JP2011006676A - ETHYLENE-α-OLEFIN COPOLYMER FOR FILM, FILM AND FOOD PACKAGING FILM - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene-α-olefin copolymer for film which is an ethylene-α-olefin copolymer excellent in moldability such as extrusion load and take-up nature, and is suited for producing a film excellent in mechanical strength and appearance and, further, excellent in cleanness.SOLUTION: The ethylene-α-olefin copolymer for film has a monomer unit based on ethylene and a monomer unit based on a 3-20C α-olefin, the density (d) is 860 to 950 kg/m, the melt flow rate (MFR) is 1 to 100 g/10 min, the Mw/Mn is 4 to 30, Mz/Mw is 2 to 5, the swell ratio (SR) is ≥1.7, the characteristic relaxation time (τ) determined by a linear viscoelastic property measurement is 0.01 to 10 s and the melting peak measured by a differential scanning calorimeter (DSC) is single.

Description

  The present invention relates to an ethylene-α-olefin copolymer for film, a film, and a film for food packaging.

The ethylene-α-olefin copolymer is formed into a film, a sheet, a bottle or the like by various molding methods and used for various applications such as food packaging materials. For example, when a film used as a food packaging material is manufactured by T-die molding, a phenomenon called “neck-in” occurs in which the film end portion shrinks toward the center. When neck-in occurs, the film width becomes narrow and the thickness of the film end becomes thicker than that of the center of the film, resulting in poor product yield. In order to minimize neck-in, it is preferable to use an ethylene-based resin having a high melt tension and swell ratio. Such characteristics are also necessary to prevent bubble fluctuation or tearing in inflation molding.
In addition, recent food packaging materials are required to have cleanliness, and there is a demand for resins that have a small amount of components eluted by solvents and that do not contain additives.

As an ethylene-α-olefin copolymer, a copolymer polymerized using a metallocene catalyst is known to be excellent in mechanical strength such as impact strength and tensile strength. Therefore, it is possible to reduce the thickness of the molded product while maintaining the mechanical strength of the conventional molded product, and it can be expected to reduce the weight and cost of the molded product. However, an ethylene-α-olefin copolymer polymerized using a conventional metallocene catalyst has a high extrusion load during extrusion and a low melt tension and swell ratio. It was sought after.

  On the other hand, recently, a novel metallocene catalyst has been studied, and a film using an ethylene-α-olefin copolymer polymerized by the catalyst has been proposed. For example, Patent Document 1 discloses a promoter component obtained by contacting silica, hexamethyldisilazane, diethyl zinc, pentafluorophenol and water, triisobutylaluminum, and racemic-ethylenebis (1-indenyl) zirconium diphenoxide. A food wrap film comprising an ethylene-α-olefin copolymer polymerized using a metallocene catalyst comprising: Patent Document 2 discloses a transition metal compound having a ligand in which two groups having a cyclopentadiene type anion skeleton are bonded via a bridging group, a group having a cyclopentadiene type anion skeleton, and a fluorenyl type anion skeleton. Polymerized using a metallocene catalyst comprising a combination of a transition metal compound having a ligand having a ligand bonded via a bridging group, and a support obtained by supporting methylalumoxane on porous silica as a co-catalyst A food packaging film containing an ethylene-α-olefin copolymer is described.

JP 2005-97390 A JP 2008-31379 A

However, the ethylene-α-olefin copolymer described in Patent Document 1 is still not fully satisfactory in terms of the extrusion load and swell ratio during molding, and the ethylene-α-olefin copolymer described in Patent Document 2 The swell ratio is still insufficient and the relaxation time of the melted ethylene-α-olefin copolymer molecular chain is long, so that the appearance of the molded product obtained by molding and the take-up property at the time of molding are further increased. There is a need for improvement. Further, the ethylene-α-olefin copolymer had a large amount of cold xylene soluble component (CXS), and the cleanliness was not sufficiently satisfactory.
Under such circumstances, the problem to be solved by the present invention is an ethylene-α-olefin copolymer that is excellent in molding processability such as extrusion load and take-off property, and is excellent in mechanical strength and appearance, and further clean. Another object is to provide an ethylene-α-olefin copolymer for film suitable for producing a film having excellent properties, a film comprising the copolymer or a resin composition containing the copolymer, and a film for food packaging.

That is, the first of the present invention has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, the density (d) is 860 to 950 kg / m ³ , The flow rate (MFR) is 1 to 100 g / 10 minutes, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4 to 30, and the Z average molecular weight (Mz) The ratio (Mz / Mw) to the weight average molecular weight (Mw) is 2 to 5, the swell ratio (SR) is 1.7 or more, and the characteristic relaxation time (τ) obtained by linear viscoelasticity measurement is 0.8. This is an ethylene-α-olefin copolymer for film having a single melting peak observed by a differential scanning calorimeter (DSC) for 01 to 10 seconds.

  The second of the present invention is a film comprising the ethylene-α-olefin copolymer or a resin composition containing the copolymer.

  Suitable for producing a film which is an ethylene-α-olefin copolymer excellent in molding processability such as extrusion load and take-off property and excellent in mechanical strength, appearance and cleanliness. Further, an ethylene-α-olefin copolymer for film, a film comprising the copolymer or a resin composition containing the copolymer, and a film for food packaging can be provided.

  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-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.

  The ethylene-α-olefin copolymer of the present invention is not limited to the above-described monomer units based on ethylene and monomer units based on α-olefins having 3 to 20 carbon atoms, and does not impair the effects of the present invention. The monomer unit may be 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 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. Further, 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 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. , 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 to 8 carbon atoms. It is a copolymer having monomer units based on α-olefin.

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

The density of the ethylene-α-olefin copolymer of the present invention (hereinafter sometimes referred to as “d”) is 860 to 950 kg / m ³ . From the viewpoint of increasing the mechanical strength of the obtained film, it is preferably 940 kg / m ³ or less, more preferably 935 kg / m ³ or less, and further preferably 930 kg / m ³ or less. Further, in view of enhancing the rigidity of the resulting film is preferably 870 kg / m ³ or more, more preferably 880 kg / m ³ or more, more preferably 890 kg / m ³ or more, particularly preferably 900 kg / m ³ or more. The density is measured according to a method defined in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. Moreover, the density of an ethylene-alpha-olefin copolymer can be changed with content of the monomer unit based on ethylene in an ethylene-alpha-olefin copolymer.

  The melt flow rate (hereinafter sometimes referred to as “MFR”) of the ethylene-α-olefin copolymer of the present invention is usually 1 to 100 g / 10 min. The melt flow rate is preferably 1.5 g / 10 min or more from the viewpoint of reducing the extrusion load during molding. Moreover, from a viewpoint of raising the mechanical strength of the film obtained, Preferably it is 50 g / 10min or less, More preferably, it is 20 g / 10min or less, More preferably, it is 10 g / 10min or less. The melt flow rate is a value measured by the 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. Further, the melt flow rate of the ethylene-α-olefin copolymer can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later. The melt flow rate of the copolymer is increased.

  The ethylene-α-olefin copolymer of the present invention has a single melting peak existing in the range from 25 ° C. to the end of melting temperature in the melting curve obtained from differential scanning calorimetry of the ethylene-α-olefin copolymer. Is a copolymer. The presence of a plurality of melting peaks means that there is a melting peak different from the maximum melting peak (melting peak having the highest peak height) in the melting curve of the ethylene-α-olefin copolymer, This means that the composition distribution of the ethylene-α-olefin copolymer (distribution of the content ratio of monomer units among the polymer components contained in the ethylene-α-olefin copolymer) is wide, and the crystal Contains ingredients with low properties. A component having low crystallinity tends to volatilize during the molding process, and it is difficult to obtain a film having excellent cleanliness. Since the ethylene-α-olefin copolymer of the present invention has a single melting peak, that is, a narrow composition distribution, a film having excellent cleanliness can be obtained.

  In addition, the melting curve of the ethylene-α-olefin copolymer is measured by using a differential scanning calorimeter (for example, a differential scanning calorimeter DSC-7 manufactured by Perkin Elmer), for example, an aluminum pan in which about 10 mg of a sample is sealed. (1) held at 150 ° C. for 5 minutes, (2) lowered from 150 ° C. to 20 ° C. at 5 ° C./minute, (3) held at 20 ° C. for 2 minutes, and (4) 20 at 5 ° C./minute. It is obtained from the differential scanning calorimetry curve obtained in (4) by raising the temperature from 0 ° C. to the melting end temperature + about 20 ° C. (usually about 150 ° C.).

The ratio of the weight average molecular weight (hereinafter sometimes referred to as “Mw”) and the number average molecular weight (hereinafter sometimes referred to as “Mn”) of the ethylene-α-olefin copolymer of the present invention. (Hereinafter may be referred to as “Mw / Mn”) is 4 to 30, and is the Z average molecular weight (hereinafter sometimes referred to as “Mz”) and the weight average molecular weight (Mw). The ratio (hereinafter sometimes referred to as “Mz / Mw”) is 2-5. If Mw / Mn is too small, the extrusion load at the time of molding may increase. Mw / Mn is preferably 4.5 or more, more preferably 5.5 or more, and further preferably 6 or more. If Mz / Mw is too large, the relaxation time of the molecular chain of the polymer in the molten state may be long. Mz / Mw is preferably 4.5 or less, more preferably 4 or less. If Mw / Mn is too large or Mz / Mw is too small, the mechanical strength of the resulting molded product may be lowered. Mw / Mn is preferably 25 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 12 or less. Mz / Mw is preferably 3 or more from the viewpoint of improving high-speed take-up performance.
In addition, this Mw / Mn and this Mz / Mw measure the number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) by gel permeation chromatography (GPC) method. And Mw is divided by Mn and Mz is divided by Mw. The Mw / Mn can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later. When the hydrogen concentration or the polymerization temperature is increased, the Mw / Mn of the ethylene-α-olefin copolymer is increased. growing. The Mz / Mw can be changed by, for example, the use ratio of the transition metal compound (A1) and the transition metal compound (A2) in the production method described later, and the use ratio of the transition metal compound (A2) is reduced. Mz / Mw of the ethylene-α-olefin copolymer becomes small.

  Mz / Mw represents the molecular weight distribution of the high molecular weight component, and the smaller Mz / Mw compared to Mw / Mn means that the molecular weight distribution of the high molecular weight component is narrow and the component ratio of very high molecular weight, that is, the relaxation time. Means that there are few very long components, and that Mz / Mw is large compared to Mw / Mn, the molecular weight distribution of the high molecular weight component is broad and the molecular weight distribution is very high, that is, the component ratio is very long. Means high. From the viewpoint of reducing the extrusion load and shortening the relaxation time, (Mw / Mn)-(Mz / Mw) is preferably 1 or more, more preferably (Mw / Mn)-(Mz / Mw). 2 or more. (Mw / Mn)-(Mz / Mw) can be changed, for example, depending on the use ratio of the transition metal compound (A1) and the transition metal compound (A2), and the use ratio of the transition metal compound (A2) is increased. Then, (Mw / Mn)-(Mz / Mw) of the ethylene-α-olefin copolymer increases. Moreover, (Mw / Mn)-(Mz / Mw) can be increased also by performing prepolymerization.

The ethylene-α-olefin copolymer of the present invention is preferably a copolymer exhibiting a unimodal molecular weight distribution. Here, the unimodal distribution means that the molecular weight distribution curve measured by gel permeation chromatography (GPC) method has one peak.
When the molecular weight distribution is a bimodal distribution, a component having a low molecular weight is included. A component having a low molecular weight is likely to volatilize during molding, and it is difficult to obtain a film having excellent cleanliness. The ethylene-α-olefin copolymer of the present invention can provide a film having a small amount of components having a low molecular weight and excellent cleanliness.

The swell ratio (hereinafter sometimes referred to as “SR”) of the ethylene-α-olefin copolymer of the present invention is 1.7 or more. If the swell ratio is too small, neck-in may increase in T-die film molding. The swell ratio is preferably 1.8 or more, more preferably 1.9 or more, and further preferably 2.0 or more. The swell ratio is preferably 2.5 or less from the viewpoint of improving the take-up property at the time of extrusion molding. When the melt flow rate (MFR) is measured, the swell ratio is obtained from an ethylene-α-olefin copolymer extruded at a length of about 15 to 20 mm from an orifice at a temperature of 190 ° C. and a load of 21.18 N. The strand was cooled in air, and the obtained solid strand was measured for the diameter D (unit: mm) of the strand at a position of about 5 mm from the upstream end of the extrusion. It is a value (D / D ₀ ) divided by 095 mm (D ₀ ). In addition, the swell ratio can be changed by, for example, the hydrogen concentration, the ethylene pressure or the electron donating compound concentration during polymerization in the production method described later. When the hydrogen concentration is increased or the ethylene pressure is decreased, ethylene- The swell ratio of the α-olefin copolymer is increased. In addition, the swell ratio can be controlled by performing prepolymerization at the time of polymerization.

