JP5392015B2 - Ethylene-α-olefin copolymer and molded product - Google Patents

Description

  The present invention relates to an ethylene-α-olefin copolymer and a molded body obtained by extruding the ethylene-α-olefin copolymer.

  For films, sheets, containers and the like used for packaging foods, pharmaceuticals, daily necessities, etc., many molded products obtained by extrusion-molding an ethylene-α-olefin copolymer are used. As such an ethylene-α-olefin copolymer, the melt tension and the melt flow rate satisfy a specific relationship, and the maximum peak temperature and density in the endothermic curve measured by a differential scanning calorimeter satisfy the specific relationship. An ethylene-1-butene copolymer (see, for example, Patent Document 1), the flow activation energy is 50 kJ / mol or more, and the melt flow rate, density, and cold xylene soluble part ratio satisfy a specific relationship. An ethylene-1-hexene copolymer (for example, see Patent Document 2) having a heat of fusion of a cold xylene soluble part of 30 J / g or more is known. Patent Document 1 describes that it is an ethylene-α-olefin copolymer having excellent melt tension and a narrow composition distribution, and Patent Document 2 describes the extrusion processability and the blocking resistance of the extruded product. It is described that the ethylene-α-olefin copolymer is excellent in balance.

JP-A-4-213309 JP 2005-97481 A

However, although the above-mentioned ethylene-α-olefin copolymer has improved mechanical strength and moldability, the level of moldability is not sufficient, and it is desired to further improve the moldability. It was.
Under such circumstances, the problem to be solved by the present invention is an ethylene-α-olefin copolymer having a short relaxation time, a high melt tension, and a small neck-in, and an extrusion molding of the copolymer. An object of the present invention is to provide a molded product and an olefin polymerization catalyst that can be used for producing the ethylene-α-olefin copolymer.

That is, the first of the present invention has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and a melt flow rate (MFR) of 0.1 to 100 g / 10 minutes, the density (d) is 850 to 940 kg / m ³ , the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 12, and the following formula ( It relates to an ethylene-α-olefin copolymer having a g * defined by I) of 0.50 to 0.75.
g * = [η] / ([η] _GPC × g _SCB *) (I)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is defined by the following formula (II). [Η] _GPC was defined by the following formula (I-II). g _SCB * is defined by the following formula (I-III).
[Η] = 23.3 × log (ηrel) (II)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (I-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (I-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.)]

  The second of the present invention relates to a molded product obtained by extrusion molding of the ethylene-α-olefin copolymer.

［式中、Ｒ¹及びＲ^３は、それぞれ独立して、置換されていてもよい炭素原子数６〜２０のアリール基を表し、Ｒ^２及びＲ^４は、それぞれ独立して、水素原子、又は置換されていてもよい炭素原子数１〜２０のハイドロカルビル基を表す。ａ及びｂは、それぞれ独立して、０〜４の整数を表し、かつ、ａ及びｂのうち少なくとも１つは１以上の整数を表す。Ｒ^１〜Ｒ^４がそれぞれ複数ある場合は、複数のＲ^１〜Ｒ^４はそれぞれ互いに同じであっても異なっていてもよい。Ｘ^１は、水素原子、ハロゲン原子、置換されていてもよい炭素原子数１〜２０のハイドロカルビル基、置換されていてもよい炭素原子数１〜２０のハイドロカルビルオキシ基、炭素原子数１〜２０の置換シリル基、又は炭素原子数１〜２０の置換アミノ基を表し、２つのＸ¹は互いに同じであっても異なっていてもよい。ｍは１〜５の整数を表し、Ｊは炭素原子、又はケイ素原子を表し、Ｊが複数ある場合は、複数のＪは互いに同じであっても異なっていてもよく、Ｒ^５は、水素原子、又は置換されていてもよい炭素原子数１〜２０のハイドロカルビル基を表し、複数のＲ^５は互いに同じであっても異なっていてもよい。］
成分（Ｂ）：下記成分（ａ）、下記成分（ｂ）、下記成分（ｃ）及び下記成分（ｄ）を接触させて形成される固体触媒成分
成分（ａ）：下記一般式（２）で表される化合物
ＺｎＬ_２ （２）
成分（ｂ）：下記一般式（３）で表される化合物

成分（ｃ）：Ｈ_２Ｏ
成分（ｄ）：ＳｉＯ_２
［式中、Ｌは、置換されていてもよい炭素原子数１〜２０のハイドロカルビル基を表し、２つのＬは互いに同じであっても異なっていてもよい。Ｒ^６は、電子吸引性基又は電子吸引性基を含有する基を表し、ｃは１〜５の整数を表し、Ｒ^６が複数ある場合は、複数のＲ^６は互いに同じであっても異なっていてもよい。］
成分（Ｃ）：有機アルミニウム化合物 The third aspect of the present invention relates to an olefin polymerization catalyst formed by contacting the following component (A), the following component (B), and the following component (C).
Component (A): Transition metal compound represented by the following general formula (1)

[Wherein, R ¹ and R ³ each independently represent an optionally substituted aryl group having 6 to 20 carbon atoms, and R ² and R ⁴ each independently represent a hydrogen atom, or It represents an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms. a and b each independently represent an integer of 0 to 4, and at least one of a and b represents an integer of 1 or more. If R ¹ to R ⁴ have multiple respectively, a plurality of ^R 1 to R ⁴ may be different from each other be the same as each other. X ¹ is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, an optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms, or the number of carbon atoms. It represents a substituted silyl group having 1 to 20 carbon atoms or a substituted amino group having 1 to 20 carbon atoms, and two X ^{1 s} may be the same or different from each other. m represents an integer of 1 to 5, J represents a carbon atom or a silicon atom, and when there are a plurality of J, the plurality of J may be the same or different from each other, and R ⁵ represents a hydrogen atom. Or an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and a plurality of R ⁵ may be the same or different from each other. ]
Component (B): Solid catalyst component formed by contacting the following component (a), the following component (b), the following component (c) and the following component (d): Component (a): in the following general formula (2) Compound represented: ZnL ₂ (2)
Component (b): Compound represented by the following general formula (3)

Component (c): H ₂ O
Component (d): SiO ₂
[Wherein L represents an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and two L may be the same or different from each other. R ⁶ represents a group containing an electron withdrawing group or an electron withdrawing group, c is an integer of 1 to 5, if R ⁶ have more than one plurality of R ⁶ are different and are the same as each other It may be. ]
Component (C): Organoaluminum compound

  According to the present invention, it is possible to provide an ethylene-α-olefin copolymer having a short relaxation time, a high melt tension, and a small neck-in, and a molded body obtained by extruding the copolymer.

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

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

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

  The ethylene-α-olefin copolymer of the present invention is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 4 to 20 carbon atoms, more preferably. Is a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 5 to 20 carbon atoms, more preferably a monomer unit based on ethylene and 6 carbon atoms. It is a copolymer having a monomer unit based on α-olefin of ˜8. When the α-olefin to be copolymerized with a monomer unit based on ethylene has a small number of carbon atoms, even if a large amount of α-olefin is copolymerized, the density does not decrease and the sticky component may increase. The amount of the sticky component can be quantified by, for example, measuring a cold xylene soluble part ratio (CXS).

  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 melt flow rate (hereinafter sometimes referred to as “MFR”) of the ethylene-α-olefin copolymer of the present invention is 0.1 to 100 g / 10 min. The melt flow rate is preferably 0.2 g / 10 min or more from the viewpoint of improving the molding processability, particularly from the viewpoint of reducing the extrusion load. Further, from the viewpoint of increasing the melt tension and the mechanical strength of the resulting molded article, it is preferably 50 g / 10 minutes or less, more preferably 30 g / 10 minutes or less, and even more preferably 20 g / 10 minutes or less. The melt flow rate is a value measured by Method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. In the measurement of the melt flow rate, usually, an ethylene-α-olefin copolymer previously blended with about 1000 ppm of an antioxidant is used. 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. When the hydrogen concentration or the polymerization temperature is increased, the ethylene-α-olefin copolymer is changed. The melt flow rate of the copolymer is increased.

The density of the ethylene-α-olefin copolymer of the present invention (hereinafter sometimes referred to as “d”) is 850 to 940 kg / m ³ , and the impact strength of the mechanical strength of the obtained molded product is shown. From the viewpoint of increasing, it is preferably 930 kg / m ³ or less. From the viewpoint of enhancing among tensile strength of mechanical strength of the resulting molded product, it 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 Is 900 kg / m ³ or more. The density is measured according to the 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 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 sometimes referred to as “Mw / Mn”) is 2-12. If Mw / Mn is too small, the extrusion load at the time of molding may increase. Mw / Mn is preferably 2.5 or more, more preferably 3 or more, still more preferably 3.5 or more, still more preferably 4 or more, and most preferably 5 or more. If Mw / Mn is too large, the mechanical strength of the resulting molded product may be reduced, or low molecular weight components that cause stickiness of the molded product may increase. The amount of the sticky component can be quantified by measuring a cold xylene soluble part ratio (CXS) or the like. Mw / Mn is preferably 10 or less, more preferably 8 or less, and even more preferably 6.5 or less. The molecular weight distribution can be controlled by adjusting various polymerization conditions. For example, the molecular weight distribution can be controlled by changing the polymerization temperature. In addition, the molecular weight distribution can also be controlled by adjusting the hydrogen concentration in the feed gas to adjust the difference between the in-system hydrogen concentration at the start of the polymerization and the in-system hydrogen concentration at the end of the polymerization.

