JP5369368B2 - Ethylene-α-olefin copolymer, molded product, and method for producing ethylene-α-olefin copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene/&alpha;-olefin copolymer that exhibits good moldability and gives a molded product of reduced flickering feeling, and a molded product of the copolymer. <P>SOLUTION: The ethylene/&alpha;-olefin copolymer comprises a monomer unit derived from ethylene and a monomer unit derived from a 3-20C &alpha;-olefin and has a melt flow rate (MFR) of 0.01-100 g/10 min, a flow activation energy (Ea) of at least 50 kJ/mol, a molecular weight distribution (Mw/Mn) of at least 3 obtained by the gel permeation chromatography and the number of microdefects of at most 2,000 pieces/m<SP>2</SP>. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to an ethylene-α-olefin copolymer, a molded product of the copolymer, and a method for producing an ethylene-α-olefin copolymer.

  For films and sheets used for packaging foods, pharmaceuticals, daily necessities, and the like, many molded products obtained by extrusion-molding an ethylene-α-olefin copolymer are used. The ethylene-α-olefin copolymer used in such a molded body is required to have excellent moldability such as a low extrusion load and good processing stability. As such an ethylene-α-olefin copolymer, for example, triisobutylaluminum is added to silica, an organoaluminum oxy compound is added, and then bis (indenyl) ethane, normal butyllithium, and zirconium tetrachloride. An ethylene-1-butene copolymer obtained by copolymerizing ethylene and 1-butene using a catalyst obtained by adding a catalyst component obtained by reacting with (for example, see Patent Document 1) has been proposed. Yes.

JP-A-4-213309

However, the molded body made of the above-mentioned ethylene-α-olefin copolymer is not fully satisfactory because the appearance of the molded body may be deteriorated due to flickering.
Under such circumstances, the problem to be solved by the present invention is an ethylene-α-olefin copolymer having good moldability, and an ethylene-α-olefin copolymer having a flickering feeling reduced. It is to provide a coalescence, a molded body of the copolymer, and a method for producing the copolymer.

  According to the present invention, an ethylene-α-olefin copolymer having good moldability, in which a molded product with reduced flickering feeling is obtained, a molded product of the copolymer, and A method for producing the copolymer can be provided.

That is, the first of the present invention has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and a melt flow rate (MFR) of 0.01 to 100 g / 10 minutes, the flow activation energy (Ea) is 50 kJ / mol or more, the molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography is 3 or more, and the number of micro defects is It relates to an ethylene-α-olefin copolymer of 2000 / m ² or less.

  A second aspect of the present invention relates to a molded body formed by molding the ethylene-α-olefin copolymer.

The third aspect of the present invention is a preliminary product obtained by prepolymerizing an olefin in the presence of a contact-treated product obtained by contact-treating the following component (C) with a contact-treated product of the following component (A) and the following component (B). A polymerized solid catalyst component, wherein the content of the prepolymer in the prepolymerized solid catalyst component is 0.1 to 500 g per 1 g of the component (A), and the heat of crystal melting of the prepolymer is 160 J / g. In the presence of a prepolymerized solid catalyst component produced by producing 0.1 to 5 g of a prepolymer component having an intrinsic viscosity of 2 to 4 dl / g or more per 1 g of component (A) from the start of prepolymerization. And an α-olefin copolymer having 3 to 20 carbon atoms and a method for producing an ethylene-α-olefin copolymer.
Component (A): Solid cocatalyst component component (B): metallocene complex component (C): alkylating agent in which a compound that ionizes a metallocene complex to form an ionic complex is supported on a particulate carrier

  The ethylene-α-olefin copolymer of the present invention is an ethylene-α-olefin copolymer containing a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms. . Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4 -Methyl- 1-hexene etc. are mention | raise | lifted and these may be used independently and 2 or more types may be used together. The α-olefin is preferably 1-hexene or 4-methyl-1-pentene.

  The content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer of the present invention is usually from 50 to 99.75 based on the total weight (100% by weight) of the ethylene-α-olefin copolymer. 5% by weight. The content of the monomer unit based on the α-olefin is usually 0.5 to 50% by weight with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer.

  The ethylene-α-olefin copolymer of the present invention is a range that does not impair the effects of the present invention in addition to the above-mentioned monomer units based on ethylene and monomer units based on α-olefins having 3 to 20 carbon atoms. In, you may have a monomer unit based on another monomer. Examples of other monomers include conjugated dienes (for example, butadiene and isoprene), non-conjugated dienes (for example, 1,4-pentadiene), acrylic acid, acrylic acid esters (for example, methyl acrylate and ethyl acrylate), and methacrylic acid. Methacrylic acid esters (for example, methyl methacrylate and ethyl methacrylate), vinyl acetate and the like.

  The ethylene-α-olefin copolymer of the present invention is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 4 to 20 carbon atoms, more preferably. Is a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 5 to 20 carbon atoms, more preferably a monomer unit based on ethylene and 6 carbon atoms. It is a copolymer having monomer units based on 20 α-olefins.

  Examples of the ethylene-α-olefin copolymer of the present invention include an ethylene-1-hexene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-octene copolymer, and ethylene-1. -Butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-octene copolymer and the like, preferably ethylene-1- A hexene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-butene-1-hexene copolymer, an ethylene-1-butene-4-methyl-1-pentene copolymer, More preferred are ethylene-1-hexene copolymer and ethylene-1-butene-1-hexene copolymer.

  The melt flow rate (MFR; unit is g / 10 minutes) of the ethylene-α-olefin copolymer of the present invention is usually 0.01 to 100 g / 10 minutes. The melt flow rate is preferably 0.05 g / 10 minutes or more, more preferably 0.1 g / 10 minutes or more, from the viewpoint of improving moldability, particularly from the viewpoint of reducing the extrusion load. Further, from the viewpoint of increasing the melt tension and the mechanical strength of the resulting molded article, it is preferably 20 g / 10 minutes or less, more preferably 10 g / 10 minutes or less, and even more preferably 6 g / 10 minutes or less. The melt flow rate is a value measured by Method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. In the measurement of the melt flow rate, usually, an ethylene-α-olefin copolymer previously blended with about 1000 ppm of an antioxidant is used.

The density (d; unit is kg / m ³ ) of the ethylene-α-olefin copolymer of the present invention is usually 890 to 970 kg / m ³ , and from the viewpoint of increasing the rigidity of the obtained molded body, preferably at 900 kg / m ³ or more, more preferably 905 kg / m ³ or more, more preferably 910 kg / m ³ or more, from the viewpoint of enhancing the impact strength of a molded article to be obtained, preferably 940 kg / m ³ or less, more preferably 930 kg / m ³ or less. The density is measured according to the method defined in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995.