The number of branches having 5 or more carbon atoms (hereinafter sometimes referred to as “N _LCB ”) of the ethylene-α-olefin copolymer of the present invention is preferably from the viewpoint of further reducing the extrusion load during the molding process. Is 0.1 / 1000 C or more, more preferably 0.12 / 1000 C or more. Moreover, from a viewpoint of raising the mechanical strength of the film obtained, Preferably it is 1 / 1000C or less, More preferably, it is 0.7 / 1000C or less. Further, the N _LCB can be changed in the production method described later, for example, depending on the concentration of the electron donating compound or the use ratio of the transition metal compound (A1) and the transition metal compound (A2). It can also be controlled by carrying out prepolymerization.

N _LCB is a branch having 7 or more carbon atoms, where the sum of the areas of all peaks observed at 5 to 50 ppm is 1000 from the ¹³ C-NMR spectrum measured by the carbon nuclear magnetic resonance ( ¹³ C-NMR) method. Is obtained by determining the area of the peak derived from the methine carbon to which is bound. The peak derived from methine carbon to which a branch having 5 or more carbon atoms is bonded is around 38.2 ppm (reference: academic literature “Macromolecules”, (USA), American Chemical Society, 1999, Vol. 32, p.3817-3819) Observed at. Since the position of the peak derived from the methine carbon to which a branch having 5 or more carbon atoms is bonded may be shifted depending on the measurement apparatus and measurement conditions, it is usually determined by measuring the standard for each measurement apparatus and measurement conditions. To do. In the spectrum analysis, it is preferable to use a negative exponential function as the window function.

  The characteristic relaxation time (hereinafter sometimes referred to as “τ”) of the ethylene-α-olefin copolymer of the present invention is 0.01 from the viewpoint of improving the take-up property during film formation and the appearance of the film. -10 seconds. The characteristic relaxation time is a numerical value indicating the length of the long chain branch of the ethylene-α-olefin copolymer. When the long chain branch is short, the characteristic relaxation time becomes a small value, and when the long chain branch is long, The characteristic relaxation time is a large value. The characteristic relaxation time is preferably 0.1 seconds or longer. The characteristic relaxation time is preferably 5 seconds or less. The characteristic relaxation time can be changed, for example, depending on the polymerization conditions such as hydrogen concentration and ethylene pressure, and the use ratio of the transition metal compound (A1) and the transition metal compound (A2). The use of the transition metal compound (A2) When the ratio is reduced, the characteristic relaxation time of the ethylene-α-olefin copolymer can be shortened.

The characteristic relaxation time is calculated from a master curve showing the dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. on the angular frequency (unit: rad / sec), which is created based on the temperature-time superposition principle. It is a numerical value. Specifically, 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, unit of angular frequency is rad / sec.) Is superposed on the melt complex viscosity-angular frequency curve at 190 ° C based on the temperature-time superposition principle, and a master curve is obtained. It is a value calculated by approximating the master curve by the following formula (I).
η = η ₀ / [1+ (τ × ω) ⁿ ] (I)
η: Complex melt viscosity (unit: Pa · sec)
ω: angular frequency (unit: rad / sec)
τ: Characteristic relaxation time (unit: sec)
η ₀ : Constant determined for each ethylene-α-olefin copolymer (unit: Pa · sec)
n: Constant determined for each ethylene-α-olefin copolymer For the above calculation, commercially available calculation software may be used. 4.4.4.

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

It is preferable that g * defined by the following formula (II) of the ethylene-α-olefin copolymer of the present invention is 0.76 to 0.95 (for g *, the following document was referred to: Developments in Polymer Characterisation-4, JV Dawkins, Ed., Applied Science, London, 1983, Chapter I, “Characterization. of Long Chain Branching in Polymers,” by Th. G. Scholte).
g * = [η] / ([η] _GPC × g _SCB *) (II)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer and is defined by the following formula (II-I). It was defined by the following formula (II-II). g _SCB * is defined by the following formula (II-III).
[Η] = 23.3 × log (ηrel) (II-I)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (II-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (II-III)
(In the formula, A can be determined directly from the measurement of the content of short chain branches in the ethylene-α-olefin copolymer.)]

[Η] _GPC is the intrinsic viscosity (unit: dl / g) of a polymer assuming that the molecular weight distribution is the same as that of the ethylene-α-olefin copolymer and the molecular chain is linear. Represents.
g _SCB * represents the contribution to g * caused by introducing short chain branching into the ethylene-α-olefin copolymer.
As the formula (II-II), the formula described in Journal of Polymer Science, 36, 130 (1959) pp. 287-294 by LH Tung was used.

  The relative viscosity (ηrel) of the ethylene-α-olefin copolymer was obtained by dissolving 100 mg of the olefin polymer at 135 ° C. in 100 ml of tetralin containing 0.5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor. A solution is prepared, and is calculated from the falling time of the sample solution and a blank solution made of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor using an Ubbelohde viscometer.

で定義され、a＝０．７２５とした。 The viscosity average molecular weight (Mv) of the ethylene-α-olefin copolymer is represented by the following formula (II-IV)

And a = 0.725.

For A in formula (II-III), the number of short-chain branched carbons is n (for example, n = 2 when butene is used as the α-olefin, n = 4 when hexene is used), and NMR Or when the number of short chain branches per 1000 carbon atoms determined by infrared spectroscopy is y,
A = ((12 × n + 2n + 1) × y) / ((1000−2y−2) × 14 + (y + 2) × 15 + y × 13)
As estimated.

  g * is an index representing the degree of contraction of a molecule in a solution caused by long chain branching. When the amount of long chain branching per molecular chain is large, the contraction of the molecular chain increases. Get smaller. From the viewpoint of reducing the extrusion load, g * of the ethylene-α-olefin copolymer is preferably 0.95 or less, more preferably 0.85 or less. When g * is large, long chain branching is not sufficiently contained, and therefore the extrusion load cannot be reduced sufficiently. Further, g * of the ethylene-α-olefin copolymer is preferably 0.76 or more from the viewpoint of improving the mechanical strength and shortening the relaxation time. If g * is too small, the molecular chain spread when the crystal is formed is too small, so that the generation probability of the tie molecule decreases, the strength decreases, and the relaxation time of the molecular chain due to the long chain branch structure It becomes too long and the appearance of the resulting film is deteriorated. g * can be controlled, for example, by carrying out prepolymerization.

  The flow activation energy of the ethylene-α-olefin copolymer of the present invention (hereinafter sometimes referred to as “Ea”) is preferably 45 kJ / from the viewpoint of further reducing the extrusion load during molding. mol or more, more preferably 60 kJ / mol or more. In addition, the flow activation energy is preferably 150 kJ / mol or less, more preferably 130 kJ / mol or less, and even more preferably 110 kJ / mol or less, from the viewpoint of enhancing the film take-up property during extrusion molding. Yes, most preferably 100 kJ / mol. In addition, the flow activation energy can be changed by, for example, the use ratio of the transition metal compound (A1) and the transition metal compound (A2) in the production method described later, and the use ratio of the transition metal compound (A2). When E is increased, Ea of the ethylene-α-olefin copolymer is increased.

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 following method. 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 (III) 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 (IV).
ln (a _T ) = m (1 / (T + 273.16)) + n (III)
Ea = | 0.008314 × m | (IV)
a _T : Shift factor Ea: Activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics is used. 4.4.4.
The shift factor (a _T ) is obtained by moving the logarithmic curve of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) = − log (X) axis direction (however, the Y axis Is the complex viscosity of the melt, and the X axis is the angular frequency.), And the amount of movement when superposed on the melt complex viscosity-angular frequency curve at 190 ° C., in the superposition, melting at each temperature (T) The logarithmic curve of complex viscosity-angular frequency shifts the angular frequency by a _T times and the melt complex viscosity by 1 / a _T times for each curve. Moreover, the correlation coefficient when calculating | requiring (I) Formula by the least squares method from the value of four points | pieces, 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is usually 0.99 or more.

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

The ethylene-α-olefin copolymer of the present invention preferably satisfies the following formula.
CXS ≦ 1.8 × 10 ⁻⁸ × MFR ^0.42 × d ⁻²¹⁶ +5
In the above formula, CXS is a cold xylene soluble part and can be analyzed according to the method defined in §175.520 of Code of federal regulations, Food Drugs Administration in the United States. When the amount of CXS in the resin does not satisfy the above formula (large), the amount of volatile components at the time of film formation is large, the cleanliness is deteriorated, and the films stick to each other, which may cause a blocking phenomenon. CXS is 0 or more. In general, the amount of the organic solvent-soluble component of the resin has a correlation with MFR, and CXS tends to increase if MFR is high. Similarly, the amount of the organic solvent-soluble component of the resin also has a correlation with the density, and the CXS tends to increase if the density is low. For example, “Metalocene Catalysts and Next-Generation Polymer Prospects” (CMMC Publishing, issued on August 20, 1993) describes the amount of room-temperature n-decane soluble part and ethylene copolymers in general ethylene polymers. The relationship with the density is shown. From this document, an exponential correlation is confirmed between the amount of the organic solvent-soluble component and the density, indicating that the amount of the organic solvent-soluble component can be represented by an exponential function of density. The above equation was obtained by regression of the data of the example, taking into account the influence of MFR on the relationship between CXS and density. The CXS range is preferably CXS ≦ 1.8 × 10 ⁻⁸ × MFR ^0.42 × d ⁻²¹⁶ +3, and more preferably CXS ≦ 1.8 × 10 ⁻⁸ × MFR ^0.42 × d ⁻²¹⁶ +2.

  As a manufacturing method of the ethylene-alpha-olefin copolymer of this invention, the transition metal compound (A1) represented by the following general formula (1) and the transition metal compound (A2) represented by the following general formula (3) ) And a cocatalyst component (B) to be described later, and a molar ratio of the transition metal compound (A1) to the transition metal compound (A2) ((A1) / (A2) 1) to 60, and a method of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a polymerization catalyst to be contacted. (A1) / (A2) is preferably 5 or more, more preferably 10 or more, from the viewpoint of shortening the relaxation time of the molecular chain of the ethylene-α-olefin copolymer in the molten state and increasing the mechanical strength. It is. Further, (A1) / (A2) is preferably 30 or less, more preferably 20 or less, from the viewpoint of increasing SR.

［式中、Ｍ¹は元素周期律表の第４族の遷移金属原子を表し、Ｘ¹およびＲ¹は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜２０の置換されていてもよいハイドロカルビル基、炭素数１〜２０の置換されていてもよいハイドロカルビルオキシ基、炭素数１〜２０の置換シリル基または炭素数１〜２０の置換アミノ基であり、複数のＸ¹は互いに同じであっても異なっていてもよく、複数のＲ¹は互いに同じであっても異なっていてもよく、Ｑ¹は下記一般式（２）で表される架橋基を表す。

（式中、ｍは１〜５の整数であり、Ｊ¹は元素周期律表の第１４族の原子を表し、Ｒ²は、水素原子、ハロゲン原子、炭素数１〜２０の置換されていてもよいハイドロカルビル基、炭素数１〜２０の置換されていてもよいハイドロカルビルオキシ基、炭素数１〜２０の置換シリル基または炭素数１〜２０の置換アミノ基であり、複数のＲ²は互いに同じであっても異なっていてもよい。）］

[Wherein, M ¹ represents a group 4 transition metal atom in the periodic table of the elements, and X ¹ and R ¹ are each independently a hydrogen atom, a halogen atom, or a C 1-20 substituted group. A good hydrocarbyl group, an optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of X ¹ May be the same as or different from each other, the plurality of R ¹ may be the same or different from each other, and Q ¹ represents a bridging group represented by the following general formula (2).

(In the formula, m is an integer of 1 to 5, J ¹ represents an atom belonging to Group 14 of the periodic table, and R ² is a hydrogen atom, a halogen atom, or a C 1-20 substituted atom. A hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group optionally having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of R ² may be the same or different from each other.)]

［式中、Ｍ²は元素周期律表の第４族の遷移金属原子を表し、Ｘ²、Ｒ³およびＲ⁴は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜２０の置換されていてもよいハイドロカルビル基、炭素数１〜２０の置換されていてもよいハイドロカルビルオキシ基、炭素数１〜２０の置換シリル基または炭素数１〜２０の置換アミノ基であり、複数のＸ²は互いに同じであっても異なっていてもよく、複数のＲ³は互いに同じであっても異なっていてもよく、複数のＲ⁴は互いに同じであっても異なっていてもよく、Ｑ²は、下記一般式（４）で表される架橋基を表す。

（式中、ｎは１〜５の整数であり、Ｊ²は元素周期律表の第１４族の原子を表し、Ｒ⁵は、水素原子、ハロゲン原子、炭素数１〜２０の置換されていてもよいハイドロカルビル基、炭素数１〜２０の置換されていてもよいハイドロカルビルオキシ基、炭素数１〜２０の置換シリル基または炭素数１〜２０の置換アミノ基であり、複数のＲ⁵は互いに同じであっても異なっていてもよい。）］

[Wherein, M ² represents a transition metal atom of Group 4 of the periodic table, and X ² , R ^3, and R ⁴ are each independently a hydrogen atom, a halogen atom, or a C 1-20 substituted group. A hydrocarbyl group optionally having 1 to 20 carbon atoms, a hydrocarbyloxy group optionally having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms. X ² may be the same or different from each other, the plurality of R ³ may be the same or different from each other, and the plurality of R ⁴ may be the same or different from each other. Q ² represents a crosslinking group represented by the following general formula (4).

