JP2003238750A - Resin composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composite material with a favorable balance between modulus of elasticity and elongation without marked decline of the elongations and impact resistance even in filler rich compositions. <P>SOLUTION: This resin composite material is composed of 90-5 pts.wt. polypropylene, 90-5 pts.wt. 1-butene polymer satisfying conditions of (1) melting point (Tm-D) of 0-100C° defined by differential scanning calorimeter (DSC), (2) 20 or less of steric regulatory index ä(mmmm)/(mmrr+rmmr)}, (3) molecular wt. distribution (Mw/Mn) of 4.0 or less determined by gel permeation chromatography (GPC) and (4) wt.-average molecular wt. (Mw) of 10,000-1,000,000 determined by GPC, and 5-90 pts.wt. organic filler and/or inorganic filler. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composite material having an excellent balance of elastic modulus and elongation even when a filler is highly blended.

[0002]

2. Description of the Related Art Conventionally, polypropylene has been widely used as a member for automobiles and home appliances. It has been widely practiced to add various inorganic or organic fillers in order to improve the dimensional stability of polypropylene and impart flame retardancy and paintability. For example, JP-A-63-142049
No. 62-246233 and 57-57.
In each publication of No. 182343, it is described that an inorganic substance is added in order to enhance dimensional stability.
Japanese Patent Publication No. 30739 discloses that an organic halogen compound is added to impart flame retardancy. However, when such an inorganic or organic filler is added to polypropylene at a high concentration, there is a problem that the polypropylene itself becomes brittle, or elongation and impact resistance are significantly reduced, and tensile elongation and impact resistance are reduced. There is a strong need for a balanced composite material that can achieve the effect of filler without degradation.

[0003]

The object of the present invention is to balance the elastic modulus and the elongation without the polypropylene itself becoming brittle and the elongation and the impact resistance being remarkably reduced even when the filler is highly blended. It is to provide a resin composite material having excellent properties.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems of the resin composite material, the present inventors have found that when polypropylene and a specific 1-butene-based polymer are used, a filler is mixed in a high proportion. Even in the above, it was found that an excellent resin composite material in which impact resistance and tensile elongation do not decrease can be obtained, and the present invention has been completed.

That is, the present invention provides the following resin composite materials. 1. 90 to 5 parts by weight of polypropylene, (1) to
A resin composite material comprising 90 to 5 parts by weight of a 1-butene polymer satisfying (4) and 5 to 90 parts by weight of an organic filler and / or an inorganic filler. (1) Using a differential scanning calorimeter (DSC), the sample was held in a nitrogen atmosphere at −10 ° C. for 5 minutes and then heated at 10 ° C./minute to obtain the highest temperature side of the melting endothermic curve. The melting point (Tm-D) defined as the peak top of the observed peak is 0 to 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 the method is 4.0 or less (4) Weight average molecular weight (Mw) measured by the GPC method
Is 10,000 to 1,000,000 2.1-Mesopentad fraction of butene-based polymer (mmm
The resin composite material according to 1 above, wherein m) is 20 to 90%. 3.1 1-butene polymer is 1-butene and ethylene and /
Or a copolymer with an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), wherein the structural unit derived from 1-butene is 90 mol% or more and the resin composite according to 1 or 2 above. material.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION [1] 1-butene polymer, [2] 1-butene polymer production method, [3] polypropylene, and [4] filler and resin composite material production method. Will be described in detail.

[1] 1-Butene polymer The 1-butene polymer in the resin composite material of the present invention is
It is a polymer having the following requirements (1) to (4), and preferably satisfies the requirement (5). (1) Using a differential scanning calorimeter (DSC), the sample was held in a nitrogen atmosphere at −10 ° C. for 5 minutes and then heated at 10 ° C./minute to obtain the highest temperature side of the melting endothermic curve. The melting point (Tm-D) defined as the peak top of the observed peak is 0 to 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 the method is 4.0 or less (4) Weight average molecular weight (Mw) measured by the GPC method
Is 10,000 to 1,000,000 (5) 1-butene homopolymer, or a copolymer of 1-butene and ethylene and / or α-olefin having 3 to 20 carbon atoms, wherein 1-butene is The structural unit derived from is 9
0 mol% or more

The 1-butene polymer in the present invention is
(1) Using a differential scanning calorimeter (DSC), the sample was held in a nitrogen atmosphere at −10 ° C. for 5 minutes and then heated at 10 ° C./minute to obtain the highest temperature side of the melting endothermic curve. The melting point (Tm-D) defined as the peak top of the observed peak is 0 to 100 ° C. By satisfying the relationship (1), the 1-butene polymer of the present invention is excellent in the balance between the amount of the sticky component, the low elastic modulus and the transparency of the resulting molded product. That is, it has a low elastic modulus, excellent softness (also called flexibility), less sticky components, and excellent surface characteristics (for example, typified by less migration of sticky components to bleed and other products), and It also has the advantage of excellent transparency. The 1-butene polymer of the present invention is (5) 1-butene homopolymer,
Or 1-butene and ethylene and / or 3 to 2 carbon atoms
It is a copolymer with 0 α-olefin, and the structural unit derived from 1-butene is preferably 90 mol% or more. By satisfying this condition (5), there is an advantage that physical properties do not change with time due to crystal modification and the molded product does not shrink.

