JP2002275277A - Injection molded article of polyolefin resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an injection molded article of a polyolefin resin composition having balanced rigidity and impact resistance. SOLUTION: The injection molded polyolefin resin composition is produced by the injection molding of a polyolefin resin composition composed of [I] 1-99 wt.% 1-butene polymer which is a crystalline resin having no melting point or a melting point (Tm-P) of 0-100 deg.C defined by a specific peak top obtained by differential scanning calorimeter(DSC), a stereospecificity index (mmmm) /(mmrr+rmmr)} of <=20, a molecular weight distribution (Mw/Mn) of <=4.0 measured by gel permeation chromatography(GPC) and a weight-average molecular weight (Mw) of 10,000-1,000,000 measured by GPC and [II] 99-1 wt.% crystalline propylene polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection molded article of a polyolefin resin composition having an excellent balance between rigidity and impact resistance.

[0002]

2. Description of the Related Art Olefin polymers, especially polypropylene, are crystalline polymers and therefore have excellent rigidity, tensile strength, heat resistance, chemical resistance, optical properties, workability, etc., and low specific gravity. It is widely used in the fields of various injection molded products, containers, packaging materials and the like. In the field of injection molded products, impact resistance is further required. Is being done. However, in the propylene-ethylene copolymer, many rubber components must be blended in order to increase the impact resistance, and at that time, there is a problem that the rigidity is greatly reduced.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an injection molded article of a polyolefin-based resin composition having excellent balance between rigidity and impact resistance in view of the above-mentioned circumstances.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a blend of a low stereoregular 1-butene polymer having excellent softness and a crystalline polypropylene can be obtained. It has been found that the use of a product makes it possible to obtain a polyolefin-based resin composition injection-molded article having an excellent balance of rigidity and physical properties of impact resistance, and has completed the present invention.

That is, the present invention provides the following injection molded article of a polyolefin resin composition. 1. Injection molding of a polyolefin resin composition comprising 1 to 99% by weight of a 1-butene polymer [I] and 99 to 1% by weight of a crystalline propylene polymer [II] satisfying the following (1) to (4). An injection molded article of a polyolefin resin composition comprising: (1) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then −1 at 5 ° C./min.
After cooling down to 0 ° C, keeping at -10 ° C for 5 minutes,
The melting point (Tm-P) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at
Crystalline resin at 100 ° C. (2) Stereoregularity index ｛(mmmm) / (mmrr + r
mmr)｝ is 20 or less (3) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by GPC method is 4.0 or less. (4) Weight average molecular weight (Mw) measured by GPC method.
Is from 10,000 to 1,000,000 2.1-butene-based polymer [I] is a 1-butene homopolymer and satisfies the following (5) and (6):
Injection molded article of the polyolefin resin composition. (5) Mesopentad fraction (mmmm) is 20 to 90% (6) (mmmm) ≦ 90−2 × (rr) where rr represents a racemic triad fraction. 3. Izod impact strength A (kJ / m 2) measured at 23 ° C. according to JIS K7110 and JIS K7113
The injection molded article of the polyolefin resin composition of the above 1 or 2, wherein the relationship of the tensile modulus E (MPa) measured according to the formula satisfies the following expression. A ≧ −0.037E + 62.2

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION [1] 1-
The butene-based polymer, [2] the crystalline polypropylene-based polymer, [3] the polyolefin-based resin composition, and [4] the injection-molded product will be sequentially described in detail.

[1] 1-Butene Polymer The 1-butene polymer used in the present invention includes a 1-butene homopolymer obtained by homopolymerizing 1-butene and 1-butene homopolymer.
-There is a 1-butene copolymer obtained by copolymerizing butene with ethylene or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), and a 1-butene homopolymer is preferably used. As the α-olefin other than 1-butene constituting the 1-butene copolymer, ethylene, propylene,
1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
-Eicosene, etc., and one or more of these can be used. As the 1-butene copolymer in the present invention, a random copolymer is preferred.
Further, the structural unit obtained from 1-butene is preferably at least 90 mol%, more preferably at least 95 mol%, particularly preferably at least 98 mol%. 1-
If the structural unit obtained from butene is less than 90 mol%, the stickiness of the surface of the molded product may be reduced.

The 1-butene polymer used in the present invention is a polymer which requires the following (1) to (4). (1) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then −1 at 5 ° C./min.
After cooling down to 0 ° C, keeping at -10 ° C for 5 minutes,
The melting point (Tm-P) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at
Crystalline resin at 100 ° C. (2) Stereoregularity index ｛(mmmm) / (mmrr + r
mmr)｝ is 20 or less (3) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by GPC method is 4.0 or less. (4) Weight average molecular weight (Mw) measured by GPC method.
Is 10,000-1,000,000

[0009] The 1-butene polymer in the present invention is a crystalline compound having at least a substantial melting point. The melting point is usually observed with a differential scanning calorimeter (DSC). In the present invention, having a melting point substantially means that a crystal melting peak is substantially observed in DSC measurement.
The crystal melting peak is, for example, the above-mentioned Tm-P or Tm-D described later, and the peak is observed under at least one of the measurement conditions. By satisfying the above relationship, the 1-butene-based polymer of the present invention has an excellent balance between the amount of the sticky component of the obtained molded article and the like, the low elastic modulus and the transparency. That is, the elastic modulus is low, the softness (also referred to as flexibility) is excellent, the sticky component is small, and the surface characteristics (for example, the transfer of the sticky component to bleed and other products are small) are excellent, and There is an advantage that transparency is also excellent.

[0010] The melting point (Tm-P) of the 1-butene polymer used in the present invention is not observed from the viewpoint of softness or is 0 to 100 ° C, preferably 0 to 80 ° C.
The 1-butene polymer has a melting point (Tm-P) of D
It is determined by SC measurement. That is, using a differential scanning calorimeter (manufactured by Perkin-Elmer Co., DSC-7), 10 mg of a sample was previously melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then cooled to −10 ° C. at 5 ° C./min. -10
After holding at 5 ° C. for 5 minutes, the melting endotherm ΔHP obtained by raising the temperature at 10 ° C./min. The peak of the peak measured at the highest temperature in the melting endothermic curve obtained at this time is the melting point: Tm-P (° C.).