  The ethylene-α-olefin copolymer of the present invention is an ethylene-α-olefin copolymer having a long chain branch and excellent moldability, and such an ethylene-α-olefin copolymer has been conventionally known. Compared with a normal linear ethylene-α-olefin copolymer, the flow activation energy (Ea; the unit is kJ / mol) is high. Conventionally known ordinary linear ethylene-α-olefin copolymers have an Ea lower than 50 kJ / mol, and a sufficiently satisfactory moldability cannot be obtained, and particularly satisfactory in an extrusion load. I couldn't.

  Ea of the ethylene-α-olefin copolymer of the present invention is preferably 55 kJ / mol or more, more preferably from the viewpoint of improving the moldability, particularly from the viewpoint of reducing the extrusion load without excessively reducing the melt tension. Is 60 kJ / mol or more. Further, from the viewpoint of increasing the gloss of the obtained molded product, Ea is preferably 100 kJ / mol or less, more preferably 90 kJ / mol or less.

The activation energy (Ea) of the flow is dependent on the angular frequency (unit: rad / sec) dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. based on the temperature-time superposition principle. It is a numerical value calculated by the Arrhenius type equation from the shift factor (a _T ) when creating the master curve shown, and is a value obtained by the method shown below. That is, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (the unit of melt complex viscosity is Pa · sec. The unit of the angular frequency is rad / sec.), Based on the temperature-time superposition principle, for each melt complex viscosity-angular frequency curve at each temperature (T), The shift factor (a _T ) at each temperature (T) obtained when superposed on the melt complex viscosity-angular frequency curve of the coalescence is obtained, and each temperature (T) and the shift factor at each temperature ( _T ) are obtained. From (a _T ), a first-order approximate expression (formula (I) below) of [ln (a _T )] and [1 / (T + 273.16)] is calculated by the method of least squares. Next, Ea is obtained from the slope m of the linear expression and the following expression (II).
ln (a _T ) = m (1 / (T + 273.16)) + n (I)
Ea = | 0.008314 × m | (II)
a _T : Shift factor Ea: Activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics is used. 4.4.4.
The shift factor (a _T ) is obtained by moving the logarithmic curve of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) = − log (X) axis direction (however, the Y axis Is the complex viscosity of the melt, and the X axis is the angular frequency.), And the amount of movement when superposed on the melt complex viscosity-angular frequency curve at 190 ° C., in the superposition, melting at each temperature (T) The logarithmic curve of complex viscosity-angular frequency shifts the angular frequency by a _T times and the melt complex viscosity by 1 / a _T times for each curve. Moreover, the correlation coefficient when calculating | requiring (I) Formula by the least squares method from the value of four points | pieces, 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is usually 0.99 or more.

  The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate interval: 1. It is performed under the conditions of 5 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec. The measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is added to the measurement sample in advance.

The molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer of the present invention is preferably 3 or more, more preferably 5 or more, from the viewpoint of improving moldability, particularly from the viewpoint of reducing extrusion load. More preferably, it is 6 or more. Moreover, from a viewpoint of raising the mechanical strength of the molded object obtained, Preferably it is 25 or less, More preferably, it is 20 or less, More preferably, it is 15 or less. The molecular weight distribution (Mw / Mn) is a value obtained by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and dividing Mw by Mn (Mw / Mn). Moreover, as measurement conditions by GPC method, the following conditions can be mention | raise | lifted, for example.
(1) Equipment: Waters 150C manufactured by Water
(2) Separation column: TOSOH TSKgelGMH6-HT
(3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refraction
(8) Molecular weight reference material: Standard polystyrene

The ethylene-α-olefin copolymer of the present invention is a copolymer having a number of minute defects (unit: number / m ² ) in an inflation film having a thickness of 30 μm of 2000 / m ² or less. If the value is too large, the flickering feeling of the molded product may be increased, and the value is preferably 1500 pieces / m ² or less, more preferably 1000 pieces / m ² or less. In the case where the ethylene-α-olefin copolymer is a polymer obtained by copolymerizing ethylene and an α-olefin using a solid catalyst component in which the catalyst component is supported on a fine particle carrier, The number of minute defects is mainly a pulverized piece of a particulate carrier, and if the particulate carrier is pulverized by polymerization and sufficiently refined, the number of minute defects is considered to be small.

The number of minute defects is determined by measuring the number of dark defects having a size of 75 μm × 70 μm to 225 μm × 214 μm using a film obtained by molding the ethylene-α-olefin copolymer of the present invention into a 30 μm-thick inflation film. The number of dark defects is expressed as the number per unit film area. The inflation film is an inflation molding machine (single shaft of a full flight type screw with a circular die) under molding conditions of a processing temperature of 170 ° C., an extrusion rate of 12.5 kg / hr, a die diameter of 75 mmφ, a lip gap of 1 mm, and a blow ratio of 1.8. It is molded by an extruder (diameter 40 mmφ, L / D = 26). Further, the number of dark defects is measured by, for example, the following conditions using a digital defect inspection apparatus (for example, GX70LT manufactured by Mamiya Oppy).
(1) Detection threshold: 30 or more
(2) Detection prohibition threshold: 24 or more
(3) Light source gain: 1.0
(4) Reading speed: 30m / min
(5) Detection lower limit size: vertical 4 pixels, horizontal 2 pixels
(6) Average transmitted light quantity: 100

  The melt flow rate ratio (MFRR) of the ethylene-α-olefin copolymer of the present invention is preferably 60 or more from the viewpoint of improving moldability, particularly from the viewpoint of reducing extrusion load. The MFRR is obtained by measuring the melt flow rate (MFR-H, unit: g / 10 minutes) measured under the conditions of a test load of 211.82 N and a measurement temperature of 190 ° C. according to JIS K7210-1995, in accordance with JIS K7210. -In the method specified in 1995, this is a value divided by the melt flow rate (MFR) measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. In the above melt flow rate measurement, a polymer in which about 1000 ppm of an antioxidant is blended in advance is usually used.

  The method for producing the ethylene-α-olefin copolymer of the present invention is preferably a method of copolymerizing ethylene and α-olefin using a solid catalyst component in which the catalyst component is supported on a particulate carrier. Is given. For example, when a metallocene complex is used as the catalyst component, a compound that forms an ionic complex by ionizing the metallocene complex (hereinafter referred to as promoter component (I)) is supported on a particulate carrier. Examples thereof include a method of copolymerizing ethylene and α-olefin using a solid promoter component. Examples of the promoter component (I) include boron compounds, zinc compounds, and organoaluminum oxy compounds.

  Examples of the boron compound of the promoter component (I) include tris (pentafluorophenyl) borane, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N -Dimethylanilinium tetrakis (pentafluorophenyl) borate and the like.

  Examples of the zinc compound of the promoter component (I) include a contact-treated product obtained by contact-treating diethylzinc, fluorinated phenol and water.

The organoaluminum oxy compound of the co-catalyst component (I) does not contain a small amount of an organoaluminum compound that has been conventionally treated as an organoaluminum oxy compound, and is a so-called dry organoaluminum oxy compound that does not substantially contain an organoaluminum compound. Examples of the compound include dry methylaluminosan and dry methylisobutylaluminosan.
Examples of the method for preparing the dry organoaluminum oxy compound include a method for drying a commercially available organoaluminum oxy compound under reduced pressure, such as the method described in JP-A-2003-128718, and a solid obtained by depressurization being washed with a hydrocarbon solvent. You can list the methods.

