymer in 200 ml of n-decane, isopropyl alcohol is added dropwise with stirring. When the solution becomes cloudy, the addition is stopped, the precipitate is separated and dried, and its ethylene content is measured. . (2) Isopropyl alcohol is further added dropwise to the solution phase of (1), and the same operation is performed to measure the ethylene content. (3) Repeat the above operation (2). By such solvent fractionation, the copolymer is fractionated into 4 to 6 fractions.
Using the highest and lowest values of the ethylene content of these fractions, the ratio of the highest / lowest value is defined as the distribution of the ethylene content. At this time, the highest value and the lowest value may be the ethylene content of the component on either the high molecular weight side or the low molecular weight side, respectively.

Melt flow rate: The melt flow rate of the ethylene random copolymer (II) of the present invention (23)
0 ° C, 2.16 kg load) (hereinafter also referred to as “MFR”)
Is 0.02 to 50 g / 10 min, preferably 0.05 to
40 g / 10 min, more preferably 0.1 to 30 g / 1
0 minutes. If the MFR is less than 0.02 g / 10 minutes, a sufficient modifying effect cannot be obtained due to poor dispersion in the polypropylene resin. On the other hand, MFR is 50 g / 1
If the time exceeds 0 minutes, the impact resistance and appearance improving effect of the polypropylene resin are inferior. This melt flow rate can be adjusted by the amount of the chain transfer agent during the polymerization, the polymerization temperature, the concentration of the polymerization catalyst, and the like.

The degree of branching index "B"; the value of the degree of branching "B" determined from the viscosity-GPC of the (II) ethylene random copolymer of the present invention is from 0.5 to 0.98, preferably 0. 0.6 to 0.97. Branch index "B" value is 0.5
If it is less than 10, the effect of improving the impact resistance of the polypropylene resin is inferior due to gelation. On the other hand, the branching degree index “B” value is 0.9.
If it is larger than 8, the polypropylene resin composition cannot obtain a fine dispersion effect at the time of kneading due to branching, and a sufficient effect of improving impact resistance cannot be obtained. The distribution of the “B” value is in the range of 1.02 to 1.5, preferably 1.05 to 1.4, in the ratio of the high “B” value / low “B” value. When the ratio of the “B” value is less than 1.02, the effect due to branching cannot be obtained or it is too strong, and the propylene-based resin composition is softened. On the other hand, when the ratio exceeds 1.5, the branching effect becomes partially strong and the gelation occurs partially, so that the physical properties in the present invention cannot be obtained. The adjustment of the branching degree index "B" value is performed by a method of mixing a plurality of ethylene-based random copolymers having different "B" values at a specific ratio, and a method of mixing a plurality of polyenes having different copolymerizabilities at a specific ratio. Copolymerization method and the like can be mentioned. The present invention is not limited to the above, as long as the effects of the present invention can be obtained.

Here, the distribution of the “B” value (ratio of high “B” value / low “B” value) is defined as follows. (1) After dissolving 5 g of the copolymer in 200 ml of n-decane, isopropyl alcohol was added dropwise with stirring. When the solution became cloudy, the addition was stopped, and the precipitate was separated and dried.
The ethylene content is measured. (2) Isopropyl alcohol is further added dropwise to the solution phase of (1), and the same operation is performed to measure the ethylene content. (3) Repeat the above operation (2). By such solvent fractionation, the copolymer is fractionated into 4 to 6 fractions.
Using the highest and lowest values of the "B" value of these fractions, the ratio of the highest value / lowest value is defined as the distribution of the "B" value.
At this time, the highest value and the lowest value may be the “B” values of the components on the high molecular weight side and the low molecular weight side, respectively.
The value of the branching degree index “B” is determined by the intrinsic viscosity [η] of the unbranched model copolymer rubber and the polystyrene equivalent value in accordance with the viscosity-GPC method [Murao Kurata, Journal of the Rubber Society of Japan (45) 1972]. Using the viscosity equation [η] = KMw obtained from the weight average molecular weight (Mw), the GP of the target copolymer rubber is used.
[Η] is calculated from Mw obtained by the C measurement, and then the actually measured [η] of the target copolymer is divided by [η] calculated from the above viscosity equation to obtain a branching degree index “B” value. I do. here,
[Η] is o-dichlorobenzene, [η] obtained at 135 ° C., and Mw is o-dichlorobenzene, 135 ° C.
Is a value obtained by the GPC measurement method.

