JP2014070217A - ETHYLENE-α-OLEFIN COPOLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene-α-olefin copolymer from which a molding having an excellent appearance can be molded.SOLUTION: Provided is an ethylene-α-olefin copolymer of ethylene and an α-olefin having 3-20 carbon atoms satisfying all of the following requisites (A) through (G): (A) that a melt flow rate (MFR) is 0.01-100 g/10 min, (B) that density is 860-970 kg/m, (C) that a swell ratio (SR) is 1.7-2.3, (D) that a ratio of Z average molecular weight (Mz) with respect to weight-average molecular weight (Mw) (Mz/Mw) is 2.5-6.0, (E) that an elongational viscosity non-linear index k is 0.8-2.0, (F) that, at the time of monoaxial elongation of a molten resin under conditions of a temperature of 130°C and a strain rate of 1 s, the melt draw ratio leading to the rupture thereof is 2.7 or above, and (G) that characteristic relaxation time (τ) and the melt flow rate (MFR) satisfy a relation of the following formula: 3.0×MFR<τ<8.0×MFR.

Description

  The present invention relates to a resin composition containing an ethylene-α-olefin copolymer, and a molded article made of the resin composition.

  Ethylene polymers are molded by various molding methods and are used for various purposes. Patent Document 1 discloses a transition metal compound having a ligand in which two groups having a cyclopentadiene type anion skeleton are bonded via a crosslinking group as an ethylene polymer having excellent moldability and mechanical strength. And ethylene-α-polymerized using a metallocene catalyst comprising a combination of a transition metal compound having a ligand in which a group having a cyclopentadiene type anion skeleton and a group having a fluorenyl type anion skeleton are bonded via a bridging group Olefin copolymers are disclosed.

Japanese Patent Application Laid-Open No. 2006-233206

  However, since the ethylene-α-olefin copolymer described in the same document has a long relaxation time for the molten ethylene-α-olefin copolymer molecular chain, the appearance of the molded product obtained by molding is still sufficiently satisfactory. It wasn't going to be good. Under such circumstances, the problem to be solved by the present invention is to provide an ethylene-α-olefin copolymer capable of forming a molded article having excellent appearance.

As a result of intensive studies to solve these problems, the present inventors have completed the present invention.
That is, the present invention is an ethylene-α-olefin copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, which satisfies all of the following requirements (A) to (G): This relates to an α-olefin copolymer.
(A) The melt flow rate (MFR) is 0.01 to 100 g / 10 min.
(B) The density is 860 to 970 kg / m ³ .
(C) The swell ratio (SR) is 1.7 to 2.3.
(D) The ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is 2.5 to 6.0.
(E) The extensional viscosity nonlinear index k is 0.8 to 2.0.
(F) When stretched uniaxially at a temperature of 130 ° C. and a strain rate of 1 s ⁻¹ , the melt draw ratio until the molten resin breaks is 2.7 or more.
(G) The characteristic relaxation time (τ) and the melt flow rate (MFR) satisfy the relationship of the following formula.
3.0 × MFR ^−0.9654 <τ <8.0 × MFR ^−0.9654

  According to the present invention, it is possible to provide an ethylene-α-olefin copolymer capable of forming a molded article having an excellent appearance.

  Hereinafter, the present invention will be described in detail.

  The ethylene-α-olefin copolymer of the present invention is a copolymer having 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 having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and the like. More preferred are 1-butene and 1-hexene. Moreover, said C3-C20 alpha olefin may be used independently and may use 2 or more types together.

  The content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer of the present invention is usually 50% by weight or more with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer. It is. The content of the monomer unit based on the α-olefin having 3 to 20 carbon atoms is usually 50% by weight or less with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer.