(In the formula, n is an integer of 1 to 5, J ² represents an atom of Group 14 of the periodic table, and R ⁵ is a hydrogen atom, a halogen atom, or a C 1-20 substituted atom. A hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group optionally having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of R ⁵ may be the same or different from each other.)]

M ^{1 in the} general formula (1) and M ^{2 in the} general formula (3) represent a group 4 transition metal atom in the periodic table of elements, and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom.

X ¹ , R ^{1 in} the general formula ( ¹ ) and X ² , R ³ , R ^{4 in} the general formula (3) may each independently be a hydrogen atom, a halogen atom, or a C 1-20 substituent. A hydrocarbyl group, an optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of X ¹ are The plurality of R ¹ may be the same or different from each other, the plurality of X ² may be the same or different from each other, and the plurality of R ³ May be the same as or different from each other, and a plurality of R ⁴ may be the same as or different from each other.

Examples of the halogen atom for X ¹ , R ¹ , X ² , R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the optionally substituted hydrocarbyl group having 1 to 20 carbon atoms of X ¹ , R ¹ , X ² , R ³ and R ⁴ include an alkyl group having 1 to 20 carbon atoms and a halogen having 1 to 20 carbon atoms. An alkyl group, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-dodecyl group, n-tridecyl group, n -Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.

  Examples of the halogenated alkyl group having 1 to 20 carbon atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, and tribromomethyl. Group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group , Pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl Group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, Perchlorododecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopenta Examples include decyl group and perbromoeicosyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (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, (4 , 6-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, -Tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropyl) (Phenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthra Cenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenyl Methyl, diphenylethyl group, diphenylpropyl group, diphenylbutyl group. Moreover, the halogenated aralkyl group etc. which these aralkyl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. Group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethyl Phenyl group, 2,4,6-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, diethylphenyl group, triethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, se -Butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecyl Examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Moreover, the halogenated aryl group etc. which these aryl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  The hydrocarbyl group having 1 to 20 carbon atoms which may be substituted includes a hydrocarbyl group substituted with a substituted silyl group, a hydrocarbyl group substituted with a substituted amino group, and a hydrocarbyloxy group. And hydrocarbyl groups substituted with.

  Hydrocarbyl groups substituted with substituted silyl groups include trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylpropyl, trimethylsilylbutyl, trimethylsilylphenyl, bis (trimethylsilyl) methyl, bis (trimethylsilyl) ethyl, bis ( Examples thereof include trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, bis (trimethylsilyl) phenyl group, and triphenylsilylmethyl group.

  Hydrocarbyl groups substituted with substituted amino groups include dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl group, bis (dimethyl Amino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis (dimethylamino) phenyl group, phenylaminomethyl group, diphenylaminomethyl group, diphenylaminophenyl group and the like.

  Hydrocarbyl groups substituted with hydrocarbyloxy groups include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, sec-butoxymethyl group, tert-butoxy Methyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl group, phenoxyethyl group, methoxy- n-propyl group, ethoxy-n-propyl group, n-propoxy-n-propyl group, isopropoxy-n-propyl group, n-butoxy-n-propyl group, sec-butoxy-n-propyl group, tert-butoxy -N-propyl group, phenoxy-n-propyl group Methoxyisopropyl group, ethoxyisopropyl group, n-propoxyisopropyl group, isopropoxyisopropyl group, n-butoxyisopropyl group, sec-butoxyisopropyl group, tert-butoxyisopropyl group, phenoxyisopropyl group, methoxyphenyl group, ethoxyphenyl group, n -Propoxyphenyl group, isopropoxyphenyl group, n-butoxyphenyl group, sec-butoxyphenyl group, tert-butoxyphenyl group, phenoxyphenyl group and the like.

Examples of the optionally substituted hydrocarbyloxy group of X ¹ , R ¹ , X ² , R ³ and R ⁴ having 1 to 20 carbon atoms include an alkoxy group having 1 to 20 carbon atoms and a carbon number of 7 to 20 carbon atoms. Examples thereof include an aralkyloxy group and an aryloxy group having 6 to 20 carbon atoms.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neo Pentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyl group Examples include oxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosoxy group and the like. . Further, halogenated alkoxy groups in which these alkoxy groups are substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom or iodine atom can be mentioned.

  Examples of the aralkyloxy group having 7 to 20 carbon atoms 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-trimethyl) Enyl) methoxy group, (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, (n-tetradecylphenyl) methoxy group, naphthylmethoxy Group, anthracenylmethoxy group and the like. In addition, a halogenated aralkyloxy group in which these aralkyloxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethyl Phenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5 -Tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethyl Ruphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n- Examples include decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. Moreover, the halogenated aryloxy group etc. which these aryloxy groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mentioned.

Examples of the substituted silyl group having 1 to 20 carbon atoms of X ¹ , R ¹ , X ² , R ³ and R ⁴ include silyl groups substituted with hydrocarbyl groups such as alkyl groups and aryl groups. Specifically, for example, methylsilyl group, ethylsilyl group, n-propylsilyl group, isopropylsilyl group, n-butylsilyl group, sec-butylsilyl group, tert-butylsilyl group, isobutylsilyl group, n-pentylsilyl group, n- 1-substituted silyl groups such as hexylsilyl group and phenylsilyl group; dimethylsilyl group, diethylsilyl group, di-n-propylsilyl group, diisopropylsilyl group, di-n-butylsilyl group, di-sec-butylsilyl group, di- disubstituted silyl groups such as tert-butylsilyl group, diisobutylsilyl group, diphenylsilyl group; trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec- Butylsilyl group, tri-tert-butyl Examples include tri-substituted silyl groups such as rusilyl group, triisobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, and triphenylsilyl group. It is done.

Examples of the substituted amino group having 1 to 20 carbon atoms of X ¹ , R ¹ , X ² , R ³ and R ⁴ include an amino group substituted with two hydrocarbyl groups such as an alkyl group and an aryl group. I can. Specifically, for example, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group, isobutylamino group, n-hexyl Amino group, n-octylamino group, n-decylamino group, phenylamino group, benzylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di -Sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group , Diphenylamino group, dibenzylamino group, tert-butylisopropylamino , Phenylethyl group, phenylpropyl group, phenylbutyl group, a pyrrolyl group, a pyrrolidinyl group, a piperidinyl group, a carbazolyl group, such as dihydroisoindolyl group.

X ¹ is preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group and a benzyl group.

R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom.

X ² is preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group and a benzyl group.

R ³ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom.

R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom.

Q ¹ in the general formula (1) represents a crosslinking group represented by the general formula ( ² ), and Q ² in the general formula (3) represents a crosslinking group represented by the general formula (4).

  M in the general formula (2) and n in the general formula (4) are integers of 1 to 5. m is preferably 1-2, and n is preferably 1-2.

J ² of J ¹ and of the general formula (2) (4) represents a Group 14 transition metal atom of the periodic table of elements, carbon atoms, a silicon atom, such as a germanium atom. Preferably, they are a carbon atom or a silicon atom.

R ^{2 in} the general formula (2) and R ^{5 in the} general formula (4) are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, or 1 to carbon atoms. A 20-substituted hydrocarbyloxy group, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of R ² may be the same or different from each other; The plurality of R ⁵ may be the same as or different from each other.

R ² and R ⁵ halogen atoms, C 1-20 optionally substituted hydrocarbyl groups, C 1-20 optionally substituted hydrocarbyloxy groups, C 1-20 carbon atoms Examples of the substituted silyl group and the substituted amino group having 1 to 20 carbon atoms include a halogen atom of X ¹ , R ¹ , X ² , R ³ and R ⁴ , and an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms. And those exemplified as the hydrocarbyloxy group optionally having 1 to 20 carbon atoms, the substituted silyl group having 1 to 20 carbon atoms, and the substituted amino group having 1 to 20 carbon atoms.

Q ¹ and Q ² are methylene group, ethylidene group, ethylene group, propylidene group, propylene group, butylidene group, butylene group, pentylidene group, pentylene group, hexylidene group, isopropylidene group, methylethylmethylene group, methylpropylmethylene group. Group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) methylene group, bis (trimethyl) Phenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenyl) methylene group, bis (Dipropylphenyl) methylene group, phenyl (butylphenyl) methylene group, di (butylphenyl) methylene group, phenyl (naphthyl) methylene group, di (naphthyl) methylene group, phenyl (biphenyl) methylene group, di (biphenyl) methylene Group, phenyl (trimethylsilylphenyl) methylene group, bis (trimethylsilylphenyl) methylene group, bis (pentafluorophenyl) methylene group,

Silanediyl group, disilanediyl group, trisilanediyl group, tetrasilanediyl group, dimethylsilanediyl group, bis (dimethylsilane) diyl group, diethylsilanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutane Examples thereof include a diyl group, a silacyclohexanediyl group, a divinylsilanediyl group, a diallylsilanediyl group, a (methyl) (vinyl) silanediyl group, and an (allyl) (methyl) silanediyl group.

Q ¹ is preferably a methylene group, an ethylene group, an isopropylidene group, a bis (cyclohexyl) methylene group, a diphenylmethylene group, a dimethylsilanediyl group, or a bis (dimethylsilane) diyl group, and more preferably an ethylene group or a dimethyl group. Silane diyl group. Q ² is preferably a methylene group, ethylene group, isopropylidene group, bis (cyclohexyl) methylene group, diphenylmethylene group, dimethylsilanediyl group, or bis (dimethylsilane) diyl group, more preferably diphenylmethylene. It is a group.

As the transition metal compound (A1) represented by the general formula (1), m ¹ is a zirconium atom and X ¹ is a chlorine atom, methylene bis (indenyl) zirconium dichloride, (Methyl) (phenyl) methylenebis (indenyl) zirconium dichloride, diphenylmethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride,

Methylenebis (methylindenyl) zirconium dichloride, isopropylidenebis (methylindenyl) zirconium dichloride, (methyl) (phenyl) methylenebis (methylindenyl) zirconium dichloride, diphenylmethylenebis (methylindenyl) zirconium dichloride, ethylenebis (methyl Indenyl) zirconium dichloride,

Methylene (indenyl) (methylindenyl) zirconium dichloride, isopropylidene (indenyl) (methylindenyl) zirconium dichloride, (methyl) (phenyl) methylene (indenyl) (methylindenyl) zirconium dichloride, diphenylmethylene (indenyl) (methyl) Indenyl) zirconium dichloride, ethylene (indenyl) (methylindenyl) zirconium dichloride,

Methylenebis (2,4-dimethylindenyl) zirconium dichloride, isopropylidenebis (2,4-dimethylindenyl) zirconium dichloride, (methyl) (phenyl) methylenebis (2,4-dimethylindenyl) zirconium dichloride, diphenylmethylenebis (2,4-dimethylindenyl) zirconium dichloride, ethylenebis (2,4-dimethylindenyl) zirconium dichloride,

Dimethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (indenyl) zirconium dichloride, di (n-propyl) silanediylbis (indenyl) zirconium dichloride, diisopropylsilanediylbis (indenyl) zirconium dichloride, dicyclohexylsilanediylbis (indenyl) Zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, di (p-tolyl) silanediylbis (indenyl) zirconium dichloride, divinylsilanediylbis (indenyl) zirconium dichloride, diallylsilanediylbis (indenyl) zirconium dichloride, (methyl) ( Vinyl) silanediylbis (indenyl) zirconium dichloride, Allyl) (methyl) silanediylbis (indenyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (indenyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (indenyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (indenyl) Zirconium dichloride, (cyclohexyl) (methyl) bis (indenyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (indenyl) zirconium dichloride,

Dimethylsilanediylbis (methylindenyl) zirconium dichloride, diethylsilanediylbis (methylindenyl) zirconium dichloride, di (n-propyl) silanediylbis (methylindenyl) zirconium dichloride, diisopropylsilanediylbis (methylindenyl) zirconium dichloride , Dicyclohexylsilanediylbis (methylindenyl) zirconium dichloride, diphenylsilanediylbis (methylindenyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (methylindenyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis ( Methylindenyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (methylindenyl) zyl Niumujikurorido, (cyclohexyl) (methyl) bis (methylindenyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (methylindenyl) zirconium dichloride,

Dimethylsilanediyl (indenyl) (methylindenyl) zirconium dichloride, diethylsilanediyl (indenyl) (methylindenyl) zirconium dichloride, di (n-propyl) silanediyl (indenyl) (methylindenyl) zirconium dichloride, diisopropylsilanediyl ( Indenyl) (methylindenyl) zirconium dichloride, dicyclohexylsilanediyl (indenyl) (methylindenyl) zirconium dichloride, diphenylsilanediyl (indenyl) (methylindenyl) zirconium dichloride, (ethyl) (methyl) silanediyl (indenyl) (methyl) Indenyl) zirconium dichloride, (methyl) (n-propyl) silanediyl (indenyl) (methylindenyl) zirconium Dichloride, (methyl) (isopropyl) silanediyl (indenyl) (methylindenyl) zirconium dichloride, (cyclohexyl) (methyl) (indenyl) (methylindenyl) zirconium dichloride, (methyl) (phenyl) silanediyl (indenyl) (methylindene) Nil) zirconium dichloride,

Dimethylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, di (n-propyl) silanediylbis (2,4-dimethylindenyl) zirconium dichloride Diisopropylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, dicyclohexylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, Ethyl) (methyl) silanediylbis (2,4-dimethylindenyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,4-dimethylindenyl) zirconium Dichloride, (methyl) (isopropyl) silanediylbis (2,4-dimethylindenyl) zirconium dichloride, (cyclohexyl) (methyl) bis (2,4-dimethylindenyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (2, 4-dimethylindenyl) zirconium dichloride and the like can be exemplified.