Mw / Mn is a value (Mw / Mn) obtained by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and dividing Mw by Mn. . Moreover, as measurement conditions by GPC method, the following conditions can be mention | raise | lifted, for example.
(1) Equipment: Waters 150C manufactured by Waters
(2) Separation column: TOSOH TSKgelGMH6-HT
(3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refractometer
(8) Molecular weight reference material: Standard polystyrene

G * defined by the following formula (I) of the ethylene-α-olefin copolymer of the present invention is 0.50 to 0.75 (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 *) (I)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is defined by the following formula (II). [Η] _GPC was defined by the following formula (I-II). g _SCB * is defined by the following formula (I-III).
[Η] = 23.3 × log (ηrel) (II)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (I-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (I-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 * produced by introducing short chain branching into the ethylene-α-olefin copolymer.
As the formula (I-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 determined by adding 100 mg of an ethylene-α-olefin copolymer at 135 ° C. to 100 ml of a tetralin solution containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor. A sample solution is prepared by dissolution, and is calculated from the falling time of the sample solution and a blank solution made of a tetralin solution 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。ここで分子量Ｍ_μの分子数をｎ_μとする。 The viscosity-average molecular weight (Mv) of the ethylene-α-olefin copolymer is the following formula (I-IV)

And a = 0.725. Here, the number of molecules having a molecular weight M _μ is defined as n _μ .

For A in formula (I-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 molecules in a solution caused by long chain branching. When the amount of long chain branching is large, the contraction of molecular chains increases and g * decreases. The g * of the ethylene-α-olefin copolymer is preferably 0.73 or less, more preferably from the viewpoint of imparting sufficient processing characteristics, particularly strain hardening characteristics, while having a short relaxation time. 70 or less. When g * is large, long chain branching is not sufficiently contained, so that sufficient strain hardening characteristics cannot be obtained. In addition, g * is large and strain hardening characteristics can be obtained, but in this case, it is necessary to increase the length of the long-chain branched chain, so that only a polymer having a long relaxation time can be obtained. I can't. Further, g * of the ethylene-α-olefin copolymer is preferably 0.55 or more from the viewpoint of improving mechanical strength. If g * is too small, the molecular chain spread when the crystal is formed is too small, so the probability of tie molecule formation decreases and the strength decreases. g * can be controlled by adjusting the polymerization temperature after selecting a transition metal compound as described later. If the polymerization temperature is increased, g * tends to be a large value.

The swell ratio of the ethylene-α-olefin copolymer of the present invention (hereinafter sometimes referred to as “SR”) is preferably 1.55 or more from the viewpoint of reducing the neck-in of the T-die film molding. Yes, more preferably 1.6 or more, still more preferably 1.65 or more, particularly preferably 1.7 or more. The swell ratio is preferably 2.5 or less, more preferably 2.1 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. A value (D / D ₀ ) divided by 095 mm (D ₀ ). Further, the swell ratio can be changed by, for example, the hydrogen concentration or the electron donating compound concentration in the production method described later.

  The melt flow rate ratio of the ethylene-α-olefin copolymer of the present invention (hereinafter sometimes referred to as “MFRR”) is preferably 30 or more from the viewpoint of further reducing the extrusion load during molding. Yes, more preferably 40 or more, still more preferably 50 or more, and most preferably 70 or more. Moreover, from a viewpoint which raises the mechanical strength of the molded object obtained more, Preferably it is 300 or less, More preferably, it is 250 or less, More preferably, it is 200 or less, Most preferably, it is 100 or less. The MFRR is a melt flow rate (hereinafter sometimes referred to as “H-MFR”) measured under conditions of a load of 211.82 N and a temperature of 190 ° C. in the method defined in JIS K7210-1995. In the method defined in JIS K7210-1995, it is a value divided by the melt flow rate (MFR) measured under conditions of a load of 21.18 N and a temperature of 190 ° C. In addition, MFRR can be changed by, for example, the hydrogen concentration in the production method described later. When the hydrogen concentration is increased, the MFRR of the ethylene-α-olefin copolymer is decreased.

The ethylene-α-olefin copolymer of the present invention preferably has a branch of a hexyl group or more from the viewpoint of increasing the melt tension and enhancing the stability of the bubble, and suppressing the neck-in during molding, The number of long chain branches (hereinafter sometimes referred to as “N _LCB ”) measured by NMR is preferably 0.3 or more. Further, from the viewpoint of increasing the mechanical strength of the molded body, it is preferably 1.0 or less, more preferably 0.7 or less, and most preferably 0.5 or less. An ethylene-α-olefin copolymer having a preferred range of N _LCB can be obtained by selecting a transition metal compound as described later and appropriately controlling the polymerization conditions such as polymerization temperature, polymerization pressure, and comonomer species. it can.

N _LCB has a carbon atom number of 5 or more, assuming that the total area of all peaks observed at 5 to 50 ppm is 1000 from a ¹³ C-NMR spectrum measured by a carbon nuclear magnetic resonance ( ¹³ C-NMR) method. It is obtained by determining the area of the peak derived from the methine carbon to which the branch is bonded. The peak derived from methine carbon to which a branch having 5 or more carbon atoms is bonded is around 38.2 ppm (Reference: Scientific Document “Macromolecules”, (USA), American Chemical Society, 1999, Vol. 32, p. 3817-3819 ). Since the position of the peak derived from methine carbon to which a branch having 5 or more carbon atoms is bonded may vary depending on the measuring device and the measuring conditions, the standard is usually measured for each measuring device and measuring conditions. decide. In the spectrum analysis, it is preferable to use a negative exponential function as the window function.

  The activation energy of the flow of the ethylene-α-olefin copolymer (hereinafter sometimes referred to as “Ea”) is preferably 55 kJ / mol or more from the viewpoint of further reducing the extrusion load during the molding process. Yes, more preferably 60 kJ / mol or more. In addition, the activation energy of the flow is preferably 150 kJ / mol or less, more preferably 130 kJ / mol or less, still more preferably 110 kJ / mol or less, from the viewpoint of improving the take-up property at the time of extrusion molding. Even more preferably, it is 90 kJ / mol, and most preferably 80 kJ / mol or less.

The activation energy (Ea) of the flow is dependent on the angular frequency (unit: rad / sec) dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. based on the temperature-time superposition principle. It is a numerical value calculated by the Arrhenius type equation from the shift factor (a _T ) when creating the master curve shown, and is a value obtained by the method shown below. That is, the melt complex viscosity-angular frequency curve of the olefin polymer 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 angular frequency) Is rad / sec.) For each melt complex viscosity-angular frequency curve at each temperature (T) based on the temperature-time superposition principle, the melt complex viscosity-angle of the olefin polymer at 190 ° C. seek shift factor (a _T) at each temperature (T) obtained when superimposed on the frequency curve, and each of the temperature (T), from a shift factor (a _T) at each temperature (T), A linear approximate expression (formula (II) 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 (III).
ln (a _T ) = m (1 / (T + 273.16)) + n (II)
Ea = | 0.008314 × m | (III)
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 (II) Formula by the least squares method from the value of four points | pieces, 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is usually 0.99 or more.

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

The elongational viscosity nonlinear index k representing the strain hardening strength of the ethylene-α-olefin copolymer of the present invention is preferably greater than 0.4, more preferably greater than 0.5, and even more preferably 0. .6, even more preferably greater than 0.7, and most preferably greater than 0.8. When k is small, it means that sufficient strain hardening is not exhibited, and processing may be inferior in various moldings. Further, the extensional viscosity nonlinear index k is preferably smaller than 1.4. If k is too large, melt elasticity is too strong, and it is expected that it will be difficult to mold into a desired shape.

The elongational viscosity nonlinearity index k is the viscosity-time curve σ ₁ (t) of the molten resin when uniaxially stretched at a temperature of 130 ° C. and a strain rate of 1 s ⁻¹ at Hencky strain, and is 0 at 130 ° C. and Hencky strain. Curve α (t) = σ ₁ (t) / σ _0.1 (t obtained by dividing by the viscosity-time curve σ _0.1 (t) of the molten resin when uniaxially stretched at a strain rate of ^{1 s −1} (5)
On the other hand, t is a value calculated as the slope of lnα (t) between 1.2 seconds and 1.5 seconds.

  The measurement of the viscosity-time curve σ (t) of the molten resin is performed using a viscoelasticity measuring apparatus (for example, ARES manufactured by TA Instruments). Note that the measurement is performed in a nitrogen atmosphere.

  The ethylene-α-olefin copolymer of the present invention has a plurality of melting peaks present 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. It is an existing copolymer. The presence of a plurality of melting peaks means that there are many melting peaks different from the maximum melting peak (melting peak with the highest peak height) in the melting curve of the ethylene-α-olefin copolymer. Yes, it means that the composition distribution of the ethylene-α-olefin copolymer (distribution of the content ratio of the monomer units among the polymer components contained in the ethylene-α-olefin copolymer) is wide. When the number of melting peaks is large, the temperature range at which the resin can be heat-sealed tends to be wide when compared with resins having the same density. When a transition metal compound described later is used, a copolymer having a plurality of melting peaks can be obtained by using a transition metal compound including both a meso form and a racemic form.

  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 by measuring from (4) by raising the temperature from 0 ° C to the melting end temperature + about 20 ° C (usually about 150 ° C).

  As the method for producing the ethylene-α-olefin copolymer of the present invention, in the presence of a polymerization catalyst formed by contacting the following component (A), the following component (B), and the following component (C), ethylene and A method of copolymerizing with an α-olefin can be mentioned.