Further, the 1-butene polymer used in the present invention is a crystalline resin having a melting point (Tm-D) of 0 to 100 ° C. by a differential scanning calorimeter (DSC) from the viewpoint of softness. Good. Tm-D is preferably from 0 to 80C. Note that Tm-D is determined by DSC measurement. That is,
Differential scanning calorimeter (Perkin-Elmer, DSC-
Using 7), 10 mg of the sample was placed at -10 ° C under a nitrogen atmosphere for 5 minutes.
After holding for 10 minutes, the melting endotherm obtained by increasing the temperature at 10 ° C./minute is defined as ΔH−D. The melting point: Tm-D is the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time. Such one
-A butene polymer is a crystalline resin satisfying the following (1 ') to (4'). (1 ′) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. (2 ') Stereoregularity index ｛(mmmm) / (mmrr +) A crystalline resin having a melting point (Tm-D) defined as the peak top of the peak observed in (2 ′).
rmmr)｝ is 20 or less. (3 ′) Gel permeation chromatograph (GP
3. The molecular weight distribution (Mw / Mn) measured by the method C) is 4.
0 or less (4 ′) Weight average molecular weight (M
w) is 10,000 to 1,000,000

In the 1-butene polymer of the present invention, the stereoregularity index {(mmmm) / (mmrr + rmmr)} obtained from the (mmmm) fraction and the (mmrr + rmmr) fraction of the 1-butene chain portion. , 20
Or less, preferably 18 or less, more preferably 1
5 or less. When the stereoregularity index exceeds 20, flexibility is reduced.

In the present invention, the mesopentad fraction (m
mmm) and abnormal insertion content (1,4 insertion fraction) are reported in Polymer Journa reported by Asakura et al.
1, 16, 717 (1984) "; Randall
"Macromol. Chem. P.
hys. , C29, 201 (1989) "and V.I. Bu
"Macromol. Ch" reported by Sico et al.
em. Phys. , 198, 1257 (1997) ". That is, the signals of methylene group and methine group are measured using ¹³ C nuclear magnetic resonance spectrum, and the fraction of mesopentad and the content of abnormal insertion in the poly (1-butene) molecule are determined. Note that ¹³
The measurement of the C nuclear magnetic resonance spectrum is performed using the following apparatus and conditions. Apparatus: JNM-EX400 type ¹³ CN manufactured by JEOL Ltd.
MR apparatus Method: Proton complete decoupling method Concentration: 230 mg / milliliter Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds integration: 10000 times Stereoregularity index ｛(mmmm) / (mmrr + rmm
r)｝ is (mmmm), (mmm
r) and (rmmr) are calculated from the measured values, and
The racemic triad fraction (rr) is also calculated by the above method.

In the present invention, the 1-butene polymer has a molecular weight distribution (Mw / Mw /
Mn) is 4.0 or less, preferably 3.5 to 1.
5, more preferably 3.0 to 1.5. If the molecular weight distribution (Mw / Mn) exceeds 4.0, stickiness may occur, and if it is less than 1.5, moldability may deteriorate. Further, the 1-butene polymer in the present invention has a weight average molecular weight Mw measured by a GPC method in addition to the above requirements.
Is 10,000 to 1,000,000. If the weight average molecular weight Mw is less than 10,000, stickiness may occur. Also, if it exceeds 1,000,000,
Moldability may be poor due to a decrease in fluidity.

The above molecular weight distribution (Mw / Mn)
Is a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene measured by the GPC method using the following apparatus and conditions. GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C. Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / milliliter Injection volume: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0)

The 1-butene polymer of the present invention has, besides the above-mentioned requirements, a melting endothermic amount ΔH-D
Is preferably 60 J / g or less, since flexibility is excellent, and more preferably 40 J / g or less. ΔH-D
Is an index indicating whether the material is soft or not, and when this value increases, it means that the elastic modulus is high and the softness is low. Note that the melting endothermic amount ΔH-D is determined by the above-described method. The 1-butene polymer in the present invention preferably has a component amount (H25) eluted in hexane at 25 ° C. of 0 to 80% by weight, more preferably 0 to 60% by weight, and most preferably 0 to 50% by weight. % By weight. H25 is
It is an index indicating whether the amount of so-called sticky components that cause stickiness and lowering of transparency is large or small, and the higher this value is, the larger the amount of sticky components is. H2
If the content of 5 exceeds 80% by weight, blocking may occur due to a large amount of the sticky component, and the secondary workability and surface characteristics may be reduced. H25 was obtained by allowing the weight (W ₀ ) (0.9 to 1.1 g) of the 1-butene polymer and the 1-butene polymer to stand in 200 ml of hexane at 25 ° C. for 4 days or more. Weight of the polymer after drying (W ₁ )
And the weight loss rate calculated by the following equation. H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%)

The 1-butene homopolymer preferably used in the present invention has a mesopentad fraction (mmmm) of 20 to 9
It is preferably 0%, more preferably 30 to 85%, and most preferably 30 to 80%. If the mesopentad fraction is less than 20%, the surface of the molded product may be sticky or the transparency may be reduced. On the other hand, 90
%, The flexibility may decrease. The 1-butene homopolymer is (mmmm) ≦ 90−
It is preferable that the relationship of 2 × (rr) is satisfied,
More preferably, the relationship of (mmmm) ≦ 87−2 × (rr) is satisfied. If this relationship is not satisfied, the surface of the molded article may be sticky or the transparency may be reduced. The 1-butene homopolymer preferably has a 1,4-insertion portion of 5% or less. If it exceeds 5%, the composition distribution of the polymer is widened, which may adversely affect the physical properties. Further, the 1-butene homopolymer preferably has a tensile modulus of 800 MPa or less, more preferably 500 MPa or less, as measured by a tensile test based on JIS K-7113. If it exceeds 800 MPa, sufficient softness may not be obtained.

The method for producing the 1-butene polymer in the present invention may be a method of homopolymerizing 1-butene using a catalyst system called a metallocene catalyst, or a method of producing 1-butene with ethylene and / or C 3-20. A method of copolymerizing an α-olefin (however, excluding 1-butene) may be mentioned. As metallocene catalysts, JP-A-58-1930
9, Japanese Patent Application Laid-Open No. 61-130314,
JP-A-163088, JP-A-4-300887, JP-A-4-21694, JP-A-1-502
A transition metal compound having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group as described in JP-A No. 036 and the like; A catalyst obtained by combining a geometrically controlled transition metal compound and a promoter is exemplified.

