JP5205899B2 - Ethylene-α-olefin copolymer and food packaging material - Google Patents

Description

  The present invention relates to an ethylene-α-olefin copolymer and a food packaging material containing the copolymer.

  For films, sheets, containers and the like used for packaging foods, pharmaceuticals, daily necessities, etc., 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 molding processability such as low extrusion load and good processing stability. For example, triisobutylaluminum and racemic -Ethylene bis (1-indenyl) zirconium diphenoxide is contact-treated, and then ethylene is produced using a catalyst obtained by contact-treating a promoter support obtained by reacting diethylzinc, pentafluorophenol, water, silica and trimethyldisilazane. A polymer (for example, see Patent Document 1) obtained by copolymerizing a olefin and an α-olefin has been proposed.

JP 2005-97481 A

However, although the above ethylene-α-olefin copolymer is excellent in molding processability, it may emit smoke during melt processing, and is not sufficiently satisfactory.
Under such circumstances, the problem to be solved by the present invention includes an ethylene-α-olefin copolymer excellent in molding processability and low smoke generation during melt processing, and the copolymer. It is to provide food packaging materials.

That is, 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 has a melt flow rate (MFR; the unit is g / 10 minutes). Is 0.01 to 100 g / 10 min, the density (d; the unit is kg / m ³ ) is 890 to 970 kg / m ³ , and the flow activation energy (Ea) is 50 kJ / mol or more. Yes, the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography is 3 or more, and the hexane extract amount (C; unit is% by weight) is 2.8% or less. The present invention relates to an ethylene-α-olefin copolymer that satisfies the above requirements.

  The present invention also relates to a food packaging material containing the ethylene-α-olefin copolymer.

  According to the present invention, it is possible to provide an ethylene-α-olefin copolymer excellent in moldability and low smoke generation during melt processing, and a food packaging material containing the copolymer.

  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, 4-methyl-1-pentene, and 1-octene, and more preferably 1-hexene and 1-octene.

  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- Hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene- 1-octene copolymer, ethylene-1-hexene-1-octene copolymer, and ethylene-1-butene-1-octene copolymer, more preferably ethylene-1-he Sen copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, an ethylene-1-butene-1-octene 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 min or more, and more preferably 0.1 g / 10 min or more from the viewpoint of improving the 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 of the ethylene -α- olefin copolymer of the present invention (d;. Unit is kg / m ³⁾ is usually 890~970kg / m ^3, from the viewpoint of reducing the smoke during melt processing, preferably at 900 kg / m ³ or more, more preferably 905 kg / m ³ or more, still more preferably 910 kg / m ³ or more. From the viewpoint of increasing the impact strength of the obtained molded article, it is preferably 940 kg / m ³ or less, more preferably 930 kg / m ³ or less, and particularly preferably 925 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 in processability, and such an ethylene-α-olefin copolymer is conventionally known. The flow activation energy (Ea; unit is kJ / mol) is higher than that of a normal linear ethylene-α-olefin copolymer. Conventionally known normal linear ethylene-α-olefin copolymers have an Ea lower than 50 kJ / mol, and a sufficiently satisfactory moldability cannot be obtained. Sometimes it was not possible.

  Ea of the ethylene-α-olefin copolymer of the present invention is preferably 55 kJ / mol or more from the viewpoint of improving the molding processability, particularly from the viewpoint of reducing the extrusion load without excessively reducing the melt tension. Preferably it 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 apparatus (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 the moldability, particularly from the viewpoint of reducing the extrusion load. Yes, more preferably 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 Waters
(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 hexane extract amount C (unit is% by weight) of the ethylene-α-olefin copolymer of the present invention is usually 2.8% or less, and preferably 2 from the viewpoint of reducing fuming during melt processing. 0.7% or less, and more preferably 2.6% or less. The hexane extraction amount C of the ethylene-α-olefin copolymer of the present invention is preferably 0.5% or more, more preferably 0.8% or more, and still more preferably, from the viewpoint of improving molding processability. 1.0% or more.

The hexane extract amount C is measured according to the following method.
(1) The ethylene-α-olefin copolymer is formed into a film having a thickness of 100 μm with a hot press at 150 ° C., and a sample of about 1 g is cut out from the sheet and placed in a flask.
(2) Add 400 ml of n-hexane to the sample in the flask, and heat and stir at 50 ° C. for 2 hours.
(3) After heating and stirring, a sample insoluble in n-hexane is removed by filtration.
(4) Remove n-hexane from the filtrate part collected by filtration, and further vacuum dry for 2 hours to obtain a dried product.
(5) Using the weight of the sample taken in the flask and the weight of the dried product obtained from the filtrate, calculate the hexane extraction amount C from the following formula.
C = 100 × {weight of dried product (g) / weight of sample (g)}

  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 the molding processability, particularly reducing the 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.