In the above exemplification, when the bridging group is in the 1-position, the η ⁵ -indenyl group is substituted in the 2-position, 3-position, 4-position, 5-position, 6-position and 7 Including all substitutions at the -position, including the substitution at the -position, even if the bridging position is other than the 1-position. Bi- or higher substituents similarly include all combinations of substituents and crosslinks. Further, X ¹ dichloride of the above transition metal compound is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, dipropoxide, dibutoxide, bis (trifluoromethoxide), diphenyl, diphenoxide, bis (2, 6-di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide) Examples thereof include compounds changed to dibenzyl and the like. Furthermore, the zirconium M ¹ of the transition metal compound may be exemplified compound was changed to titanium or hafnium.

  The transition metal compound (A1) represented by the general formula (1) is preferably ethylene bis (indenyl) zirconium diphenoxide, ethylene bis (indenyl) zirconium dichloride, or dimethylsilylene bis (indenyl) zirconium dichloride.

As the transition metal compound (A2) represented by the general formula (3), M ² is a zirconium atom, X ² is a chlorine atom, and the bridging group Q ² is a diphenylmethylene group. Pentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2, , 5-Trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetramethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2, , 5-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tri-n-propyl-1-cyclo) Pentadienyl) (9-fluorenyl) zyl Nium dichloride, diphenylmethylene (2,3,5-tri-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium Chloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmeth Len (2,3,5-triphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclo Ntadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris ( Trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Trimethyl-1- Clopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclo) Pentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Triethyl-1- Clopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopenta Dienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7 -Dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Di-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (2 , 7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmeth Len (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tri-n-propyl- 1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1-cyclopentadienyl) (2,7-dimethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) ( 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-trif Nyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5- Tetraphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9- Fluorenyl) Jill Nium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) ) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Trimethyl-1- Clopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclo) Pentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Triethyl-1- Clopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopenta Dienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7 -Diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Di-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (2 , 7-diethyl-9-fluorenyl) zirconium dichloride, diphenylme Len (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tri-n-propyl- 1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1-cyclopentadienyl) (2,7-diethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) ( 2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-trif Nyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5- Tetraphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9- Fluorenyl) Jill Nium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) ) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-trimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) ) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) ) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,5-di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4 -Di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirco Um dichloride, diphenylmethylene (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4) 5-tri-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1- Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2, 7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2 , 7-Di-t-butyl-9-fluorenyl) zirconium Chloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, dipheny Methylene (2,3,4-triphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1- Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-di-t -Butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl)- 1-cyclopentadienyl) (2,7-di-t- Til-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) ( 2,7-di-t-butyl-9-fluorenyl) zirconium dic It can be exemplified Lido like.

The dichloride of X ² in the transition metal compound, difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, Jipuropokishido, Jibutokishido, bis (trifluoromethyl methoxide), diphenyl, diphenoxide, bis (2,6 -Di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide), Examples include compounds changed to dibenzyl and the like. Further, the diphenylmethylene group of Q ² of the transition metal compound is a methylene group, ethylene group, isopropylidene group, methylphenylmethylene group, dimethylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, etc. Examples of the compound can be exemplified. Furthermore, the zirconium M ² of the transition metal compound may be exemplified compound was changed to titanium or hafnium.

  The transition metal compound (A2) represented by the general formula (3) is preferably diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride.

The promoter component (B) used for the preparation of the polymerization catalyst used in the production of the ethylene-α-olefin copolymer of the present invention includes the following component (b1), the following component (b2), and the following component (b3). And a solid catalyst component formed by contacting the following component (b4).
(B1): Compound represented by the following general formula (5)
M ³ L _x (5)
[Wherein M ³ is lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom, lead atom, antimony Represents an atom or a bismuth atom, and x represents a number corresponding to the valence of M ³ . L represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbyl group, and when a plurality of L are present, they may be the same as or different from each other. ]
(B2): Compound represented by the following general formula (6)
R ⁶ _t-1 T ¹ H (6)
[Wherein T ¹ represents an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and t represents a number corresponding to the valence of T ¹ . R ⁶ represents a halogen atom, an electron-withdrawing group, a group containing a halogen atom or a group having an electron-withdrawing group, and when a plurality of R ⁶ are present, they may be the same or different from each other. ]
(B3): Compound represented by the following general formula (7)
R ⁷ _s-2 T ² H ₂ (7)
[Wherein T ² represents an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and s represents a number corresponding to the valence of T ² . R ⁷ represents a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group. ]
(B4): particulate carrier

M ^{3 in the} general formula (5) is lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom, lead An atom, an antimony atom or a bismuth atom. Preferred is a magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, more preferred is a magnesium atom, zinc atom, tin atom or bismuth atom, still more preferred. It is a zinc atom.

X in the general formula (5) represents a number corresponding to the valence of M ³ . For example, when M ³ is a zinc atom, x is 2.

  L in the general formula (5) represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbyl group, and when a plurality of L are present, they may be the same or different from each other.

  Examples of the halogen atom for L include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the optionally substituted hydrocarbyl group for L include an alkyl group, an aralkyl group, an aryl group, and a halogenated alkyl group.

  As the alkyl group of L, an alkyl group having 1 to 20 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl. Group, n-pentyl group, neopentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-nonyl group, n-decyl group, n-dodecyl group, n -Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like. Preferably, they are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group.

  As the halogenated alkyl group of L, a halogenated alkyl group having 1 to 20 carbon atoms is preferable, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a bromomethyl. Group, dibromomethyl group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl Group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, per group Fluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, Perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group Group, perbromopentadecyl group, perbromoeicosyl group and the like.

  As the aralkyl group of L, an aralkyl group having 7 to 20 carbon atoms is preferable. For example, a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (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-dimethyl) Phenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) Phenyl) 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) 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-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, (n- Tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, phenylethyl group, phenylpropyl group Phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group. Preferably, it is a benzyl group. Moreover, the C7-20 halogenated aralkyl group etc. with which these aralkyl groups were substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  The aryl group of L is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, and 2,4-xylyl group. Group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,4-trimethylphenyl group, 2,4,6-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, diethylphenyl group, triethylphenyl group, n-propylphenyl group, isopropylphenyl group, -Butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl Group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like. Preferably, it is a phenyl group. Moreover, the C6-C20 halogenated aryl group etc. which these aryl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  L is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and still more preferably an alkyl group.

T ^{1 in the} general formula (6) is an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or an oxygen atom, and more preferably an oxygen atom.

The t in the general formula (6) represents a valence of T ^1, if T ¹ is an oxygen atom or a sulfur atom, t is 2, if T ¹ is a nitrogen atom or phosphorus atom, t is 3 .

R ^{6 in the} general formula (6) represents a halogen atom, an electron-withdrawing group, a group containing a halogen atom, or a group having an electron-withdrawing group, and represents a group containing an electron-withdrawing group or an electron-withdrawing group. , R ⁶ may be the same as or different from each other. As an index of electron withdrawing property, Hammett's rule substituent constant σ and the like are known, and functional groups having positive Hammett's rule substituent constant σ are listed as electron withdrawing groups.

Examples of the halogen atom for R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the electron-withdrawing group for R ⁶ include a cyano group, a nitro group, a carbonyl group, a hydrocarbyloxycarbonyl group, a sulfone group, and a phenyl group.

Examples of the group containing a halogen atom of R ⁶ include halogenated hydrocarbyl groups such as halogenated alkyl groups, halogenated aralkyl groups, halogenated aryl groups, and (halogenated alkyl) aryl groups; halogenated hydrocarbyloxy groups A halogenated hydrocarbyloxycarbonyl group and the like. Examples of the group having an electron-withdrawing group of R ⁶ include a cyanated hydrocarbyl group such as a cyanated aryl group and a nitrated hydrocarbyl group such as a nitrated aryl group.

Examples of the halogenated alkyl group for R ⁶ include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a diiodomethyl group, a trifluoromethyl group, a trichloromethyl group, and a tribromomethyl group. Group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group, 2,2,3 , 3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1-trichloromethyl Til group, 2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2,2, 2-trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group, 1 , 1-bis (triiodomethyl) -2,2,2-triiodoethyl group, and the like.

As the halogenated aryl group for R ⁶ , 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl Group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2 -Naphthyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2,6- Chlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group, penta Chlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1-naphthyl group, perchloro-2- Naphtyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromo Phenyl group, 2,4,6-tribromophenyl group, 3,4,5-tribromophenyl group, 2,3,5,6-tetrabromophenyl Phenyl group, pentabromophenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group, 2,3,5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthyl group Perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4-diiodophenyl group, 2,6-diiodophenyl group, 3,4-diiodo Phenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, pentaiodophenyl Group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, periodate 1-naphthyl group, etc. Payodo-2-naphthyl group.

As the (halogenated alkyl) aryl group of R ⁶ , 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (trimethyl) Fluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoromethyl) phenyl group, etc. can give.

Examples of the cyanated aryl group for R ⁶ include a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group.

Examples of the nitrated aryl group for R ⁶ include a 2-nitrophenyl group, a 3-nitrophenyl group, and a 4-nitrophenyl group.

Examples of the hydrocarbyloxycarbonyl group for R ⁶ include an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, and the like. More specifically, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, Examples thereof include an isopropoxycarbonyl group and a phenoxycarbonyl group.

Examples of the halogenated hydrocarbyloxycarbonyl group for R ⁶ include a halogenated alkoxycarbonyl group, a halogenated aralkyloxycarbonyl group, a halogenated aryloxycarbonyl group, and the like, and more specifically, a trifluoromethoxycarbonyl group, And pentafluorophenoxycarbonyl group.

R ⁶ is preferably a halogenated hydrocarbyl group, more preferably a halogenated alkyl group or a halogenated aryl group, still more preferably a fluorinated alkyl group, a fluorinated aryl group, a chlorinated alkyl group or A chlorinated aryl group, particularly preferably a fluorinated alkyl group or a fluorinated aryl group. The fluorinated alkyl group is preferably a fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2 , 2-trifluoro-1-trifluoromethylethyl group or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, more preferably trifluoromethyl group, 2,2 , 2-trifluoro-1-trifluoromethylethyl group or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group. As the fluorinated aryl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2, 3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group or perfluoro-2-naphthyl group More preferably a 3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group or a penta group. Is a Ruorofeniru group. The chlorinated alkyl group is preferably a chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2 -Trichloro-1-trichloromethylethyl group or 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group. The chlorinated aryl group is preferably a 4-chlorophenyl group, a 2,6-dichlorophenyl group, a 3.5-dichlorophenyl group, a 2,4,6-trichlorophenyl group, a 3,4,5-trichlorophenyl group or a pentachlorophenyl group. It is.

T ^{2 in the} general formula (7) is an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or an oxygen atom, more preferably an oxygen atom.

The s of the general formula (7) represents a valence of T ^2, if T ² is an oxygen atom or a sulfur atom, s is 2, if T ² is a nitrogen atom or a phosphorus atom, s is 3 .

R ^{7 in the} general formula (7) represents a hydrocarbyl group or a halogenated hydrocarbyl group. Examples of the hydrocarbyl group of R ⁷ include an alkyl group, an aralkyl group, and an aryl group, and examples thereof include the groups exemplified as the alkyl group, aralkyl group, and aryl group of L. The halogenated hydrocarbyl group R ^7, a halogenated alkyl group, halogenated aralkyl group, halogenated aryl group, and halogenated hydrocarbyl groups, such as (halogenated alkyl) aryl group and the like, the R ⁶ The groups exemplified as the halogenated alkyl group, the halogenated aryl group, and the (halogenated alkyl) aryl group can be exemplified.

R ⁷ is preferably a halogenated hydrocarbyl group, and more preferably a fluorinated hydrocarbyl group.

As the compound represented by the general formula (5) of the component (b1), as a compound in which M ³ is a zinc atom, dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc Dialkyl zinc such as diisobutyl zinc and di-n-hexyl zinc; diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; Methyl zinc, ethyl zinc chloride, n-propyl zinc chloride, isopropyl zinc chloride, n-butyl zinc chloride, isobutyl zinc chloride, n-hexyl zinc chloride, methyl zinc bromide, ethyl zinc bromide, n-propyl zinc bromide, Isopropyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, n-hexyl zinc bromide, yo Alkyl zinc halides such as methyl zinc iodide, ethyl zinc iodide, n-propyl zinc iodide, isopropyl zinc iodide, n-butyl zinc iodide, isobutyl zinc iodide, n-hexyl zinc iodide; zinc fluoride, Examples thereof include zinc halides such as zinc chloride, zinc bromide and zinc iodide.

  The compound represented by the general formula (5) of the component (b1) is preferably dialkyl zinc, more preferably dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc. Diisobutylzinc or di-n-hexylzinc, particularly preferably dimethylzinc or diethylzinc.