In the present invention, the mesopentad fraction (m
mmm) and the abnormal insertion content (1,4 insertion fraction) were reported by Asakura et al. in “Polymer Journal”.
1, 16, 717 (1984) ", J. Randall
"Macromol. Chem. P."
hys. , C29, 201 (1989) "and V. Bu
"Macromol. Ch reported by Sico et al.
em. Phys. , 198, 1257 (1997) ”. That is, ¹³ C
The signals of the methylene group and the methine group are measured by using nuclear magnetic resonance spectrum to determine the mesopentad fraction and the abnormal insertion content in the poly (1-butene) molecule. ^{The 13} C nuclear magnetic resonance spectrum is measured with the following equipment and conditions. Device: JEOL Ltd. JNM-EX400 type ¹³ C-N
MR device method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: Mixed solvent temperature of the volume ratio of 1,2,4-trichlorobenzene and heavy benzene is 90:10: 130 ° C Pulse width: 45 ° Pulse repetition time: 4 seconds integration: 10,000 times In the present invention, stereoregularity index {(mmmm) / (m
mrr + rmmr)} is (mmm + rmmr)} by the above method.
m), (mmmr) and (rmmr) are calculated from the measured values.

[A] 1-Butene Homopolymer The 1-butene homopolymer of the present invention has a stereoregularity index {(mmmm) / (mmrr + rmmr)} of 20 or less, preferably 18 or less, and more preferably. 15
It is the following. When the stereoregularity index exceeds 20, the flexibility, the low-temperature heat-sealing property, and the hot tack property deteriorate. Further, the 1-butene homopolymer in the present invention has a molecular weight distribution (Mw / M measured by GPC method).
n) is 4 or less, preferably 3.5 or less, and particularly preferably 3.0 or less. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur. Furthermore, the 1-butene homopolymer in the present invention has a weight average molecular weight (Mw) of 10,000 to 1, measured by GPC method.
, 000,000, preferably 100,000 to 1,000
50,000, more preferably 100,000 to 50
It is 10,000. If the Mw is less than 10,000, stickiness may occur. On the other hand, when it exceeds 1,000,000, the fluidity is lowered and the moldability may be poor.

The Mw / Mn is a value calculated from the polystyrene-equivalent mass average molecular weight Mw and number average molecular weight Mn measured by the GPC method under the following apparatus and conditions. GPC measuring instrument column: TOSO GMHHR-H (S) HT detector: RI detector for liquid chromatogram W
ATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibra
analysis program: HT-GPC (Ver.1.0)

The 1-butene homopolymer in the present invention is
The melting point (Tm-D) is soft because of its differential scanning calorimeter (D
(SC) requires a crystalline resin of 0 to 100 ° C, preferably 0 to 80 ° C. In addition,
Tm-D is determined by DSC measurement. That is, a differential scanning calorimeter (Perkin Elmer, DSC-7)
10 mg of the sample was kept at −10 ° C. for 5 minutes in a nitrogen atmosphere and then heated at 10 ° C./min, and the peak top of the peak observed on the highest temperature side of the melting endothermic curve was the melting point: Tm-D. Further, the 1-butene homopolymer in the present invention has DS in addition to the above requirements.
It is preferable that the melting endotherm ΔH-D measured by C is 50 J / g or less because of excellent flexibility. ΔH-D is an index indicating whether or not it is soft, and when this value is large, it means that the elastic modulus is high and the flexibility is lowered. In addition, ΔH
-D is obtained by the method described later.

The 1-butene homopolymer in the present invention is
The mesopentad fraction (mmmm) is preferably 20 to 90%, more preferably 30 to 85%, and most preferably 30 to 80%. If the mesopentad fraction is less than 20%, the surface of the molded article may become sticky or the transparency may be reduced. On the other hand, if it exceeds 90%, the flexibility, the low-temperature heat-sealing property, and the hot tack property may deteriorate. Further, the 1-butene homopolymer according to the present invention is obtained according to JIS K-7113.
Has a tensile modulus of 500 measured by a tensile test according to
The pressure is preferably MPa or less, and more preferably 300 MPa or less. This is because if it exceeds 500 MPa, sufficient softness may not be obtained.

[A '] 1-Butene Copolymer The 1-butene copolymer according to the present invention has the above-mentioned (1).
Is a copolymer of 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), which has the requirement of (4) or (5), and 1-butene. And an α-olefin copolymer having 3 to 20 carbon atoms are preferable.