  In addition to the monomer unit based on ethylene and the monomer unit based on an α-olefin having 3 to 20 carbon atoms, the ethylene-α-olefin copolymer of the present invention is within a range not impairing the effects of the present invention. May have a monomer unit based on a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the monomer include 1,3-butadiene, 2-methyl-1 Conjugated dienes such as 1,3-butadiene; non-conjugated dienes such as 1,4-pentadiene and 1,5-hexadiene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, butyl acrylate, Examples thereof include unsaturated carboxylic acid esters such as methyl methacrylate and ethyl methacrylate; vinyl ester compounds such as vinyl acetate.

  Examples of the ethylene-α-olefin copolymer of the present invention include an ethylene homopolymer, an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-4-methyl- 1-pentene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1- Examples include butene-1-octene copolymer. Preferably, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-1 -An octene copolymer, more preferably an ethylene-1-hexene copolymer.

  The melt flow rate (MFR) of the ethylene-α-olefin copolymer of the present invention is 0.01 to 100 g / 10 min. In order to obtain a molded article having good mechanical strength, the MFR is preferably 20 g / 10 min or less, more preferably 10 g / 10 min or less, still more preferably 8 g / 10 or less, and even more preferably. Is 7 g / 10 or less. Further, from the viewpoint of workability, it is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, still more preferably 1.0 g / 10 min or more, and even more preferably 2.0 g / 10 min or more. The MFR is measured by the A method according to JIS K7210-1995 under conditions of a temperature of 190 ° C. and a load of 21.18N.

The density of the ethylene-α-olefin copolymer of the present invention is 860 to 970 kg / m ³ . It said seal degree, in view of enhancing the mechanical strength, is preferably 940 kg / m ^3, more preferably at most 930 kg / m ^3. Moreover, it said seal degree, in view of enhancing the rigidity, is preferably 890 kg / m ³ or more, more preferably 900 kg / m ³ or more, more preferably 910 kg / m ³ or more, even more preferably 912 kg / m ³ That's it. In addition, this density is measured according to the A method prescribed | regulated to JISK7112-1980 using the sample which annealed as described in JISK6760-1995.

The swell ratio (SR) of the ethylene-α-olefin copolymer of the present invention is 1.7 to 2.3. From the viewpoint of reducing the neck-in of the T-die film molding, it is preferably 1.80 or more, more preferably 1.85 or more. Further, from the viewpoint of improving the take-up property when melted and molded, it is preferably 2.25 or less, more preferably 2.20 or less, still more preferably 2.15 or less, and still more preferably 2.10 or less. 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 swell ratio calculation method is as follows. First, in the measurement of the melt flow rate, an ethylene-α-olefin copolymer extruded at a length of about 15 to 20 mm from an orifice under the conditions of a temperature of 190 ° C. and a load of 21.18 N. The combined strand is cooled in air to obtain a solid strand. Next, the diameter D (unit: mm) of the strand at a position 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.

  The ratio (Mz / Mw) of z-average molecular weight (Mz) and weight-average molecular weight (Mw) in terms of polystyrene of the ethylene polymer of the present invention is 2.5 to 6.0. In order to obtain a molded article having good mechanical strength, Mz / Mw of the ethylene polymer is preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.5 or less. Yes, even more preferably 3.3 or less. Moreover, from a workability viewpoint, Preferably it is 2.7 or more, More preferably, it is 2.8 or more, More preferably, it is 2.9 or more, More preferably, it is 3.0 or more.

  The ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight (Mw) to number average molecular weight (Mn) of the ethylene-α-olefin copolymer of the present invention is preferably 4.0 to 10.0. In order to obtain a molded article having good mechanical strength, the Mw / Mn of the ethylene-α-olefin copolymer is preferably 7.0 or less, and more preferably 6.5 or less. Moreover, from a workability viewpoint, Preferably it is 5.0 or more, More preferably, it is 5.5 or more.