As a method for producing a 1-butene polymer in the present invention, it is preferable that the ligand comprises a transition metal compound forming a crosslinked structure via a crosslinking group. A method of homopolymerizing 1-butene using a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure with a cocatalyst via 1- or 1-butene and ethylene and / or α having 3 to 20 carbon atoms A method of copolymerizing an olefin (excluding 1-butene) is suitably used.

Specifically, (A) the general formula (I)

[0021]

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[Wherein, M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentade group, respectively. A ligand selected from a dienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, forming a crosslinked structure via A ¹ and A ² And they may be the same or different from each other, X represents a σ-binding ligand, and when X is plural,
A plurality of X may be the same or different, and other X,
It may be crosslinked with E ¹ , E ² or Y. Y represents a Lewis base, if Y is plural, the plurality of Y may be the same or different, other Y, it may be crosslinked E ^1, E ² or X, A ¹ and A ² A divalent cross-linking group bonding the two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group,
Germanium-containing group, tin-containing group, -O-, -CO-,
_{-S -, - SO 2 -,} - Se -, - NR 1 -, - PR 1
-, - P (O) R 1 -, - BR 1 - or -AlR ¹ - are shown, R ¹ represents a hydrogen atom, a halogen atom, having from 1 to 20 carbon atoms
Or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. q represents an integer of 1 to 5 and represents ((valence of M) -2), and r represents an integer of 0 to 3. (B) (B-1) a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) or a derivative thereof; and (B-2) A method of homopolymerizing 1-butene in the presence of a polymerization catalyst containing a component selected from aluminoxane, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) ) Is copolymerized.

In the general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series;
Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid-based metals. Of these, titanium, zirconium, and hafnium are preferable in terms of olefin polymerization activity. It is suitable. E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (-N <), and a phosphine group (-P <),
Hydrocarbon group [>CR-,> C <] and silicon-containing group [> S
iR-,> Si <] (where R is hydrogen or carbon number 1-2)
0 is a hydrocarbon group or a hetero atom-containing group), and forms a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferred.

X represents a σ-binding ligand, and when there are a plurality of Xs, a plurality of Xs may be the same or different and are cross-linked to other X, E ¹ , E ² or Y. You may.
Specific examples of X include a halogen atom and a carbon atom having 1 to 20 carbon atoms.
Hydrocarbon group, C1-20 alkoxy group, C6-20 aryloxy group, C1-20 amide group, C1-20 silicon-containing group, C1-20 phosphide Group, sulfide group having 1 to 20 carbon atoms, 1 carbon atom
And 20 acyl groups. On the other hand, Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked to another Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

Next, A ¹ and A ² are divalent bridging groups for bonding the two ligands, and include a hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group containing 1 to 20 carbon atoms. , Silicon-containing group, germanium-containing group, tin-containing group, -O-, -C
O -, - S -, - SO 2 -, - Se -, - NR 1 -, -
PR ^1- , -P (O) R ^1- , -BR ¹ -or -AlR
¹ - shows a, R ¹ represents a hydrogen atom, a hydrocarbon group having a halogen atom or having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, they may be the same with or different from each other. As such a crosslinking group, for example, a general formula

[0026]

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(D is carbon, silicon or tin, R ² and R
³ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, or may be bonded to each other to form a ring structure. e is 1
Shows an integer of ~ 4. ). Specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, a 1,2-cyclohexylene group, a vinylidene group (CH ₂ = C =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisilylene group, diphenyldisilylene group, and the like. Among these, an ethylene group, an isopropylidene group and a dimethylsilylene group are preferred. q represents an integer of 1 to 5 and represents ((valence of M) -2), and r represents an integer of 0 to 3. Among such transition metal compounds represented by general formula (I), general formula (II)

[0028]

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A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferable. In the general formula (II), M, A ¹ , A ² , q and r are the same as above. X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same as those exemplified in the description of X in the general formula (I). Y
¹ represents a Lewis base, and when there are a plurality of Y ¹ ,
¹ may be the same or different, and may be crosslinked with another Y ¹ or X ¹ . Specific examples of Y ¹ include the same as those exemplified in the description of Y in the general formula (I). R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
The halogen-containing hydrocarbon group, silicon-containing group or heteroatom-containing group, at least one of which must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same or different from each other, and adjacent groups may be bonded to each other to form a ring. Among them, it is preferable that R ⁶ and R ⁷ form a ring, and that R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ , groups containing a heteroatom such as oxygen, halogen, silicon and the like are preferable because of their high polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in a bridging group between the ligands. Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-
Ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene)
(2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene)
(2,1′-isopropylidene) -bis (indenyl)
Zirconium dichloride, (1,2'-ethylene)
(2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-ethylene)
-Ethylene) (2,1'-ethylene) -bis (4,7-
Diisopropylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
Ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′
-Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'- Isopropylidene) -bis (indenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) ) Zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-i-propylindenyl) Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene ) Screw (3
-Phenylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di -I-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4
-Phenylindenyl) zirconium dichloride, (1
, 2'-Dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene ) Screw (5, 6)
-Benzoindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) zirconium Dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) ) -Bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Isopropylidene) -bis (3-phenylindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride , (1,2 '
-Dimethylsilylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethyl (Indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride,
2'-diphenylsilylene) (2,1'-methylene)-
Bis (indenyl) zirconium dichloride, (1,
2'-diphenylsilylene) (2,1'-methylene)-
Bis (3-methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) )
(2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 '-Methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
Isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3'-
Methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride,
(1,2′-isopropylidene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 ′
-Methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) (Enyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,
2'-dimethylsilylene) (2,1'-ethylene)
(3,4-dimethylcyclopentadienyl) (3 ′,
4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′
-Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-methylene)
(2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropyl) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,
2'-isopropylidene) (2,1'-isopropylidene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-
Methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-
Methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl)
(3′-methyl-5′-ethylcyclopentadienyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ) (2,
1′-methylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Methylene) (3-methyl-
5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2'-Ethylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5 '-I-propylcyclopentadienyl) zirconium dichloride, (1,
2′-methylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1 , 2'-methylene) (2,
1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i
-Propylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bisindenyl zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-dimethyl (Silylene) bisindenyl zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bisindenyl zirconium dichloride, (1,1′-diisopropylsilylene) (2,2 ′
-Dimethylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) (2,2′-
(Diisopropylsilylene) bisindenyl zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1 ′
-Diphenylsilyleneindenyl) (2,2'-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1'-diphenylsilyleneindenyl) (2,2'-dimethylsilylene-3-trimethylsilylindenyl) Zirconium dichloride,
(1,1′-dimethylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-diphenylsilylene) ( Indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene)
(2,2′-dimethylsilylene) (indenyl) (3-
Trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-
Diisopropylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-diisopropylsilylene) (indenyl) (3-trimethylsilyl (Indenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-diisopropylpropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2 ,
2′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium Dichloride,
(1,1′-diphenylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1 ′
-Dimethylsilylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-dimethylsilylene) (indenyl) (3 -Trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-diisopropylsilylene) Examples thereof include (2,2′-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these. In addition, a similar compound of a metal element of another group or a lanthanoid series may be used. In the above compound, (1,1 ′-) (2,2′-) is replaced with (1,2′-)
(2,1′-), and (1,2 ′-) (2,
1′-) may be (1,1 ′-) (2,2′-).