  Examples of the compound represented by the general formula (6) of the component (b2) include amines, phosphines, alcohols, thiols, phenols, thiophenols, naphthols, naphthylthiols, and carboxylic acid compounds.

  Examples of the amine include di (fluoromethyl) amine, bis (difluoromethyl) amine, bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3, 3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl ) Amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) Amine, bis (2,4,6-trifluorophenyl) amine, bis (3,4,5-trifluorophenyl) amine, bis (penta Fluorophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine, bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di) (Trifluoromethyl) phenyl) amine, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) Amine, (3-cyanophenyl) amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) amine, bis (1H, 1H-perfluorobutyl) amine, bis (1H, 1H-perfluoropentyl) amine, bis (1H, 1H-per Fluorohexyl) amine, bis (1H, 1H-perfluorooctyl) amine, bis (1H, 1H-perfluorododecyl) amine, bis (1H, 1H-perfluoropentadecyl) amine, bis (1H, 1H-perfluoroeico) Syl) amine and the like. In addition, amines in which the fluoro of these amines is changed to chloro, bromo or iodo can be mentioned.

  Examples of the phosphine include compounds in which the nitrogen atom of the amine is changed to a phosphorus atom. Those phosphines are compounds represented by replacing the amine in the amine with phosphine.

  Examples of the alcohol include fluoromethanol, difluoromethanol, trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoro Fluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1H, 1H-perfluorobutanol, 1H, 1H-perfluoropentanol, 1H, 1H-perfluorohexanol, Examples thereof include 1H, 1H-perfluorooctanol, 1H, 1H-perfluorododecanol, 1H, 1H-perfluoropentadecanol, 1H, 1H-perfluoroeicosanol and the like. Moreover, the alcohol which changed fluoro of these alcohol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of the thiol include compounds in which the oxygen atom of the alcohol is changed to a sulfur atom. Those thiols are compounds represented by substituting the thiols in the alcohol with thiols.

  As phenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,4 , 6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethylphenol 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol and the like. Moreover, the phenol which changed fluoro of these phenol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of the thiophenol include compounds in which the oxygen atom of the phenol is changed to a sulfur atom. Those thiophenols are compounds represented by replacing phenol in the phenol with thiophenol.

  As naphthol, perfluoro-1-naphthol, perfluoro-2-naphthol, 4,5,6,7,8-pentafluoro-2-naphthol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) ) Phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, Examples include 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol. Moreover, the naphthol which changed fluoro of these naphthol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of naphthylthiol include compounds in which the oxygen atom of the naphthol is changed to a sulfur atom. Those naphthols are compounds represented by replacing naphthol in the naphthol with naphthylthiol.

  Examples of the carboxylic acid compound include pentafluorobenzoic acid, perfluoroethanoic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoro. Examples include heptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid.

  The compound represented by the general formula (6) of the component (b2) is preferably an amine, alcohol or phenol compound, and the amine is preferably bis (trifluoromethyl) amine, bis (2,2,2-trimethyl). Fluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (Trifluoromethyl) -2,2,2-trifluoroethyl) amine or bis (pentafluorophenyl) amine, and the alcohol is preferably trifluoromethanol, 2,2,2-trifluoroethanol, 2,2 , 3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanol Is 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, preferably 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol as phenol 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol or 3,4 , 5-tris (trifluoromethyl) phenol.

  More preferably, the compound represented by the general formula (6) of the component (b2) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1 -Trifluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3 , 5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol Or 2,4,6-tris (trifluoromethyl) phenol More preferably 3,5-difluorophenol, 3,4,5-fluorophenol, pentafluorophenol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol.

  Examples of the compound represented by the general formula (7) of the component (b3) include water, hydrogen sulfide, amine, aniline compound and the like.

  Examples of the amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, n-hexylamine, alkylamines such as n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine; benzylamine, (2-methylphenyl) methylamine, (3-methylphenyl) methylamine , (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methylamine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) ) Methylamine, (3, -Dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine, (2,3,4-trimethylphenyl) methylamine, (2,3,5-trimethylphenyl) methylamine, (2,3,6) -Trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2,4,6-trimethylphenyl) methylamine, (2,3,4,5-tetramethylphenyl) methylamine, ( 2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n-propyl) Phenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (s c-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (neopentylphenyl) methylamine, (n-hexylphenyl) methylamine, (n-octylphenyl) methyl Aralkylamines such as amine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthracenylmethylamine; allylamine; cyclopentadienylamine and the like.

  Examples of the amine include fluoromethylamine, difluoromethylamine, trifluoromethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,2- Trifluoro-1-trifluoromethylethylamine, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, Examples thereof include halogenated alkylamines such as perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, and perfluoroeicosylamine. In addition, amines in which the fluoro of these amines is changed to chloro, bromo or iodo can be mentioned.

  Examples of aniline compounds include aniline, naphthylamine, anthracenylamine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2 , 6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4 , 6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline Pentamethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-diethylaniline 2,4-diethylaniline, 2,5-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline, 3,5-diethylaniline, 2,3,4-triethylaniline, 2,3,5 -Triethylaniline, 2,3,6-triethylaniline, 2,4,6-triethylaniline, 3,4,5-triethylaniline, 2,3,4,5-tetraethylaniline, 2,3,4,6- Examples thereof include tetraethylaniline, 2,3,5,6-tetraethylaniline, pentaethylaniline and the like. Moreover, the ethyl of these aniline compounds is n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n -An aniline compound changed to tetradecyl and the like.

  Examples of aniline compounds include 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4, 5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3 , 5-di (trifluoromethyl) aniline, 2,4,6-tri (trifluoromethyl) aniline, 3,4,5-tri (trifluoromethyl) aniline, and the like. Moreover, the aniline compound which changed fluoro of these aniline compounds into chloro, bromo, iodo etc. can be mention | raise | lifted.

  The compound represented by the general formula (7) of the component (b3) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutyl. Amine, n-octylamine, aniline, 2,6-dimethylaniline, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluoro Butylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroanily 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2 -(Trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4,6-tris (trifluoromethyl) aniline or 3,4,5-tris (trifluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine , Perfluoropentadecylamine, 2-fluoroaniline, 3-fur Roaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoro Methyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4, 6-Tris (trifluoromethyl) aniline or 3,4,5-tris (trifluoromethyl) aniline, most preferably water or pentafluoroaniline.

  As the particulate carrier of component (b4), a solvent for preparing a polymerization catalyst or a solid substance insoluble in the polymerization solvent is preferably used, a porous substance is more preferably used, and an inorganic substance or an organic polymer is used. More preferably, inorganic substances are particularly preferably used.

  The particulate carrier of component (b4) is preferably of a uniform particle size, and the volume standard geometric standard deviation of the particle size of the particulate carrier of component (b4) is preferably 2.5 or less. More preferably, it is 2.0 or less, More preferably, it is 1.7 or less.

  Examples of the inorganic substance of the particulate carrier of the component (b4) include inorganic oxides, clays, clay minerals and the like. A plurality of these may be mixed and used.

As the inorganic _{oxide, SiO 2, Al 2 O 3} , MgO, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO 2, SiO 2 -MgO, SiO 2 -Al 2 O 3, SiO _{2 -TiO 2, SiO 2 -V 2} O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO, and, can be mentioned mixtures of two or more of these. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and SiO ₂ (silica) is particularly preferable. The inorganic oxide is a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. Carbonic acid salts such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

  In addition, a hydroxyl group is usually generated and present on the surface of the inorganic oxide, but as the inorganic oxide, modified inorganic oxides in which active hydrogen of the surface hydroxyl group is substituted with various substituents may be used. . Examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane; triarylchlorosilanes such as triphenylchlorosilane; dialkyldichlorosilanes such as dimethyldichlorosilane; diaryldichlorosilanes such as diphenyldichlorosilane. Alkyltrichlorosilanes such as methyltrichlorosilane; aryltrichlorosilanes such as phenyltrichlorosilane; trialkylalkoxysilanes such as trimethylmethoxysilane; triarylalkoxysilanes such as triphenylmethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane; Diaryl dialkoxy silanes such as diphenyldimethoxysilane; alkyltrimethoxy silanes such as methyltrimethoxysilane Coxysilane; aryltrialkoxysilane such as phenyltrimethoxysilane; tetraalkoxysilane such as tetramethoxysilane; alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane; tetrachlorosilane; methanol, ethanol Examples thereof include: alcohols such as phenol; dialkylmagnesium such as dibutylmagnesium, butylethylmagnesium and butyloctylmagnesium; and inorganic oxides contacted with alkyllithium such as butyllithium.

  Furthermore, after contact with a trialkylaluminum, an inorganic oxide contacted with a dialkylamine such as diethylamine and diphenylamine, an alcohol such as methanol and ethanol, or phenol.

  In addition, the strength of the inorganic oxide itself may increase due to hydrogen bonding between hydroxyl groups. In that case, if all the active hydrogens of the surface hydroxyl group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to substitute all the active hydrogens on the surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl groups may be determined as appropriate. The method for changing the substitution rate of the surface hydroxyl group is not particularly limited. As this method, the method of changing the usage-amount of the compound used for a contact can be illustrated, for example.

  Clay or clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophyllite, talc, unmo group, smectite, montmorillonite group, hectorite, laponite, saponite, vermiculite, ryokdeite group, Examples include palygorskite, kaolinite, nacrite, dickite and halloysite. Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

  An inorganic oxide is preferably used as the inorganic substance. The inorganic substance is preferably dried and substantially free of moisture, and is preferably dried by heat treatment. The heat treatment is usually performed at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method of drying by circulating an inert gas (for example, nitrogen or argon) dried during heating at a constant flow rate, a method of heating and depressurizing under reduced pressure, and the like.

The average particle diameter of the inorganic substance is usually 1 to 5000 μm, preferably 5 to 1000 μm, more preferably 10 to 500 μm, and further preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  The organic polymer of the particulate carrier of component (b4) is preferably a polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group.

  As functional groups having active hydrogen, primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group Sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group, carbazolyl group and the like. Preferred are primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group and thiol group. Particularly preferred are a primary amino group, a secondary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  The non-proton-donating Lewis basic functional group is a functional group having a Lewis base moiety that does not have an active hydrogen atom, and includes pyridyl group, N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azide group, -Substituted imino group, N, N-substituted amino group, N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group , Alkoxy groups, alkyloxycarbonyl groups, N, N-substituted carbamoyl groups, thioalkoxy groups, substituted sulfinyl groups, substituted sulfonyl groups, substituted sulfonic acid groups, and the like. Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  In the organic polymer, the content of the functional group having active hydrogen or the non-proton-donating Lewis basic functional group is preferably 0.01 to as the molar amount of the functional group per gram of polymer unit constituting the organic polymer. 50 mmol / g, more preferably 0.1 to 20 mmol / g.

  Examples of the method for producing a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group include, for example, a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and 1 Examples thereof include a method of homopolymerizing a monomer having one or more polymerizable unsaturated groups and a method of copolymerizing the monomer and another monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

  Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group and allyl group; alkynyl groups such as ethyne group and the like.

  Examples of monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, vinyl group-containing hydroxy compounds, and the like. be able to. Specific examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methyl. Amine, 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-butene-1- For example, all.

  Examples of monomers having a functional group having a Lewis base having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, vinyl (N-substituted) indazole and the like. be able to.

  Examples of other monomers having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compound, and cyclic olefin. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene, and dicyclopentadiene. Two or more of these monomers may be used. Preferably, they are ethylene and styrene. Examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

The average particle diameter of the organic polymer is usually 1 to 5000 μm, preferably 5 to 1000 μm, and more preferably 10 to 500 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 50 to 500 m ² / g.

  The organic polymer is preferably dried and substantially free of moisture, and is preferably dried by heat treatment. The temperature of the heat treatment is usually 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method in which a dry inert gas (for example, nitrogen or argon) is circulated and dried at a constant flow rate during heating, a method of heat drying under reduced pressure, and the like.

The promoter component (B) is formed by bringing the component (b1), the component (b2), the component (b3), and the component (b4) into contact with each other. The contact order of the component (b1), the component (b2), the component (b3) and the component (b4)) includes the following order.
<1> The component (b1) and the component (b2) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b4).
<2> The component (b1) and the component (b2) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b3).
<3> The component (b1) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b2), and the contact product resulting from the contact is brought into contact with the component (b4).
<4> The component (b1) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b2).
<5> The component (b1) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b2), and the contact product resulting from the contact is brought into contact with the component (b3).
<6> The component (b1) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b2).
<7> The component (b2) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b4).
<8> The component (b2) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b1).
<9> The component (b2) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b3).
<10> The component (b2) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b1).
<11> The component (b3) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b2).
<12> The component (b3) and the component (b4) are brought into contact with each other, the contact with the contact is brought into contact with the component (b2), and the contact with the contact is brought into contact with the component (b1).

  The contact with the component (b1), the component (b2), the component (b3) and the component (b4) is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Further, a solvent may be used for the contact, and these compounds may be directly contacted without being used.