  As the promoter component (I), a boron compound or a zinc compound is preferable.

As the fine particle carrier, a porous material is preferable, and inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; smectite, Clay and clay minerals such as montmorillonite, hectorite, laponite and saponite; organic polymers such as polyethylene, polypropylene and styrene-divinylbenzene copolymer are used. The 50% volume average particle diameter of the fine particle carrier is usually 10 to 500 μm, and the 50% volume average particle diameter is measured by a light scattering laser diffraction method or the like. Moreover, the pore volume of the particulate carrier is usually 0.3 to 10 ml / g, and the specific surface area of the particulate carrier is usually 10 to 1000 m ² / g. The pore volume and the specific surface area are measured by a gas adsorption method. The pore volume is obtained by analyzing the gas desorption amount by the BJH method, and the specific surface area by analyzing the gas adsorption amount by the BET method.

The metallocene complex is preferably a transition metal compound represented by the following general formula [1] or a μ-oxo type transition metal compound dimer thereof.
L ² _a M ² X ¹ _b [1]
(In the formula, M ² is a transition metal atom of Groups 3 to 11 of the periodic table or a lanthanoid series. L ² is a group having a cyclopentadiene-type anion skeleton, and are a plurality of L ² linked directly to each other? Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and X ¹ is a halogen atom, a hydrocarbon group (provided that the cyclopentadiene form (Excluding a group having an anion skeleton), or a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8.

In the general formula [1], M ² is a transition metal atom of Group 3 to 11 of the periodic table (IUPAC 1989) or a lanthanoid series. Specific examples include scandium atoms, yttrium atoms, titanium atoms, zirconium atoms, hafnium atoms, vanadium atoms, niobium atoms, tantalum atoms, chromium atoms, iron atoms, ruthenium atoms, cobalt atoms, rhodium atoms, nickel atoms, palladium atoms. , Samarium atoms, ytterbium atoms, and the like. M ² in the general formula [4] is preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a chromium atom, an iron atom, a cobalt atom or a nickel atom, particularly preferably a titanium atom, a zirconium atom or a hafnium atom. And most preferably a zirconium atom.

In the general formula [1], L ² is a group having a cyclopentadiene type anion skeleton, and a plurality of L ² may be the same or different. The plurality of L ² may be directly connected to each other, or may be connected via a bridging group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Examples of the group having a cyclopentadiene-type anion skeleton in L ² include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group and the like. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -ethylcyclopentadienyl group, η ⁵ -n-butylcyclopentadienyl group, η ⁵ -Tert-butylcyclopentadienyl group, η ⁵ -1,2-dimethylcyclopentadienyl group, η ⁵ -1,3-dimethylcyclopentadienyl group, η ⁵ -1-methyl-2-ethylcyclopenta Dienyl group, η ⁵ -1-methyl-3-ethylcyclopentadienyl group, η ⁵ -1-tert-butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert-butyl-3-methyl Cyclopentadienyl group, η ⁵ -1-methyl-2-isopropylcyclopentadienyl group, η ⁵ -1-methyl-3-isopropylcyclopentadienyl group, η ⁵ -1-methyl-2-n-butyl Cyclopentadienyl group, η ⁵ -1-methyl-3-n-butylcyclopentadienyl group, η ⁵ -1,2,3-trimethylcyclopentadienyl group, η ⁵ -1,2,4-trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ^{5-4,5,6,7-tetrahydroindenyl} group, η ⁵ -2-methylindenyl group, η ⁵ -3-methylindenyl group, η ⁵ -4-methylindenyl group, η ⁵ -5-methylindenyl group, η ⁵ -6-methylindenyl group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, η ⁵ -3-tert- butyl indenyl group, η ⁵ -4-tert- butylindenyl group, eta ⁵ -5 -Tert-butylindenyl group, η ^5-6 -tert-butylindenyl group, η ⁵ -7-tert-butylindenyl group, η ⁵ -2,3-dimethylindenyl group, η ⁵ -4,7-dimethylindenyl group, η ^5- 2,4,7-trimethylindenyl group, η ⁵ -2-methyl-4-isopropylindenyl group, η ⁵ -4,5-benzindenyl group, η ⁵ -2-methyl-4,5-benzindenyl group, η ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ^{5-2-methyl-4-phenyl} indenyl group, eta ^{5-2-methyl-4-naphthyl} indenyl group , Η ⁵ -fluorenyl group, η ⁵ -2,7-dimethylfluorenyl group, η ⁵ -2,7-di-tert-butylfluorenyl group, and substituted products thereof. In the present specification, “η ⁵ −” may be omitted for the names of transition metal compounds.

  The groups having a cyclopentadiene type anion skeleton may be directly connected to each other, and are connected via a bridging group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Also good. Examples of such cross-linking groups include: alkylene groups such as ethylene groups and propylene groups; substituted alkylene groups such as dimethylmethylene groups and diphenylmethylene groups; or substituted silylenes such as silylene groups, dimethylsilylene groups, diphenylsilylene groups, and tetramethyldisilylene groups. Groups; heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom.

X ¹ in the general formula [1] is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group here does not include a group having a cyclopentadiene type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Examples of the hydrocarbon oxy group include an alkoxy group, an aralkyloxy group, and an aryloxy group.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, amyl group, n -Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, and these alkyl groups are all fluorine atom, chlorine atom, bromine atom, It may be substituted with a halogen atom such as an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Examples thereof include a fluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group. Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group.

  Examples of the aralkyl group include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2, 4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl Group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) ) Methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) Nyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl Group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexyl) Phenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc., and these aralkyl groups Are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group An alkoxy group such as ethoxy group; a portion at an aralkyl group such as aryloxy or benzyloxy group, such as phenoxy group may be substituted.

  Examples of the aryl group include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, and 2,6-xylyl group. Group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,4 6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6- Tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentyl Phenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. All of the aryl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; and aralkyloxy groups such as benzyloxy group May be partially substituted.

  Examples of the alkenyl group include an allyl group, a methallyl group, a crotyl group, and a 1,3-diphenyl-2-propenyl group.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n -Octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, and these alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methoxy group, An alkoxy group such as an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n -Octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, and these alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methoxy group, An alkoxy group such as an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

  Examples of the aralkyloxy group include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, ( 2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) ) Methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5- Trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy , (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, Pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert -Butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group, etc. All of the aralkyloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. Emissions atoms; an alkoxy group such as methoxy group and ethoxy group; a portion at an aralkyl group such as aryloxy or benzyloxy group, such as phenoxy group may be substituted.

  Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, and 2,5-dimethylphenoxy group. Group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6- Trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2- tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl- 3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3, 4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6- Trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl group -3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n -Butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group, etc. These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; and benzyloxy groups. Partially placed with an aralkyloxy group, etc. It may be replaced.