［式中、Ｒ¹及びＲ^３は、それぞれ独立して、置換されていてもよい炭素原子数６〜２０のアリール基を表し、Ｒ^２及びＲ^４は、それぞれ独立して、水素原子、又は置換されていてもよい炭素原子数１〜２０のハイドロカルビル基を表し、ａ及びｂは、それぞれ独立して、０〜４の整数を表し、かつ、ａ及びｂのうち少なくとも１つは１以上の整数を表し、Ｒ^１〜Ｒ^４がそれぞれ複数ある場合は、複数のＲ^１〜Ｒ^４はそれぞれ互いに同じであっても異なっていてもよく、Ｘ^１は、水素原子、ハロゲン原子、置換されていてもよい炭素原子数１〜２０のハイドロカルビル基、置換されていてもよい炭素原子数１〜２０のハイドロカルビルオキシ基、炭素原子数１〜２０の置換シリル基、又は炭素原子数１〜２０の置換アミノ基を表し、２つのＸ¹は互いに同じであっても異なっていてもよく、ｍは１〜５の整数を表し、Ｊは炭素原子、又はケイ素原子を表し、Ｊが複数ある場合は、複数のＪは互いに同じであっても異なっていてもよく、Ｒ^５は、水素原子、又は置換されていてもよい炭素原子数１〜２０のハイドロカルビル基を表し、複数のＲ^５は互いに同じであっても異なっていてもよい。］ Component (A): Transition metal compound represented by the following general formula (1)

[Wherein, R ¹ and R ³ each independently represent an optionally substituted aryl group having 6 to 20 carbon atoms, and R ² and R ⁴ each independently represent a hydrogen atom, or Represents an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, a and b each independently represent an integer of 0 to 4, and at least one of a and b is 1; represents an integer greater than or equal, if R ¹ to R ⁴ have multiple respectively, a plurality of R ¹ to R ⁴ may be different from each other be the same as each other, X ¹ is a hydrogen atom, a halogen atom, a substituted Optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms, substituted silyl group having 1 to 20 carbon atoms, or carbon atom Represents a substituted amino group of formula 1-20, and 2 X ¹ of may be different be the same as each other, m represents an integer of 1 to 5, J stands for carbon atom, or silicon atom, if J have more than one plurality of J is the same as each other R ⁵ represents a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and a plurality of R ⁵ may be the same or different from each other. It may be. ]

成分（ｃ）：Ｈ_２Ｏ
成分（ｄ）：ＳｉＯ_２
［式中、Ｌは、置換されていてもよい炭素原子数１〜２０のハイドロカルビル基を表し、２つのＬは互いに同じであっても異なっていてもよく、Ｒ^６は、電子吸引性基又は電子吸引性基を含有する基を表し、ｃは１〜５の整数を表し、Ｒ^６が複数ある場合は、複数のＲ^６は互いに同じであっても異なっていてもよい。］
成分（Ｃ）：有機アルミニウム化合物 Component (B): Solid catalyst component component (a) formed by contacting the following component (a), the following component (b), the following component (c) and the following component (d): with the following general formula (2) Compound represented by ZnL ₂ (2)
Component (b): Compound represented by the following general formula (3)

Component (c): H ₂ O
Component (d): SiO ₂
[Wherein L represents an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, two Ls may be the same or different from each other, and R ⁶ represents an electron-withdrawing group. represents a group containing a group or an electron withdrawing group, c is an integer of 1 to 5, if R ⁶ have more than one plurality of R ⁶ may be different from one another the same. ]
Component (C): Organoaluminum compound

R ¹ and R ³ in the general formula (1) are each independently an aryl group having 6 to 20 carbon atoms which may be substituted, if R ¹ is plural, a plurality of R ¹ each other or different and the same, if there are a plurality of R ^3, a plurality of R ³ may be different from one another the same.

As the optionally substituted aryl group having 6 to 20 carbon atoms of R ¹ and R ³ , an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, An aryl group having 6 to 20 carbon atoms substituted with a substituted silyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted with a substituted amino group having 1 to 20 carbon atoms, and a carbon atom Examples include an aryl group having 6 to 20 carbon atoms substituted with a hydrocarbyloxy group having 1 to 20 carbon atoms.

  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, 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, 2,3,6- 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, n-butylphenyl group, ec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetra Examples include decylphenyl group, naphthyl group, anthracenyl group and the like.

  Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4 -Chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group and the like.

Examples of the aryl group having 6 to 20 carbon atoms substituted with a substituted silyl group having 1 to 20 carbon atoms include a trimethylsilylphenyl group and a bis (trimethylsilyl) phenyl group.
Examples of the aryl group having 6 to 20 carbon atoms substituted with a substituted amino group having 1 to 20 carbon atoms include a dimethylaminophenyl group, a bis (dimethylamino) phenyl group, and a diphenylaminophenyl group.
Examples of the aryl group having 6 to 20 carbon atoms substituted with a hydrocarbyloxy group having 1 to 20 carbon atoms include, for example, a methoxyphenyl group, an ethoxyphenyl group, an n-propoxyphenyl group, an isopropoxyphenyl group, n -Butoxyphenyl group, sec-butoxyphenyl group, tert-butoxyphenyl group, phenoxyphenyl group and the like can be mentioned.

R ¹ and R ³ are preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group.

R ² and R ^{4 in} the general formula (1) each independently represent a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and when there are a plurality of R ² , a plurality of R ² may be different from one another the same, if the R ⁴ have more than one plurality of R ⁴ may be different from one another the same.

Examples of the optionally substituted hydrocarbyl group having 1 to 20 carbon atoms of R ² and R ⁴ include an optionally substituted alkyl group having 1 to 20 carbon atoms and an optionally substituted carbon atom. Examples thereof include an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms which may be substituted.

  Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a halogen atom, and 1 to 20 carbon atoms. An alkyl group having 1 to 20 carbon atoms substituted with a substituted silyl group, an alkyl group having 1 to 20 carbon atoms substituted with a substituted amino group having 1 to 20 carbon atoms, and hydro having 1 to 20 carbon atoms And an alkyl group having 1 to 20 carbon atoms substituted with a carbyloxy group.

  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, and neopentyl group. , Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-nonyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, Examples thereof include n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a 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, perfluoropentyl 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, perbromododecyl group Examples include a bromopentadecyl group and a perbromoeicosyl group.

  Examples of the alkyl group having 1 to 20 carbon atoms substituted with a substituted silyl group having 1 to 20 carbon atoms include, for example, a trimethylsilylmethyl group, a trimethylsilylethyl group, a trimethylsilylpropyl group, a trimethylsilylbutyl group, and a bis (trimethylsilyl) methyl group. Bis (trimethylsilyl) ethyl group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, triphenylsilylmethyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms substituted with a substituted amino group having 1 to 20 carbon atoms include dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, bis ( Examples thereof include dimethylamino) methyl group, bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, phenylaminomethyl group, diphenylaminomethyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms substituted with a hydrocarbyloxy group having 1 to 20 carbon atoms include, for example, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, n -Butoxymethyl group, sec-butoxymethyl group, tert-butoxymethyl 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 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 Etc.

  Examples of the optionally substituted aralkyl group having 7 to 20 carbon atoms include an aralkyl group having 7 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms substituted with a halogen atom.

  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-dimethyl). (Phenyl) 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, , 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-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group Anthracenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, di- Enirumechiru group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms substituted with a halogen atom include a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2-chlorobenzyl group, and a 3-chlorobenzyl group. 4-chlorobenzyl group, 2-bromobenzyl group, 3-bromobenzyl group, 4-bromobenzyl group, 2-iodobenzyl group, 3-iodobenzyl group, 4-iodobenzyl group and the like.

Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include the same groups as those exemplified as the optionally substituted aryl group having 6 to 20 carbon atoms of R ¹ and R ^3. it can.

R ² and R ⁴ are 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. is there.

  In the general formula (1), a and b each independently represent an integer of 0 to 4, and at least one of a and b represents an integer of 1 or more.

X ^{1 in the} general formula (1) is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, or an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms. It represents an oxy group, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and two X ^{1 s} may be the same as or different from each other.

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

Examples of the hydrocarbyl group having 1 to 20 carbon atoms that may be substituted for X ¹ are those exemplified as the hydrocarbyl group having 1 to 20 carbon atoms that may be substituted for R ² and R ^4. The same thing can be given.

Examples of the optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms of X ¹ include an optionally substituted alkoxy group having 1 to 20 carbon atoms and an optionally substituted 7 carbon atom. -20 aralkyloxy groups, optionally substituted aryloxy groups having 6 to 20 carbon atoms, and the like.

  Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include an alkoxy group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms substituted with a halogen atom.

  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, Neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetra Examples include decyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosoxy group and the like.

  Examples of the alkoxy group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyloxy group, a difluoromethyloxy group, a trifluoromethyloxy group, a chloromethyloxy group, a dichloromethyloxy group, and a trichloromethyloxy group. Bromomethyloxy group, dibromomethyloxy group, tribromomethyloxy group, iodomethyloxy group, diiodomethyloxy group, triiodomethyloxy group, fluoroethyloxy group, difluoroethyloxy group, trifluoroethyloxy group, Tetrafluoroethyloxy group, pentafluoroethyloxy group, chloroethyloxy group, dichloroethyloxy group, trichloroethyloxy group, tetrachloroethyloxy group, pentachloroethyloxy group, bromoethyloxy group, dibromoe Ruoxy group, tribromoethyloxy group, tetrabromoethyloxy group, pentabromoethyloxy group, perfluoropropyloxy group, perfluorobutyloxy group, perfluoropentyloxy group, perfluorohexyloxy group, perfluorooctyloxy group Perfluorododecyloxy group, perfluoropentadecyloxy group, perfluoroeicosyloxy group, perchloropropyloxy group, perchlorobutyloxy group, perchloropentyloxy group, perchlorohexyloxy group, perchlorooctyloxy group Perchlorododecyloxy group, perchloropentadecyloxy group, perchloroeicosyloxy group, perbromopropyloxy group, perbromobutyloxy group, perbromopentyloxy group, perbromohexyl Oxy group, perbromohexyl group, perbromooctyl group, perbromododecyl group, such as par-bromo eicosyloxy group.

  Examples of the optionally substituted aralkyloxy group having 7 to 20 carbon atoms include an aralkyloxy group having 7 to 20 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms substituted with a halogen atom. .

  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) Ruphenyl) 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.