Further, the 1-butene-based copolymer in the present invention is preferably a random copolymer. Also, 1-
The structural unit obtained from butene is preferably 90 mol% or more, more preferably 95 mol% or more.
If the structural unit derived from 1-butene is less than 90 mol%, the surface of the molded article may become sticky or the transparency may be reduced. Also, the stereoregularity index {(mmmm) / (mmrr + rmmr)} obtained from the (mmmm) fraction and the (mmrr + rmmr) fraction of the 1-butene chain portion.
Is required to be 20 or less, preferably 18
Or less, more preferably 15 or less. When the stereoregularity index exceeds 20, the flexibility, the low-temperature heat-sealing property, and the hot tack property deteriorate. The 1-butene-based copolymer in the present invention has a molecular weight distribution (Mw / Mn) measured by a gel permeation (GPC) method.
Is 4.0 or less, preferably 3.5 or less, and particularly preferably 3.0 or less. When the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur. The 1-butene-based copolymer in the present invention has a weight average molecular weight Mw of 10,000 to 1,000,000 measured by the GPC method.
0, preferably 100,000 to 1,000,000,
More preferably, it is 100,000-500,000. When the weight average molecular weight is less than 10,000, stickiness may occur, and when it exceeds 1,000,000, fluidity may be deteriorated, resulting in poor moldability. The method of measuring Mw / Mn and Mw is the same as above.

The 1-butene copolymer in the present invention is
The melting point (Tm-D) is required to be 0 to 100 ° C, preferably 0 to 80 ° C. The Tm-D is obtained by the above-mentioned DSC measurement method.

Regarding the 1-butene-based copolymer in the present invention, as the α-olefin having 3 to 20 carbon atoms, propylene, 1-pentene, 4-methyl-1-pentene, 1-
Hexene, 1-octene, 1-decene, 1-dodecene,
Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and in the present invention, one kind or two or more kinds thereof can be used. Further, the 1-butene-based copolymer of the present invention has a JIS
The tensile modulus measured by a tensile test according to K-7113 is preferably 500 MPa or less, 30
It is more preferably 0 MPa or less. 500MP
This is because if it exceeds a, sufficient softness may not be obtained.

[2] Method for Producing 1-Butene Polymer As the method for producing a 1-butene polymer in the present invention, a method of homopolymerizing 1-butene using a catalyst system called metallocene catalyst or 1- Butene and ethylene and /
Alternatively, a method of copolymerizing an α-olefin having 3 to 20 carbon atoms (however, excluding 1-butene) can be mentioned. As the metallocene catalyst, JP-A-58-19309, JP-A-61-130314 and JP-A-3-16308 are available.
No. 8, Japanese Patent Application Laid-Open No. 4-3008887, Japanese Patent Application Laid-Open No. 4-1998
No. 211694, Japanese Patent Publication No. 1-502036, etc., and a transition having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group. Examples thereof include metal compounds and catalysts obtained by combining a transition metal compound in which the ligand is geometrically controlled with a cocatalyst.

In the present invention, among the metallocene catalysts, it is preferable that the ligand comprises a transition metal compound forming a crosslinked structure through a crosslinking group, and among them, 2
Method for homopolymerizing 1-butene using a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure through individual crosslinking groups and a cocatalyst, or 1-butene and ethylene and / or 3 carbon atoms A method of copolymerizing .about.20 .alpha.-olefin (excluding 1-butene) is more preferable. As a specific example, (A) general formula (I)

[0020]

[Chemical 1]

[Wherein M is a group 3-10 group or a group of the periodic table]
Indicate the metal elements of the tantanoid series, E ¹And E²Is it
Each substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group, substituted
Telocyclopentadienyl group, amide group, phosphide
Ligands selected from groups, hydrocarbon groups and silicon-containing groups
And A¹And A²Forming a crosslinked structure through
And they can be the same or different
X represents a σ-bonding ligand, and when there are a plurality of Xs,
Multiple X's may be the same or different, other X's,
E¹, E²Alternatively, it may be crosslinked with Y. Y is Lewis salt
A group, and when there are plural Ys, the plural Ys may be the same or different.
May be other Y, E¹, E²Or by cross-linking with X
You may have A¹And A²Is a bond that connects two ligands
Valent bridging group, which is a hydrocarbon group having 1 to 20 carbon atoms, charcoal
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing group, tin-containing group, -O-, -CO-,
-S-, -SO₂-, -Se-, -NR¹-,-PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹−
Show, R¹Is a hydrogen atom, a halogen atom, or a carbon number of 1 to 20
Hydrocarbon group or halogen-containing hydrocarbon water having 1 to 20 carbon atoms
Indicates a radical, whether they are the same or different
Good. q is an integer of 1 to 5 and represents [(valence of M) -2].
And r represents an integer of 0 to 3. ] Transition metallization
Compound, and (B) (B-1) transition metallization of the (A) component
Reacts with compounds or their derivatives to form ionic complexes
Compounds and (B-2) aluminoxane
1-butene alone in the presence of a polymerization catalyst containing components
Polymerization method, or 1-butene and ethylene and / or
Α-olefins having 3 to 20 carbon atoms (however, 1-butene is
(Excluding) is copolymerized.