  When a solvent is used, a component that does not react with the component (b1), the component (b2), the component (b3), the component (b4), and their contacts is used. However, as described above, when each component is contacted step by step, even if the solvent reacts with a component at a certain stage, the solvent does not react with each component at another stage. The solvent can be used in other stages. That is, the solvents in each stage are the same or different from each other. Examples of the solvent include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents; halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, and nitrile solvents. Examples thereof include polar solvents such as solvents, nitro compounds, amine solvents, sulfur compounds and the like. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; dichloromethane, difluoromethane , Halogenated solvents such as chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene Dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran Ether solvents such as tetrahydropyran; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Alcohol solvents such as ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, and glycerin; phenol solvents such as phenol and p-cresol; acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride Carbonyl solvents such as ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; Phosphoric acid derivatives such as oxamethylphosphoric triamide and triethyl phosphate; nitrile solvents such as acetonitrile, propionitrile, succinonitrile and benzonitrile; nitro compounds such as nitromethane and nitrobenzene; amine solvents such as pyridine, piperidine and morpholine; Examples thereof include sulfur compounds such as dimethyl sulfoxide and sulfolane.

  When the contact (c) obtained by contacting the component (b1), the component (b2) and the component (b3) and the component (b4) are contacted, that is, the above <1>, <3>, < In each of the methods 7>, the solvent (s1) for producing the contact product (c) is preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

On the other hand, as the solvent (s2) when the contact product (c) and the component (b4) are contacted, a polar solvent is preferable. As an index representing the polarity of the solvent, E _T ^N value (C.Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag (1988).) And the like are known, 0.8 ≧ A solvent satisfying the range of E _T ^N ≧ 0.1 is particularly preferable.

  Examples of the polar solvent include dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol Cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, Examples thereof include ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide, sulfolane and the like.

  More preferably, the solvent (s2) is dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl). ) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, particularly preferably di-n-butyl ether, methyl- ert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol Most preferred are tetrahydrofuran, methanol, ethanol, 1-propanol, and 2-propanol.

  As the solvent (s2), a mixed solvent of these polar solvents and hydrocarbon solvents can be used. As the hydrocarbon solvent, compounds exemplified as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are used. Examples of the mixed solvent of the polar solvent and the hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane / 2-propanol mixed solvent, heptane / methanol mixed solvent, heptane. / Ethanol mixed solvent, heptane / 1-propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent, xylene / Methanol mixed solvent, xylene / ethanol mixed solvent, xylene / 1-propanol mixed solvent, xylene / 2-propanol mixed solvent and the like. Preferably, hexane / methanol mixed solvent, hexane / ethanol mixed solvent, heptane / methanol mixed solvent, heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent It is. More preferred are a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a toluene / methanol mixed solvent, and a toluene / ethanol mixed solvent. Most preferred is a toluene / ethanol mixed solvent. Moreover, the preferable range of the ethanol fraction in a toluene / ethanol mixed solvent is 10-50 volume%, More preferably, it is 15-30 volume%.

  When the contact (c) formed by bringing the component (b1), the component (b2) and the component (b3) into contact with the component (b4), that is, the above <1>, <3>, In each method of <7>, a hydrocarbon solvent can also be used as the solvent (s1) and the solvent (s2). In this case, after the component (b1), the component (b2) and the component (b3) are contacted, it is preferable that the time until the obtained contact product (c) and the component (b4) are contacted is short. The time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. The temperature at which the contact (c) and the component (b4) are contacted is usually -100 ° C to 40 ° C, preferably -20 ° C to 20 ° C, and most preferably -10 ° C to 10 ° C. It is.

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12> above, both the above nonpolar solvent and polar solvent should be used. Can do. Preferably, it is a nonpolar solvent. This is because a contact product between component (b1) and component (b3) or a contact product between component (b1) and component (b2) and component (b3) is generally non-contact. Since the solubility in the polar solvent is low, when the component (b4) is present in the reaction system when these contact products are formed, the contact product precipitates on the surface of the component (b4) and is more easily immobilized. Because it is considered.

The amount of component (b2) and component (b3) used per mole of component (b1) is preferably satisfied by the following relational expression (V).
| M ³ valence-Mole amount of component (b2) -2 × Mole amount of component (b3) | ≦ 1 (V)
Moreover, the usage-amount of the component (b2) per 1 mol of usage-amount of a component (b1) becomes like this. Preferably it is 0.01-1.99 mol, More preferably, it is 0.1-1.8 mol, Furthermore, Preferably it is 0.2-1.5 mol, Most preferably, it is 0.3-1 mol. Use amount of component (b1) Preferred use amount, more preferred use amount, more preferred use amount, and most preferred use amount of component (b3) per mole are the valence of M ^{3 and} the use of the above component (b1). The amount of component (b2) used per 1 mol of the amount is calculated according to the relational expression (I).

  The amount of component (b1) and component (b2) used is the number of moles of metal atoms in which the metal atom derived from component (b1) contained in promoter component (B) is contained per 1 g of promoter component (B). The amount is preferably 0.1 mmol or more, and more preferably 0.5 to 20 mmol.

  In order to advance the reaction faster, a heating step at a higher temperature may be added after the contact as described above. In the heating step, it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature. In performing the heating step, the solvent used in the contact may be replaced with another solvent having a higher boiling point.

  As a result of such contact, the cocatalyst component (B) may be the raw material component (b1), component (b2), component (b3) and / or component (b4) remaining as an unreacted substance. However, it is preferable to perform a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  Moreover, after such a contact or washing treatment, it is preferable to distill off the solvent from the product, and then to dry under reduced pressure for 1 to 24 hours at a temperature of 0 ° C or higher. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., and particularly preferably 2 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 4 to 18 hours at a temperature of 15 ° C to 160 ° C.

  The total amount of the transition metal compound (A1) and the transition metal compound (A2) used is usually 1 to 10000 μmol / g, preferably 10 to 1000 μmol / g, per 1 g of the promoter component (B). Preferably it is 20-500 micromol / g.

  In the preparation of the polymerization catalyst, the organoaluminum compound (C) may be contacted in addition to the transition metal compound (A1), the transition metal compound (A2) and the promoter component (B). The amount of the organoaluminum compound (C) used is preferably as the number of moles of aluminum atoms in the organoaluminum compound (C) per mole of the total number of moles of the transition metal compound (A1) and the transition metal compound (A2), It is 0.1-1000, More preferably, it is 0.5-500, More preferably, it is 1-100.

  Examples of the organoaluminum compound (C) include trialkylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like. Aluminum: Dialkylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride, etc .; methylaluminum dichloride, ethylaluminum dichloride , N-propylaluminum dichloride, n-butylaluminum dichloride, isobutyl Alkyl aluminum dichloride such as rualuminum dichloride, n-hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-hexylaluminum hydride Dialkylaluminum hydrides such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, alkyl (dialkoxy) aluminum such as methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, methyl ( dialkyl (alkoxy) al such as tert-butoxy) aluminum Aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methyl bis (2,6-diisopropylphenoxy) aluminum, methyl bis (2,6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, dimethyl (2,6- Examples thereof include dialkyl (aryloxy) aluminum such as diisopropylphenoxy) aluminum and dimethyl (2,6-diphenylphenoxy) aluminum. These organoaluminum compounds may be used alone or in combination of two or more.

  The organoaluminum compound (C) is preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. More preferred are triisobutylaluminum and tri-n-octylaluminum.

  In the preparation of the polymerization catalyst, the electron donating compound (D) may be contacted in addition to the transition metal compound (A1), the transition metal compound (A2) and the promoter component (B). The amount of the electron-donating compound (D) used is preferably 0.1 as the number of moles of the electron-donating compound (D) per mole of the total number of moles of the transition metal compound (A1) and the transition metal compound (A2). It is 01-100, More preferably, it is 0.1-50, More preferably, it is 0.25-5.

  Examples of the electron donating compound (D) include triethylamine and trinormaloctylamine.

  The transition metal compound (A1), the transition metal compound (A2), the promoter component (B), and, if necessary, the contact between the organoaluminum compound (C) and the electron donating compound (D) is performed in an inert gas atmosphere. It is preferably carried out below. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 30 minutes to 100 hours. Further, the contact may be carried out in the polymerization reactor with each component being charged separately into the polymerization reaction vessel.

  Examples of the method for producing the ethylene-α-olefin copolymer of the present invention include a method of copolymerizing ethylene and α-olefin by a gas phase polymerization method, a slurry polymerization method, a bulk polymerization method or the like. 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 polymerization catalyst and each catalyst component to the polymerization reaction tank, a method for supplying the catalyst in a moisture-free state using an inert gas such as nitrogen or argon, hydrogen, ethylene, etc. A method of dissolving or diluting and supplying in a solution or slurry state is used.

  In the case of vapor phase polymerization of ethylene and α-olefin, the polymerization temperature is usually less than the temperature at which the ethylene-α-olefin copolymer melts, preferably 0 to 150 ° C, more preferably 30 to 100. ° C. An inert gas may be introduced into the polymerization reaction tank, and hydrogen may be introduced as a molecular weight regulator. Further, an organoaluminum compound (C) and an electron donating compound (D) may be introduced.

  The α-olefin used for the polymerization is propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene. And α-olefins having 3 to 20 carbon atoms such as 4-methyl-1-hexene. These may be used independently and may use 2 or more types together. 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred. Examples of combinations of ethylene and α-olefin include ethylene / 1-butene, ethylene / 1-hexene, ethylene / 4-methyl-1-pentene, ethylene / 1-octene, ethylene / 1-butene / 1-hexene, ethylene / 1 / butene / 4-methyl-1-pentene, ethylene / 1-butene / 1-octene, ethylene / 1-hexene / 1-octene, etc., preferably ethylene / 1-hexene, ethylene / 4-methyl -1-pentene, ethylene / 1-butene / 1-hexene, ethylene / 1-butene / 1-octene, and ethylene / 1-hexene / 1-octene.

  In the copolymerization of ethylene and α-olefin, if necessary, another monomer is introduced into the polymerization reaction vessel, and the other monomer is copolymerized within a range not impairing the effects of the present invention. It may be polymerized. Examples of the other monomers include diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, α, β-unsaturated carboxylic acids, and the like.

  Specific examples thereof include 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2 -Norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene , 1,3-cyclooctadiene, 1,3-cyclohexadiene and other diolefins; cyclopentene, Chlohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclo Hexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene Cyclic olefins such as 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, and 8-cyanotetracyclododecene; Alkenylbenzene such as tylene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butylstyrene, p-second Alkyl styrene such as grade butyl styrene, bisalkenyl benzene such as divinylbenzene, alkenyl aromatic hydrocarbon such as alkenyl naphthalene such as 1-vinylnaphthalene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride Acid, bicyclo (2,2,1) -5-heptene-2, Α, β-unsaturated carboxylic acids such as 3-dicarboxylic acids; metal salts of α, β-unsaturated carboxylic acids such as sodium, potassium, lithium, zinc, magnesium, calcium; methyl acrylate, ethyl acrylate, acrylic acid α such as n-propyl, isopropyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , Β-unsaturated carboxylic acid alkyl esters; unsaturated dicarboxylic acids such as maleic acid and itaconic acid; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. Vinyl ester; acrylic acid Rishijiru, glycidyl methacrylate, and unsaturated carboxylic acid glycidyl ester of itaconic acid monoglycidyl ester.

  As the method for producing the ethylene-α-olefin copolymer of the present invention, a transition metal compound (A1), a transition metal compound (A2), a promoter component (B), and, if necessary, an organoaluminum compound ( A prepolymerized solid component obtained by polymerizing a small amount of olefin (hereinafter referred to as prepolymerization) using C) and an electron donating compound (D) is used as a polymerization catalyst component or a polymerization catalyst. Thus, a method of copolymerizing ethylene and α-olefin is preferable.

  Examples of the olefin used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene and cyclohexene. These can be used alone or in combination of two or more. Preferably, ethylene alone, or a combination of ethylene and α-olefin, more preferably ethylene alone, or at least one α-olefin selected from 1-butene, 1-hexene and 1-octene, and ethylene Is used in combination.

  The content of the prepolymerized polymer in the prepolymerized solid component is preferably 0.01 to 1000 g, more preferably 0.05 to 500 g, and still more preferably, per 1 g of the promoter component (B). 0.1 to 200 g.

  The preliminary polymerization method may be a continuous polymerization method or a batch polymerization method, and examples thereof include a batch type slurry polymerization method, a continuous slurry polymerization method, and a continuous gas phase polymerization method. In a polymerization reaction tank for performing prepolymerization, a transition metal compound (A1), a transition metal compound (A2), a promoter component (B), and, if necessary, an organoaluminum compound (C) and an electron donating compound (D) As a method of charging, normally, an inert gas such as nitrogen or argon, hydrogen, ethylene or the like is used in a moisture-free state, each component is dissolved or diluted in a solvent, and a solution or slurry A method of charging in a state is used.

  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.

  Moreover, when prepolymerization is performed by the slurry polymerization method, as the slurry concentration, the amount of the promoter component (B) per liter of the solvent is usually 0.1 to 600 g, preferably 0.5 to 300 g. . The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed. Moreover, the partial pressure of olefins in the gas phase part during prepolymerization is usually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

  As a method of supplying the prepolymerized prepolymerized solid catalyst component to the polymerization reaction tank, a method of supplying an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in a state free from moisture, each component Is dissolved or diluted in a solvent and supplied in a solution or slurry state.