In the general formula [1], a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M ² . When M ² is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

As a specific example of a metallocene complex,
Bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butyl) Cyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadienyl) titanium dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadi) Enyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n) -Butylcyclopentadi Nyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methyl) Cyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methylcyclopentadienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,2 4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6, 7-tetra Doroindeniru) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenyl indenyl) titanium dichloride,

Bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride , Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindene) Nil) titanium dichloride,

Dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2, 3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) titanium Dichloride, dimethylsilylene bis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylene bis (4,5-benzindenyl) titanium dichloride, dimethyl Silylene bis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylene bis (2-phenylindenyl) titanium dichloride, dimethylsilylene bis (4-phenyl) Indenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-naphthyl) Indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl (Indenyl) (fluorenyl) titanium dichloride, dimethylsilylene bis (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) ) Titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) ) Titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethyl) Phenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) thi Njikuroraido, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2) -Phenoxy Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-) 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Id, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) 5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl Down (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (n- Tilcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) ( 3,5-diamil- -Phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium Dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (tert-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1- Naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadi) Enyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl) Rudimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamil-2-phenoxy) titanium dichloride Dimethylsilylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) ( -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamil-2-phenoxy) ) Titanium dichloride, dimethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1-naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyltitanium dichloride, (tert-butylamide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphide) tetramethylcyclopentadi Enyldimethylsilane titanium dichloride, (tert-butylamido) indenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) tetrahydroyl Denyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium Dichloride, (tert-butylamido) fluorenyldimethylsilane titanium dichloride,

(Dimethylaminomethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyl titanium (III) dichloride (N-pyrrolidinylethyl) tetramethylcyclopentadienyl titanium dichloride, (B-dimethylaminoborabenzene) cyclopentadienyl titanium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) titanium dichloride, Or compounds in which titanium of these compounds is changed to zirconium or hafnium, (2-phenoxy) is changed to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-ter -Butyldimethylsilyl-2-phenoxy), dimethylsilylene changed to methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride changed to difluoride, di Compound, trichloride changed to bromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide), diphenoxide, or di (pentafluorophenoxide) Trifluoride, tribromide, triiodide, trimethyl, triethyl, triisopropyl, triphenyl, tribenzyl, trimethoxide, trieth Sid, tri (n- propoxide), tri (isopropoxide), tri phenoxide or a compound was changed to tri (pentafluorophenyl phenoxide), etc., can be exemplified.

  Specific examples of the transition metal compound of the transition metal compound represented by the general formula [1] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chloride], μ-oxobis [ Sopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) chita Chloride], .mu. Okisobisu [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], and the like. Examples include compounds in which the chloride of these compounds is changed to fluoride, bromide, iodide, methyl, ethyl, isopropyl, phenyl, benzyl, methoxide, ethoxide, n-propoxide, isopropoxide, phenoxide, or pentafluorophenoxide. can do.

  As the method for producing the ethylene-α-olefin copolymer of the present invention, particularly preferably, a promoter support (A) on which the following promoter component (I) is supported, an alkylene group, a silylene group, and the like are used. In the presence of a polymerization catalyst obtained by contacting a metallocene complex (B) having a ligand having a structure in which two cyclopentadienyl type anion skeletons are bonded with a bridging group and an organoaluminum compound (C), ethylene And α-olefin can be copolymerized.

[Cocatalyst carrier (A)]
Component (a) Diethylzinc, Component (b) Two types of fluorinated phenols, Component (c) Water, Component (d) Inorganic particulate carrier and Component (e) Trimethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH) is a carrier obtained by contact.

  Examples of the fluorinated phenol of component (b) include pentafluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol, 2,4,6-trifluorophenol and the like. From the viewpoint of increasing the flow activation energy (Ea) of the ethylene-α-olefin copolymer, it is preferable to use two types of fluorinated phenols having different fluorine numbers. For example, pentafluorophenol / 3,4,5-tri Combinations of fluorophenol, pentafluorophenol / 2,4,6-trifluorophenol, pentafluorophenol / 3,5-difluorophenol, and the like are preferable, preferably pentafluorophenol / 3,4,5-trifluorophenol. It is a combination. The molar ratio of the fluorinated phenol having a large number of fluorine and the fluorinated phenol having a small number of fluorine is usually 10/90 to 90/10. From the viewpoint of increasing the molecular weight distribution of the resulting ethylene-α-olefin copolymer, the molar ratio is preferably large and is preferably 50/50 or more.

  The inorganic particulate carrier of component (d) is preferably silica gel.

Component (a) diethyl zinc, component (b) 2 types of fluorinated phenol, component (c) The amount of each component used is not particularly limited, but the molar ratio of each component used is the component (a) diethyl. When the molar ratio of zinc: component (b) 2 types of fluorinated phenol: component (c) water = 1: x: y, x and y preferably satisfy the following formula.
| 2-x-2y | ≦ 1
X in the above formula is preferably a number from 0.01 to 1.99, more preferably a number from 0.10 to 1.80, and still more preferably a number from 0.20 to 1.50. Most preferably, the number is 0.30 to 1.00.

  The amount of component (d) inorganic fine particle carrier used for component (a) diethyl zinc is included in the particles obtained by contacting component (a) diethyl zinc and component (d) inorganic fine particle carrier. The amount of the zinc atom derived from the component (a) diethylzinc is preferably 0.1 mmol or more and 0.5 to 20 mmol in terms of the number of moles of zinc atoms contained in 1 g of the obtained particles. It is more preferable that The amount of component (e) trimethyldisilazane used for component (d) inorganic particulate carrier is such that component (e) trimethyldisilazane is 0.1 mmol or more per gram of component (d) inorganic particulate carrier. The amount is preferably 0.5 to 20 mmol, and more preferably 0.5 to 20 mmol.

  As a metal atom of the metallocene complex (B) having a ligand having a structure in which two cyclopentadienyl type anion skeletons are bonded by a bridging group such as an alkylene group or a silylene group, a group IV atom of the periodic table is Zirconium and hafnium are preferred. The ligand is preferably an indenyl group, a methylindenyl group, a methylcyclopentadienyl group, or a dimethylcyclopentadienyl group, and the crosslinking group is preferably an ethylene group, a dimethylmethylene group, or a dimethylsilylene group. Furthermore, as a remaining substituent which a metal atom has, a diphenoxy group and a dialkoxy group are preferable. Preferred examples of the metallocene complex (B) include ethylene bis (1-indenyl) zirconium diphenoxide.

  Examples of the organoaluminum compound (C) include trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, and trinormaloctylaluminum, with triisobutylaluminum and trinormaloctylaluminum being preferred.

The amount of the metallocene complex (B) used is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol with respect to 1 g of the promoter support (A). The amount of the organoaluminum compound (C) used is preferably expressed by the ratio (Al / M) of the number of moles of aluminum atoms in the organoaluminum compound (C) to the number of moles of metal atoms in the metallocene complex (B). 1 to 2000.