The number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) of the ethylene-α-olefin copolymer of the present invention are measured by the following methods.
The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) measurement are calculated, and the value obtained by dividing Mw by Mn is the molecular weight distribution (Mw / Mn). did. Further, the polystyrene-equivalent Z-average molecular weight (Mz) and weight-average molecular weight (Mw) obtained by gel permeation chromatography (GPC) measurement were calculated, and the ratio of Mz to Mw was defined as Mz / Mw.
Apparatus: Waters 150C manufactured by Waters
Separation column: TOSOH TSKgelGMH-HT
Measurement temperature: 140 ° C
Carrier: Orthodichlorobenzene Flow rate: 1.0 mL / min Injection volume: 500 μL

  The elongational viscosity nonlinear index k representing the strain hardening strength of the ethylene-α-olefin copolymer of the present invention is preferably 0.85 or more, more preferably 0.90 or more, and even more preferably 0. .95 or more. When k is small, it means that sufficient strain-hardening property is not exhibited, and there are cases where processing is troubled in various moldings. For example, it is conceivable that the neck-in at the time of processing the T-die film becomes large. Further, the extensional viscosity nonlinear index k is preferably 2.00 or less, more preferably 1.50 or less, still more preferably 1.40 or less, still more preferably 1.30 or less, Especially preferably, it is 1.20 or less. If k is too large, the melt elasticity is too strong, and it tends to be difficult to mold into a desired shape.

  The elongational viscosity nonlinear index k is an index indicating the fluidity and molding processability of the resin. When the elongational viscosity nonlinear index k is small, the moldability is inferior, and as a result, foam breakage during foaming and uneven thickness of the film are caused. It becomes. On the other hand, if the elongational viscosity nonlinear index k is too large, gel is likely to be generated in the molded product, and the flowability is poor, so that the moldability is deteriorated.

The elongation-viscosity nonlinearity index k of the ethylene-α-olefin copolymer of the present invention is a 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. And the following function obtained from a viscosity-time curve σ _0.1 (t) of the molten resin when uniaxially stretched at a temperature of 130 ° C. and a strain rate of 0.1 s ⁻¹ :
α (t) = σ ₁ (t) / σ _0.1 (t)
In this function, t is a value calculated as the slope of lnα (t) between 1.4 seconds and 3.0 seconds, and k when the correlation coefficient r ² at the time of linear approximation is 0.99 or more. adopt. The measurement of the viscosity-time curve σ (t) of the molten resin is performed using a viscoelasticity measuring device (for example, ARES manufactured by TA Instruments). Note that the measurement is performed in a nitrogen atmosphere.

In the measurement of the extensional viscosity, depending on the type of resin, there is a resin having a so-called strain hardening property in which the extensional viscosity is suddenly increased from the linear region in a high strain region. In this case, the logarithm of α (t) (k = ln (α (t))) is known to increase linearly with respect to the amount of Henky distortion [= ln (l / l ₀ )] (here Where l ₀ and l are the lengths of the samples at elongation times 0 and t, respectively) [Reference: Kiyoto Koyama, Osamu Ishizuka; Textile Society Journal, 37, T-258 (1981)]. In the case of a resin having no strain-hardening property, α (t) is 1 for an arbitrary amount of stretching strain, and a logarithm of α (t) (ln (α (t))) plotted with a stretching time is a straight line. The slope k is 0. In the case of a resin having strain hardening property, the slope k of the straight line plot does not become 0 particularly in a high strain region. In the present invention, the slope of a straight line obtained by plotting the logarithm (ln (α (t))) of the nonlinear parameter α (t) against the extension time is defined as k as a parameter representing the degree of strain hardening.

The melt draw ratio t _H of the ethylene-α-olefin copolymer of the present invention is a 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. The amount of Henky strain at the melt fracture point at is defined as t _H. The melt draw ratio t _H of the ethylene-α-olefin copolymer of the present invention is 2.7 or more. Although it may be stretched in a molten state during molding, from the viewpoint of stretchability in the molten state, it is preferably 3.0 or more, more preferably 3.2 or more, and even more preferably 3.3 or more. Even more preferably, it is 3.4 or more, particularly preferably 3.5 or more.