From the viewpoint of enhancing high-speed processability, the ethylene-α-olefin copolymer of the present invention preferably has a high maximum take-up rate (MTV) (unit: m / min) measured under the following conditions.
[Measurement method of maximum take-off speed (MTV)] (Unit: m / min)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a barrel of 9.5 mmφ at a predetermined temperature has a piston descending speed of 5.5 mm / min (shear speed of 7.4 sec ⁻¹ ) and a diameter of 2 0.09mmφ, 8mm long extruded from the orifice, the extruded molten resin is taken up at a take-up speed of 40rpm / min using a take-up roll having a diameter of 50mmφ, and taken up immediately before the molten resin breaks The speed is the maximum take-off speed at that temperature. The maximum take-up speed at 150 ° C. is MTV ₁₅₀ and the maximum take-up speed at 190 ° C. is MTV ₁₉₀ .
The MTV ₁₅₀ is preferably 15 or more, and more preferably 20 or more. MTV ₁₉₀ is preferably 5 or more, and more preferably 8 or more.
The MTV of the resulting ethylene-α-olefin copolymer can also be adjusted by adjusting the amount of hydrogen added when polymerizing ethylene and the α-olefin. When the amount of hydrogen added is decreased, the MTV of the obtained ethylene-α-olefin copolymer tends to decrease, and when the amount of addition is increased, the MTV of the obtained ethylene-α-olefin copolymer increases. Tend.

From the viewpoint of improving the moldability, the ethylene-α-olefin copolymer of the present invention preferably has a high melt tension (MT) (unit: cN) measured under the following conditions.
[Measuring method of melt tension (MT)] (unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a barrel of 9.5 mmφ at a predetermined temperature has a piston descending speed of 5.5 mm / min (shear speed of 7.4 sec ⁻¹ ) and a diameter of 2 0.09mmφ, 8mm in length, extruded from an orifice, and the extruded molten resin was wound at a winding speed of 40rpm / min using a winding roll having a diameter of 50mmφ, and the tension value immediately before the molten resin broke Is the melt tension at that temperature. The melt tension at 150 ° C. is MT ₁₅₀ and the melt tension at 190 ° C. is MT ₁₉₀ .
MT ₁₅₀ is preferably 5 or more, more preferably 7 or more, still more preferably 8 or more, and particularly preferably 9 or more. MT ₁₉₀ is preferably 3.5 or more, more preferably 4 or more, more preferably 5 or more, and particularly preferably 6 or more.
By adjusting the amount of hydrogen added when polymerizing ethylene and α-olefin, the MT of the resulting ethylene-α-olefin copolymer can also be adjusted. When the amount of hydrogen added is decreased, the MT of the resulting ethylene-α-olefin copolymer tends to increase, and when the amount added is increased, the MT of the obtained ethylene-α-olefin copolymer decreases. Tend.

  As a method for producing the ethylene-α-olefin copolymer of the present invention, a solid promoter comprising a metallocene complex and an activation promoter component (hereinafter referred to as promoter component (I)) supported on a particulate carrier. Examples thereof include a method of copolymerizing ethylene and α-olefin using a metallocene olefin polymerization catalyst formed by contact treatment with a catalyst component. An example of the promoter component (I) is a zinc compound.

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

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 [1] 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.

  The method for producing the ethylene-α-olefin copolymer of the present invention includes two promoters (A) on which the following promoter component (I) is supported and a crosslinking group such as an alkylene group or a silylene group. In the presence of a polymerization catalyst obtained by contacting a metallocene complex (B) having a ligand having a structure with a cyclopentadienyl-type anion skeleton and an organoaluminum compound (C), ethylene and an α-olefin The method of copolymerizing can be mentioned.

[Cocatalyst carrier (A)]
Diethyl zinc (hereinafter referred to as component (a)), fluorinated phenol (hereinafter referred to as component (b)), water (hereinafter referred to as component (c)), inorganic particulate carrier (hereinafter referred to as component (d) And trimethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH) (hereinafter referred to as component (e)).

  As component (b), 3,4,5-trifluorophenol, 3,4,5-tris (trifluoromethyl) phenol, 3,4,5-tris (pentafluorophenyl) phenol, 3,5-difluoro- By using 4-pentafluorophenylphenol or 4,5,6,7,8-pentafluoro-2-naphthol, an ethylene-α-olefin copolymer having a small C value can be obtained.

  More preferably, component (b) is 3,4,5-trifluorophenol or 4,5,6,7,8-pentafluoro-2-naphthol, more preferably 3,4,5-trifluorophenol. It is.