The (II) ethylene random copolymer may be used alone or as a mixture. If the α-olefin content, MFR and branching index “B” value are within the above ranges with the values after mixing, two or more types can be used in combination.

The α-olefin content in the (II) ethylene random copolymer of the present invention is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and still more preferably 20 to 40% by weight. It is.

Further, the weight average molecular weight of the (II) ethylene random copolymer is usually 100,000 to 500,000, preferably 150,000 to 400,000.

The polymerization reaction for producing the (II) ethylene random copolymer of the present invention is usually carried out in an inert hydrocarbon solvent. As such an inert hydrocarbon solvent, specifically, pentane, hexane, heptane,
Aliphatic hydrocarbons such as octane, decane and dodecane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene. These hydrocarbon solvents can be used alone or in combination of two or more. Further, the raw material monomer can be used as a hydrocarbon solvent.

Hereinafter, the polymerization catalyst used for producing the (II) ethylene random copolymer of the present invention will be described.
The present invention will be described in detail with reference to examples. However, the present invention is not limited thereto, and any known catalyst can be appropriately used without departing from the scope of the present invention. Examples of the polymerization catalyst used for producing the ethylene-based random copolymer (II) of the present invention include, for example, a catalyst comprising the following components (A) and (B), or the following components (C) and (D) ). Component (A) is a transition metal compound represented by the following general formula (I). In the formula, M is a metal of Group 4 of the periodic table, (C ₅ R _m ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R may be the same or different and includes a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded. E is an atom having a non-bonded electron pair, R 'is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a carbon atom having 7 to 8 carbon atoms. 40 alkaryl groups or 7 to 7 carbon atoms
40 is an aralkyl group, R ″ is an alkylene group having 1 to 20 carbon atoms, dialkyl silicon or dialkyl germanium, and is a group that binds two ligands;
Is 1 or 0; when s is 1, m is 4; n is a number smaller than the valence of E by 2; when s is 0, m is 5,
n is a number less than the valence of E; when n ≧ 2, each R ′ may be the same or different; each R ′ may be bonded to form a ring; and Q is a hydrogen atom A halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, and p and q are 0 to 4
And satisfies the relationship 0 <p + q ≦ 4.

Specific examples of the component (A) include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) ) Zirconium diphenyl, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, bis (Indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dichloride, methylenebis (indenyl) zircon Umujikurorido, bis (4,
5,6,7-tetrahydroindenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride , Dimethylsilylbis (4,5
6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadiene) Enyl) zirconium dimethyl, dimethylsilylbis (3-methyl-1-cyclopentadienyl) zirconium dichloride, methylenebis (3-methyl-1-cyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium Dichloride, dimethylsilylbis (3-t-butyl-1-cyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4-dimethyi) 1-cyclopentadienyl)
Zirconium dichloride, bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,3,5-trimethyl-1-cyclopentadienyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, dimethyl Silylbis (fluorenyl) zirconium dichloride, (fluorenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilyl (fluorenyl) (cyclopentadienyl) zirconium dichloride, (t-butylamide) (1,2,3,4,5- Pentamethylcyclopentadienyl) zirconium dichloride, dimethylsilyl (t-butylamide) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (t- Chiruamido) (2,3,4,5
Tetramethyl-1-cyclopentadienyl) zirconium dichloride, (phenoxy) (1,2,3,4,5-
Pentamethylcyclopentadienyl) zirconium dichloride, dimethylsilyl (o-phenoxy) (2,3
4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (o-phenoxy)
(2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, ethylene (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, Bis (dimethylamido) zirconium dichloride, bis (diethylamido) zirconium dichloride, bis (di-t-butylamido) zirconium dichloride, dimethylsilylbis (methylamido) zirconium dichloride, dimethylsilylbis (t-butylamido) zirconium dichloride, and the like, and these compounds In which zirconium is replaced by titanium or hafnium, but is not limited thereto. The above transition metal compounds can be used alone or in combination of two or more.