  Examples of the aralkyloxy group having 7 to 20 carbon atoms substituted with a halogen atom include a 2-fluorobenzyloxy group, a 3-fluorobenzyloxy group, a 4-fluorobenzyloxy group, a 2-chlorobenzyloxy group, 3-chlorobenzyloxy group, 4-chlorobenzyloxy group, 2-bromobenzyloxy group, 3-bromobenzyloxy group, 4-bromobenzyloxy group, 2-iodobenzyloxy group, 3-iodobenzyloxy group, 4 -An iodobenzyloxy group etc. are mention | raise | lifted.

  Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include an aryloxy group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms substituted with a halogen 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, 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- Trimethylphenoxy 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, pen Methylphenoxy 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.

  Examples of the aryloxy group having 6 to 20 carbon atoms substituted with a halogen atom include 2-fluorophenyloxy group, 3-fluorophenyloxy group, 4-fluorophenyloxy group, 2-chlorophenyloxy group, 3 -Chlorophenyloxy group, 4-chlorophenyloxy group, 2-bromophenyloxy group, 3-bromophenyloxy group, 4-bromophenyloxy group, 2-iodophenyloxy group, 3-iodophenyloxy group, 4-iodophenyl An oxy group etc. are mention | raise | lifted.

Examples of the substituted silyl group having 1 to 20 carbon atoms of X ¹ include a 1-substituted silyl group substituted with a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms. Examples thereof include a substituted disubstituted silyl group and a trisubstituted silyl group substituted with a hydrocarbyl group having 1 to 20 carbon atoms. Examples of the hydrocarbyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Examples of the monosubstituted silyl group substituted with a hydrocarbyl group having 1 to 20 carbon atoms include, for example, methylsilyl group, ethylsilyl group, n-propylsilyl group, isopropylsilyl group, n-butylsilyl group, sec-butylsilyl group, Examples thereof include a tert-butylsilyl group, an isobutylsilyl group, an n-pentylsilyl group, an n-hexylsilyl group, and a phenylsilyl group. Examples of the disubstituted silyl group substituted with a hydrocarbyl group having 1 to 20 carbon atoms include a dimethylsilyl group, a diethylsilyl group, a di-n-propylsilyl group, a diisopropylsilyl group, and a di-n-butylsilyl group. , Di-sec-butylsilyl group, di-tert-butylsilyl group, diisobutylsilyl group, diphenylsilyl group and the like. Examples of the trisubstituted silyl group substituted with a hydrocarbyl group having 1 to 20 carbon atoms include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, and a tri-n-butylsilyl group. , Tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, tri Examples thereof include a phenylsilyl group.

Examples of the substituted amino group having 1 to 20 carbon atoms of X ¹ include an amino group substituted with a hydrocarbyl group having 1 to 20 carbon atoms. Examples of the hydrocarbyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Examples of the amino group substituted with a hydrocarbyl group having 1 to 20 carbon atoms include a phenylamino group, a benzylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a diisopropyl group, -N-butylamino group, di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino Group, diphenylamino group, dibenzylamino group, tert-butylisopropylamino group, phenylethylamino group, phenylpropylamino group, phenylbutylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroisoindolyl group Etc.

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.

  M in the general formula (1) is an integer of 1 to 5. m is preferably 1 or 2.

  J in the general formula (1) represents a carbon atom or a silicon atom. When there are a plurality of Js, the plurality of Js may be the same as or different from each other.

R ^{5 in the} general formula (1) is each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and a plurality of R ⁵ may be the same or different. It may be.

As hydrocarbyl groups substituted carbon atoms which may have 1 to 20 of R ⁵ include those exemplified as hydrocarbyl group of R ² and R ⁴ substituted carbon atoms which may have from 1 to 20 The same thing can be given.

例えば、メチレン基、エチリデン基、エチレン基、プロピリデン基、プロピレン基、ブチリデン基、ブチレン基、ペンチリデン基、ペンチレン基、ヘキシリデン基、イソプロピリデン基、メチルエチルメチレン基、メチルプロピルメチレン基、メチルブチルメチレン基、ビス（シクロヘキシル）メチレン基、メチルフェニルメチレン基、ジフェニルメチレン基、フェニル（メチルフェニル）メチレン基、ジ（メチルフェニル）メチレン基、ビス（ジメチルフェニル）メチレン基、ビス（トリメチルフェニル）メチレン基、フェニル（エチルフェニル）メチレン基、ジ（エチルフェニル）メチレン基、ビス（ジエチルフェニル）メチレン基、フェニル（プロピルフェニル）メチレン基、ジ（プロピルフェニル）メチレン基、ビス（ジプロピルフェニル）メチレン基、フェニル（ブチルフェニル）メチレン基、ジ（ブチルフェニル）メチレン基、フェニル（ナフチル）メチレン基、ジ（ナフチル）メチレン基、フェニル（ビフェニル）メチレン基、ジ（ビフェニル）メチレン基、フェニル（トリメチルシリルフェニル）メチレン基、ビス（トリメチルシリルフェニル）メチレン基、ビス（ペンタフルオロフェニル）メチレン基、シランジイル基、ジシランジイル基、トリシランジイル基、テトラシランジイル基、ジメチルシランジイル基、ビス（ジメチルシラン）ジイル基、ジエチルシランジイル基、ジプロピルシランジイル基、ジブチルシランジイル基、ジフェニルシランジイル基、シラシクロブタンジイル基、シラシクロヘキサンジイル基、ジビニルシランジイル基、ジアリルシランジイル基、（メチル）（ビニル）シランジイル基、（アリル）（メチル）シランジイル基等があげられる。 As the crosslinking group represented by the following general formula (4) of the general formula (1),

For example, methylene, ethylidene, ethylene, propylidene, propylene, butylidene, butylene, pentylidene, pentylene, hexylidene, isopropylidene, methylethylmethylene, methylpropylmethylene, methylbutylmethylene Bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) methylene group, bis (trimethylphenyl) methylene group, phenyl (Ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenyl) methylene group, bis (dipropylphenyl) Nyl) 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, silacyclobutanediyl group, silacyclohexanediyl group, divinylsilanediyl group, diallylsila Diyl group, (methyl) (vinyl) silanediyl group, silanediyl group and the like (allyl) (methyl).

  The cross-linking group represented by the general formula (4) is preferably a methylene group, ethylene group, isopropylidene group, bis (cyclohexyl) methylene group, diphenylmethylene group, dimethylsilanediyl group, bis (dimethylsilane) diyl group, diphenyl. A silanediyl group, more preferably an isopropylidene group or a dimethylsilanediyl group.

  Examples of the transition metal compound represented by the general formula (1) of the component (A) include dimethylsilylene bis (2-phenylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium. Dichloride, dimethylsilylenebis (2,3-diphenylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-diphenylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,5-diphenylcyclopentadienyl) Zirconium dichloride, dimethylsilylenebis (3,4-diphenylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,4-triphenylcyclopentadienyl) zirconium dichloride Dimethylsilylene bis (2,3,5-triphenylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (tetraphenylcyclopentadienyl) zirconium dichloride, and “dimethylsilylene” of these compounds as “methylene” , “Ethylene”, “isopropylidene”, “bis (cyclohexyl) methylene”, “diphenylmethylene”, “dimethylsilanediyl”, “bis (dimethylsilane) diyl”, or “diphenylsilanediyl”, “Dichloride” is replaced by “Difluoride”, “Dibromide”, “Diiodide”, “Dimethyl,“ Diethyl ”,“ Diisopropyl ”,“ Diphenyl ”,“ Dibenzyl ”,“ Dimethoxide ”,“ Diethoxide ”,“ Di (n-propoxy) ” ) "," Di (isopropoxide) ", compounds obtained by replacing the" diphenoxide "or" di (pentafluorophenyl phenoxide) ", and the like.

  The transition metal compound represented by the general formula (1) of the component (A) is preferably dimethylsilylene bis (3-phenylcyclopentadienyl) dichloride.

  L in the general formula (2) represents an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and two Ls may be the same as or different from each other.

  Examples of the optionally substituted hydrocarbyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms that may be substituted, and 7 to 20 carbon atoms that may be substituted. And an aryl group having 6 to 20 carbon atoms which may be substituted.

  Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms substituted with a halogen atom.

  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, and neopentyl group. , Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, Examples thereof include n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like. A methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group is preferable.

  Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a 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, perfluoropentyl 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, perbromododecyl group Examples include a bromopentadecyl group and a perbromoeicosyl group.

  Examples of the optionally substituted aralkyl group having 7 to 20 carbon atoms include an aralkyl group having 7 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms substituted with a halogen atom.

  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-dimethyl). (Phenyl) 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, , 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-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group Anthracenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, di- Enirumechiru group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group. Preferably, it is a benzyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms substituted with a halogen atom include a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2-chlorobenzyl group, and a 3-chlorobenzyl group. 4-chlorobenzyl group, 2-bromobenzyl group, 3-bromobenzyl group, 4-bromobenzyl group, 2-iodobenzyl group, 3-iodobenzyl group, 4-iodobenzyl group and the like.

  Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include an aryl group having 6 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms substituted with a halogen atom.

  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, 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, 2,3,6- 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, n-butylphenyl group, ec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetra Examples include decylphenyl group, naphthyl group, anthracenyl group and the like. Preferably, it is a phenyl group.

  Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4 -Chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group and the like.

  L is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

  Examples of the compound represented by the general formula (2) of the component (a) include dialkylzinc, diarylzinc, dialkenylzinc, bis (cyclopentadienyl) zinc, halogenated alkylzinc and the like. Examples of the dialkyl zinc include dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n-hexyl zinc and the like. Examples of the diaryl zinc include diphenyl zinc, dinaphthyl zinc, bis (pentafluorophenyl) zinc and the like. Examples of dialkenyl zinc include diallyl zinc. Examples of the alkyl zinc halide include methyl zinc chloride, ethyl zinc chloride, n-propyl zinc chloride, isopropyl zinc chloride, n-butyl zinc chloride, isobutyl zinc chloride, n-hexyl chloride, methyl zinc bromide, bromide Ethyl zinc, n-propyl zinc bromide, isopropyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, n-hexyl zinc bromide, methyl zinc iodide, ethyl zinc iodide, n-propyl zinc iodide Isopropyl zinc iodide, n-butyl zinc iodide, isobutyl zinc iodide, n-hexyl zinc iodide and the like.