  In the polymerization catalyst obtained by contacting the promoter support (A), the metallocene complex (B) and the organoaluminum compound (C), the promoter support (A) and the metallocene complex (B ) And the organoaluminum compound (C) may be a polymerization catalyst obtained by contacting the electron donating compound (D). Preferred examples of the electron donating compound (D) include triethylamine and trinormaloctylamine.

  From the viewpoint of increasing the molecular weight distribution of the obtained ethylene-α-olefin copolymer, the electron donating compound (D) is preferably used, and the amount of the electron donating compound (D) used is an organoaluminum compound. The amount is more preferably 0.1 mol% or more, still more preferably 1 mol% or more, relative to the number of moles of aluminum atoms in (C). The amount used is preferably 10 mol% or less, more preferably 5 mol% or less, from the viewpoint of increasing the polymerization activity.

  As a method for producing the ethylene-α-olefin copolymer of the present invention, a small amount of olefin is polymerized (hereinafter referred to as prepolymerization) using a solid promoter component in which the promoter component (I) is supported on a particulate carrier. Obtained by polymerizing a small amount of olefin using a prepolymerized solid catalyst component obtained by, for example, a solid promoter component, a metallocene complex, and an alkylating agent (such as an organoaluminum compound). A method of copolymerizing ethylene and an α-olefin using a prepolymerized solid catalyst component as a catalyst component or a catalyst is preferred.

  Examples of the organoaluminum compound used for the alkylating agent include trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, and trinormaloctylaluminum, with triisobutylaluminum and trinormaloctylaluminum being preferred.

  Examples of the olefin used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene and cyclohexene. These can be used alone or in combination of two or more. From the viewpoint of reducing the number of micro defects in the obtained ethylene-α-olefin copolymer, ethylene is preferably used alone, or olefin other than ethylene and ethylene. More preferably, ethylene is used alone.

  The intrinsic viscosity ([η]; the unit is dl / g) of the prepolymerized polymer in the prepolymerized solid catalyst component is the viewpoint of reducing the number of micro defects in the obtained ethylene-α-olefin copolymer. Therefore, it is preferably 1.2 dl / g or more, more preferably 1.4 dl / g or more, still more preferably 1.6 dl / g or more, and most preferably 1.7 dl / g or more. The intrinsic viscosity is preferably 2 dl / g or less from the viewpoint of reducing fish eyes of the obtained ethylene-α-olefin copolymer. Examples of the method for bringing the intrinsic viscosity into a specific range include a method of adjusting the concentration of a molecular weight regulator such as hydrogen in the prepolymerization. (1) A multistage prepolymerization is performed, In the polymerization, pre-polymerization is started at a hydrogen concentration of zero to low hydrogen concentration, and a polymer having an intrinsic viscosity higher than the intended intrinsic viscosity is produced in the first stage, and then the second stage of pre-polymerization at a high hydrogen concentration. After the first stage, a polymer having an intrinsic viscosity lower than the intended intrinsic viscosity is produced in the second and subsequent stages, and the prepolymerized polymer as a whole is a polymer having a desired intrinsic viscosity. A method of adjusting the hydrogen concentration so as to form a coalescence, and (2) a method of maintaining the hydrogen concentration during the prepolymerization at a predetermined concentration so as to obtain a polymer having an intrinsic viscosity of a target value. . From the viewpoint of reducing the number of minute defects in the obtained ethylene-α-olefin copolymer, the method (1) is preferred.

  The amount of the prepolymerized polymer in the prepolymerized solid catalyst component, that is, the prepolymer, is preferably 0.1 g or more, more preferably 0.5 g or more, and still more preferably, per 1 g of the solid promoter component. 1 g or more. The amount of the prepolymer is preferably 1000 g or less, more preferably 500 g or less, and still more preferably 200 g or less.

  The crystal melting heat quantity of the prepolymer is preferably 160 J / g or more, more preferably 180 J / g or more. As such a polymer, for example, in a polymer having an ethylene-based monomer unit as a main unit (ethylene-based polymer), the content of the ethylene-based monomer unit is usually 96% by weight or more. A certain ethylene polymer is mentioned.

  From the viewpoint of reducing the number of micro defects in the obtained ethylene-α-olefin copolymer, in the prepolymerization, a prepolymer component having an intrinsic viscosity of 2 dl / g or more is introduced from the start of the prepolymerization per 1 g of the solid cocatalyst component. It is preferable to produce 0.1 g or more, and more preferably 0.5 g or more. The production amount of the prepolymer component is preferably 5 g or less, more preferably 2 g or less, and further preferably 1 g or less.

  The intrinsic viscosity of the prepolymer component is preferably 2 dl / g or more from the viewpoint of reducing the number of micro defects in the obtained ethylene-α-olefin copolymer. Further, the intrinsic viscosity of the prepolymer component is preferably 4 dl / g or less, more preferably 3.5 dl / g or less, from the viewpoint of reducing fish eyes of the obtained ethylene-α-olefin copolymer. is there.

  The preliminary polymerization method may be a continuous polymerization method or a batch polymerization method, and examples thereof include a batch type slurry polymerization method, a continuous slurry polymerization method, and a continuous gas phase polymerization method. As a method for introducing each catalyst component such as a solid cocatalyst component, a metallocene complex, an alkylating agent (such as an organoaluminum compound) into a polymerization reaction tank for performing prepolymerization, an inert gas such as nitrogen or argon is usually used. , Hydrogen, ethylene, or the like, and a method of adding in a water-free state, or a method of dissolving or diluting each component in a solvent and adding in a solution or slurry state. In addition, as a method for introducing each catalyst component into the polymerization reaction tank, from the viewpoint of reducing the number of micro defects in the obtained ethylene-α-olefin copolymer, the contact treatment product of the solid promoter component and the metallocene complex is used. It is preferable to add each catalyst component so that a contact-treated product obtained by contact treatment with an alkylating agent becomes a prepolymerization catalyst. For example, (1) a solid promoter component and a metallocene complex are charged into a polymerization reaction tank. Then, a method of charging the alkylating agent into the polymerization reaction tank, (2) contacting the solid promoter component and the metallocene complex in advance, and charging the contact treated product obtained by the contact into the polymerization reaction tank; , A method of charging an alkylating agent into a polymerization reaction tank, (3) a solid cocatalyst component and a metallocene complex are contacted in advance, and the contact treatment product obtained by the contact is already charged with an alkylating agent. (4) After bringing the solid promoter component and the metallocene complex into contact with each other, the contact treated product obtained by the contact is brought into contact with an alkylating agent, so that the solid promoter component and the metallocene are brought into contact with each other. Examples include a method in which a contact-treated product of a system complex and an alkylating agent is prepared in advance, and then the contact-treated product is charged into a polymerization reaction tank. The polymerization temperature in the prepolymerization is usually a temperature lower than the melting point of the prepolymerized polymer, preferably 0 to 100 ° C, more preferably 10 to 70 ° C.