In the above general formula (I), M represents a metal element of Group 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. It is suitable. E ¹ and E ² are respectively a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (-N <), a phosphine group (-P <),
Hydrocarbon group [>CR-,> C <] and silicon-containing group [> S
iR-,> Si <] (wherein R is hydrogen or 1 to 2 carbon atoms)
0 is a hydrocarbon group or a hetero atom-containing group) and forms a crosslinked structure via A ¹ and A ² . Further, E ¹ and E ² may be the same or different from each other. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable.

X represents a σ-bonding ligand, and when there are a plurality of X's, the plurality of X's may be the same or different and are cross-linked with another X, E ¹ , E ² or Y. May be.
Specific examples of X include a halogen atom and 1 to 20 carbon atoms.
Hydrocarbon group, C1-C20 alkoxy group, C6-C20 aryloxy group, C1-C20 amide group, C1-C20 silicon-containing group, C1-C20 phosphide Group, sulfide group having 1 to 20 carbon atoms, 1 carbon atom
.About.20 acyl groups and the like. On the other hand, Y represents a Lewis base, and when there are plural Y's, the plural Y's may be the same or different and may be cross-linked with other Y or 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 which bond two ligands, and are a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. , Silicon-containing groups, germanium-containing groups, tin-containing groups, -O-, -C
O -, - S -, - SO 2 -, - Se -, - NR 1 -, -
^{PR 1 -, - P (O} ) R 1 -, - BR 1 - or -AlR
^1- , R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Examples of such a crosslinking group include those represented by the general formula

[0025]

[Chemical 2]

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

[0027]

[Chemical 3]

A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the 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 are the same as those exemplified in the description of X in the general formula (I). Y
¹ represents a Lewis base, and when Y ¹ is plural, plural Y
^1's may be the same or different and may be crosslinked with another Y ¹ or X ¹ . Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I). R ^{4 to} R ⁹ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms.
The halogen-containing hydrocarbon group, the silicon-containing group or the hetero atom-containing group of 1 is shown, but at least one of them is required not to 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 , a group containing a hetero atom such as oxygen, halogen and silicon is preferable because the polymerization activity becomes high.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the crosslinking 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) (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, (1,
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′-isopropyloxy) Ridene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,
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-phenylcyclopentdienyl) (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) bisindenylzirconium 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) bisindenyl zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-
Diisopropylsilylene) bisindenylzirconium dichloride, (1,2′-dimethylsilylene) (2,2
1′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride,
(1,2′-diphenylsilylene) (2,1′-diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-dimethylsilylene)
(Indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-diphenylsilylene) (indenyl)
(3-Trimethylsilylindenyl) zirconium dichloride, (1,2′-diisopropylsilylene) (2,
1′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride,
(1,2′-Dimethylsilylene) (2,1′-diisopropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-
Diisopropylsilylene) (2,1′-diisopropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilyl) Methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-diphenylsilylene) (indenyl)
(3-Trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-diphenylsilylene)
(2,1'-Dimethylsilylene) (indenyl) (3-
Trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride,
(1,2′-diisopropylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,
2'-Dimethylsilylene) (2,1'-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-
Examples thereof include diisopropylsilylene) (2,1′-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, and compounds in which zirconium in these compounds is replaced with titanium or hafnium. Of course, it is not limited to these. Further, it may be a compound similar to a metal element of another group or lanthanoid series. In addition, in the above compound, (1,1 '-) (2,2'
-) May be (1,2 '-) (2,1'-),
(1,2 '-) (2,1'-) is (1,1'-) (2
2'-).

Next, as the component (B-1) of the component (B), any component can be used as long as it is a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex. The following general formulas (III) and (IV) ([L ¹ -R ¹⁰ ] ^{k +} ) _a ([Z] ^- ) _b ... (III) ([L ² ] ^{k +} ) _{a can also be used.} ([Z] ^- ) _b ... (IV) (where L ² is M ² , R ¹¹ R ¹² M ³ , R ¹³ ₃ C or R
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 of Groups 5 to 15 of the periodic table, preferably ^{13 to 1} of the periodic table.
Indicates a Group 5 element. G ^{1 to} G ^f are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms and 2 to 4 carbon atoms, respectively.
0 dialkylamino group, C1-20 alkoxy group, C6-20 aryl group, C6-20 aryloxy group, C7-40 alkylaryl group, C7-40 Arylalkyl group, carbon number 1
20 shows a halogen-substituted hydrocarbon group, a C1-C20 acyloxy group, an organic metalloid group, or a C2-C20 hetero atom-containing hydrocarbon group. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(central metal M
Represents an integer of ¹ valence) +1]. ), [Z ^{2] -} is
The logarithm (pKa) of the reciprocal of the acid dissociation constant is a Bronsted acid alone or a conjugated base of a combination of Bronsted acid and Lewis acid, or a conjugate base of an acid generally defined as a super strong acid. Also, a Lewis base may be coordinated. R ¹⁰ represents 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, and 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 ] and is an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² contains elements of Groups 1 to 11, 11 to 13 and 17 of the periodic table, and M ³ represents elements of Groups 7 to 12 of the periodic table. ] What is represented by these can be used conveniently.