  The compound represented by the general formula (2) of the component (a) is preferably dialkyl zinc, and 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.

R ⁶ in the general formula (3) represents a group containing an electron withdrawing group or an electron withdrawing group, if R ⁶ have more than one plurality of R ⁶ may be different be the same as 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 constant σ are listed as electron withdrawing groups.

Examples of the electron-withdrawing group for R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. Examples of the group containing an electron-withdrawing group of R ⁶ include halogenated alkyl groups, halogenated aryl groups, (halogenated alkyl) aryl groups, cyanated aryl groups, nitrated aryl groups, ester groups (alkoxycarbonyl groups, aralkyloxy groups). Carbonyl group, aryloxycarbonyl group), acyl group and the like.

R ⁶ is preferably a halogen atom, more preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom.

  C of general formula (3) represents the integer of 1-5.

  Examples of the compound represented by the general formula (3) of the component (b) include 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, perfluoro-1-naphthol, perfluoro-2-naphthol, 2-chloro Phenol, 3-chlorophenol, 4-chlorophenol, 2,4-dichloropheno 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 2,3,5,6-tetrachlorophenol, pentachlorophenol, 2, 3,5,6-tetrachloro-4-trichloromethylphenol, 2,3,5,6-tetrachloro-4-pentachlorophenylphenol, perchloro-1-naphthol, perchloro-2-naphthol, 2-bromophenol, 3 -Bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4,6-tribromophenol, 2,3 , 5,6-tetrabromophenol, pentabromophenol, 2,3,5,6-te Labromo-4-tribromomethylphenol, 2,3,5,6-tetrabromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo-2-naphthol, 2-iodophenol, 3-iodophenol, 4- Iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol, 2,4,6-triiodophenol, 2,3,5 , 6-tetraiodophenol, pentaiodophenol, 2,3,5,6-tetraiodo-4-triiodomethylphenol, 2,3,5,6-tetraiodo-4-pentaiodophenylphenol, periodio-1-naphthol , Periododo-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 (trifluoro Methyl) phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like.

  The compound represented by the general formula (3) of the component (b) is preferably 3,4,5-trifluorophenol.

The component (d) SiO ₂ preferably has a uniform particle size, and the volume-based geometric standard deviation of the particle size of the component (d) SiO ₂ is preferably 2.5 or less, more Preferably it is 2.0 or less, More preferably, it is 1.7 or less.

The average particle diameter of SiO ₂ is usually 1～5000Myuemu, preferably a 5 to 1000 m, more preferably from 10 to 500 [mu] m, more preferably from 10 to 100 [mu] m. 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.

Also, usually SiO _2, a hydroxyl group is generated exists on the surface, as SiO _2, may be used modified SiO ₂ obtained by substituting an active hydrogen of the surface hydroxyl groups with a variety of substituents. Examples of the modified SiO ₂ include trialkylchlorosilane, triarylchlorosilane, dialkyldichlorosilane, diaryldichlorosilane, alkyltrichlorosilane, aryltrichlorosilane, trialkylalkoxysilane, triarylalkoxysilane, dialkyldialkoxysilane, and diaryldioxide. Examples include SiO _{2 in} contact with alkoxysilane, aryltrialkoxysilane, tetraalkoxysilane, alkyldisilazane, tetrachlorosilane, alcohol, phenol, dialkylmagnesium, alkyllithium and the like. Examples of the trialkylchlorosilane include trimethylchlorosilane and tert-butyldimethylchlorosilane. Examples of the triarylchlorosilane include triphenylchlorosilane. Examples of the dialkyldichlorosilane include dimethyldichlorosilane. Examples of diaryldichlorosilane include diphenyldichlorosilane. Examples of the alkyltrichlorosilane include methyltrichlorosilane. Examples of the aryltrichlorosilane include phenyltrichlorosilane. Examples of the trialkylalkoxysilane include trimethylmethoxysilane. Examples of the triarylalkoxysilane include triphenylmethoxysilane. Examples of the dialkyl dialkoxysilane include dimethyldimethoxysilane. Examples of the diaryl dialkoxysilane include diphenyldimethoxysilane. Examples of the alkyltrialkoxysilane include methyltrimethoxysilane. Examples of the aryltrialkoxysilane include phenyltrimethoxysilane. Examples of tetraalkoxysilane include tetramethoxysilane. Examples of the alkyldisilazane include 1,1,1,3,3,3-hexamethyldisilazane. Examples of the alcohol include methanol and ethanol. Examples of the dialkyl magnesium include dibutyl magnesium, butyl ethyl magnesium, butyl octyl magnesium and the like. Examples of the alkyl lithium include butyl lithium and the like.

Furthermore, can be exemplified after contact with trialkylaluminum, dialkyl amines, alcohols, and SiO _2, which is contacted with the phenol. Examples of the dialkylamine include diethylamine and diphenylamine. Examples of the alcohol include methanol and ethanol.

Further, SiO ₂ is the strength of the SiO ₂ itself is increasing by the hydroxyl groups are hydrogen bonded. 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 SiO ₂ , 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.

SiO ₂ is preferably dried to substantially remove moisture, and is preferably dried by heat treatment. The heat treatment is usually carried out at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. with respect to SiO _{2 in} which 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 an inert gas (for example, nitrogen or argon) dried during heating is circulated and dried at a constant flow rate, a method in which heat is reduced under reduced pressure, and the like.

Component (B) is formed by contacting component (a), component (b), component (c) and component (d). Examples of the contact order of the component (a), the component (b), the component (c), and the component (d) include the following orders.
<1> The component (a) is contacted with the component (b), the contact product resulting from the contact is contacted with the component (c), and the contact product resulting from the contact is contacted with the component (d).
<2> The component (a) and the component (b) are brought into contact with each other, the contact product resulting from the contact is brought into contact with the component (d), and the contact product resulting from the contact is brought into contact with the component (c).
<3> The component (a) is contacted with the component (c), the contact product resulting from the contact is contacted with the component (b), and the contact product resulting from the contact is contacted with the component (d).
<4> The component (a) is contacted with the component (c), the contact product due to the contact is contacted with the component (d), and the contact product due to the contact is contacted with the component (b).
<5> The component (a) is contacted with the component (d), the contact product resulting from the contact is contacted with the component (b), and the contact product resulting from the contact is contacted with the component (c).
<6> The component (a) is contacted with the component (d), the contact product resulting from the contact is contacted with the component (c), and the contact product resulting from the contact is contacted with the component (b).
<7> The component (b) and the component (c) are brought into contact with each other, the contact product resulting from the contact is brought into contact with the component (a), and the contact product resulting from the contact is brought into contact with the component (d).
<8> The component (b) and the component (c) are brought into contact with each other, the contact product resulting from the contact is brought into contact with the component (d), and the contact product resulting from the contact is brought into contact with the component (a).
<9> The component (b) and the component (d) are brought into contact with each other, the contact product resulting from the contact is brought into contact with the component (a), and the contact product resulting from the contact is brought into contact with the component (c).
<10> The component (b) and the component (d) are brought into contact with each other, the contact product resulting from the contact is brought into contact with the component (c), and the contact product resulting from the contact is brought into contact with the component (a).
<11> The component (c) and the component (d) are brought into contact with each other, the contact product resulting from the contact is brought into contact with the component (a), and the contact product resulting from the contact is brought into contact with the component (b).
<12> The component (c) and the component (d) are brought into contact with each other, the contact product resulting from the contact is brought into contact with the component (b), and the contact product resulting from the contact is brought into contact with the component (a).

  Contact with the component (a), the component (b), the component (c) and the component (d) 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, the solvent may be used for the contact and these components may be directly contacted without using.

  When a solvent is used, those that do not react with component (a), component (b), component (c) and component (d), and their contacts are 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 and polar solvents.

  Examples of the nonpolar solvent include a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent include butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane and the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like.

  Examples of the polar solvent include halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, nitrile solvents, nitro compounds, amine solvents, sulfur compounds and the like. Examples of the halide solvent include dichloromethane, difluoromethane, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Examples thereof include bromobenzene and o-dichlorobenzene. Examples of the ether solvent include dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxy Ethyl) ether, tetrahydrofuran, tetrahydropyran and the like. Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Examples include ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, glycerin and the like. Examples of the phenol solvent include phenol and p-cresol. Examples of the carbonyl solvent include 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 etc. are mention | raise | lifted. Examples of phosphoric acid derivatives include hexamethylphosphoric triamide, triethyl phosphate, and the like. Examples of nitrile solvents include acetonitrile, propionitrile, succinonitrile, benzonitrile and the like. Examples of the nitro compound include nitromethane and nitrobenzene. Examples of the amine solvent include ethylenediamine, pyridine, piperidine, morpholine and the like. Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.

  In the above methods <1>, <3>, and <7>, a contact product (hereinafter referred to as “component (e)”) formed by contacting component (a), component (b), and component (c). As the solvent (hereinafter sometimes referred to as “solvent (s1)”), preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether. It is a system solvent.

Moreover, as a solvent (henceforth described as "solvent (s2)") when contacting component (e) and component (d), it is preferably a polar solvent, more preferably the polarity of the solvent. The E _T ^N value (C. Reichardt, “Solvants and Solvents Effects in Organic Chemistry”, 2nd ed., VCH Verlag (1988).) As an index to represent is in the range of 0.8 ≧ E _T ^N ≧ 0.1. It is a satisfactory solvent.