  When the prepolymerization is performed by a slurry polymerization method, examples of the solvent include hydrocarbons having 20 or less carbon atoms. For example, saturated aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane, octane, and decane; aromatic hydrocarbons such as benzene, toluene, and xylene, which are used alone Alternatively, two or more kinds are used in combination.

  As a method for producing an ethylene-α-olefin copolymer, a continuous polymerization method involving the formation of particles of an ethylene-α-olefin copolymer is preferable. For example, a continuous gas phase polymerization method, a continuous slurry polymerization method, a continuous bulk weight It is a legal method, preferably a continuous gas phase polymerization method. The gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method for supplying the prepolymerized prepolymerized solid catalyst component to the continuous polymerization reaction tank accompanied by the formation of ethylene-α-olefin copolymer particles, it is usually an inert gas such as nitrogen or argon, hydrogen, ethylene, etc. And a method of supplying in a water-free state, and a method of supplying each component in a solution or slurry after dissolving or diluting each component in a solvent.

  The polymerization temperature of continuous polymerization involving the formation of ethylene-α-olefin copolymer particles is usually less than the temperature at which the ethylene-α-olefin copolymer melts, preferably 0 to 150 ° C, more Preferably it is 30-100 degreeC. From the viewpoint of further increasing the gloss of the resulting molded article, a temperature lower than 90 ° C., specifically in the range of 70 ° C. to 87 ° C., is preferable. Further, hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the ethylene-α-olefin copolymer. An inert gas may coexist in the mixed gas. In addition, when using a prepolymerization solid catalyst component, you may use promoter components, such as an organoaluminum compound, suitably.

  The ethylene-α-olefin copolymer of the present invention may contain known additives as necessary. Examples of the additive include antioxidants, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, dripping agents, pigments, fillers and the like.

  The ethylene-α-olefin copolymer in the present invention can be produced by various known molding methods, for example, an extrusion molding method such as an inflation film molding method and a T-die film molding method, an injection molding method, a compression molding method, and the like. Molded into a molded body (film, sheet, bottle, tray, etc.). As the molding method, an extrusion molding method is preferably used, and the obtained extrusion molding is used for various applications such as food packaging and surface protection.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

[Physical properties of polymer]
(1) Melt flow rate (MFR, unit: g / 10 minutes)
In the method defined in JIS K7210-1995, measurement was performed by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(2) Melt flow rate ratio (MFRR)
In the method specified in JIS K7210-1995, the melt flow rate (MFR-H, unit: g / 10 minutes) measured under conditions of a test load of 211.82 N and a measurement temperature of 190 ° C. is specified in JIS K7210-1995. In this method, the value divided by the melt flow rate (MFR) measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. was defined as MFRR.

(3) Density (Unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(4) Flow activation energy (Ea, unit: kJ / mol)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured under the following measurement conditions. From the obtained melt complex viscosity-angular frequency curve, calculation software Rhios V. Using 4.4.4, a master curve of a melt complex viscosity-angular frequency curve at 190 ° C. was created, and activation energy (Ea) was determined.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(5) Molecular weight distribution (Mw / Mn)
Using a gel permeation chromatograph (GPC) method, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured under the following conditions (1) to (8), and the molecular weight distribution (Mw / Mn) was determined. The baseline on the chromatogram is a stable horizontal region with a sufficiently long retention time than the appearance of the sample elution peak and a stable horizontal region with a sufficiently long retention time than the solvent elution peak was observed. A straight line formed by connecting the points.
(1) Equipment: Waters 150C manufactured by Water
(2) Separation column: TOSOH TSKgelGMH6-HT
(3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refraction
(8) Molecular weight reference material: Standard polystyrene

(6) Intrinsic viscosity ([η], unit: dl / g)
A tetralin solution (hereinafter, referred to as a blank solution) in which 2,6-di-t-butyl-p-cresol (BHT) is dissolved at a concentration of 0.5 g / L and an ethylene-α-olefin copolymer are concentrated. A solution (hereinafter referred to as a sample solution) dissolved in a blank solution so as to be 1 mg / ml is measured, and the falling time of the blank solution and the sample solution at 135 ° C. is measured with an Ubbelohde viscometer, After obtaining the relative viscosity (ηrel) at 135 ° C. from the falling time, it was calculated from the following formula.
[Η] = 23.3 × log (ηrel)

(7) Heat of crystal melting (unit: J / g)
Using a differential scanning calorimeter (PYRIS Diamond DSC, manufactured by PERKIN-ELMER, an input compensation type), samples 8 to 10 mg were heated to 150 ° C. and melted to 40 ° C. at a rate of 5 ° C. per minute. The temperature was lowered and the state was adjusted, and then the temperature was raised to 150 ° C. at a rate of 5 ° C. per minute. From the thermograph at this temperature rise, the heat of crystal fusion per unit mass was measured.

(8) Intrinsic viscosity (unit: dl / g) of the polymer component produced in the second pre-polymerization step
The intrinsic viscosity of the polymer component produced in the second stage prepolymerization step was calculated from the following formula.
[Η] 2 = ([η] T− [η] 1 × W1 / (W1 + W2)) × (W1 + W2) / W2
[Η] 1: Intrinsic viscosity (dl / g) of the polymer produced in the first stage prepolymerization step
[Η] 2: Intrinsic viscosity (dl / g) of the polymer produced in the second pre-polymerization step
[Η] T: Intrinsic viscosity of the polymer formed in the first and second pre-polymerization steps
(Dl / g)
W1: Amount of polymer component (% by weight) produced in the first stage prepolymerization step
W2: Amount of polymer component (% by weight) produced in the second stage prepolymerization step

(9) Number of minute defects (unit: piece / m ² )
Using an inflation film molding machine manufactured by Sumitomo Heavy Industries Modern Co., Ltd. (full-flight type screw single screw extruder (diameter 40 mmφ, L / D = 26), circular die (die diameter 75 mmφ, lip gap 1 mm)), processing temperature 170 ° C. An inflation film having a thickness of 30 μm was formed under the processing conditions of an extrusion rate of 12.5 kg / hr and a blow ratio of 1.8. Next, five test pieces each having a size of 30 cm in length and 20 cm in width were sampled from the obtained inflation film, and each test piece was 75 μm × 70 μm using a digital defect inspection apparatus (GX70LT manufactured by Mamiya Op Co., Ltd.). To 225 μm × 214 μm, the number of dark defects was measured under the following conditions and expressed as the number of dark defects per 1 m ^{2 of} the test piece.
(1) Detection threshold: 30 or more
(2) Detection prohibition threshold: 24 or more
(3) Light source gain: 1.0
(4) Reading speed: 30m / min
(5) Detection lower limit size: vertical 4 pixels, horizontal 2 pixels
(6) Average transmitted light quantity: 100
(7) Measurement range: 12cm long x 16.35cm wide

[Formability]
(10) Resin pressure (unit: MPa)
Using an inflation film molding machine manufactured by Plako (full flight type screw single screw extruder (diameter 30 mmφ, L / D = 28), dice (die diameter 50 mmφ, lip gap 0.8 mm), double slit air ring) The resin pressure of the extruder when a blown film having a thickness of 50 μm was formed under the processing conditions of a processing temperature of 170 ° C., an extrusion rate of 5.5 kg / hr, a frost line distance (FLD) of 200 mm, and a blow ratio of 1.8 was measured. The lower the resin pressure, the better the moldability.