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, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile.

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

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

Further, a non-coordinating anion, that is, pKa
There -10 or less Bronsted acid alone or a combination of conjugate base of a Bronsted acid and Lewis acid [Z ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (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 ) ^- , Fluorosulfonate anion (FS
O ₃ ) ^- , Chlorosulfonate 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 / 5-antimony fluoride (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) are as follows.
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, Methyldiphenylammonium tetrakis (pentafluorophenyl) borate, Triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, Methylanilinium tetrakis (pentafluorophenyl) borate, Tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, 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 fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate theoraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate. (B-1) may be used alone or in combination of two or more kinds.

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

[Chemical 4] (In the formula, R ¹⁵ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 or a halogen atom,
w represents an average degree of polymerization and is usually 2 to 50, preferably 2 to
It is an integer of 40. Each R ¹⁵ may be the same or different. ) A chain aluminoxane represented by the general formula (VI)

[0037]

[Chemical 5] (In the formula, R ¹⁵ and w are the same as those in the general formula (V).) The cyclic aluminoxane represented by the formula can be given.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other. The means therefor 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 then water is added, water of crystallization contained in a metal salt, an inorganic substance Or a method of reacting water adsorbed on an organic substance with an organoaluminum compound,
There is a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and then reacting with water. The aluminoxane may be insoluble in toluene.

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 10: 1 to 1: 100, and Preferably 2: 1
The range of 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer becomes high,
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 of 1:10 to 1: 10000 is desirable. When it deviates from this range, the catalyst cost per unit mass polymer becomes high, which is not practical. As the catalyst component (B), (B-1) and (B-2) can be used alone or in combination of two or more kinds.

In the polymerization catalyst in the method for producing a 1-butene polymer of the present invention, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, the organoaluminum compound as the component (C) is 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
Is an aryl group or a halogen atom, and v is an integer of 1 to 3] is used. Specific examples of the compound represented by the general formula (VII) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride. , Diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum 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-based polymer of the present invention, preliminary contact can be performed using the above-mentioned component (A), component (B) and component (C). Pre-contact with component (A)
For example, it can be carried out by bringing the component (B) into contact, but the method is not particularly limited, and a known method can be used. The preliminary contact is effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the use ratio of the component (B) which is the cocatalyst. In addition,
By bringing the component (A) and the component (B-2) into contact with each other,
In addition to the above effects, the effect of improving the molecular weight is also observed. The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably-
10 ° C to 150 ° 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 molar ratio of the (A) catalyst component to the (C) catalyst component is preferably 1: 1 to 1: 1000.
The range of 0, more preferably 1: 5 to 1: 2000, and even more preferably 1:10 to 1: 1000 is desirable.
By using the (C) catalyst component, the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. In the present invention,
At least one of the catalyst components can be used by supporting it on a suitable carrier. The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and organic carriers can be used, but an inorganic oxide carrier or another inorganic carrier is particularly preferable.

Specific examples of the inorganic oxide carrier include 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, such as silica-alumina, zeolite, ferrite, and glass fiber.
Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and 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 and the} like
Examples thereof include magnesium compounds represented by gR ¹⁷ _X X ¹ _y and complex salts thereof. Here, R ¹⁷ has 1 carbon atom
To an alkyl group having 20 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
Each 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.

The carrier used in the present invention includes
MgCl₂, MgCl (OC₂H_Five), Mg (OC₂H
_Five)₂, SiO₂, Al₂O₃Are preferred. Also bear
The physical properties of the body vary depending on the type and manufacturing method, but the average grain
The diameter is usually 1 to 300 μm, preferably 10 to 200 μm
m, more preferably 20 to 100 μm. Small particle size
If the particle size is large, the fine powder in the polymer increases, and if the particle size is large, the polymer
Coarse particles in the inside increase, resulting in a decrease in bulk density and clogging of the hopper.
Cause The specific surface area of the carrier is usually 1 to 10
00m²/ G, preferably 50-500 m²/ G, pore
The volume is usually 0.1-5 cm³/ G, preferably 0.3-
3 cm ³/ 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 obtained from the volume of the nitrogen gas adsorbed according to the BET method, for example. Furthermore, when the above carrier is an inorganic oxide carrier, it is desirable to use it after firing at usually 150 to 1000 ° C, preferably 200 to 800 ° C. When at least one catalyst component is supported on the carrier, at least one of (A) catalyst component and (B) catalyst component, preferably (A)
It is desirable to support both the catalyst component and the (B) catalyst component.

The method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited, but for example, at least one of the component (A) and the component (B) is mixed with the carrier. Method, method of treating carrier with organoaluminum compound or halogen-containing silicon compound, and then mixing with component (A) and / or component (B) in an inert solvent, carrier and component (A) and / or
Alternatively, 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 with the component (B) or the component (A). , A method of mixing a contact reaction product of the component (A) and the component (B) with a carrier, and a method of allowing a carrier to coexist in the contact reaction of the component (A) and the component (B).