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

In the present invention, the use amount of each component of component (a), component (b), and component (c) is the molar ratio of the use amount of each component: component (a): component (b): component (c) = When 1: y: z, y and z are used so as to satisfy the following formula.
| 2-y-2z | ≦ 1 (2)
z ≧ −2.5y + 2.48 (3)
y <1 (4)
(In the above formulas (2) to (4), y and z represent numbers greater than 0.)
The molar ratio y of the usage amount of the component (b) to the usage amount of the component (a) and the molar ratio z of the usage amount of the component (c) to the usage amount of the component (a) are the above formulas (2) and (3). As long as the above and (4) are satisfied, there is no particular limitation. When the value of z is smaller than the value on the right side of Formula (3), the flow activation energy (Ea) of the resulting ethylene-α-olefin copolymer may be low, and the value of y may be Formula (4). When the value is larger than the value on the right side, the flow activation energy (Ea) of the ethylene-α-olefin copolymer may be low. Specifically, y usually takes a value of 0.55 to 0.99, more preferably 0.55 to 0.95, still more preferably 0.6 to 0.9, and most preferably 0. .7 to 0.8.

  The amount of component (d) used relative to component (a) is zinc derived from diethylzinc of component (a) contained in particles obtained by contact between component (a) and component (d). The amount of atoms is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol, in terms of the number of moles of zinc atoms contained in 1 g of the obtained particles. The amount of the component (e) used for the inorganic fine particle carrier of the component (d) is such that the trimethyldisilazane of the component (e) is 0.1 mmol or more per 1 g of the inorganic fine particle carrier of the component (d). 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 “copolymer catalyst carrier (A)”) in which the promoter component (I) is supported on a particulate carrier. This is referred to as prepolymerization.) A prepolymerization catalyst component obtained by polymerization, for example, a prepolymer obtained by polymerizing a small amount of olefin using the promoter support (A), a metallocene complex, and an organoaluminum compound. The polymerization catalyst component can be obtained by a method of copolymerizing ethylene and α-olefin using the catalyst component or catalyst.

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

As a method for producing a prepolymerized catalyst component used in producing the ethylene-α-olefin copolymer of the present invention, a co-catalyst carrier (by a treatment step having the following steps (1), (2) and (3) is used. Examples thereof include a method in which A), a metallocene complex, and an organoaluminum compound are contact-treated.
Step (1): A step of heat-treating a saturated aliphatic hydrocarbon compound solvent containing a metallocene complex at 40 ° C. or higher.
Step (2): A step of contacting the heat-treated product obtained by heat treatment in step (1) with the cocatalyst support (A).
Step (3): a step of contact-treating the contact-treated product obtained by the contact treatment in Step (2) and the organoaluminum compound.

  Step (1) is a step of heat-treating a saturated aliphatic hydrocarbon compound solvent containing a metallocene complex at 40 ° C. or higher. The saturated aliphatic hydrocarbon compound solvent containing the metallocene complex is prepared by a method of introducing the metallocene complex into the saturated aliphatic hydrocarbon compound solvent. The metallocene complex is usually charged as a powder or a slurry of a saturated aliphatic hydrocarbon compound liquid.

  Examples of the saturated aliphatic hydrocarbon compound used for the preparation of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane and the like. It is done. These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or less at normal pressure, more preferably 90 ° C. or less at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane. More preferred is cyclohexane.

  The heat treatment of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex may be performed by adjusting the temperature of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex to a temperature of 40 ° C. or higher. Further, during the heat treatment, the solvent may be allowed to stand or the solvent may be stirred. The temperature is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of improving molding processability. Moreover, from a viewpoint of improving a catalyst activity, Preferably it is 100 degrees C or less, More preferably, it is 80 degrees C or less. The heat treatment time is usually 0.5 to 12 hours. The time is preferably 1 hour or more, and more preferably 2 hours or more, from the viewpoint of improving molding processability. Moreover, from stability of catalyst performance, Preferably it is 6 hours or less, More preferably, it is 4 hours or less.

  Step (2) is a step of contact-treating the heat-treated product (that is, a saturated aliphatic hydrocarbon compound solvent containing a metallocene complex) heat-treated in step (1) above and the promoter support (A). is there. In the contact treatment, the heat-treated product and the cocatalyst support (A) may be brought into contact with each other. Usually, the method of introducing the promoter support (A) into the heat-treated product, the heat-treated product and the cocatalyst in the saturated aliphatic hydrocarbon compound. A method of charging the carrier (A) is used. The cocatalyst carrier (A) is usually charged as a powder or a slurry of a saturated aliphatic hydrocarbon compound solvent.