[Physical properties of film]
(11) Flickering feeling The 50 μm-thick inflation film obtained above was held over a fluorescent lamp, and the flickering state of the film by the light of the fluorescent lamp was visually evaluated as follows.
○: There is very little flickering feeling.
X: There is much flickering feeling.

Example 1
(1) Preparation of co-catalyst support Silica (Sypolol 948 manufactured by Devison Corp .; 50% volume average particle size = 55 μm; pore capacity = 1.67 ml / g; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.91, 1 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene was kept for 33 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 21 kg of toluene. Thereafter, 6.9 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 2.05 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 1.3 kg of hexane were added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.77 kg of pentafluorophenol and 1.17 kg of toluene was added dropwise over 61 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Thereafter, the mixture was cooled to 5 ° C., and 0.11 kg of H ₂ O was added dropwise over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours, then heated to 55 ° C. and stirred at 55 ° C. for 2 hours. Thereafter, 1.4 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 0.8 kg of hexane were added at room temperature. After cooling to 5 ° C., a mixed solution of 0.44 kg of 3,4,5-trifluorophenol and 0.77 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Then cooled to 5 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O0.077kg the temperature of the reactor to 5 ° C.. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, then heated to 40 ° C, stirred at 40 ° C for 2 hours, further heated to 80 ° C, and stirred at 80 ° C for 2 hours. After stirring, at room temperature, the supernatant was withdrawn to a residual amount of 16 L, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours. After stirring, the supernatant liquid was extracted at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, drying was performed to obtain a solid component (hereinafter referred to as a promoter support (a)).

(2) Preparation of prepolymerization catalyst component 80 liters of butane was added to an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 106 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added to the autoclave. The mixture was heated to 50 ° C. and stirred for 2 hours. Next, 0.7 kg of the cocatalyst carrier (a) is charged, the autoclave is cooled to 30 ° C. and the system is stabilized, and then ethylene is charged in an amount of 0.03 MPa at the gas phase pressure in the autoclave, followed by triisobutyl. Polymerization was started by charging 158 mmol of aluminum. After 30 minutes while continuously supplying ethylene at 0.7 kg / Hr, the temperature was raised to 51 ° C., and ethylene and hydrogen were respectively 3.5 kg / Hr and 5.5 liters (normal temperature and normal pressure volume) / Hr. A total of 4 hours of prepolymerization was carried out by continuous feeding. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged, and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component containing 15 g of polyethylene per 1 g of the promoter support (a). The polyethylene [η] was 1.75 dl / g, and the heat of fusion was 190 J / g.
In addition, in the prepolymerization, a small amount of sampling was performed from the bottom of the reactor when 30 minutes had elapsed after the addition of triisobutylaluminum. The prepolymerization amount of polyethylene in the sampled prepolymerization catalyst component was 0.6 g per 1 g of the cocatalyst support (a), and the [η] of the polyethylene was 3.0 dl / g. It was 1.7 dl / g when [(eta)] of the polyethylene produced | generated after 30 minutes passed after triisobutylaluminum addition was calculated.

(3) Production of ethylene-α-olefin copolymer Using the prepolymerization catalyst component obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus to obtain a polymer powder. It was. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.4%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 0.7%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the prepolymerization catalyst component, triisobutylaluminum, and triethylamine (a molar ratio of 3% with respect to triisobutylaluminum) were continuously supplied, and the total powder weight of 80 kg in the fluidized bed was kept constant. The average polymerization time was 4 hours. The obtained polymer powder was blended with 750 ppm of an antioxidant (Sumitomo Chemical Co., Ltd., Sumitizer GP), and using an extruder (LCM50, manufactured by Kobe Steel), the feed speed was 50 kg / hr, the screw rotation speed was 450 rpm, and the gate was opened. An ethylene-1-hexene copolymer was obtained by granulation under conditions of a degree of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-hexene copolymer.

Example 2
(1) Preparation of pre-polymerization catalyst component After adding 80 liters of butane to an autoclave equipped with a stirrer with an internal volume of 210 liters, which was previously purged with nitrogen, 108 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added, and the autoclave The mixture was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature of the autoclave was lowered to 30 ° C. and the system was stabilized, ethylene was charged in an amount of 0.03 MPa at the gas phase pressure in the autoclave, and the promoter support obtained in (1) Preparation of promoter support in Example 1 (A) 0.7 kg was charged, and then 158 mmol of triisobutylaluminum was charged to initiate polymerization. After 30 minutes while ethylene is continuously supplied at 0.7 kg / Hr, the temperature is raised to 50 ° C., and ethylene and hydrogen are continuously supplied at 3.5 kg / Hr and 7 liters (room temperature and normal pressure volume) / Hr, respectively. Thus, prepolymerization was carried out for a total of 4 hours. After the polymerization was completed, ethylene, butane, hydrogen gas and the like were purged, and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component containing 16 g of polyethylene per 1 g of the promoter support (a). [Η] of polyethylene was 1.64 dl / g.

(2) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component obtained above, the hydrogen molar ratio to ethylene was 1.5%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1. The copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus in the same manner as in Example 1 except that the content was changed to 1%. A 1-hexene copolymer was obtained. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-hexene copolymer.

Example 3
(1) Preparation of prepolymerization catalyst component Same as preparation of (1) prepolymerization catalyst component in Example 2 except that racemic-ethylenebis (1-indenyl) zirconium diphenoxide was changed to 73 mmol and triisobutylaluminum was changed to 210 mmol. Thus, prepolymerization was carried out to obtain a prepolymerization catalyst component containing 14 g of polyethylene per 1 g of the promoter support (a). [Η] of polyethylene was 1.53 dl / g.

(2) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component obtained above, the hydrogen molar ratio to ethylene was 1.2%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1. Except for the change to%, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus in the same manner as in Example 1, granulated in the same manner as in Example 1, and ethylene-1- A hexene copolymer was obtained. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-hexene copolymer.