In the above reactions and,
It is also possible to add an organoaluminum compound as the component (C). In the present invention, the above (A), (B),
The catalyst may be prepared by irradiating an elastic wave when the (C) is brought into contact with the catalyst. As the elastic wave, a sound wave is usually used, and an ultrasonic wave is particularly preferable. Specifically, the frequency is 1 to 1
Ultrasonic wave of 000 kHz, preferably 10 to 500 kHz
Ultrasonic waves.

The catalyst thus obtained may be used for the polymerization after the solvent is once distilled off and taken out as a solid, or may be used for the polymerization as it is. Further, in the present invention, the catalyst can be produced by carrying out the loading operation of at least one of the component (A) and the component (B) on the carrier in the 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, and an olefin such as ethylene is added at atmospheric pressure to 2 MPa (gauge).
In addition, a method of preliminarily polymerizing at −20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

In the present invention, the ratio of the component (B-1) to the carrier used is preferably 1: 5 to 1:10 in mass ratio.
000, more preferably 1:10 to 1: 500, and the ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000 by mass ratio, more preferably It is desirable that the ratio is 1: 1 to 1:50. When two or more components (B) are mixed and used, it is desirable that the ratio of each component (B) to be used be within the above range in terms of mass ratio. Further, the ratio of the component (A) and the carrier to be used is preferably 1: 5 to 1: 10000, and more preferably 1:10 to 1: 500 by mass ratio.

Component (B) [Component (B-1) or (B-
If the ratio of the component (2)] to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may decrease. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 1
It is 0 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g. If the average particle size is less than 2 μm, the amount of fine powder in the polymer may increase.
If it exceeds 0 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 of the present invention, the amount of transition metal in 100 g of the carrier is usually 0.05 to 1
It is preferably 0 g, particularly 0.1 to 2 g. If the amount of transition metal is out of the above range, the activity may decrease.

By thus supporting the polymer on the carrier, it is possible to obtain a polymer having industrially advantageous high bulk density and excellent particle size distribution. The 1-butene polymer used in the present invention is a homopolymerization of 1-butene using the above-mentioned polymerization catalyst, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (provided that 1 -Except 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 or a suspension polymerization method may be used. Polymerization methods are particularly preferred.

Regarding the polymerization conditions, the polymerization temperature is usually -1.
0 to 250 ° C, preferably -50 to 200 ° C, more preferably
It is preferably 0 to 130 ° C. Also, for the reaction raw materials
The ratio of the catalyst used is as follows: raw material monomer / component (A) above
Ratio) is preferably 1-10 ⁸, Especially from 10 to 10^FiveWhen
It is preferable that Further, the polymerization time is usually 5 minutes to 1
For 0 hours, the reaction pressure is preferably normal pressure to 20 MPa (ga
more preferably atmospheric pressure to 10 MPa (gaug)
e).

The method for controlling the molecular weight of the polymer includes the selection of the type and amount of each catalyst component, the polymerization temperature, and further the 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, aliphatic hydrocarbons such as pentane, hexane, heptane and octane. , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as α-olefin may be used as a solvent. Depending on the polymerization method, it can be carried out without a solvent.

Upon polymerization, preliminary polymerization can be carried out using the above-mentioned polymerization catalyst. The prepolymerization can be performed by 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 in the prepolymerization is not particularly limited, and the same olefins as those exemplified above, such as ethylene and α-C 3-20 can be used.
Examples thereof include olefins and mixtures thereof, but it is advantageous to use the same olefin as that used in the polymerization.

The prepolymerization temperature is usually from -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0
~ 80 ° C. In the prepolymerization, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferable. Further, the prepolymerization may be carried out without a solvent. In the prepolymerization, the intrinsic viscosity [η] of the prepolymerized product (measured in decalin at 135 ° C.) is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, per 1 mmol of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product with respect to 1 to 10000 g, particularly 10 to 1000 g.

[3] Polypropylene The polypropylene in the resin composite material of the present invention is not particularly limited, and crystalline or amorphous polypropylene is used. However, crystalline polypropylene is preferably used in terms of the heat resistance of the resin composite material and the strength of the molded product produced from the composite material. Examples of the crystalline polypropylene include a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene-1-butene random copolymer, a propylene-ethylene block copolymer and the like. The molecular weight is selected from the viewpoint of moldability, and it is preferable that the melt index (MI) is about 5 to 100 g / 10 minutes. As a specific example of the crystalline polypropylene, a propylene homopolymer having a high melting point and high crystallinity is preferable for applications where heat resistance is important, as described in, for example, JP-A-8-85711. The thing can be illustrated.