The component (B) is an aluminoxane compound having a unit represented by the following general formula (II), and although the chemical structure is not necessarily clear, a linear, cyclic or cluster compound, Alternatively, it is presumed to be a mixture of these compounds. -[Al (R "")-O]-... (II) wherein R "" is an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms.
An aryl group having from 40 to 40, an alkaryl group having from 7 to 40 carbon atoms or an aralkyl group having from 7 to 40 carbon atoms, preferably a methyl group, an ethyl group and an isobutyl group, particularly preferably a methyl group. The aluminoxane compound is a compound of the formula
It can be produced by a known method via a reaction between an organoaluminum compound having at least one group and water. The ratio of the components (A) and (B) used is usually 1: 1 to 1 in terms of the molar ratio of the transition metal to the aluminum atom.
1: 100,000, preferably 1: 5 to 1: 50,0
00 range.

Next, the component (C) is a transition metal alkyl compound represented by the following general formula (III). In the formula, M is a metal of Group 4 of the periodic table, (C ₅ R _m ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, each R may be the same or different, and represents a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded. E is an atom having a non-bonded electron pair, R 'is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a carbon atom having 7 to 8 carbon atoms. 40 alkaryl groups or 7 to 7 carbon atoms
40 is an aralkyl group, R ″ is an alkylene group having 1 to 20 carbon atoms, dialkyl silicon or dialkyl germanium, and is a group that binds two ligands;
Is 1 or 0; when s is 1, m is 4; n is a number smaller than the valence of E by 2; when s is 0, m is 5,
n is a number smaller than the valence of E by 1; when n ≧ 2, each R ′ may be the same or different; each R ′ may be bonded to form a ring; C1-C20 alkyl group, C6-C40 aryl group, C7-C
An alkaryl group of 40 or an aralkyl group of 7 to 40 carbon atoms, p and q are integers of 0 to 3,
<P + q ≦ 4.

Specific examples of component (C) include bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium diisobutyl, and bis (cyclopentadienyl) Zirconium diphenyl, bis (cyclopentadienyl) zirconium di {bis (trimethylsilyl) methyl}, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium diisobutyl, methylenebis (cyclopentadienyl) ) Zirconium dimethyl, ethylene bis (cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (indenyl) zirconium diisobutyl, dimethyl Rubis (indenyl) zirconium dimethyl, methylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7 -Tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-
Tetrahydro-1-indenyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (3-methyl-1-cyclopentadienyl) zirconium dimethyl, bis (t-
Butylcyclopentadienyl) zirconium dimethyl,
Dimethylsilylbis (3-t-butyl-1-cyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl,
Bis (1,3-dimethylcyclopentadienyl) zirconium diisobutyl, dimethylsilylbis (2,4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, methylenebis (2,4-dimethyl-1-cyclopentadienyl) Zirconium dimethyl, ethylene bis (2,4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, bis (1,2,4-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (2,3,5-trimethyl) -1-cyclopentadienyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, dimethylsilylbis (fluorenyl) zirconium dimethyl, (fluorenyl)
(Cyclopentadienyl) zirconium dimethyl, dimethylsilyl (fluorenyl) (cyclopentadienyl)
Zirconium dimethyl, (t-butylamide) (1,
2,3,4,5-pentamethylcyclopentadienyl)
Zirconium dimethyl, dimethylsilyl (t-butylamide) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, methylene (t-
Butylamide) (2,3,4,5-tetramethyl-1-
Cyclopentadienyl) zirconium dimethyl, (phenoxy) (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (o-phenoxy) (2,3,4,5-tetramethyl −
1-cyclopentadienyl) zirconium dimethyl, methylene (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, bis (dimethylamide) zirconium dimethyl, bis (diethylamide) Zirconium dimethyl, bis (di-t-butylamido) zirconium dimethyl, dimethylsilylbis (methylamido) zirconium dimethyl, dimethylsilylbis (t-butylamido) zirconium dimethyl and the like, and compounds obtained by substituting zirconium in these compounds with titanium or hafnium But are not limited to these. The above transition metal alkyl compounds can be used alone or in combination of two or more. The transition metal alkyl compound,
It may be used by synthesizing it in advance, or the above-mentioned general formula (III)
By contacting a transition metal halide in which R ″ is substituted with a halogen atom with an organometallic compound such as trimethylaluminum, triethylaluminum, diethylaluminum monochloride, triisobutylaluminum, methyllithium or butyllithium in a reaction system. It may be formed.