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

  In the methods <1>, <3>, and <7>, when a hydrocarbon solvent is used as the solvent (s1) and the solvent (s2), the component (a), the component (b), and the component It is preferable that the time from the contact of (c) to the contact of the obtained component (e) and the component (d) is short. The time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. Moreover, the temperature which contacts a component (e) and a component (d) is -100 degreeC-40 degreeC normally, Preferably it is -20 degreeC-20 degreeC, Most preferably, it is -10 degreeC-10 degreeC. .

  In the above methods <2>, <4>, <5>, <6>, <8>, <9>, <10>, <11>, <12>, the solvent used is preferably non- It is a polar solvent.

As the usage-amount of said component (a), (b) and (c), the molar ratio of the usage-amount of component (a), (b), (c) used for contact is (a) :( b) :( c) = 1: When y: z, it is possible to obtain a higher molecular weight olefin polymer by using those components so that y and z satisfy the following formulas (IV), (V) and (VI). From the viewpoint of high polymerization activity.
| 2-y-2z | ≦ 1 (IV)
z ≧ −2.5y + 2.48 (V)
y <1 (VI)
[However, in the above formulas (IV) to (VI), y and z represent a number larger than 0. ]
y is preferably 0.5 to 0.99, more preferably 0.55 to 0.95, still more preferably 0.6 to 0.9, and most preferably 0.7 to 0. .8.

  The amount of component (a) and component (b) used is preferably such that the metal atoms derived from component (a) contained in component (B) are in moles of metal atoms contained per gram of component (B). The amount is 0.1 mmol or more, 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.

  In component (B), at least one of component (a), component (b), component (c) and component (d) as raw materials may remain as an unreacted material, but the cleaning treatment To remove unreacted substances. The solvent used for the washing treatment may be the same as or different from the solvent used for the 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.

  Component (C) organoaluminum compounds include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, dialkylaluminum hydride, alkyl (dialkoxy) aluminum, dialkyl (alkoxy) aluminum, alkyl (diaryloxy) aluminum, dialkyl (aryl) And oxy) aluminum.

  Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

  Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride.

  Examples of the alkyl aluminum dichloride include methyl aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride and the like.

  Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, and di-n-hexylaluminum hydride.

  Examples of the alkyl (dialkoxy) aluminum include methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and methyl (di-tert-butoxy) aluminum.

  Examples of the dialkyl (alkoxy) aluminum include dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, and dimethyl (tert-butoxy) aluminum.

  Examples of the alkyl (diaryloxy) aluminum include methyl (diphenoxy) aluminum, methyl bis (2,6-diisopropylphenoxy) aluminum, and methyl bis (2,6-diphenylphenoxy) aluminum.

Examples of the dialkyl (aryloxy) aluminum include dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, and dimethyl (2,6-diphenylphenoxy) aluminum.
These organoaluminum compounds may be used alone or in combination of at least two kinds.

  The organoaluminum compound 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.

  The number of moles of aluminum atoms of the organoaluminum compound per mole of component (A) is preferably 0.1 to 1000, more preferably 0.5 to 500, and still more preferably 1 to 100. It is.

  Further, in the preparation of the polymerization catalyst, in addition to the component (A), the component (B), and the component (C), an electron donating compound (hereinafter sometimes referred to as “component (D)”) is brought into contact. May be. The amount of component (D) used is preferably 0.01 to 100, more preferably 0.1 to 50, as the number of moles of component (D) per mole of component (A). More preferably, it is 0.25-5.

  Examples of the component (D) include triethylamine and trinormaloctylamine.

  It is preferable that the contact of the component (A), the component (B), the component (C), and the component (D) as necessary is performed 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 30 minutes to 100 hours. In addition, the contact may be performed in the polymerization reaction tank with each component separately charged into the polymerization reaction tank.

  Examples of the method for producing the ethylene-α-olefin copolymer of the present invention include a gas phase polymerization method, a slurry polymerization method, and a bulk polymerization method. 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, usually, use inert gas such as nitrogen and argon, hydrogen, ethylene, etc., and dissolve or dilute each component in a solvent in the absence of moisture. Thus, a method of 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. Moreover, you may introduce | transduce a component (D).

  Examples of the α-olefin having 3 to 20 carbon atoms used for polymerization 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 and the like can be mentioned. These may be used alone or in combination of two or more. 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred. As a combination of ethylene and an α-olefin having 3 to 20 carbon atoms, a combination of ethylene and 1-butene, a combination of ethylene and 1-hexene, a combination of ethylene and 4-methyl-1-pentene, ethylene And 1-octene, ethylene, 1-butene and 1-hexene, ethylene, 1-butene and 4-methyl-1-pentene, ethylene, 1-butene and 1-octene A combination of ethylene, 1-hexene and 1-octene, preferably a combination of ethylene and 1-butene, a combination of ethylene and 1-hexene, and a combination of ethylene and 4-methyl-1-pentene. A combination of ethylene, 1-butene and 1-hexene, a combination of ethylene, 1-butene and 1-octene, It is the combination of the down and the 1-hexene and 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 added to the olefin as long as the effects of the present invention are not impaired. You may use together. Examples of the other monomer include diolefin, cyclic olefin, alkenyl aromatic hydrocarbon, α, β-unsaturated carboxylic acid, metal salt of α, β-unsaturated carboxylic acid, α, β-unsaturated. Examples thereof include carboxylic acid alkyl esters, unsaturated dicarboxylic acids, vinyl esters, and unsaturated carboxylic acid glycidyl esters.

  Examples of the diolefin 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, , 3-cyclooctadiene, 1,3-cyclohexadiene and the like.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclo Pentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl- 5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene, etc. It is below.

  Examples of the alkenyl aromatic hydrocarbon include alkenylbenzene such as styrene, 2-phenylpropylene, 2-phenylbutene, and 3-phenylpropylene, p-methylstyrene, m-methylstyrene, o-methylstyrene, and p-ethylstyrene. M-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p- Examples thereof include alkyl styrenes such as tertiary butyl styrene and p-secondary butyl styrene, bisalkenyl benzenes such as divinyl benzene, and alkenyl naphthalenes such as 1-vinyl naphthalene.

  Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3- And dicarboxylic acid.

  Examples of the metal salt of α, β-unsaturated carboxylic acid include sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt and the like of the α, β-unsaturated carboxylic acid.

  Examples of the α, β-unsaturated carboxylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and methacrylic acid. Examples thereof include ethyl acid, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate.

  Examples of the unsaturated dicarboxylic acid include maleic acid and itaconic acid, and examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, And fluorovinyl acetate.

  Examples of the unsaturated carboxylic acid glycidyl ester include glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

  In the method for producing an ethylene-α-olefin copolymer of the present invention, a small amount of olefin is obtained using component (A), component (B), component (C) and, if necessary, component (D). Olefin can also be polymerized using a prepolymerized solid component obtained by polymerizing (hereinafter referred to as prepolymerization).

  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 may 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 0.001 g per 1 g of the component (B). 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. As a method for introducing the component (A), the component (B), the component (C), and, if necessary, the component (D) into a polymerization reaction tank for performing prepolymerization, nitrogen, argon or the like is usually used. A method in which an inert gas, hydrogen, ethylene, or the like is used, is charged in a moisture-free state, or a method in which each component is dissolved or diluted in a solvent and charged in a solution or slurry state.

  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, as a slurry density | concentration, the quantity of the component (B) per liter of solvent is 0.1-600g normally, Preferably it is 0.5-300g. The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. Moreover, the partial pressure of olefins in the gas phase part during the prepolymerization is usually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

  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.

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

  Further, the ethylene-α-olefin copolymer of the present invention can be made into a thermoplastic resin composition by blending other thermoplastic resins other than the ethylene-α-olefin copolymer of the present invention. Other thermoplastic resins include, for example, crystalline thermoplastic resins such as polyolefins, polyamides, polyesters, polyacetals, etc., amorphous materials such as polystyrene, acrylonitrile / butadiene / styrene copolymers (ABS), polycarbonates, polyphenylene oxides, polyacrylates, etc. A thermoplastic resin, polyvinyl chloride, and the like.

Examples of the polyolefin include polyethylene, polypropylene, polybutene, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, and polyhexene.
Examples of the polyamide include aliphatic amides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon 46, and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines.
Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polycaprolactone, and polyhydroxybutyrate.
Examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like.

The polystyrene may be a homopolymer of styrene, or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene.
ABS includes a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and a structural unit derived from styrene. ABS contained in an amount of 40 to 60 mol% is preferably used.
Examples of the polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy). And polymers obtained from phenyl) butane and the like.
Examples of polyphenylene oxide include poly (2,6-dimethyl-1,4-phenylene oxide).
Examples of the polyacrylate include polymethyl methacrylate and polybutyl acrylate.

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

  The ethylene-α-olefin copolymer of the present invention is molded into various forms and used. Although the form of a molded article is not specifically limited, it is used for a film, a sheet, a container (tray, bottle, etc.), etc. The molded article is also suitably used for applications such as food packaging materials; pharmaceutical packaging materials; electronic component packaging materials used for packaging semiconductor products and the like; surface protection materials.

Hereinafter, the present invention will be described by way of examples.
The physical properties in the 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) Number of short chain branches (N _SCB , unit: 1 / 1000C)
Using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation), the number of short chain branches per 1000 carbon atoms (N _SCB ) was determined using a calibration curve from the characteristic absorption of ethylene and α-olefin. This N _SCB value represents the content of monomer units derived from an α-olefin in a copolymer of ethylene and an α-olefin.

(3) 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.

(4) Melt flow rate ratio (MFRR)
In the method specified in JIS K7210-1995, the test load is 211.82N, the melt flow rate (H-MFR) measured at a measurement temperature of 190 ° C., and the method specified in JIS K7210-1995 is the load 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.

(5) Swell ratio (SR)
In the measurement of the melt flow rate in (3), the strand of ethylene-α-olefin copolymer extruded at a length of about 15 to 20 mm from the 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.