  The temperature of the contact treatment in the step (2) is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, preferably 10 ° C. or higher, more preferably 20 ° C. or higher. The time for the contact treatment is usually 0.1 to 2 hours.

  In step (3), the contact-treated product obtained by contact treatment in step (2) (that is, the contact-treated product of the heat-treated product heat-treated in step (1) and the cocatalyst support (A)) and organoaluminum This is a step of contact treatment with a compound. In the contact treatment, the contact treatment product formed in the step (2) may be brought into contact with the organoaluminum compound. Usually, the organoaluminum compound is introduced into the contact treatment product obtained in the contact treatment in the step (2). A method is used in which a contact-treated product obtained by contact treatment in step (2) and an organoaluminum compound are introduced into a saturated aliphatic hydrocarbon compound.

  The temperature of the contact treatment in the step (3) is preferably 70 ° C. or lower, more preferably 60 ° C. or lower. Further, from the viewpoint of efficiently expressing the prepolymerization activity, the temperature is preferably 10 ° C or higher, more preferably 20 ° C or higher. The time for the contact treatment is usually 0.01 hours to 0.5 hours.

  The contact treatment in the step (3) is preferably performed in the presence of an olefin. As the olefin, an olefin that is a raw material in prepolymerization is usually used. The amount of olefin is preferably 0.05 to 1 g per 1 g of the promoter support (A).

  The above steps (1) to (3) are carried out by separately introducing the saturated aliphatic hydrocarbon compound, the promoter support (A), the metallocene complex and the organoaluminum compound into the prepolymerization reactor. The step may be performed in the prepolymerization reactor, the steps (2) and (3) may be performed in the prepolymerization reactor, and the step (3) may be performed in the prepolymerization reactor. .

  The prepolymerization is carried out in the presence of a contact-treated product obtained by contact-treating the cocatalyst support (A), the metallocene complex and the organoaluminum compound by the treatment step having the steps (1), (2) and (3). The olefin is prepolymerized (a small amount of olefin is polymerized). The prepolymerization is usually performed by a slurry polymerization method, and the prepolymerization may be performed by any of batch, semi-batch, and continuous methods. Furthermore, the prepolymerization may be performed by adding a chain transfer agent such as hydrogen.

  When the prepolymerization is performed by a slurry polymerization method, a saturated aliphatic hydrocarbon compound is usually used as the solvent, and examples thereof include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane and the like. . These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or less at normal pressure, more preferably 90 ° C. or less at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane. More preferred is cyclohexane.

  When the prepolymerization is performed by the slurry polymerization method, the slurry concentration is usually 0.1 to 600 g, preferably 0.5 to 300 g, of the promoter support (A) per liter of the solvent. The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed, but the temperature at which the prepolymerization is started is preferably 45 ° C. or less, and preferably 40 ° C. or less. Moreover, the partial pressure of olefins in the gas phase part during the prepolymerization is usually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

  Examples of the olefin used for the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene, cyclohexene and the like. These may be used alone or in combination of two or more, preferably ethylene alone, or ethylene and α-olefin in combination, more preferably ethylene alone, or 1-butene, 1-hexene and 1 -It is used in combination with at least one α-olefin selected from octene and ethylene.

  The content of the prepolymerized polymer in the prepolymerized catalyst component is usually 0.01 to 1000 g, preferably 0.05 to 500 g, more preferably 0.00, per 1 g of the promoter support (A). 1 to 200 g.

  As a manufacturing method of an ethylene-α-olefin copolymer, a gas phase polymerization method is preferable, and a continuous gas phase polymerization method is more preferable. 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 catalyst component to the continuous polymerization reaction tank accompanied by the formation of ethylene-α-olefin copolymer particles, an inert gas such as nitrogen and argon, hydrogen, ethylene, etc. are usually used. And a method in which the components are supplied without moisture, and a method in which each component is dissolved or diluted in a solvent and supplied in a solution or slurry state.

  The polymerization temperature for the gas phase polymerization of the ethylene-α-olefin copolymer is usually lower than the temperature at which the ethylene-α-olefin copolymer melts, preferably 0 to 150 ° C, more preferably 30 to 30 ° C. 100 ° C. More preferably, the temperature is lower than 90 ° C, specifically in the range of 70 ° C to 87 ° C. 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 catalyst component, you may use promoter components, such as an organoaluminum compound, suitably.

  By adjusting the amount of hydrogen added, the C value of the resulting ethylene-α-olefin copolymer can also be adjusted. When the addition amount of hydrogen is decreased, the C value of the obtained ethylene-α-olefin copolymer tends to be small, and when the addition amount is increased, the C value of the obtained ethylene-α-olefin copolymer is There is a tendency to grow. The amount of hydrogen added is usually 0.0001 to 50%, preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less, as a molar ratio to ethylene.