The component (D) is an ionic compound represented by the following general formula (IV). In the formula, [L] ^{k +} is a Bronsted acid or a Lewis acid, M ′ is an element belonging to Groups 13 to 15 of the periodic table, and A ₁ to
_An is a hydrogen atom, a halogen atom, and a carbon number of 1 to 2, respectively.
0 alkyl group, C1-C30 dialkylamino group, C1-C20 alkoxy group, C6-C40 aryl group, C6-C40 aryloxy group, C7-C40 alka A reel group, an aralkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 40 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, or an organic metalloid group; Is an integer, p is an integer of 1 or more, and q = (k × p).

Specific examples of component (D) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, methyl (dibutyl) ammonium tetraphenylborate, dimethylanilinium tetraphenylborate, and tetraphenylborate. Methylpyridinium, methyl tetraphenylborate (2-cyanopyridinium), methyl tetraphenylborate (4-cyanopyridinium), trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate,
Tributylammonium tetrakis (pentafluorophenyl) borate, methyl (dibutyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenylphenyl) methyl borate (4-cyanopyridinium), tetrakis [bis (3
5-Di-trifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, and the like, but are not limited thereto. The above ionic compounds can be used alone or in combination of two or more. The molar ratio of the component (C) to the component (D) is usually from 1: 0.5 to 1:20, preferably from 1: 0.8 to 1:10.

The polymerization catalyst used for producing the (II) ethylene random copolymer of the present invention can be used by supporting at least a part of those components on a suitable carrier. The type of carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In addition, there is no particular limitation on the loading method, and a known method may be appropriately used.

The polypropylene resin composition of the present invention comprises:
A composition comprising (I) a polypropylene-based resin and (II) an ethylene-based random copolymer as main components and having an excellent balance between impact resistance, hardness and appearance of a molded surface. In the present invention, the mixing ratio of the (I) polypropylene resin and the (II) ethylene random copolymer is such that the component (I) is 30 to 9
5% by weight, preferably 50 to 90% by weight, and the component (II) is 70 to 5% by weight, preferably 50 to 10% by weight.
Less than 30% by weight of component (I) or 70% by weight of component (II)
If the content exceeds% by weight, the rigidity is reduced, which is not preferable.
On the other hand, if the amount of the component (I) exceeds 95% by weight or the amount of the component (II) is less than 30% by weight, the impact resistance is undesirably reduced.

The production of the polypropylene resin composition of the present invention is not particularly limited, and a known method can be used. For example, the composition of the present invention can be obtained by kneading the components with various extruders, Banbury mixers, kneaders, rolls, and the like. In the composition of the present invention, if necessary, various additives such as antioxidants, heat stabilizers, ultraviolet absorbers, stabilizers such as copper damage inhibitors, silica, talc, carbon, calcium carbonate, magnesium carbonate , Glass fiber, metal fiber, glass beads, mica,
Fillers such as potassium titanate whisker, aramid fiber, charcoal, cork powder, cellulose powder, and rubber powder can be used in combination. In addition, a softener such as a plasticizer, an oil, or a low molecular weight polymer can be used together with the above additives.

[0030]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. In the examples, parts and percentages are by weight unless otherwise specified. Various measurements in the examples were based on the following methods. Ethylene content Measured by ¹³ C-NMR method. It was measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with MFR JIS K6383.

Izod impact strength Measured according to JIS K7110. The flexural modulus was measured according to JIS K7203. Rockwell strength Measured according to ASTM D785. The gloss was measured at an incident angle of 60 ° according to ASTM D-523.

The polymers used in Examples and Comparative Examples were
These are: (I) Polypropylene resin; propylene-ethylene block polymer [BC06C, manufactured by Mitsubishi Chemical Corporation] (II) Ethylene random copolymer; those shown in Table 1 were used. These manufacturing methods are illustrated in the following examples. Talc; LSM # 200 manufactured by Fuji Talc Co., Ltd.

Reference Example 1 (Ethylene random copolymer A
Synthesis of 1) In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, 800 ml of purified toluene, 350 ml of propylene, 12 ml of 7-methyl-1,6-octadiene, and aluminum dissolved in 4 ml of purified toluene. After adding 6 mmol of methylaluminoxane in terms of atoms and raising the temperature to 40 ° C,
Pressurize with ethylene, ethylene partial pressure 2.5kg / cm ²
-Adjusted to G.