  You may make a film using the ethylene-alpha-olefin copolymer of this invention contain a well-known additive as needed. Examples of the additive include antioxidants, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, dripping agents, pigments, fillers, and the like.

As a method for producing the film for food packaging of the present invention, components (such as the above-mentioned additives and other resins) further blended into the ethylene-α-olefin copolymer of the present invention as necessary are used as a tumbler blender. After mixing with a Henschel mixer, etc., a method of forming by a known film forming method, or after mixing the above components with a tumbler blender, Henschel mixer, etc., further melt-kneading with a single screw extruder or multi-screw extruder Or a kneaded material obtained by melt-kneading with a kneader or a Banbury mixer, etc., by a known film forming method.

Known film forming methods include, for example, an inflation film forming method, a T-die cast film forming method, and the like, and the T-die film forming method is particularly preferably used. The extrusion temperature is usually 110 to 250 ° C., although it depends on the type of extrusion method used.

  As described above, the ethylene-α-olefin copolymer of the present invention is excellent in molding processability such as extrusion load and take-up property during molding process. Therefore, the neck-in at the time of T-die film molding can also become low. Moreover, the take-up property at the time of extrusion molding is also good. Moreover, since the film obtained using the ethylene-α-olefin copolymer of the present invention or the resin composition containing the copolymer is excellent in mechanical strength, appearance, and cleanliness, it is suitable for food packaging. Is preferred.

  The ethylene-α-olefin copolymer of the present invention can be blended in an appropriate amount with a conventional ethylene polymer for the purpose of improving neck-in of the ethylene polymer inferior to neck-in. For example, by blending the ethylene-α-olefin copolymer of the present invention in an appropriate amount with an ethylene polymer such as linear low-density polyethylene, neck-in can be greatly improved.

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) 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.

(2) 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.

(3) Melt flow rate ratio (MFRR)
In the method defined in JIS K7210-1995, the test load was 211.82N, the melt flow rate (H-MFR) measured at a measurement temperature of 190 ° C., and in the method defined in JIS K7210-1995, the load was 21 The melt flow rate (MFR) measured under the conditions of .18 N and a temperature of 190 ° C. was measured, and a value obtained by dividing H-MFR by MFR was obtained.

(4) Swell ratio (SR)
In the measurement of the melt flow rate in (2), an ethylene-α-olefin copolymer strand extruded at a length of about 15 to 20 mm from an orifice under conditions of a temperature of 190 ° C. and a load of 21.18 N Cooled to obtain a solid strand. Next, the diameter D (unit: mm) of the strand at a position of about 5 mm from the upstream end of extrusion of the strand was measured, and the value obtained by dividing the diameter D by the orifice diameter 2.095 mm (D ₀ ) (D / D ₀ ) was calculated and used as the swell ratio.

(5) Molecular weight distribution (Mw / Mn, Mz / Mw)
Using gel permeation chromatograph (GPC) method, z average molecular weight (Mz), weight average molecular weight (Mw) and number average molecular weight (Mn) are measured under the following conditions (1) to (8). Mw / Mn and Mz / Mw were obtained. 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

(6) Number of branches having 5 or more carbon atoms (N _LCB , unit: 1 / 1000C)
A carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) was measured by the carbon nuclear magnetic resonance method under the following measurement conditions, and determined by the following calculation method.
<Measurement conditions>
Apparatus: AVANCE600 manufactured by Bruker
Measuring solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4
= 75/25 (volume ratio) mixed liquid Measurement temperature: 130 ° C
Measurement method: proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Trimethylsilane Window function: Negative exponential function <Calculation method>
The peak area of the peak having a peak top in the vicinity of 38.22 to 38.27 ppm was determined with the sum of all peaks observed at 5 to 50 ppm being 1000. The peak area of the peak was defined as the area of the signal in the range from the chemical shift of the valley with the adjacent peak on the high magnetic field side to the chemical shift of the valley with the adjacent peak on the low magnetic field side. In the measurement of the ethylene-1-octene copolymer under the present conditions, the position of the peak top of the peak derived from methine carbon to which a branch having 6 carbon atoms was bonded was 38.21 ppm.

(7) Number of short chain branches (N _SCB , unit: 1 / 1000C)
The number of short chain branches in the ethylene-α-olefin copolymer was determined from an infrared absorption spectrum. Measurement and calculation were carried out using characteristic absorption derived from α-olefin according to the method described in the literature (Die Makromoleculare Chemie, 177, 449 (1976) McRae, MA, Madams, WF). The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation).

(8) g *
G * was determined by the formula (II).
[Η] represents the relative viscosity (ηrel) of the ethylene-α-olefin copolymer in 100 ml of tetralin containing 0.5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor, and ethylene-α-olefin. A sample solution was prepared by dissolving 100 mg of the copolymer at 135 ° C., and using a Ubbelohde viscometer, the sample solution and a blank solution composed of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor Calculated from the fall time and determined by the formula (II-I), [η] _GPC is determined by the formula (II-II) from the measurement of the molecular weight distribution of the ethylene-α-olefin copolymer of (5), g _SCB * was determined by the formula (II-III) from the measurement of the number of short chain branches of the ethylene-α-olefin copolymer of (7).

(9) Melt complex viscosity (η *, unit: Pa · sec)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 190 ° C. was measured under the following measurement conditions, and a melt complex viscosity measured at an angular frequency of 100 rad / sec. Asked. The lower the melt complex viscosity, the better the extrusion load during extrusion molding.
<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

(10) Maximum take-up speed (MTV, unit: m / min)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, an ethylene-α-olefin copolymer was melt-extruded from an orifice having a diameter of 2.095 mm and a length of 8 mm at a temperature of 150 ° C. and an extrusion speed of 0.32 g / min. The melted ethylene-α-olefin copolymer was taken up into a filament shape by a take-up roll at a take-up rate of 6.3 (m / min) / min. The take-up speed when the filamentous ethylene-α-olefin copolymer was cut was defined as the maximum take-up speed. The higher this value, the better the take-up property at the time of extrusion molding.

(11) Impact strength (unit: kJ / m ² )
Measurements were made according to ASTM D1822-68.

(12) Characteristic relaxation time (τ) (sec)
Using a viscoelasticity measuring apparatus (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), the 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 manufactured by Rheometrics R. Using 4.4.4, a master curve of the melt complex viscosity-angular frequency curve at 190 ° C. was prepared, and the characteristic relaxation time (τ) was obtained.
<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

(13) Flow activation energy (Ea, unit: kJ / mol)
Using a viscoelasticity measuring apparatus (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), the 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 manufactured by Rheometrics R. Using 4.4.4, a master curve of a melt complex viscosity-angular frequency curve at 190 ° C. was prepared, and activation energy (Ea) was obtained.
<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

(14) Cold xylene soluble part (CXS)
The method specified in §175.520 of Code of federal regulations, Food Drugs Administration, USA was followed.

(15) Melting curve (DSC)
This was measured using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer. An aluminum pan enclosing about 10 mg of sample (1) held at 150 ° C. for 5 minutes, (2) lowered from 150 ° C. to 20 ° C. at 5 ° C./minute, and (3) held at 20 ° C. for 2 minutes, (4) Raise the temperature from 20 ° C. at 5 ° C./minute to the melting end temperature + about 20 ° C. (usually about 150 ° C.), and calculate the number of melting peaks from the differential scanning calorimetry curve obtained in (4) measurement. Asked.

[Physical properties of film]

(16) Transparency: When the film is visually observed and the other side looks beautiful, ○, and when the other side appears blurred due to the roughness of the film surface, ×.

(17) Tensile strength at break (unit: MPa)
From the formed film, the longitudinal direction becomes the take-off direction (MD) and the direction (TD) perpendicular to the MD direction, respectively, according to the sample collection method for tensile cutting load measurement described in JIS K 6781 6.4. A test piece was prepared, and using this test piece, a tensile test was performed under the conditions of 80 mm between chucks, 40 mm between marked lines, and a tensile speed of 500 mm / min, and the tensile breaking strength was obtained. It shows that it is excellent in film strength, so that this value is high.

(18) Tear strength (unit: kN / m)
The Elmendorf tear strength was measured according to the method specified in ASTM D1922-67. The smaller this value, the better the film cutability.

(19) Heat sealability (unit: N / 15mm width)
Two sample films were overlapped, and using a heat sealer manufactured by Tester Sangyo Co., Ltd., sealing temperature: 160 ° C., sealing surface pressure: 0.098 MPa, sealing time: 1 second, sealing width: 10 mm, sealing length Heat sealing was performed under the condition of 15 mm. And using the tensile tester, it pulled so that it might peel in the width direction of a heat seal part at a speed | rate of 200 mm / min, and made the maximum load produced at that time into heat seal strength. The higher this value, the better the heat sealability.

(20) Neck-in (NI) (Unit: mm)
The difference (total value on both sides) between the opening of the die and the resin film of the multilayer film at the time of extrusion was measured under conditions of a molten resin extrusion thickness of 50 μm and a processing speed of 1.5 m / min. The smaller this value, the better the moldability.

(21) Drawdown property (DD) (unit: m / min)
Under the condition that the extrusion amount of the molten resin was 550 g / hr, the winding speed at the time of extrusion was increased, and the winding speed when the resin was cut and could not be wound was measured as drawdown. The higher this value, the better the high speed processability.

(22) Extrusion load (unit: A)
The current value of the extruder at the time of extrusion processing was measured under the conditions of a molten resin extrusion thickness of 50 μm and a processing speed of 1.5 m / min. The smaller this value, the smaller the extrusion load during molding and the better the workability.

Example 1
(1) Preparation of solid catalyst component In a reactor equipped with a nitrogen-replaced stirrer, silica heat-treated at 300 ° C. under nitrogen flow (Sypolol 948 manufactured by Devison; 50% volume average particle size = 55 μm; pore volume = 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 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was kept 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, the supernatant was withdrawn to a residual amount of 16 L at room temperature, 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 catalyst component was obtained by drying.
(2) Polymerization After vacuum drying, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure became 0.03 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.84 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and a concentration adjusted to 0.1 μmol / ml 0.8 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above was added. 38.7 mg of catalyst component was added. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.25 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 182 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 2
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.04 MPa, 200 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 2.21 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.3 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and a concentration adjusted to 0.1 μmol / ml 0.5 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above 16.4 mg of the catalyst component was charged. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.25 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene, and hydrogen were purged to obtain 101 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 3
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.04 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 2.12 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and a concentration adjusted to 0.1 μmol / ml 0.8 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above was added. 29.2 mg of the catalyst component was added. During the polymerization, the polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.27 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 189 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 4
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.04 MPa, 160 ml of 1-hexene and butane as a polymerization solvent. Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 2.52 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and a concentration adjusted to 0.1 μmol / ml 0.8 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above was added. 20.6 mg of catalyst component was added. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.25 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 135 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 5
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.06 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 3.56 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and a concentration adjusted to 0.1 μmol / ml 0.8 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above was added. 23.1 mg of the catalyst component was added. During the polymerization, the polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.29 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene, and hydrogen were purged to obtain 118 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 6
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.04 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 2.41 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.45 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and the concentration adjusted to 0.1 μmol / ml 0.3 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to the transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above. 9.9 mg of catalyst component was charged. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.25 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene, and hydrogen were purged to obtain 124.4 g of an ethylene-1-hexene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

Example 7
(1) Preparation of prepolymerization catalyst component After adding 833 g of butane to an autoclave equipped with a stirrer with an internal volume of 5 liters previously purged with nitrogen, the autoclave was heated to 50 ° C., and then 28 g of ethylene was charged. Stabilized. Next, 57 mg of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] and racemic-ethylenebis (1-indenyl) zirconium in a separate 50 ml flask under nitrogen atmosphere Diphenoxide [corresponding to transition metal compound (A1)] 0.67 g and 4.1 mL of triisobutylaluminum hexane solution having a triisobutylaluminum concentration of 1 mmol / mL as the organoaluminum compound (C) were mixed at 50 ° C. The solution stirred and mixed for 4 hours was put into an autoclave. Subsequently, 10.4 g of the solid catalyst component prepared in Example 1 was added to initiate polymerization. A prepolymerization was carried out at 50 ° C. for 80 minutes while continuously supplying a mixed gas of ethylene and hydrogen having a hydrogen concentration of 0.2%. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was dried at room temperature to obtain a prepolymerized catalyst component containing 17.5 g of polyethylene per 1 g of the solid catalyst component.
(2) Polymerization The inside of a 3 liter autoclave equipped with a stirrer was vacuum-dried after drying under reduced pressure, and hydrogen was added so that the partial pressure became 0.035 MPa, and 180 ml of 1-hexene and 650 g of butane were charged. After raising the temperature to 70 ° C., ethylene was introduced so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 2.15 mol%. To this, 0.9 mL of a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL as the organoaluminum compound (C) was added. Next, 363 mg of the prepolymerized catalyst component obtained in Example 7 (1) was added. During the polymerization, the polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.24 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene, and hydrogen were purged to obtain 128 g of an ethylene-1-hexene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