Comparative Example 1
(1) Preparation of prepolymerization catalyst component Into an autoclave with a stirrer with an internal volume of 210 liters, which was previously purged with nitrogen, 0.7 kg of the promoter support (a) obtained in (1) Preparation of promoter support of Example 1 was charged. After charging 3 liters of hydrogen (room temperature and normal pressure volume) and 80 liters of butane, the autoclave was heated to 30 ° C. Further, 0.03 MPa of ethylene was charged at a gas phase pressure in the autoclave, and after the system was stabilized, 210 mmol of triisobutylaluminum and 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. While raising the temperature to 31 ° C., 30 minutes passed while continuously supplying ethylene and hydrogen at 0.4 kg / Hr and 3.2 liters (normal temperature and normal pressure volume) / Hr, respectively, and further raising the temperature to 51 ° C. A total of 4 hours of prepolymerization was carried out by continuously supplying ethylene and hydrogen at 2.8 kg / Hr and 28 liters (room temperature and normal pressure volume) / Hr, respectively. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component containing 13 g of polyethylene per 1 g of the promoter support (a). [Η] of polyethylene was 0.83 dl / g.

(2) Production of ethylene-α-olefin copolymer Using the prepolymerization catalyst component obtained above, the polymerization temperature is 75 ° C., the hydrogen molar ratio to ethylene is 0.6%, and the total of ethylene and 1-hexene is Except that the 1-hexene molar ratio was changed to 1.5%, the copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus in the same manner as in Example 1, and as in Example 1. Granulation gave an ethylene-1-hexene copolymer. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-hexene copolymer.

Comparative Example 2
(1) Preparation of prepolymerization catalyst component Into an autoclave with a stirrer with an internal volume of 210 liters, which was previously purged with nitrogen, 0.7 kg of the promoter support (a) obtained in (1) Preparation of promoter support of Example 1 was charged. After charging 80 liters of butane, the autoclave was heated to 30 ° C. Further, 0.03 MPa of ethylene was charged at a gas phase pressure in the autoclave, and after the system was stabilized, 210 mmol of triisobutylaluminum and 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. While raising the temperature to 31 ° C. and 30 minutes after continuously supplying ethylene and hydrogen at 0.5 kg / Hr and 0.5 liter (room temperature and normal pressure volume) / Hr, respectively, the temperature is further raised to 51 ° C. A total of 4 hours of prepolymerization was carried out by continuously supplying ethylene and hydrogen at 2.8 kg / Hr and 4.1 liter (room temperature and normal pressure volume) / Hr, respectively. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component containing 10 g of polyethylene per 1 g of the promoter support (a). [Η] of polyethylene was 1.53 dl / g.

(2) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component obtained above, the hydrogen molar ratio to ethylene was 1%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.5. % In the same manner as in Comparative Example 1, except that ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus, granulated in the same manner as in Example 1, and ethylene-1- A hexene copolymer was obtained. The results of physical property evaluation using the obtained ethylene-1-hexene copolymer are shown in Table 1.

Comparative Example 3
(1) Preparation of co-catalyst support Silica (Dyson Corp. Sypolol 948; 50% volume average) after a nitrogen-substituted SUS reactor having an internal volume of 180 liters having a stirrer and a jacket was replaced with nitrogen. (Particle diameter = 58 μm; pore volume = 1.65 ml / g; specific surface area = 298 m ² / g) 9.7 kg and 100 liters of toluene were charged. After cooling to 2 ° C., 23.3 kg (75.9 mol as Al atoms) of methylaluminoxane in toluene (PMAO-s manufactured by Tosoh Finechem) was added dropwise over 62 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 30 minutes, heated to 95 ° C. over 2 hours, and stirred at 95 ° C. for 4 hours. Thereafter, the temperature was lowered to 40 ° C., and the mixture was transferred to a SUS reactor having an internal volume of 180 liters having a nitrogen-replaced stirrer and jacket. The silica-derived component was allowed to settle for 50 minutes to remove the liquid layer component. Thereafter, as a washing operation, 100 liters of toluene was added and stirred for 10 minutes, and then the silica-derived component was allowed to settle for about 45 minutes, and the upper layer component of the slurry was removed. The above washing operation was repeated a total of 3 times. Subsequently, the slurry was transferred with 120 liters of toluene to a SUS filter (filter having a filter, a stirrer, and a jacket) having an internal volume of 430 liters purged with nitrogen. The mixture was stirred for 10 minutes and filtered, 100 liters of toluene was added, and the mixture was stirred again for 10 minutes and filtered. Further, as a washing operation, 100 liters of hexane was added and stirred for 10 minutes, followed by filtration. This washing operation was repeated twice in total. Silica-derived components were transferred to a SUS-made dryer (dryer having a stirrer and a jacket) having an internal volume of 210 liters substituted with nitrogen with 70 liters of hexane. Subsequently, nitrogen circulation drying was performed for 7.5 hours at a jacket temperature of 80 ° C. to obtain 12.6 kg of a solid component (hereinafter referred to as a promoter support (S)).

(2) Preparation of prepolymerization catalyst component 120 liters of butane containing triisobutylaluminum at a concentration of 2.5 mmol / liter in an autoclave equipped with a stirrer with an internal volume of 210 liters previously purged with nitrogen, and 40 liters of hydrogen (room temperature and normal pressure volume) The autoclave was heated up to 47 ° C. Further, ethylene was charged in an amount of 0.3 MPa at the gas phase pressure in the autoclave. After the system was stabilized, 300 mmol of triisobutylaluminum, 15 mmol of racemic-ethylenebis (1-indenyl) zirconium dichloride, and then the promoter support (S) Polymerization was started by adding 0.25 kg, and prepolymerization was carried out for a total of 4 hours while continuously supplying ethylene and hydrogen. After the completion of the polymerization, ethylene, butane, hydrogen and the like were purged, and the resulting solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component containing 33 g of polyethylene per 1 g of the promoter support (S). [Η] of polyethylene was 0.85 dl / g.

(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component obtained above, the polymerization temperature is 85 ° C., the hydrogen molar ratio to ethylene is 0.15%, and the total of ethylene and 1-hexene The copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus in the same manner as in Comparative Example 1 except that the 1-hexene molar ratio was changed to 1.8% and no triethylamine was supplied. The polymer powder was granulated with a single screw extruder to obtain an ethylene-1-hexene copolymer. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-hexene copolymer.

Claims (2)

An ethylene-α-olefin copolymer obtained by polymerizing ethylene and an α-olefin having 3 to 20 carbon atoms using a solid catalyst component in which the catalyst component is supported on a particulate carrier,
Having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms,
Melt flow rate (MFR) is 0.1 to 6 g / 10 min, flow activation energy (Ea) is 60 to 90 kJ / mol, and molecular weight distribution obtained by gel permeation chromatographic measurement ( Mw / Mn) is 5 to 20, and the number of micro defects that are pulverized pieces of the fine particle carrier pulverized by polymerization is 650 to 1500 / m ² .
The number of minute defects was determined by measuring the number of dark defects having a size from 75 μm × 70 μm to 225 μm × 214 μm using a film obtained by molding the ethylene-α-olefin copolymer into a 30 μm-thick inflation film. The said ethylene-alpha-olefin copolymer which represents the number of this dark defect as a number per film unit area. The molded object formed by shape | molding the ethylene-alpha-olefin copolymer of Claim 1 .