Next, as the component (B-1) of the component (B), any compound which can react with the transition metal compound of the above component (A) to form an ionic complex can be used. The following general formulas (III), (IV) ([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b ... (III) ([L ² ] ^{k +} ) _a ([Z] ^-) _b ··· (IV) (provided that, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R
A ¹⁴ M ^3. In the formulas (III) and (IV), L ¹ is a Lewis base, and [Z] ⁻ is
Non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 1 G 1 G 2 ··· G} f ] ^- ( Here, M ¹ is an element belonging to Groups 5 to 15 of the periodic table, preferably ^{13 to 1} of the periodic table.
Shows Group 5 elements. G ^{1 to} G ^f each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 2 to 4 carbon atoms.
0 dialkylamino group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C7-C40 alkylaryl group, C7-C40 Arylalkyl group, 1 to 1 carbon atoms
A halogen-substituted hydrocarbon group of 20; an acyloxy group of 1 to 20 carbon atoms; an organic metalloid group; or a heteroatom-containing hydrocarbon group of 2 to 20 carbon atoms. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(center metal M
Represents an integer of ¹ valence) +1]. ), [Z ² ] ^-
A conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or a conjugate base of an acid generally defined as a super strong acid is shown. Further, a Lewis base may be coordinated. Further, R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, R ¹¹ and R ¹²
Represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is an ionic valence of [L ¹ -R ¹⁰ ] and [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² contains an element of Groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents an element of Groups 7 to 12 of the periodic table. ] Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ¹³ include a phenyl group, a p-tolyl group, a p-methoxyphenyl group and the like, and specific examples of R ¹⁴ include a tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ¹ G ¹ G
² ... G ^f ], B and A are specific examples of M ^1.
l, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, and methoxy, ethoxy, n-butoxy groups as alkoxy or aryloxy groups.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, hydrocarbon groups such as phenoxy
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group and bis (trimethylsilyl) methyl group, as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , a fluorosulfonic acid anion (FS
O ₃ ) ^- , chlorosulfonic acid anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As)
F ₅₎ ^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n-butyl) Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium) , Triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate Rosenium, tetrakis (pentafluorophenyl)
(1,1'-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate. (B-1) may be used alone, or two or more kinds may be used in combination.

On the other hand, the aluminoxane of the component (B-2) is represented by the general formula (V):

[0038]

Embedded image

(Wherein R ¹⁵ is an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. In addition, each R ¹⁵ may be the same or different. Aluminoxane represented by the general formula (VI):

[0040]

Embedded image (In the formula, R ¹⁵ and w are the same as those in the above general formula (V).)

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be carried out according to a known method. For example,
A method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and water is added later, water of crystallization contained in a metal salt, etc., inorganic substances Reacting water adsorbed on organic substances with organic aluminum compounds,
There is a method in which a tetraalkyldialuminoxane is reacted with a trialkylaluminum and then with water. The aluminoxane may be toluene-insoluble.

These aluminoxanes may be used alone or in combination of two or more. When the (B-1) compound is used as the (B) catalyst component, the molar ratio of the (A) catalyst component to the (B) catalyst component is preferably from 10: 1 to 1: 100, Preferably 2: 1
If the ratio deviates from the above range, the catalyst cost per unit mass polymer increases,
Not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1,000,000,
More preferably, the range is from 1:10 to 1: 10000. If the ratio is outside this range, the cost of the catalyst per unit mass of the polymer increases, which is not practical. As the catalyst component (B), (B-1) and (B-2) may be used alone or in combination of two or more.

As the polymerization catalyst for producing the 1-butene polymer, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of the component (C), a compound represented by the general formula (VII) R ¹⁶ _v AlJ _3-v (VII) wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms, and J is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
And v is an integer of 1 to 3]. Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

These organoaluminum compounds may be used alone or in combination of two or more. In the method for producing a 1-butene polymer, preliminary contact can also be performed using the above-mentioned components (A), (B) and (C). The preliminary contact is carried out on the component (A) by, for example,
It can be performed by contacting the component (B),
The method is not particularly limited, and a known method can be used. These preliminary contacts are effective for reducing the catalyst cost, such as improving the catalytic activity and reducing the use ratio of the component (B), which is a promoter. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be observed in addition to the above effects. The pre-contact temperature is usually -20C to 200C, preferably -10C to 1C.
The temperature is 50 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.

The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 1000 in molar ratio.
0, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1: 1000.
By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. In the production of the 1-butene polymer, at least one of the catalyst components can be used by being supported on a suitable carrier. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers and organic carriers can be used,
In particular, inorganic oxide carriers or other inorganic carriers are preferred.

As the inorganic oxide carrier, specifically, S
_{iO 2, Al 2 O 3,} MgO, ZrO 2, TiO 2, F
e ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like.
Among them, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate, or the like.

On the other hand, as a carrier other than the above, MgC
general formula M represented by l ₂ , Mg (OC ₂ H ₅ ) _2, etc.
gR magnesium compound or a complex salt represented by the ¹⁷ _X X ¹ _y can be exemplified. Here, R ¹⁷ has 1 carbon atom.
An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y
Is 0 to 2 and x + y = 2. Each R ¹⁷ and each X
¹ may be the same or different. As the organic carrier, polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-
Examples thereof include polymers such as butene, substituted polystyrene, and polyarylate, starch, and carbon.