(6) Molecular weight distribution (Mw / Mn)
Using a gel permeation chromatograph (GPC) method, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured under the following conditions (1) to (8) to obtain Mw / Mn. It was. 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 refractometer
(8) Molecular weight reference material: Standard polystyrene

(7) Number of long chain branches (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 a peak having a peak top in the vicinity of 38.22 to 38.27 ppm was determined with the sum of the areas 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-α-olefin copolymer under these conditions, the position of the peak top of the peak derived from methine carbon bonded with a branch having 5 carbon atoms was 38.21 ppm.

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

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

(10) g *
G * was determined by the formula (I).
In addition, [η] represents the relative viscosity (ηrel) of the ethylene-α-olefin copolymer in 100 ml of a tetralin solution containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor, and the ethylene-α-olefin copolymer. A sample solution is prepared by dissolving 100 mg of a polymer at 135 ° C., and using a Ubbelohde viscometer, the sample solution and a blank solution composed of a tetralin solution containing only 0.5% by weight of BHT as a thermal degradation inhibitor Calculated from the fall time and determined by the formula (II), [η] _GPC is determined by the formula (I-II) from the measurement of the molecular weight distribution of the ethylene-α-olefin copolymer of (6), g _SCB * was calculated | required by Formula (I-III) from the measurement of the number of short chain branches of the ethylene-alpha-olefin copolymer of (2).

(11) Measurement of extensional viscosity of molten resin Extensional viscosity of molten resin at 130 ° C. at an Henky speed of 0.1 s ⁻¹ and 1 s ⁻¹ using an extension viscosity measuring device (ARES manufactured by TA Instruments) A time curve was measured. As a measurement test piece, a sheet of 18 mm × 10 mm and thickness 0.7 mm obtained by press molding was used.

(12) Melt tension (MT, unit: cN)
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 190 ° C. and an extrusion speed of 0.32 g / min. The melted ethylene-α-olefin copolymer was drawn into a filament by a take-up roll at a take-up rate of 6.3 (m / min) / min, and the tension during take-up was measured. The maximum tension from the start of take-up until the filamentous ethylene-α-olefin copolymer was cut was defined as the melt tension.

(13) Cold xylene soluble part ratio (CXS, unit:%)
The cold xylene soluble part ratio is obtained by dissolving about 5 g of a polymer sample in 1 liter of boiling xylene containing an antioxidant, cooling to room temperature over about 2 hours, and then allowing to stand at 25 ° C. for 20 hours. The insoluble part was precipitated, and the soluble part was taken out by removing the solvent from the filtrate part collected by filtration. The soluble part was taken out, and the taken out soluble part was determined as a value corrected by the following equation.
Cold xylene soluble part ratio = [[soluble part (g) × (1 / filtrate (liter))] / total amount of polymer sample (5 g)] × 100 (% by weight)

(14) Melting peak number in melting curve The ethylene-α-olefin copolymer was pressed at a pressure of 10 MPa for 5 minutes by a 150 ° C. hot press machine, then cooled for 5 minutes by a 30 ° C. cooling press machine, A sheet of about 100 μm was formed, and a sample of about 10 mg was cut out from the sheet and sealed in an aluminum pan. Next, the aluminum pan in which the sample was sealed was held at a differential scanning calorimeter (differential scanning calorimeter DSC-7 manufactured by Perkin Elmer Co., Ltd.) (1) at 150 ° C. for 5 minutes, and (2) 5 ° C. (3) Hold at 20 ° C. for 2 minutes, (4) Increase the temperature from 20 ° C. to 150 ° C. at 5 ° C./minute, and calculate the melting curve in (4) It was measured. From the melting curve thus obtained, the number of peaks observed between 25 ° C. and the melting end temperature (the temperature at which the melting curve returns to the high temperature side baseline) was determined.

Example 1
(1) Preparation of solid catalyst component (B) Silica (Sypolol 948 manufactured by Debison Co., Ltd .; 50% volume average particle size = 55 μm; fine) in a reactor equipped with a nitrogen-replaced stirrer and heated at 300 ° C. under nitrogen flow (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. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 1.73 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 1.02 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of 3,4,5-trifluorophenol and 1.44 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Then cooled to 22 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O0.11kg the temperature of the reactor 22 ° C.. After completion of dropping, the mixture was stirred at 22 ° C. for 1.5 hours, then heated to 40 ° C., stirred at 40 ° C. for 2 hours, further heated to 80 ° C., and stirred at 80 ° C. for 2 hours. After stirring, at room temperature, the supernatant was withdrawn to a residual amount of 16 L, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours. After stirring, the supernatant liquid was extracted at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Then, the solid catalyst component (B) was obtained by drying.

(2) Polymerization After drying under reduced pressure, 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 0.001 MPa, and 30 g of 1-butene was polymerized as a comonomer. 720 g of butane was charged as a solvent, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer 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 as follows: hydrogen = 0.035 mol%, 1-butene = 3.38 mol%. To this, 0.9 ml of a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1 mol / l was added. Next, 0.25 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 2 μmol / ml was added. Subsequently, 5.1 mg of the solid catalyst component (B) obtained in Example 1 (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding ethylene gas so as to keep the total pressure constant. As a result, 35 g of an olefin polymer was obtained. The polymerization activity per hour per zirconium atom was 7.0 × 10 ⁷ g / molZr · h.

Example 2
(1) 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 0.002 MPa, 100 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 = 0.09 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, 1 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 1 μmol / ml was added, Subsequently, 8.3 mg of the solid catalyst component obtained in Example 1 (1) was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.07 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 65 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 3
(1) 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 was about 0.004 MPa, and 100 ml of 1-hexene was used as a polymerization solvent. 650 g of butane was charged and the temperature was raised 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 = 0.17 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, 1 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 1 μmol / ml was added, Subsequently, 15.3 mg of the solid catalyst component obtained in Example 1 (1) was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.04 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 113 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 4
(1) 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 was about 0.005 MPa, and 100 ml of 1-hexene was used as a polymerization solvent. 650 g of butane was charged and the temperature was raised 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 = 0.21 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, 1 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 1 μmol / ml was added, Subsequently, 13.7 mg of the solid catalyst component obtained in Example 1 (1) was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.07 mol%). The gas composition in the system after completion of the polymerization was hydrogen = 0.32 mol%. After completion of the polymerization, butane, ethylene, and hydrogen were purged to obtain 104 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 5
(1) 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 was about 0.004 MPa, and 100 ml of 1-hexene was used as a polymerization solvent. 650 g of butane was charged and the temperature was raised 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 = 0.24 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, 1 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 1 μmol / ml was added, Subsequently, 6.2 mg of the solid catalyst component obtained in Example 1 (1) was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.09 mol%). The gas composition in the system after the completion of polymerization was hydrogen = 0.28 mol%. Thereafter, butane, ethylene, and hydrogen were purged to obtain 33 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 approximately 0.007 MPa, and 100 ml of 1-hexene was used as a polymerization solvent. 650 g of butane was charged and the temperature was raised 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 = 0.31 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, 1 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 1 μmol / ml was added, Subsequently, 7.0 mg of the solid catalyst component obtained in Example 1 (1) was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.07 mol%). Thereafter, butane, ethylene, and hydrogen were purged to obtain 48 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 7
(1) 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 approximately 0.009 MPa, and 100 ml of 1-hexene was used as a polymerization solvent. 650 g of butane was charged and the temperature was raised 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 = 0.42 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, 1 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 1 μmol / ml was added, Subsequently, 10.3 mg of the solid catalyst component obtained in Example 1 (1) was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.07 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 54 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 8
(1) 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 0.003 MPa, 120 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 = 0.08 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, 1 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 1 μmol / ml was added, Subsequently, 15.8 mg of the solid catalyst component obtained in Example 1 (1) was added. During the polymerization, polymerization was performed at 70 ° C. for 80 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.05 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 192 g of an ethylene-1-hexene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

Example 9
(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 0.001 MPa, 60 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 0.8 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.06 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, 1 ml of a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) (A) adjusted to a concentration of 1 μmol / ml was added, Subsequently, 13 mg of the solid catalyst component obtained in Example 1 (1) was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.05 mol%). Thereafter, butane, ethylene, and hydrogen were purged to obtain 37 g of an ethylene-1-hexene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

Example 10
(1) Polymerization After drying under reduced pressure, 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 was 0.002 MPa, and 55 g of 1-butene was polymerized as a comonomer. 695 g of butane was charged as a solvent, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer 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 as follows: hydrogen = 0.032 mol%, 1-butene = 2.74 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, a toluene solution of dimethylsilylenebis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) adjusted to a concentration of 2 μmol / ml as the transition metal compound (A) 0.75 ml was added, and then 15.2 mg of the solid catalyst component (B) obtained in Example 1 (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding ethylene gas so as to keep the total pressure constant. As a result, 119 g of an olefin polymer was obtained. The physical properties of the obtained copolymer are shown in Table 2.

Example 11
(1) Polymerization After drying under reduced pressure, 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 was 0.002 MPa, and 55 g of 1-butene was polymerized as a comonomer. 695 g of butane was charged as a solvent, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer 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 as follows: hydrogen = 0.096 mol%, 1-butene = 2.90 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, a toluene solution of dimethylsilylenebis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) adjusted to a concentration of 2 μmol / ml as the transition metal compound (A) 0.75 ml was charged. Subsequently, 0.9 ml of a toluene solution of triethylamine adjusted to a concentration of 0.1 mol / l as an electron donating compound (D) was added, and then the solid catalyst component (B) obtained in Example 1 (1) above was added. ) 9.0 mg was charged. Polymerization was carried out at 70 ° C. for 1 hour while feeding ethylene gas so as to keep the total pressure constant. As a result, 40 g of an olefin polymer was obtained. The physical properties of the obtained copolymer are shown in Table 2.