  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.

  For the ethylene-α-olefin copolymer of the present invention, a known molding method such as an extrusion molding method such as an inflation film molding method or a T-die film molding method, an injection molding method, a compression molding method, or the like is used. An extrusion method is preferably used.

  The ethylene-α-olefin copolymer of the present invention is molded into various forms and used. The shape of the molded product is not particularly limited, but it can be used for films, sheets, containers (tray, bottle, etc.) and the like. The molded article is used in the form of a single layer composed of the copolymer or a multilayer including the copolymer. In addition, the molded product is a food packaging material used for packaging milk (raw milk, milk, etc.), dairy products (butter, fermented milk, etc.), dried foods, etc .; pharmaceutical packaging materials; electronic products used for packaging semiconductor products, etc. Component packaging material; suitably used for applications such as surface protection materials.

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.

(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 (d, 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) Maximum take-up speed (MTV, unit: m / min)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a barrel of 9.5 mmφ at a predetermined temperature has a piston descending speed of 5.5 mm / min (shear speed of 7.4 sec ⁻¹ ) and a diameter of 2 0.09mmφ, 8mm long extruded from the orifice, the extruded molten resin is taken up at a take-up speed of 40rpm / min using a take-up roll having a diameter of 50mmφ, and taken up immediately before the molten resin breaks The speed is the maximum take-off speed at that temperature. The maximum take-up speed at 150 ° C. is MTV ₁₅₀ and the maximum take-up speed at 190 ° C. is MTV ₁₉₀ . It shows that it is excellent in high-speed workability, so that these values are large.

(6) Melt tension (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a barrel of 9.5 mmφ at a predetermined temperature has a piston descending speed of 5.5 mm / min (shear speed of 7.4 sec ⁻¹ ) and a diameter of 2 0.09mmφ, 8mm in length, extruded from an orifice, and the extruded molten resin was wound at a winding speed of 40rpm / min using a winding roll having a diameter of 50mmφ, and the tension value immediately before the molten resin broke Is the melt tension at that temperature. The melt tension at 150 ° C. is MT ₁₅₀ and the melt tension at 190 ° C. is MT ₁₉₀ . It shows that it is excellent in workability, so that these values are large.

(7) 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 Waters
(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

(8) Kneading torque value (unit: N · m)
Using a Brabender Plasticcoder PLV-151 manufactured by Brabender, the mixing part volume was 60 cc, the resin amount was 40 g, the temperature was 160 ° C., and the rotation speed was 60 rpm, and the torque after 30 minutes was measured. It shows that it is excellent in molding processability, so that this figure is low.

(9) Amount of hexane extracted (C, unit: wt%)
The ethylene-α-olefin copolymer was formed into a film having a thickness of 100 μm by a heat press at 150 ° C., and a sample of about 1 g was cut out from the sheet and taken into a flask. 400 ml of n-hexane was added to the sample in the flask, and the flask was placed in a water bath adjusted to 50 ° C. ± 0.2 ° C. and heated. After the temperature of n-hexane in the flask reached 50 ° C., stirring was performed for 2 hours using a magnetic stirrer. After stirring, a sample insoluble in n-hexane was removed by filtration. The filtrate part collected by filtration removed n-hexane and further dried for 2 hours in a vacuum dryer to obtain a dried product. Using the weight of the sample taken in the flask and the weight of the dried product obtained from the filtrate part, the value calculated by the following formula was used as the hexane extraction amount.
C = 100 × {weight of dried product (g) / weight of sample (g)}

(10) Smoke generation during melt processing (unit: CPM)
A T-die (die width 200 mm, die lip 0.4 mm) was attached to a Union φ30 mm extruder, and the die temperature was set to 290 ° C. Each ethylene-α-olefin copolymer was extruded at 4 kg / h from this extruder, smoke generated in one minute was collected, and the amount of smoke was measured using a digital dust meter MODEL 3411 manufactured by Nippon Kanomax. As the amount of smoke generated, a value obtained by averaging five measurement values was used. Further, 1 CPM represents the amount of smoke generated at 0.01 mg / m ³ of stearic acid particles of 0.3 μm.

Reference 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. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 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 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 3.46 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 2.05 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 1.54 kg of 3,4,5-trifluorophenol and 2.88 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 O0.221kg 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 promoter support (a1)).