A catalyst used for producing a 1-butene polymer
As the carrier of the medium, MgCl_Two, MgCl (OC
_TwoH_Five), Mg (OC_TwoH_Five)_Two, SiO_Two, Al_TwoO
_ThreeAre preferred. The nature of the carrier depends on its type and
The average particle size is usually from 1 to 300 μm,
Preferably 10 to 200 μm, more preferably 20 to 10 μm
0 μm. Small particle size increases fines in polymer
When the particle size is large, the coarse particles in the polymer increase and the bulk density increases.
Of the hopper and clogging of the hopper. In addition, the carrier
The specific surface area is usually 1 to 1000 m^Two/ G, preferably 5
0-500m^Two/ G, pore volume is usually 0.1-5 cm^Three
/ G, preferably 0.3-3 cm ^Three/ G.

If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method. further,
When the carrier is an inorganic oxide carrier, usually 150
It is desirable to use it after firing at 1000 to 1000C, preferably 200 to 800C. When at least one of the catalyst components is supported on the carrier, it is desirable that at least one of the catalyst component (A) and the catalyst component (B), and preferably both the catalyst component (A) and the catalyst component (B) be supported. .

The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, at least one of the component (A) and the component (B) is mixed with the carrier. Method, a method of treating a carrier with an organoaluminum compound or a halogen-containing silicon compound, and then mixing the carrier with at least one of the component (A) and the component (B) in an inert solvent.
Or a method of reacting the component (B) with an organoaluminum compound or a halogen-containing silicon compound, a method of supporting the component (A) or the component (B) on a carrier, and then mixing the component (B) or the component (A). And a method of mixing the contact reactant of the components (A) and (B) with the carrier, and a method of coexisting the carrier during the contact reaction between the components (A) and (B).

In the above and methods,
An organoaluminum compound as the component (C) can be added. In the production of the catalyst used for producing the 1-butene polymer, the catalyst may be prepared by irradiating an elastic wave when the above (A), (B) and (C) are brought into contact.
Examples of the elastic wave include a sound wave, particularly preferably an ultrasonic wave. Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz is used.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. Also, 1-
In the production of a butene-based polymer, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system.
For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added.
A method may be used in which pre-polymerization is performed at −20 to 200 ° C. for about 1 minute to 2 hours in addition to MPa (gauge) to generate catalyst particles.

The use ratio of the component (B-1) and the carrier in the catalyst used for producing the 1-butene polymer is as follows:
The mass ratio is preferably from 1: 5 to 1: 10000, more preferably from 1:10 to 1: 500, and (B
-2) The use ratio of the component to the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1: by mass ratio.
It is desirable to set it to 50. When two or more of the components (B) are used as a mixture, it is desirable that the ratio of each component (B) to the carrier be within the above range in terms of mass ratio. Also,
The use ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1 by mass.
It is desirable to set 1: 500.

Component (B) [Component (B-1) or (B-
If the usage ratio of [2) component] and the carrier or the usage ratio of component (A) and the carrier deviates from the above range, the activity may be reduced. The average particle size of the polymerization catalyst thus prepared is usually 2 to 200 μm, preferably 10 to 15 μm.
0 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50
５００500 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst used for producing the 1-butene-based polymer, the amount of the transition metal in 100 g of the carrier is usually 0.05 to 10 g, particularly preferably 0.1 to 2 g. If the amount of the transition metal is out of the above range, the activity may be low.

By supporting on a carrier as described above, a polymer having an industrially advantageous high bulk density and excellent particle size distribution can be obtained. The 1-butene polymer used in the present invention is obtained by homopolymerizing 1-butene or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms using the above-described polymerization catalyst (provided that (Excluding 1-butene). In this case, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. The polymerization method is particularly preferred.

Regarding the polymerization conditions, the polymerization temperature is usually -1.
00 to 250 ° C, preferably -50 to 200 ° C, more preferably
Preferably it is 0-130 degreeC. In addition,
The ratio of the catalyst used is determined by the ratio of the raw material monomer / component (A)
Ratio is preferably 1 to 10. ⁸, Especially 100 to 10^FiveWhen
Preferably, The polymerization time is usually 5 minutes to 10 hours,
The reaction pressure is preferably from normal pressure to 20 MPa (gaug).
e), more preferably normal pressure to 10 MPa (gaug)
e).

Methods for controlling the molecular weight of the polymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane And halogenated hydrocarbons such as chloroform and dichloromethane. These solvents may be used alone or in a combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the polymerization, preliminary polymerization can be carried out using the polymerization catalyst. The prepolymerization can be carried out by, for example, bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and may be the same as those exemplified above, for example, ethylene, α- having 3 to 20 carbon atoms.
An olefin or a mixture thereof can be mentioned, but it is advantageous to use the same olefin as the olefin used in the polymerization.

The prepolymerization temperature is usually from -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0 ° C.
８０80 ° C. In the prepolymerization, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, and per 1 mmol of the transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is 1 to 10,000 g, particularly 10 to 1000 g.

[2] Crystalline propylene polymer The above-mentioned crystalline propylene polymer [II] in the present invention
Is not particularly limited as long as it is a propylene polymer showing crystallinity. For example, propylene homopolymer,
Propylene-ethylene random copolymer, propylene-
Ethylene-1-butene random copolymer, propylene-
Examples include an ethylene block copolymer. Further, the molecular weight of the crystalline propylene polymer [II] is selected from the viewpoint of moldability, and the melt index (MI)
Is preferably about 5 to 100 g / 10 min. If the crystalline propylene-based polymer [II] does not exhibit crystallinity, the heat resistance of the injection molded article may be reduced.