Example 12
(1) Polymerization After drying under reduced pressure, 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 0.008 MPa, and 30 g of 1-butene as a comonomer was polymerized. 720 g of butane was charged as a solvent, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer 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 = 0.36 mol% and 1-butene = 1.60 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, a toluene solution of dimethylsilylenebis (3-phenylcyclopentadienyl) zirconium dichloride (racemic / meso ratio = 49.2 / 50.8) adjusted to a concentration of 2 μmol / ml as the transition metal compound (A) 0.75 ml was added, and then 17.1 mg of the solid catalyst component (B) obtained in Example 1 (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding ethylene gas so as to keep the total pressure constant. As a result, 123 g of an olefin polymer was obtained. The physical properties of the obtained copolymer are shown in Table 2.

Comparative Example 1
(1) Preparation of solid catalyst component 9.68 kg of silica (Sypolpol 948, manufactured by Devison Co., Ltd.), which was heat-treated at 300 ° C. under a nitrogen stream as a particulate carrier, was placed in a reactor equipped with a nitrogen-substituted stirrer. 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 solid polymerization catalyst To a four-necked flask equipped with a stirrer with an internal volume of 200 milliliters purged with nitrogen, 7.7 g of the solid catalyst component prepared in Comparative Example 3 (1) and 50 ml of toluene were added to form a slurry. Then, 38 ml of racemic dimethylsilylene bis (2-methyl-1-indenyl) zirconium dichloride adjusted to a concentration of 5.3 μmol / ml and meso-dimethylsilylene bis (2 2.6 ml of (methyl-1-indenyl) zirconium dichloride was added (racemic / meso ratio = 96.9 / 3.1), and the mixture was stirred at room temperature for 1 hour. Then, 7.8g of solid polymerization catalysts were obtained by performing drying at 50 degreeC under pressure reduction for 9 hours.
(3) Polymerization After drying under reduced pressure, 32.6 g of NaCl that had been dried under reduced pressure at 140 ° C. for 6 hours was placed in an autoclave equipped with a stirrer with an internal volume of 3 liters substituted with argon. The partial pressure was added to 0.017 MPa, 6 g of 1-butene was charged as a comonomer, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the pressure inside the autoclave became 2.0 MPa, and the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.80 mol% and 1-butene = 4.75 mol%. To this, 0.3 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as an organoaluminum compound (C) was added. Next, 42.7 mg of the solid polymerization catalyst prepared in Comparative Example 3 (2) was added. An ethylene / hydrogen / 1-butene mixed gas (hydrogen = 0.50 mol%, 1-butene = 5.0 mol%) so that the total pressure and the hydrogen and 1-butene concentrations in the gas are kept constant during the polymerization. Was continuously polymerized at 70 ° C. for 2 hours. As a result, 56 g of an olefin polymer was obtained. The physical properties of the obtained copolymer are shown in Table 2.

Comparative Example 2
(1) Production of modified particles In a 5-liter four-necked flask purged with nitrogen, 2 liters of tetrahydrofuran and hexane solution of diethyl zinc (2M) (1.35 liters (2.7 mol)) were placed at -50 ° C. Cooled down. A solution prepared by dissolving 251.5 g (1.37 mol) of pentafluorophenol in 390 ml of tetrahydrofuran was added dropwise thereto over 25 minutes. After completion of the dropping, the temperature was gradually raised to room temperature and stirred for 3 hours. Then, it heated at 45 degreeC and stirred for 1 hour. The temperature was lowered to 20 ° C. in an ice bath, and 37.72 g (2.09 mol) of H ₂ O was added dropwise over 1.4 hours. As a result, it was separated into a yellow transparent liquid and a yellow gel. After completion of the dropping, the mixture was stirred for 2 hours, heated to 40 ° C., and further stirred for 1 hour. After standing at room temperature overnight, 72% by weight of the yellow transparent liquid and the total amount of the yellow gel were separated into separate flasks each purged with nitrogen, and each volatile component was distilled off under reduced pressure. Then, drying was performed at 120 ° C. for 8 hours. Thereafter, the solid derived from the yellow transparent liquid was dissolved in 3 liters of tetrahydrofuran, and transferred to a 5 liter flask containing the solid derived from the yellow gel. After leaving still at room temperature for 69 hours, it dried under reduced pressure at 120 degreeC for 8 hours. As a result, 374 g of a solid product was obtained.

  Into a 5-liter four-necked flask purged with nitrogen, 374 g of the above solid product and 3 liters of tetrahydrofuran were added and stirred. To this was added 282 g of silica (Sypolol 948 manufactured by Devison; average particle size = 61 μm; pore volume = 1.61 ml / g; specific surface area = 296 m 2 / g) manufactured at 300 ° C. under nitrogen flow. After heating to 40 ° C. and stirring for 2 hours, the solid component was allowed to settle, and the upper slurry portion was removed. As a washing operation, 3 liters of tetrahydrofuran was added thereto and stirred, and then the solid component was allowed to settle, and the upper slurry portion was removed. The above washing operation was repeated 5 times in total. After removing the liquid component with a glass filter, drying was performed at 120 ° C. for 8 hours under reduced pressure to obtain 452 g of modified particles.

(2) After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon is evacuated, hydrogen is added so that the partial pressure is 0.001 MPa, 680 g of butane, 70 g of 1-butene The temperature was raised 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 = 0.04 mol% and 1-butene = 3.21 mol%. To this was added 0.9 ml of a heptane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as the organoaluminum compound (C). Next, the racemic-ethylenebis (1-indenyl) hafnium dichloride concentration was 0.84 μmol / ml, the racemic-ethylenebis (1-indenyl) zirconium dichloride concentration was 0.06 μmol / ml, and bis (n-butylcyclopentadienyl). ) 7.9 ml of a mixed toluene solution of three kinds of transition metal compounds adjusted to a zirconium dichloride concentration of 0.25 μmol / ml was added, and then modified particles obtained in Comparative Example 4 (1) 14.0 mg Was charged as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.09 mol% of hydrogen so as to keep the total pressure constant. As a result, 98 g of ethylene-1-butene copolymer was obtained. The physical properties of the obtained copolymer are shown in Table 3.

Comparative Example 3
(1) Preparation of Solid Catalyst Component (S) In a reactor equipped with a stirrer substituted with nitrogen, 9.68 kg of silica (Sypolol 948 manufactured by Devison) heated at 300 ° C. under nitrogen flow as a component (b4) particulate carrier was added. I put it in. 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) Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [transition metal compound (A1) adjusted to a concentration of 2 μmol / ml in a nitrogen-substituted 100 ml glass flask 12.5 ml of toluene solution and 1 ml of toluene solution of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] adjusted to a concentration of 2 μmol / ml After that, 200 mg of the solid catalyst component (S) prepared in the above (1) 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 catalyst component (Cat-1) prepared in the above (2) was added. 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. The physical properties of the obtained copolymer are shown in Table 3.

Comparative Example 4
(1) 42 mg of EIZC was added to a four-necked flask with an internal volume of 50 ml replaced with nitrogen gas. Thereafter, 6.0 ml of a toluene solution of PMAO (2.72 mmol / ml) was added, 9 ml of toluene was further added, and the mixture was heated to 65 ° C. with stirring. When the temperature reached 65 ° C., 2.10 g of dry silica preliminarily dried under nitrogen at 800 ° C. was added, and stirring was continued for 1 hour. Thereafter, toluene was removed in vacuo to obtain 2.43 g of a dry powder (S2).

(2) Polymerization After drying under reduced pressure, 27.3 g of NaCl that had been dried under reduced pressure at 140 ° C. for 6 hours was placed in an autoclave equipped with a stirrer with an internal volume of 3 liters substituted with argon, then the inside was evacuated and used as a comonomer. 6 g of 1-butene was charged and the temperature was raised to 75 ° C. Thereafter, ethylene was added as a monomer so that the pressure inside the autoclave was 0.8 MPa, and the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was 1-butene = 10.3 mol%. To this, 0.3 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as an organoaluminum compound (C) was added. Next, 110.9 mg of the dry powder (S2) prepared in Comparative Example 6 (1) was added. During the polymerization, the ethylene / 1-butene mixed gas (1-butene = 3.8 mol%) was continuously fed at 75 ° C. so as to keep the total pressure and the 1-butene concentration in the gas constant. Polymerization was performed for 2 hours. As a result, 39 g of an olefin polymer was obtained. The physical properties of the obtained copolymer are shown in Table 3.

-*：未測定

-*: Not measured

-*：未測定

-*: Not measured

-*：未測定

-*: Not measured

Claims (5)

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 melt flow rate (MFR) of 0.1 to 100 g / 10 min, and a density (d) Is 850 to 940 kg / m ³ , the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 12, and g ^* defined by the following formula (I) is 0.50 to 0.75, the flow activation energy is 55 kJ / mol or more, and in the melting curve obtained from differential scanning calorimetry, a plurality of melting peaks exist in the range from 25 ° C. to the end temperature of melting. Present ethylene-α-olefin copolymer.
g ^* = [η] / ([η] _GPC × g _SCB ^* ) (I)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is defined by the following formula (I-I). [Η] _GPC was defined by the following formula (I-II). g _SCB ^* is defined by the following formula (I-III).
[Η] = 23.3 × log (ηrel) (II)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (I-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB ^* = (1-A) ^1.725 (I-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.)]   The ethylene-α-olefin copolymer according to claim 1, wherein the swell ratio (SR) is 1.55 or more.   The ethylene α-olefin copolymer according to claim 1, wherein the melt flow rate ratio (MFRR) is 30 or more.   The ethylene-α-olefin copolymer according to any one of claims 1 to 3, wherein the number of short chain branches per 1000 carbon atoms is 13.24 or more.   The molded object formed by extrusion-molding the ethylene-alpha-olefin copolymer in any one of Claims 1-4.