(2) 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 previously purged with nitrogen, 144 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, 0.5 kg of the cocatalyst carrier (a1) is charged, the autoclave is cooled to 31 ° C., and the system is stabilized. Then, 0.1 kg of ethylene and 0.1 liter of hydrogen (room temperature and normal pressure volume) are charged. Subsequently, 207 mmol of triisobutylaluminum was added to initiate polymerization. After 30 minutes while continuously supplying ethylene and hydrogen at 0.6 kg / Hr and 0.5 liter (room temperature and normal pressure volume), respectively, the temperature was raised to 50 ° C., and ethylene and hydrogen were each 3.6 kg / Hr. And 10.9 liters (normal temperature and normal pressure volume) / Hr were continuously fed to carry out preliminary polymerization for a total of 6 hours. 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 37 g of polyethylene per 1 g of the promoter support (a1). The [η] of the polyethylene was 1.51 dl / g.

(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 85 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.5%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.0%. 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 3.8 hr. 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 1
(1) Preparation of pre-polymerization catalyst component Into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, 80 liters of butane was added, and then 146 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, after the temperature of the autoclave was lowered to 31 ° C. and the system was stabilized, 0.1 kg of ethylene and 0.1 liter of hydrogen (room temperature and normal pressure volume) were charged to prepare (1) promoter support in Reference Example 1. 0.7 kg of the obtained cocatalyst carrier (a1) was charged, and then 280 mmol of triisobutylaluminum was charged to initiate polymerization. After 30 minutes while continuously supplying ethylene and hydrogen at 0.6 kg / Hr and 0.7 liter (normal temperature and normal pressure volume), respectively, the temperature was raised to 51 ° C., and ethylene and hydrogen were respectively 4.5 kg / Hr. And 13.4 liters (room temperature and normal pressure volume) / Hr were continuously fed to carry out preliminary polymerization for a total of 6 hours. After completion of the polymerization, 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 33.5 g of polyethylene per 1 g of the promoter support (a1). [Η] of polyethylene was 1.45 dl / g.

(2) Production of ethylene-α-olefin copolymer Using the prepolymerization catalyst component obtained above, ethylene, 1-butene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus. A coalesced powder was obtained. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.3%, and the 1-butene and 1-hexene molar ratios to the total of ethylene, 1-butene and 1-hexene were respectively 2.1% and 0.7%. During the polymerization, ethylene, 1-butene, 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 4.4 hr. 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-butene-1-hexene copolymer was obtained by granulation under the 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-butene-1-hexene copolymer.

Reference example 2
(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. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 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 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 1.73 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 1.02 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of 3,4,5-trifluorophenol and 1.44 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 22 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O0.11kg the temperature of the reactor 22 ° C.. After completion of dropping, the mixture was stirred at 22 ° 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, the promoter support (a2) was obtained by drying.

(2) Preparation of pre-polymerization catalyst component 80 liters of butane was charged into an autoclave with a stirrer having an internal volume of 210 liters previously purged with nitrogen, and then 91 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was charged into 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, 0.1 kg of ethylene and 0.1 liter of hydrogen (room temperature and normal pressure volume) were charged to prepare (1) promoter support in Reference Example 2. 0.7 kg of the obtained promoter support (a2) was charged, and then 263 mmol of triisobutylaluminum was charged to initiate polymerization. After 30 minutes passed while continuously supplying ethylene and hydrogen at 0.9 kg / Hr and 0.7 liter (normal temperature and normal pressure volume), respectively, the temperature was raised to 50 ° C. and ethylene and hydrogen were respectively 4.5 kg / Hr. And 13.4 liters (room temperature and normal pressure volume) / Hr were continuously fed to carry out preliminary polymerization for a total of 6 hours. After completion of the polymerization, 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 33.8 g of polyethylene per 1 g of the promoter support (a2). [Η] of polyethylene was 1.21 dl / g.

(3) Production of ethylene-α-olefin copolymer Using the prepolymerization catalyst component obtained above, the polymerization temperature was 84 ° C., the hydrogen molar ratio to ethylene was 1.2%, and the total of ethylene and 1-hexene was except for changing 1-Hekisenmoru ratio to 1.4% in the same manner as in reference example 1, was carried out copolymerization of ethylene and 1-hexene in a continuous type fluidized bed gas phase polymerization apparatus, in the same manner as in reference 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.

Example 2
(1) Production of ethylene-α-olefin copolymer
Using the prepolymerization catalyst component obtained in (3) of Reference Example 2 , the polymerization temperature was 84 ° C., the hydrogen molar ratio to ethylene was 0.8%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1. was changed to 5% in the same manner as in reference example 1, continuous fluidized bed gas phase polymerization apparatus to implement the copolymerization of ethylene and 1-hexene, ethylene -1 granulated in the same manner as in reference example 1 -A hexene copolymer was obtained. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-hexene copolymer.