As the crystalline propylene polymer [II],
To give a specific example, a propylene homopolymer having a high melting point and high crystallinity is preferable for applications where heat resistance is important, and examples thereof include those described in JP-A-8-85711. . That is, as the crystalline propylene polymer [II] in the present invention, (1) the isotactic Ventad fraction (P) which is a stereoregularity index is 8
5.0 to 92.0 mol% and the n-heptane insoluble content (H) is 98.0 to 97.0% by weight, and P and H
Satisfies the equation 0.750P + 27.125 <H, and (2) the melt index (MI)
Is 1 to 20 g / 10 min, and at a temperature of 175 ° C., a frequency ω ⁰ = 1 obtained by frequency dispersion measurement
Relaxation time τ (sec) at ⁰ rad / sec and M
A polypropylene-based polymer whose relationship with I satisfies the formula τ ≦ 0.65-0.025MI is exemplified.

As the crystalline propylene polymer [II],
More preferably, the isotactic Ventad fraction (P) as the (1 ′) stereoregularity index is from 85.0 to 92.0.
0 mol% and n-heptane insoluble part (H) is 86.0 to
97.0% by weight, and the relationship between P and H satisfies the equation 0.750P1026.000 <H, and (2 ′) melt index (M
I) is 1 to 25 g / 10 min and the temperature is 175
In ° C., the frequency ω ⁰ obtained by the frequency dispersion measurement
= 10 ⁰ rad / sec relaxation time in τ (sec)
And a MI is such that a polypropylene-based polymer satisfies the formula τ ≦ 0.63-0.025MI. In addition,
Regarding the meanings of P, H, MI, ω ⁰ and τ, the measuring method and the method for producing a propylene-based polymer, see JP-A-Hei-8.
-85711.

[3] Polyolefin Resin Composition The polyolefin resin composition of the present invention is prepared by drying the above-mentioned 1-butene polymer [I] and the crystalline propylene polymer [II] using a Henschel mixer or the like. It may be blended, or may be melt-kneaded using a single or twin screw extruder, Banbury mixer or the like. The proportion of the compound is usually 1 to 99% by weight, preferably 10 to 90% by weight, particularly preferably 20 to 80% by weight of the 1-butene polymer [I]. If the 1-butene polymer [I] is less than 1% by weight, the flexibility may be reduced. In the polyolefin-based resin composition of the present invention, the amount of the component (H25) eluted in hexane at 25 ° C is preferably 0 to 25% by weight, more preferably 0 to 10% by weight. When H25 exceeds 25% by weight, the amount of the sticky component is large,
May not be used for food or medical products. In addition,
H25 of the polyolefin resin composition can be calculated in the same manner as in the case of the 1-butene polymer described above.

Various additives may be added to the polyolefin resin composition of the present invention as desired. Various additives used as desired include an antioxidant, a neutralizing agent, an antifogging agent, and an antistatic agent. These additives may be used alone or in a combination of two or more. For example, examples of the antioxidant include a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.

Specific examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite, tris (2,4-di-
t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-
t-butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphonite,
ADK STAB 1178 (Asahi Denka), Sumilizer TN
P (Sumitomo Chemical), JP-135 (Johoku Chemical), ADK STAB 2112 (Asahi Denka), JPP-2000 (Johoku Chemical), Weston 618 (GE), ADK STAB PEP-24G (Asahi Denka), ADK STAB PE
P-36 (manufactured by Asahi Denka), ADK STAB HP-10 (manufactured by Asahi Denka), Sandstab P-EPQ (manufactured by Sando), Phosphite 168 (manufactured by Ciba-Geigy) and the like.

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol,
n-octadecyl-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) )
Isocyanurate, 4,4'-butylidenebis- (3-
Methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-
Bis {2- [3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy] -1,1-
Dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, Sumilizer BHT (Sumitomo Chemical), Yoshinox BHT (Yoshitomi Pharmaceutical), Antage BHT (Kawaguchi Chemical), Irganox 1076
(Manufactured by Ciba-Geigy), Irganox 1010 (manufactured by Ciba-Geigy), ADK STAB AO-60 (manufactured by Asahi Denka), Sumilizer BP-101 (manufactured by Sumitomo Chemical), Tomminox TT (manufactured by Yoshitomi Pharmaceutical), TTHP (manufactured by Toray) ), Irganox 3114 (Ciba-Geigy), ADK STAB AO-20 (Asahi Denka), ADK STAB AO-40
(Made by Asahi Denka), Sumilizer BBM-S (made by Sumitomo Chemical), Yoshinox BB (made by Yoshitomi Pharmaceutical), Antage W
-300 (manufactured by Kawaguchi Chemical), Irganox 245 (manufactured by Ciba-Geigy), ADK STAB AO-70 (manufactured by Asahi Denka), Tominox 917 (manufactured by Yoshitomi Pharmaceutical), ADK STAB AO-80 (manufactured by Asahi Denka), Sumilizer GA- 80
(Manufactured by Sumitomo Chemical Co., Ltd.).

Specific examples of the sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-
3,3'-thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate), Sumilizer TPL (Sumitomo Chemical), Yoshinox DLT
P (manufactured by Yoshitomi Pharmaceutical), Antiox L (manufactured by NOF Corporation),
Sumilizer TPM (Sumitomo Chemical), Yoshinox DM
TP (manufactured by Yoshitomi Pharmaceutical), Antiox M (manufactured by NOF Corporation), Sumilizer TPS (manufactured by Sumitomo Chemical), Yoshinox DSTP (manufactured by Yoshitomi Pharmaceutical), Antiox S (manufactured by NOF Corporation), ADK STAB AO-412S (manufactured by Asahi Denka) , S
EENOX412S (Cipro), Sumilizer T
DP (manufactured by Sumitomo Chemical) and the like.

Antioxidants for use in injection molded articles include Irganox 1010: substance name: pentaerythrityl-
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], irgafos 16
8: Substance name: tris (2,4-di-t-butylphenyl) phosphite, Irganox 1076: Substance name: octadecyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate, Irganox 1330: Substance name: 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Irganox 3114: Substance: tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate , P-EPQ: Substance name:
Tetrakis (2,4-di-t-butylphenyl) 4
4'-biphenylene-di-phosphite is particularly preferred.

When an antioxidant is used, the antioxidant is added in an amount of 0.0 to 100 parts by weight of the polyolefin resin composition.
It is sufficient to add about 01 to 1 part by weight. This is preferable because yellowing and the like can be prevented. Specific examples of use of the above antioxidant include: Example 1: Irganox 1010 1000 ppm PEP-Q 1000 ppm Example 2: Irganox 1076 1200 ppm PEP-Q 600 ppm Irgafos 168 800 ppm Example 3: Irganox 1010 400 to 1000 ppm Irgafos 168 750 to 1500 ppm.