Example 8
(1) Polymerization After drying under reduced pressure, the inside of a 3 liter autoclave equipped with a stirrer substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.03 MPa, and 120 ml of 1-hexene and 650 g of butane were charged. After raising the temperature to 70 ° C., ethylene was introduced so that the partial pressure became 1.0 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 2.37 mol%. To this, 0.9 mL of a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL as the organoaluminum compound (C) was added. Next, 289 mg of the prepolymerized catalyst component obtained in Example 7 (1) was charged. The polymerization was carried out at 70 ° C. for 120 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.24 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 79 g of an ethylene-1-hexene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

Example 9
(1) Preparation of prepolymerization catalyst component After adding 836 g of butane to an autoclave equipped with a stirrer with an internal volume of 5 liters previously purged with nitrogen, the autoclave was heated to 50 ° C. and then charged with 28 g of ethylene. Stabilized. Next, 0.25 g of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] in a 50 ml flask under a nitrogen atmosphere, and racemic-ethylenebis (1-indenyl) ) 0.52 g of zirconium diphenoxide [corresponding to transition metal compound (A1)] and 4.3 mL of a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL are mixed and stirred at 50 ° C. for 4 hours. The solution was put into an autoclave. Thereafter, 10.3 g of the solid catalyst component obtained in Example 1 (1) was added to initiate polymerization. While continuously supplying a mixed gas of ethylene and hydrogen having a hydrogen concentration of 0.2%, prepolymerization was performed at 50 ° C. for 100 minutes. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was dried at room temperature to obtain a prepolymerized catalyst component containing 15.9 g of polyethylene per 1 g of the solid catalyst component.
(2) Polymerization After drying under reduced pressure, the inside of a 3 liter autoclave equipped with a stirrer substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.08 MPa, 180 ml of 1-hexene and 650 g of butane were charged. After raising the temperature to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 4.73 mol%. To this, 0.9 mL of a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL as the organoaluminum compound (C) was added. Next, 333 mg of the prepolymerized catalyst component obtained in Example 9 (1) was added. The polymerization was carried out at 70 ° C. for 120 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.33 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 78 g of an ethylene-1-hexene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

Example 10
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.035 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.9 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.613 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and diphenyl adjusted to a concentration of 1 μmol / ml 0.1 ml of a toluene solution of methylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component obtained in Example 1 (1) above. 21 mg was charged. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.26 mol%). Thereafter, butane, ethylene, and hydrogen were purged to obtain 214 g of an ethylene-1-hexene copolymer. The same polymerization operation was repeated a total of 4 times to melt-knead all the obtained copolymers. In the melt-kneading, a polymer sample weighed so that the total weight of the four copolymers is about 30 g so that the ratio of the obtained polymer yields is 150 ° C. with a biaxial roll in different directions. The blending process for 5 minutes was carried out until there were no copolymer samples. The physical properties of the obtained roll kneaded material are shown in Table 2.

Comparative Example 1
(1) Preparation of solid catalyst component (S) Silica (Sypolol 948, manufactured by Devison Corp .; average particle diameter = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 9.68 kg was added. After adding 100 liters of toluene, it was cooled to 2 ° C. To this, 26.3 liters of a toluene solution of methylalumoxane (2.9M) was added dropwise over 1 hour. After stirring at 5 ° C. for 30 minutes, the mixture was heated to 95 ° C. over 90 minutes and stirred for 4 hours. After cooling to 40 ° C., the mixture was allowed to stand for 40 minutes to allow the solid component to settle, and the upper slurry portion was removed. As a washing operation, 100 liters of toluene was added thereto, and the mixture was stirred for 10 minutes. Then, the stirring was stopped and the mixture was allowed to stand to settle the solid component. Similarly, the upper slurry portion was removed. The above washing operation was repeated 3 times in total. Furthermore, after adding 100 liters of toluene and stirring, it filtered simultaneously with stopping stirring. After repeating this operation once more, 110 liters of hexane was added, and filtration was performed in the same manner. This operation was repeated once more. Then, 12.6 kg of solid catalyst components were obtained by performing drying at 70 degreeC under nitrogen distribution for 7 hours. As a result of elemental analysis, it was Al = 4.4 mmol / g.

(2) Preparation of slurry catalyst component (Cat-1) 200 mg of the solid catalyst component (S) prepared in (1) above was added to a nitrogen-substituted 100 ml glass flask. Next, 12.5 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and diphenyl adjusted to a concentration of 2 μmol / ml 1 ml of a toluene solution of methylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added and reacted at room temperature for 5 minutes. Thereafter, the supernatant was removed by decantation and then washed twice with hexane to obtain 6 ml of hexane slurry.

(3) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, charged with 180 ml of 1-hexene and 650 g of butane as a polymerization solvent, and heated to 70 ° C. Thereafter, an ethylene / hydrogen mixed gas (hydrogen = 0.33 mol%) was added so that the partial pressure of the mixed gas was 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.15 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 6 ml of the slurry-like catalyst component (Cat-1) prepared in the above (2) was charged. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.33 mol%). Thereafter, butane, ethylene, and hydrogen were purged to obtain 71 g of an ethylene-1-hexene copolymer. Table 3 shows the physical properties of the obtained copolymer.

Comparative Example 2
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, charged with 180 ml of 1-hexene and 650 g of butane as a polymerization solvent, and heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 6 ml of a slurry catalyst component (Cat-1) prepared under the same conditions as in Comparative Example 1 (2) was added. During the polymerization, polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.23 mol%). Thereafter, butane, ethylene, and hydrogen were purged to obtain 123 g of an ethylene-1-hexene copolymer. Table 3 shows the physical properties of the obtained copolymer.

Example 11
(1) Granulation Using a 15 mmφ single screw extruder (manufactured by S. Labo), the ethylene-α-olefin copolymer obtained in Example 10 was used under the conditions of an extruder setting temperature of 170 ° C. and an extrusion rate of 80 g / hr. The polymer was granulated. Hereinafter, the granulated ethylene-α-olefin copolymer of Example 10 is referred to as ethylene-based resin (A1).

(2) T-die film forming An extruder equipped with a 150-mm wide T-die (straight manifold) was used at the tip of a 15 mmφ single-screw extruder manufactured by Landcastle.
A T-die cast film forming apparatus in which a cooling roll made by Landcastle Co., Ltd. and a winding apparatus are arranged in the extrusion apparatus is installed, and the A1 pellets obtained above are processed under conditions of 230 ° C. and an air gap of 30 mm to obtain a thickness. A 50 micron monolayer film was obtained. Table 6 shows the physical property evaluation results of the obtained film.

Example 12
(1) The inside of an autoclave with a stirrer having an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, hydrogen was added so that the partial pressure became 0.03 MPa, 170 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.7 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.250 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and the concentration adjusted to 0.1 μmol / ml 0.4 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to the transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above. 34 mg of the catalyst component was added. During the polymerization, polymerization was carried out at 70 ° C. for 120 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.19 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 235 g of an ethylene-1-hexene copolymer (hereinafter referred to as A2). Table 4 shows the physical properties of the obtained copolymer.

(2) Granulation Using the above-obtained ethylene-α-olefin copolymer, a 15 mmφ single-screw extruder (manufactured by S. Labo), conditions of an extruder set temperature of 170 ° C. and an extrusion rate of 80 g / hr To obtain A2 pellets.

(3) T-die film formation An extruder equipped with a 150-mm wide T-die (straight manifold) was used at the tip of a 15 mmφ single-screw extruder manufactured by Landcastle.
A T-die cast film forming apparatus in which a cooling roll manufactured by Landcastle Co., Ltd. and a winding apparatus are arranged in the extrusion apparatus is installed, and the A2 pellets obtained above are processed under conditions of 230 ° C. and an air gap of 30 mm to obtain a thickness. A 50μ monolayer film was obtained. Table 6 shows the physical property evaluation results of the obtained film.

Example 13
(1) The inside of an autoclave with a stirrer having an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, hydrogen was added so that the partial pressure became 0.075 MPa, 170 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 4.2 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.450 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and diphenyl adjusted to a concentration of 1 μmol / ml 0.45 ml of a toluene solution of methylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component obtained in Example 1 (1) above. 39 mg was charged. During the polymerization, polymerization was carried out at 70 ° C. for 90 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.39 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 212 g of an ethylene-1-hexene copolymer (hereinafter referred to as A3). Table 4 shows the physical properties of the obtained copolymer.

(2) Granulation Using the above-obtained ethylene-α-olefin copolymer, a 15 mmφ single-screw extruder (manufactured by S. Labo), conditions of an extruder set temperature of 170 ° C. and an extrusion rate of 80 g / hr To obtain A3 pellets.

(3) T-die film formation An extruder equipped with a 150-mm wide T-die (straight manifold) was used at the tip of a 15 mmφ single-screw extruder manufactured by Landcastle.
A T-die cast film forming apparatus in which a cooling roll made by Landcastle Co., Ltd. and a winding apparatus are arranged in the extrusion apparatus is installed, and the A3 pellets obtained above are processed under the conditions of 230 ° C. and an air gap of 30 mm to obtain a thickness. A 50 micron monolayer film was obtained. Table 6 shows the physical property evaluation results of the obtained film.

Example 15
(1) The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, hydrogen was added so that the partial pressure was 0.095 MPa, 160 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 4.7 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.40 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] having a concentration adjusted to 2 μmol / ml, and diphenyl having a concentration adjusted to 1 μmol / ml 0.80 ml of a toluene solution of methylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component obtained in Example 1 (1) above 50 mg was added. During the polymerization, polymerization was carried out at 70 ° C. for 90 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.48 mol%). Then, butane, ethylene, and hydrogen were purged to obtain 191 g of an ethylene-1-hexene copolymer (hereinafter referred to as A5). Table 3 shows the physical properties of the obtained copolymer.

(2) Granulation Using the above-obtained ethylene-α-olefin copolymer, a 15 mmφ single-screw extruder (manufactured by S. Labo), conditions of a set temperature of the extruder of 170 ° C. and an extrusion rate of 80 g / hr To obtain A5 pellets.

(3) T-die film formation An extruder equipped with a 150-mm wide T-die (straight manifold) was used at the tip of a 15 mmφ single-screw extruder manufactured by Landcastle.
A T-die cast film forming apparatus in which a cooling roll made by Landcastle Co., Ltd. and a winding apparatus are arranged in the extrusion apparatus is installed, and the A5 pellet obtained above is processed under the conditions of 230 ° C. and an air gap of 30 mm to obtain a thickness. A 50 micron monolayer film was obtained. Table 6 shows the physical property evaluation results of the obtained film.

Comparative Example 3
(1) The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, hydrogen was added so that the partial pressure was 0.070 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 3.9 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.30 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and diphenyl adjusted to a concentration of 1 μmol / ml 0.30 ml of a toluene solution of methylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component obtained in Example 1 (1) above 28 mg was charged. During the polymerization, polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.31 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 202 g of an ethylene-1-hexene copolymer (hereinafter referred to as B1). The physical properties of the obtained copolymer are shown in Table 5.

(2) Granulation Using the above-obtained ethylene-α-olefin copolymer, a 15 mmφ single-screw extruder (manufactured by S. Labo), conditions of a set temperature of the extruder of 170 ° C. and an extrusion rate of 80 g / hr To obtain pellets of B1.

(3) T-die film formation An extruder equipped with a 150-mm wide T-die (straight manifold) was used at the tip of a 15 mmφ single-screw extruder manufactured by Landcastle.
A T-die cast film forming apparatus in which a cooling roll made by Landcastle Co., Ltd. and a take-up apparatus are arranged in the extrusion apparatus is installed. A 50 micron monolayer film was obtained. Table 7 shows the physical property evaluation results of the obtained film.

Comparative Example 4
In the T-die film processing, the same procedure as in Example 11 was conducted except that ethylene resin (B2) (linear low density polyethylene, physical property values are shown in Table 5) was used instead of ethylene resin (A1). Went to. Table 7 shows the physical property evaluation results of the obtained film.

Comparative Example 5
In T-die film processing, the same procedure as in Example 11 was performed except that ethylene resin (B3) (high-pressure method low-density polyethylene, physical property values are shown in Table 5) was used instead of ethylene resin (A1). went. Table 7 shows the physical property evaluation results of the obtained film.

Claims (4)

It has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, has a density (d) of 860 to 950 kg / m ³ , and a melt flow rate (MFR) of 1 to 1. 100 g / 10 min, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4 to 30, and the Z average molecular weight (Mz) and the weight average molecular weight (Mw) The ratio (Mz / Mw) is 2 to 5, the swell ratio (SR) is 1.7 or more, the characteristic relaxation time (τ) determined by linear viscoelasticity measurement is 0.01 to 10 seconds, and the differential An ethylene-α-olefin copolymer for film having a single melting peak observed by a scanning calorimeter (DSC). ^The ethylene-α-olefin copolymer for film according to claim 1, wherein the number of branches having 5 or more carbon atoms (N _LCB ) measured by ¹³ C-NMR is 0.1 or more per 1000 carbon atoms.   A film comprising the ethylene-α-olefin copolymer according to claim 1 or 2 or a resin composition containing the copolymer.   The film according to claim 3, which is for food packaging.