Reference example 3
(1) Preparation of prepolymerization catalyst component 80 liters of butane was charged into 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 charged into the autoclave. The mixture was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature of the autoclave was lowered to 31 ° C. and the inside of the system was stabilized, 0.2 kg of ethylene and 2 liters of hydrogen (room temperature and normal pressure volume) were charged, and obtained by (1) Preparation of a promoter support in Reference Example 1. Copolymer support (a1) 0.7 kg was charged, and then 158 mmol of triisobutylaluminum was charged to initiate polymerization. After 30 minutes while continuously supplying ethylene and hydrogen at 0.7 kg / Hr and 4.2 liters (room temperature and normal pressure volume), respectively, the temperature was raised to 51 ° C. and ethylene and hydrogen were respectively supplied at 3.5 kg / Hr. And 21 liters (room temperature and normal pressure volume) / Hr were continuously fed for a prepolymerization 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 16.2 g of polyethylene per 1 g of the promoter support (a1). [Η] of polyethylene was 1.04 dl / g.

(2) 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 1.4%, and the total of ethylene and 1-hexene. except for changing 1-Hekisenmoru ratio to 1.4% in the same manner as in reference example 1, was carried out copolymerization of ethylene and 1-hexene in a continuous type fluidized bed gas phase polymerization apparatus, in the same manner as in reference 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.

Reference example 4
(1) Production of ethylene-α-olefin copolymer
Using the prepolymerization catalyst component obtained in (1) of Reference Example 3 , the polymerization temperature was 85 ° C., the hydrogen molar ratio to ethylene was 1.8%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1. was changed to 3% in the same manner as in reference example 1, continuous fluidized bed gas phase polymerization apparatus to implement the copolymerization of ethylene and 1-hexene, ethylene -1 granulated in the same manner as in reference example 1 -A 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 pre-polymerization catalyst component 80 liters of butane was charged into an autoclave with a stirrer having an internal volume of 210 liters previously purged with nitrogen, and then 87 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was charged into the autoclave. The mixture was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature of the autoclave was lowered to 31 ° C. and the system was stabilized, 0.1 kg of ethylene and 0.1 liter of hydrogen (room temperature and normal pressure volume) were charged to prepare (1) promoter support in Reference Example 2. 0.7 kg of the obtained promoter support (a2) was charged, and then 263 mmol of triisobutylaluminum was charged to initiate polymerization. After 30 minutes have elapsed while continuously supplying ethylene and hydrogen at 1.0 kg / Hr and 1.9 liters (room temperature and normal pressure volume), respectively, the temperature was raised to 50 ° C. and ethylene and hydrogen were each 3.1 kg / Hr. And 9.4 liters (room temperature and normal pressure volume) / Hr were continuously fed for a total of 6 hours of prepolymerization. After the completion of the polymerization, 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 21.1 g of polyethylene per 1 g of the promoter support (a2).

(2) 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 1.4%, and the total of ethylene and 1-hexene. except for changing 1-Hekisenmoru ratio to 1.3% in the same manner as in reference example 1, was carried out copolymerization of ethylene and 1-hexene in a continuous type fluidized bed gas phase polymerization apparatus, in the same manner as in reference 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.

Example 4
(1) Production of ethylene-α-olefin copolymer Using a prepolymerized catalyst component prepared in the same manner as in Example 7 (1), the polymerization temperature was 82 ° C, the molar ratio of hydrogen to ethylene was 1.2%, In the same manner as in Reference Example 1 except that the molar ratio of 1-octene to the total of 1-octene was changed to 0.39%, ethylene and 1-octene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus, Granulation was performed in the same manner as in Reference Example 1 to obtain an ethylene-1-octene copolymer. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-octene copolymer.

Reference Example 5
(1) Production Example 3 of Ethylene-α-Olefin Copolymer Using a prepolymerization catalyst component prepared in the same manner as in (1), the polymerization temperature was 84 ° C., the molar ratio of hydrogen to ethylene was 1.4%, and ethylene Continuous fluidized bed as in Reference Example 1 except that the molar ratio of 1-butene and 1-octene to the sum of 1-butene and 1-octene was changed to 1.1% and 0.34%, respectively. Ethylene, 1-butene and 1-octene were copolymerized in a gas phase polymerization apparatus and granulated in the same manner as in Reference Example 1 to obtain an ethylene-1-butene-1-octene copolymer. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-butene-1-octene copolymer.

Comparative 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. Then, the solid component (henceforth a promoter support (b)) was obtained by drying.