Next, 1.2 μmol of ethylenebis (indenyl) zirconium dichloride dissolved in 1.2 ml of toluene was added to initiate polymerization. During the reaction, the temperature was maintained at 40 ° C. and the ethylene partial pressure was 2.5 kg /
The reaction was carried out for 30 minutes while continuously supplying ethylene so as to be maintained at cm ² · G. After completion of the reaction, the polymer solution was poured into a large amount of methanol to precipitate a polymer, and the polymer was collected by filtration, dried under reduced pressure, and dried.
g of polymer were obtained. This polymer has an ethylene content of 72%, an MFR of 1.5 g / 10 min, and a branching index "B".
It was an ethylene random copolymer A′1 having a value of 0.9. Next, an ethylene-based random copolymer A ″ 1 obtained in the same manner as described above was obtained by changing the α-olefin, the non-conjugated diene species, and the copolymerization amount. %, MFR was 4.0 g / 10 min, and the value of branching index "B" was 1.0. The above polymer A'1
And polymer A ″ 1 by A′1 / A ″ 1 (weight ratio) = 50 /
The mixture was mixed at 50 to obtain a polymer A1.

Reference Examples 2 to 12 (Synthesis of Ethylene Random Copolymers A2 to A12)
To A′12 and A ″ 2 to A ″ 12 were obtained, and these were mixed to obtain polymers A2 to A12. The compositions of the polymers A1 to A12 are shown in Tables 1 and 2.

[0036]

[Table 1]

[0037]

[Table 2]

Example 1 (Preparation of Composition) The polymer A1 obtained above was used as a polypropylene resin (P
P) and talc, twin screw extruder (diameter 45m)
m, L / D = 32) and pelletized. From the obtained composition, test pieces for evaluating physical properties were prepared by injection molding. Table 3 shows the compounding ratio and the results of the physical property evaluation.

Examples 2 to 5 (Preparation of Composition) In Example 1, the α-olefin and the non-conjugated polyene were changed instead of the polymer A1 as the ethylene random copolymer. Synthetic polymer A
It evaluated using 2-A5. Table 3 shows the results. Each of these examples is a composition using an ethylene-based random copolymer within the scope of the present invention, and has impact resistance, rigidity,
Excellent balance of surface gloss.

Comparative Examples 1 to 6 (Preparation of Composition) In the same manner as in Example 1, a composition using an ethylene random copolymer blended at a ratio outside the range of the present invention was used. The balance of impact resistance, rigidity and balance of surface gloss are significantly deteriorated. The results are shown in Tables 4 and 5.

Comparative Examples 7 and 8 (Preparation of Composition) In the same manner as in Example 1, the composition was such that the composition ratio of ethylene random copolymer / polypropylene resin was out of the range of the present invention. . The fluidity, impact resistance, and rigidity were significantly deteriorated. Table 5 shows the results.

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[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

* 1) 7-methyl-1,6-octadiene * 2) ethylidene norbornene * 3) 1,9-decadiene * 4) dicyclopentadiene

[0046]

The polypropylene resin composition of the present invention is obtained by mixing a polypropylene resin with a novel ethylene copolymer having a fixed composition ratio, fluidity, and branching, and blending the polypropylene resin with impact resistance. Excellent balance of hardness, molding surface appearance.

Claims (1)

[Claims] An ethylene random copolymer comprising (I) 30 to 95% by weight of a polypropylene resin, (II) ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and satisfying the following requirements: A polypropylene resin composition containing 70 to 5% by weight (where (I) + (II) = 100% by weight) as a main component. The ethylene content is in the range of 50 to 90% by weight;
The distribution of ethylene content is in the range of 1.05 to 2.5 in the ratio of high ethylene content part / low ethylene content part. Melt flow rate (MFR) (230 ° C, 2.16
kg load) is in the range of 0.02 to 50 g / 10 minutes. Viscosity-gel permeation chromatography (G
PC) the degree of branching index “B” value determined from 0.5 to 0.5
0.98, and the distribution of the “B” value is in the range of 1.02 to 1.5 in the ratio of the high “B” value / low “B” value.