[4] Method for Producing Filler and Resin Composite Material The composite material of the present invention comprises polypropylene 90 to 5 parts by weight (preferably 50 to 10 parts by weight), specific 1-butene polymer 90 to 5 An inorganic or organic filler is mixed in an amount of 5 to 90 parts by weight (preferably 10 to 50 parts by weight) with respect to parts by weight (preferably 50 to 10 parts by weight). In the above, if the amount of polypropylene is less than 5 parts by weight, heat resistance becomes insufficient, and if it exceeds 90 parts by weight, elongation at break and strength become insufficient. If the amount of the 1-butene polymer is less than 5 parts by weight, the elongation at break becomes insufficient, and if it exceeds 90 parts by weight, the heat resistance and the strength become insufficient. If the amount of the filler is less than 5 parts by weight, the effect of addition such as strength does not appear, and if it exceeds 90 parts by weight, the elongation at break becomes insufficient.

The inorganic filler that can be used in the present invention is, for example, a spherical filler, a plate-like filler, a fibrous filler, or an inorganic flame retardant. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, perlite, shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina or calcium silicate. Examples of the plate-like filler include talc and mica. The average particle size of these spherical fillers and plate-like fillers is preferably 0.01 to 100 μm. If the average particle size is less than 0.01 μm, it may be difficult to manufacture a molded product, and if it exceeds 100 μm, the impact resistance may be deteriorated. Examples of the fibrous filler include needle-shaped ones such as wollastonite, magnesium oxysulfate (trade name: Mosheiji, manufactured by Ube Industries, Ltd.), potassium titanate fibers, or fibers such as fibrous calcium carbonate. In addition, a fibrous material such as glass fiber and a completely fibrous material such as glass fiber can be used. The fiber length of the fibrous filler is preferably 10 μm
~ 3 mm. The diameter is 0.1 to 50 μm. When the fiber length is less than 10 μm, the reinforcing effect is less developed, and when it exceeds 3 mm, injection molding becomes difficult.

Examples of the inorganic flame retardant which can be used in the present invention include hydrated aluminum, hydrated gypsum, zinc borate, barium borate, borax, kaolin, clay, calcium carbonate, alumite, basic carbonic acid. Mention may be made of magnesium, calcium hydroxide, and magnesium hydroxide. The average particle size of the inorganic flame retardant is usually 80.
It is not more than μm, preferably not more than 20 μm. If the average particle size exceeds 80 μm, the tensile elongation may decrease. The organic filler that can be used in the present invention is, for example, 10 to 325 mesh (preferably 10 to 20 mesh) wood particles, chaff, polycarbonate, crosslinked rubber, and other plastic powders. Average particle size is 3
If an organic filler having a size of more than 25 mesh is used, the impact resistance may decrease.

If desired, the composite material of the present invention contains various additives and reinforcing materials such as heat resistance stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, pigments, dyes, or ethylene-based materials.
An impact improver such as propylene rubber (EPR) may be contained and used within a range not impairing the object of the present invention. The method for preparing the composite material of the present invention is not particularly limited, and a method conventionally used for producing a polypropylene resin composition can be adopted. In addition, the order of mixing the components is arbitrary. It can be prepared by blending the respective components and then kneading them using a kneader, roll, Banbury mixer, single-screw or twin-screw extruder.

[0062]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. First, the method for evaluating the resin properties and physical properties of the polymer of the present invention will be described. (1) Measurement of Mesopentad Fraction, Abnormal Insertion Amount, and Stereoregularity Index It was measured by the methods described in the specification. (2) Weight average molecular weight (Mw) and molecular weight distribution (Mw /
Measurement of Mn) It was measured by the method described in the specification.

(3) DSC measurement (measurement of Tm-D) It was measured by the method described in the text of the specification. That is, a differential scanning calorimeter (manufactured by Perkin Elmer, DS
C-7), 10 mg of a sample was placed under a nitrogen atmosphere at -10
The melting endotherm obtained by holding at 5 ° C. for 5 minutes and then raising the temperature at 10 ° C./minute was defined as ΔH-D. Further, the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time was defined as the melting point: Tm-D. (4) Measurement of Tensile Elastic Modulus A polymer is press-molded to prepare a test piece, and JIS K-
The tensile test according to 7113 was performed under the following conditions. -Crosshead speed: 50 mm / min (5) Measurement of tensile elongation at break It was measured according to JIS K-7113.

Example 1 Catalyst Preparation (1) Preparation of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride In a Schlenk bottle, '-Dimethylsilylene) (2,
3.0 g (6.97 mmol) of a lithium salt of 1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF and cooled to -78 ° C. 2.1 ml of iodomethyltrimethylsilane (14.2 mmo
1) was slowly added dropwise, 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 is dried to remove the solvent (1,2′-dimethylsilylene) (2,
3.04 g (5.88 mmol) of 1'-dimethylsilylene) -bis (3-trimethylsilylmethylindene)
Was obtained (yield 84%). Next, 3.04 g (5.88) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream.
(mmol) and 50 ml of ether were added. -7
The mixture was cooled to 8 ° C. and n-BuLi hexane solution (1.54
M, 7.6 ml (1.7 mmol)) was added dropwise. After raising the temperature to room temperature and stirring for 12 hours, ether was distilled off.
The obtained solid was washed with 40 ml of hexane to give 3.06 g of a lithium salt as an ether adduct.
(5.07 mmol) was obtained (yield 73%). ^The measurement result by ¹ H NMR (90 MHz, THF-d ₈ ) was 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
It was -7.7 (m, 8H, Ar-H). The lithium salt obtained under a nitrogen stream was dissolved in 50 ml of toluene. It was cooled to −78 ° C., and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride previously cooled to −78 ° C. in toluene (20 ml) was added dropwise thereto. After the dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. By recrystallizing the obtained residue with dichloromethane, (1,2′-dimethylsilylene) (2,
1'-Dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added to 0.2%.
9 g (1.33 mmol) was obtained (yield 26%). ^The measurement result by ¹ H NMR (90 MHz, CDCl ₃ ) shows δ 0.0 (s, 18 H, trimethylsilyl);
1.02, 1.12 (s, 12H, dimethylsilylene); 2.51 (dd, 4H, methylene); 7.1-
It was 7.6 (m, 8H, Ar-H).