(2) Preparation of prepolymerization catalyst component 80 liters of butane was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, and then 109 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was charged into 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, 0.05 kg of ethylene and 0.05 liter of hydrogen (room temperature and normal pressure volume) were charged, and 0.7 kg of the promoter support (b) was charged. Subsequently, 158 mmol of triisobutylaluminum was added to initiate polymerization. After 30 minutes while continuously supplying ethylene and hydrogen at 0.7 kg / Hr and 0.7 liter (room temperature and normal pressure volume), respectively, the temperature was raised to 50 ° C. and ethylene and hydrogen were respectively supplied at 3.5 kg / Hr. And 10.2 liters (room temperature and normal pressure volume) / Hr were continuously fed to carry out preliminary polymerization 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 15.9 g of polyethylene per 1 g of the promoter support (b). [Η] of polyethylene was 1.45 dl / g.

(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component obtained above, the polymerization temperature is 90 ° C., the hydrogen molar ratio to ethylene is 1.8%, and the total of ethylene and 1-hexene. except for changing 1-Hekisenmoru ratio to 1.1% in the same manner as in reference example 1, was carried out copolymerization of ethylene and 1-hexene in a continuous type fluidized bed gas phase polymerization apparatus, in the same manner as in reference 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) Production of ethylene-α-olefin copolymer Using the prepolymerization catalyst component obtained in (2) of Comparative Example 1, the polymerization temperature was 85 ° C., the molar ratio of hydrogen to ethylene was 1.5%, and ethylene and 1 -Continuous fluidized bed gas phase polymerization in the same manner as in Example 1 except that the molar ratio of 1-butene and 1-hexene to the sum of butene and 1-hexene was changed to 2.1% and 0.6%. Copolymerization of ethylene, 1-butene and 1-hexene was carried out using an apparatus, and granulation was carried out in the same manner as in Example 1 to obtain an ethylene-1-butene-1-hexene copolymer. Table 1 shows the results of physical properties evaluation of the obtained ethylene-1-butene-1-hexene copolymer.

Comparative Example 3
(1) Preparation of prepolymerization catalyst component Into an autoclave with a stirrer having an internal volume of 210 liters which had been previously purged with nitrogen, 80 liters of butane was added, and then 74 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, after the temperature of the autoclave was lowered to 33 ° C. and the system was stabilized, 0.2 kg of ethylene and 2.0 liters of hydrogen (room temperature and normal pressure volume) were charged, and 0.7 kg of the promoter support (b) was charged. Subsequently, 210 mmol of triisobutylaluminum was added to initiate polymerization. After 30 minutes while continuously supplying ethylene and hydrogen at 0.7 kg / Hr and 4.2 liters (room temperature and normal pressure volume), respectively, the temperature was raised to 50 ° C. and ethylene and hydrogen were respectively supplied at 3.5 kg / Hr. And 21.0 liters (normal temperature and normal pressure volume) / Hr were continuously fed to carry out preliminary polymerization 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 17.2 g of polyethylene per 1 g of the promoter support (b). [Η] of polyethylene was 0.56 dl / g.

(2) Production of ethylene-α-olefin copolymer Using the pre-polymerization catalyst component obtained above, the polymerization temperature is 86 ° C., the hydrogen molar ratio to ethylene is 1.6%, and the total of ethylene and 1-hexene is except for changing 1-Hekisenmoru ratio to 1.2% in the same manner as in reference example 1, was carried out copolymerization of ethylene and 1-hexene in a continuous type fluidized bed gas phase polymerization apparatus, in the same manner as in reference 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.

Claims (7)

It has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and has a melt flow rate (MFR; the unit is g / 10 minutes) of 0.01 to 100 g. / 10 min, a density (d;. unit is kg / ^{m 3)} is 890~970kg / ^{m 3,} the flow activation energy (Ea) is at 50 kJ / mol or more, gel Pamiei molecular weight distribution measured by Deployment chromatography measurement (Mw / Mn) of 3 or more, hexane extraction (C;. units are% by weight) of Ri der less 2.8%, at 190 ° C. An ethylene-α-olefin copolymer satisfying a melt tension MT ₁₉₀ of 6.0 or more .   The ethylene-α-olefin copolymer according to claim 1, which is obtained by a gas phase polymerization method in the presence of a metallocene olefin polymerization catalyst.   The ethylene-α-olefin copolymer according to claim 1 or 2, which is an ethylene-1-hexene copolymer.   The ethylene-α-olefin copolymer according to claim 1 or 2, which is an ethylene-1-octene copolymer.   The ethylene-α-olefin copolymer according to claim 1 or 2, which is an ethylene-1-butene-1-hexene copolymer.   The ethylene-α-olefin copolymer according to claim 1 or 2, which is an ethylene-1-butene-1-octene copolymer.   The food packaging material containing the ethylene-alpha-olefin copolymer in any one of Claims 1-5.