Examples of neutralizing agents for use in injection-molded articles include calcium stearate, zinc stearate, magnesium stearate, and hydrotalcite (DHT-4A): composition formula: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3. 5H ₂ O
And the like are particularly preferred.

[4] Injection molded article The injection molded article of the present invention is a molded article obtained by injection molding the above-mentioned polyolefin resin composition. The injection molded article is characterized in that it has an excellent balance of physical properties of rigidity and impact resistance. That is, the injection molded article of the present invention
The relationship between the Izod impact strength A (kJ / m ² ) measured at 23 ° C. according to K7110 and the tensile modulus E (MPa) measured according to JIS K7113 is A ≧ −.
0.037E + 62.2, preferably A ≧ −0.037E + 66.7, more preferably A ≧
−0.054E + 88.8. Tensile modulus, which is an index of flexibility in the injection molded article of the present invention,
Preferably it is 800 MPa or less. 80 tensile modulus
If it exceeds 0 MPa, flexibility is lost and impact resistance is reduced. The lower limit of the tensile modulus is 6 MPa,
If it is less than Pa, stickiness may occur. Also,
The injection molded article of the present invention preferably has a total light transmittance of 50% or more, more preferably 60% or more, in a molded article having a thickness of 3 mm. Thus, a polyolefin resin composition having an excellent balance of physical properties of rigidity and impact resistance and having good transparency has characteristics not found in conventional block polypropylene and the like. As a molding method of the injection molded article of the present invention, other than ordinary injection molding, injection compression molding,
Assist injection molding method and the like can be mentioned. The molding conditions are not particularly limited as long as the resin is at a temperature at which the resin can melt and flow.

[0072]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. First, the method for evaluating the resin properties of the 1-butene-based polymer and the physical properties of the injection-molded polyolefin-based resin composition of the present invention will be described.

(Resin Properties of 1-Butene Polymer) (1) Mesopentad Fraction, Racemic Triad Fraction, Abnormal Insertion Amount, and Stereoregularity Index Measured by the method described in the text of the specification. (2) Weight average molecular weight (Mw) and molecular weight distribution (Mw /
Mn) It was measured by the method described in the specification text. (3) Measurement of H25 It was measured by the method described in the text of the specification. (4) DSC Measurement (Melting Point: Measurement of Tm-P and Tm-D, Melting Endotherm: Measurement of ΔHP and ΔHD) Measured by the method described in the text of the specification.

(Evaluation of Physical Properties of Injection Molded Polyolefin Resin Composition) (5) Tensile Modulus A pellet of the resin composition was press-molded to prepare a test piece, and the test piece was prepared under the following conditions in accordance with JIS K-7113. It was measured.・ Test piece (No. 2 dumbbell) Thickness: 1 mm ・ Cross head speed: 50 mm / min ・ Load cell: 100 kg (6) Izod impact strength Using a test piece similar to that used for the above tensile modulus, J
It measured at 23 degreeC by the test method based on ISK7110. (7) Measurement of H25 It was measured by the method described in the text of the specification. (8) Total light transmittance According to JIS K-7105, an injection molded product of a polyolefin resin composition (63 mm × 12 mm) was used as a test piece.
× 3 mm).

Production Example 1 (Preparation of Polymerization Catalyst) (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) used as a catalyst in the production of a polymer by the following method Nyl) zirconium dichloride was prepared. In a Schlenk bottle, 3.0 g (6.97 mmol) of a lithium salt of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF and cooled to −78 ° C. Then, 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly dropped, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried and the solvent was removed, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Was obtained (yield 84%).

Next, (1,2′-dimethylsilylene) (2,2) obtained above was placed in a Schlenk bottle under a nitrogen stream.
3.04 g (5.88 mmol) of 1'-dimethylsilylene) -bis (3-trimethylsilylmethylindene)
And 50 ml of ether, cooled to −78 ° C., and a hexane solution of n-BuLi (1.54 M,
7.6 ml (1.7 mmol)) were added dropwise.
After raising the temperature to room temperature and stirring for 12 hours, ether was distilled off. The solid obtained was washed with 40 ml of hexane to convert the lithium salt into an ether adduct of 3.06 g.
(5.07 mmol) was obtained (yield 73%). ¹ H N
The result of the measurement by MR (90 MHz, THF-d ₈ ) is δ 0.04 (s, 18H, trimethylsilyl);
0.48 (s, 12H, dimethylsilylene); 1.10.
(T, 6H, methyl); 2.59 (s, 4H, methylene); 3.38 (q, 4H, methylene), 6.2-7.
7 (m, 8H, Ar-H).

The lithium salt obtained in a nitrogen stream was dissolved in 50 ml of toluene, cooled to -78 ° C, and zirconium tetrachloride 1.2, previously cooled to -78 ° C.
g (5.1 mmol) of toluene (20 ml)
The suspension was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 6 hours, and the solvent of the reaction solution was distilled off. The obtained residue was recrystallized from dichloromethane to give (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3
-Trimethylsilylmethylindenyl) 0.9 g (1.33 mmol) of zirconium dichloride was obtained (yield 26%). ¹ H NMR (90 MHz, CDCl ₃ )
Results from δ 0.0 (s, 18H, trimethylsilyl); 1.02, 1.12 (s, 12H, dimethylsilylene); 2.51 (dd, 4H, methylene);
7.1-7.6 (m, 8H, Ar-H).

Production Example 2 (Production of 1-butene-based polymer) Heptane (4
L), 1-butene (2.6 kg), triisobutylaluminum (10 mmol), and 0.08 MPa of hydrogen were introduced. Thereafter, methylaluminoxane (10 mmol) manufactured by Albemarle Co., Ltd. was added, and the temperature was adjusted to 60 ° C. with stirring. Screw (3
-Trimethylsilylindenyl) zirconium dichloride (10 μmol) was added. After stirring for 150 minutes, methanol (20 mL) was added, the pressure was released, and the polymerization solution was dried under reduced pressure to obtain poly (1-butene).