Polymerization Heat-dried 1 liter autoclave was charged with heptane 4
L, 1-butene 2.5 kg, and methylaluminoxane 10 mmol were added, and hydrogen was further introduced at 0.03 MPa. After the temperature was raised to 60 ° C. with stirring, the obtained (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2 ′) was obtained. -Dimethylsilylene) (2,1'-dimethylsilylene) -bis (indenyl) zirconium dichloride was added in an amount of 10 μmol and polymerized for 60 minutes. After the completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 770 g of a 1-butene copolymer. About the obtained 1-butene-based copolymer, the mesopentad fraction (mmmm) by the above method,
Stereoregularity index {(mmmm) / (mmrr + rmm
r)}, abnormal insertion amount, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), melting point (Tm-D) and melting endotherm (ΔH-D) were measured. The results are shown below.

Mesopentad fraction (mmmm) 74 mol% Abnormal insertion amount (1,4 insertion fraction) 0 mol% Stereoregularity index {(mmmm) / (mmrr + rmmr)} 10 Weight average molecular weight (Mw) 42 × 10 ⁴ molecular weight distribution (Mw / Mn) 2.0 melting point (Tm-D) 67 ° C. melting endotherm (ΔH-D) 38 J / g

Blending and Kneading 25 parts by weight of the above-mentioned 1-butene copolymer, polypropylene resin (F300SP manufactured by Idemitsu Petrochemical Co., Ltd.) 37.5
Parts by weight and magnesium hydroxide (Kyowa Kismer 5L)
37.5 parts by weight was extruded and granulated with a twin-screw kneading and granulating machine NEX-T60 (Kobe Steel Co., Ltd.) to obtain pellets. Table 1 shows the results obtained by press-molding the obtained pellets and measuring the tensile modulus and the elongation at break by the above-mentioned methods.

Comparative Example 1 In Example 1, extrusion granulation was carried out without using the 1-butene copolymer to obtain pellets. Table 1 shows the results of measuring the tensile elastic modulus and the elongation at break of the obtained pellets by press molding.

Comparative Example 2 The same procedure as in Example 1 was carried out except that 5 parts by weight of liquid paraffin was used as a softening agent instead of the 1-butene copolymer in Example 1. Table 1 shows the results of measuring the tensile elastic modulus and the elongation at break of the obtained pellets by press molding. The breaking strength is inferior in Comparative Examples 1 and 2.

[0070]

[Table 1]

[0071]

EFFECTS OF THE INVENTION The resin composite material of the present invention has an excellent balance of elastic modulus and elongation without brittleness of polypropylene itself and remarkable reduction of elongation and impact resistance even when a filler is highly blended. It is widely used as a member for automobiles and home appliances.

Continued front page    F-term (reference) 4J002 AC00Y AH00Y BB12W BB15W                       BB17X BP02W CG00Y DE076                       DE086 DE146 DE236 DE266                       DJ036 DK006 FD016 GC00                 4J100 AA02Q AA03Q AA04P AA07Q                       AA15Q AA16Q CA01 CA04                       CA11 DA04 DA22 FA10 JA43                       JA57

Claims (3)

[Claims] 1. 90 to 5 parts by weight of polypropylene, 90 to 5 parts by weight of a 1-butene polymer satisfying the following (1) to (4), and an organic filler and / or an inorganic filler 5 to 90.
A resin composite material comprising a part by weight. (1) Using a differential scanning calorimeter (DSC), the sample was held in a nitrogen atmosphere at −10 ° C. for 5 minutes and then heated at 10 ° C./minute to obtain the highest temperature side of the melting endothermic curve. The melting point (Tm-D) defined as the peak top of the observed peak is 0 to 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 the method is 4.0 or less (4) Weight average molecular weight (Mw) measured by the GPC method
Is 10,000 to 1,000,000 2. The resin composite material according to claim 1, wherein the 1-butene polymer has a mesopentad fraction (mmmm) of 20 to 90%. 3. A 1-butene polymer is a copolymer of 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), wherein 1-butene is used. The resin composite material according to claim 1 or 2, wherein the structural unit derived from is 90 mol% or more.