The results of evaluation of the resin properties of the obtained 1-butene-based polymer (1-butene homopolymer) are as follows. Mesopentad fraction (mmmm): mol% 72 Racemic triad fraction (rr): mol% 4 90-2 × (rr) 82.0 Abnormal insertion amount (1,4 insertion fraction): mol% 0 Stereoregularity index ( mmmm) / (mmrr + rmmr) 9 Weight average molecular weight (Mw) 33 × 10 ⁴ Molecular weight distribution (Mw / Mn) 2.5 Melting point (Tm-P: DSC measurement): ° C. Not observed. Endotherm of melting (ΔH-P): J / g Not observed. Melting point (Tm-D: DSC measurement): ° C 73 Melting endotherm (ΔH-D): J / g 35 H25: 41

Example 1 (Production of polyolefin resin composition) 50 parts by weight of the 1-butene homopolymer obtained in Production Example 2 and 50 parts by weight of polypropylene (J2000G, manufactured by Idemitsu Petrochemical) were mixed with the following additives. After prescription, single screw extruder (manufactured by Tsukada Juki Seisakusho: TLC3
The mixture was extruded and granulated using a 5-20 type) to obtain pellets. Antioxidant Irganox 1010: 500 ppm Irgafos 168: 1000 ppm (Injection molding) Injection is performed at a resin temperature of 240 ° C. and a mold temperature of 45 ° C. from the obtained polyolefin resin composition pellets using a Toshiba Machine Injection Molding Machine IS100FIII. A molded article was obtained. (Evaluation of resin properties and physical properties) Evaluation was made by the above-mentioned evaluation methods. Table 1 shows the obtained results.

Example 2 Except that in producing the polyolefin resin composition of Example 1, 70 parts by weight of the 1-butene homopolymer obtained in Production Example 2 and 30 parts by weight of polypropylene (J2000G, manufactured by Idemitsu Petrochemical) were used. Was similarly evaluated for granulation, injection molding, resin properties and physical properties. Table 1 shows the obtained results.

Production Example 3 (Preparation of Solid Catalyst Component) After replacing a 0.5-liter three-necked flask equipped with a stirrer with nitrogen gas, 60 ml of dehydrated octane and 16 g of diethoxymagnesium were added. 40
C., 2.4 ml of silicon tetrachloride was added and stirred for 20 minutes, and then 1.6 ml of dibutyl phthalate was added. The temperature of the solution was raised to 80 ° C., and 77 ml of titanium tetrachloride was added dropwise.
The contact operation was performed by stirring at 2 ° C. for 2 hours. Thereafter, the stirring was stopped to allow the solid to settle, and the supernatant was extracted. 1
After adding 00 ml of dehydrated octane, the temperature was raised to 125 ° C. with stirring and maintained for 1 minute. Then, the stirring was stopped to precipitate the solid, and the supernatant was taken out. This operation 7
Repeated times. Further, 122 ml of titanium tetrachloride was added, and the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to perform a contact operation. Thereafter, the above-mentioned washing with dehydrated octane is performed 6 times.
This was repeated twice to obtain a solid catalyst component.

Production Example 4 (Production of Propylene Polymer) A stainless steel autoclave with an internal volume of 1 liter and having a stirrer was sufficiently dried, and after replacement with nitrogen, 400 ml of octane dehydrated at room temperature was added. 2.0 ml of triethylaluminum, 0.1 mmol of dicyclopentyldimethoxysilane, 0.005 mmol of the solid component obtained in Production Example 3 in terms of Ti atom were added, hydrogen was added at 0.05 MPa, and then propylene was introduced. While raising the temperature and pressure to 80 ° C. and a total pressure of 0.8 MPa, polymerization was carried out for 2 hours. Thereafter, the temperature was lowered and the pressure was released, and the contents were taken out and poured into 2 liters of methanol to deactivate the catalyst. It was filtered off and dried under vacuum to obtain a propylene polymer.

Example 3 In Example 1, 50 parts by weight of the 1-butene homopolymer obtained in Production Example 2 and 50 parts by weight of the propylene polymer obtained in Production Example 4 were used.
Granulation, injection molding, evaluation of resin properties and physical properties were carried out in the same manner except that the weight parts were used. Table 1 shows the obtained results.

Comparative Example 1 In Example 1, polypropylene (J2 manufactured by Idemitsu Petrochemical Co., Ltd.)
000G) alone, and granulation, injection molding, evaluation of resin properties and physical properties were performed. Table 1 shows the obtained results.

[0086]

[Table 1]

[0087]

As is clear from the above examples, the injection molded article of the polyolefin resin composition of the present invention is excellent in rigidity and physical properties of impact resistance, high in transparency and sticky (H25). Is low. Therefore, the injection molded article of the polyolefin resin composition of the present invention is a container,
It can be advantageously used in a wide range of injection molded articles, such as automotive interior materials and housing materials for home appliances.

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F071 AA15X AA20 AA20X AA21 AA80 AA80X AA81 AA81X AA87 AA87X AF02 AF14Y AF15Y AF29 AF45 AF53 AH04 AH05 BA01 BB05 BC07 4F206 AA11A AA11C AA11K12XAB12 AB12A12A

Claims (3)

[Claims] 1. A polyolefin resin comprising 1-99% by weight of a 1-butene polymer [I] and 99-1% by weight of a crystalline propylene polymer [II] satisfying the following (1)-(4): An injection molded article of a polyolefin resin composition obtained by injection molding the composition. (1) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then −1 at 5 ° C./min.
After cooling down to 0 ° C, keeping at -10 ° C for 5 minutes,
The melting point (Tm-P) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at
Crystalline resin at 100 ° C. (2) Stereoregularity index ｛(mmmm) / (mmrr + r
mmr)｝ is 20 or less (3) Gel permeation chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by GPC method is 4.0 or less. (4) Weight average molecular weight (Mw) measured by GPC method.
Is 10,000-1,000,000 2. The injection molded article of the polyolefin resin composition according to claim 1, wherein the 1-butene-based polymer [I] is a 1-butene homopolymer and satisfies the following (5) and (6). . (5) Mesopentad fraction (mmmm) is 20 to 90% (6) (mmmm) ≦ 90−2 × (rr) where rr represents a racemic triad fraction. 3. Izod impact strength A (kJ / m ² ) measured at 23 ° C. according to JIS K7110 and JIS
Tensile modulus E (MP
The injection molded article of the polyolefin resin composition according to claim 1 or 2, wherein the relationship of a) satisfies the following expression. A ≧ −0.037E + 62.2