The characteristic relaxation time τ of the ethylene-α-olefin copolymer of the present invention is measured under the following conditions (a) to (d) using a strain-controlled rotary viscometer (rheometer). . The characteristic relaxation time is calculated from a master curve showing the dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. on the angular frequency (unit: rad / sec), which is created based on the temperature-time superposition principle. It is a numerical value. Specifically, the melt complex viscosity-angular frequency curve of the ethylene polymer at each temperature (T, unit: ° C.) of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (unit of melt complex viscosity is Pa · sec, The unit of the angular frequency is rad / sec.) Is superposed on the melt complex viscosity-angular frequency curve at 190 ° C. based on the temperature-time superposition principle, and a master curve is obtained. It is a value calculated by approximating with the following formula. The measurement is performed under nitrogen. Calculation software includes Rohms V. from Reometrics. 4.4.4 is used, and the value when the correlation coefficient r2 in the linear approximation in the Arrhenius type plot log (aT) − (1 / T) is 0.99 or more is adopted.

Condition (a) Geometry: Parallel plate, diameter 25 mm, plate interval: 1.5-2 mm
Condition (b) Strain: 5%
Condition (c) Shear rate: 0.1 to 100 rad / sec
Condition (d) Temperature: 190, 170, 150, 130 ° C

η = η ₀ / [1+ (τ × ω) ⁿ ]
η: Complex melt viscosity (unit: Pa · sec)
ω: angular frequency (unit: rad / sec)
τ: Characteristic relaxation time (unit: sec)
η ₀ : Constant determined for each ethylene polymer (unit: Pa · sec)
n: Constant determined for each ethylene polymer

  The characteristic relaxation time (τ) of the resin corresponds to the time for relaxation of the polymer chain in the resin. The slower the relaxation (the longer the characteristic relaxation time), the more the surface of the molded body using the resin is Get rough. Therefore, from the viewpoint of obtaining a molded article having a good appearance, it is preferable that the resin property relaxation time is short (see, for example, H. Zhu et. Al. Polymer 48, (2007) 5098-5106).

  The characteristic relaxation time (τ) is a numerical value related to the length of the long chain branching and the amount of long chain branching of the ethylene-α-olefin copolymer, and the long chain branching is short (or the long chain branching amount). The characteristic relaxation time (τ) becomes a small value when the long chain branch is long (or the amount of long chain branching is large), and the characteristic relaxation time (τ) becomes a large value. In order to obtain high melt tension and high strain hardening characteristics, a sufficient amount or length of long chain branching needs to be introduced into the molecular chain, and it has a certain relaxation time (τ). Is preferred. On the other hand, a polymer having a too long relaxation time (τ) has high strain hardening characteristics, but the take-up property of the molten resin with respect to the melt tension is deteriorated, that is, the balance between the melt tension and the take-up property is deteriorated. The characteristic relaxation time (τ) can be changed, for example, depending on polymerization conditions such as hydrogen concentration, ethylene pressure, and polymerization temperature, and the characteristic relaxation time (τ) of the ethylene-α-olefin copolymer can be changed.

The characteristic relaxation time (τ) of the ethylene-α-olefin copolymer of the present invention satisfies the following relational expression (1-1), and the first ethylene-α-olefin copolymer of the present invention is From the viewpoint of the surface appearance of the film formed using, preferably satisfies the relational expression of formula (1-2), more preferably satisfies the relational expression of formula (1-3), and more preferably the formula (1). -4) is satisfied.
τ <8.0 × MFR ^−0.9654 Formula (1-1)
τ <7.5 × MFR ^−0.9654 Formula (1-2)
τ <7.0 × MFR ^−0.9654 Formula (1-3)
τ <6.5 × MFR ^−0.9654 (1-4)

In general, it is known that the following formula is established for a polymer having sufficient entanglement.
τ = A · η ₀ formula (2)
Further, in FIG. 14 of Macromolecules, 33, 7489 (2000) (PM Wood-Adams et al.), In a metallocene polyethylene containing long chain branches, log-log plots of η ₀ and Mw can be expressed by straight lines. This has been reported, that is, for polyethylene containing long chain branches, the following formula η ₀ = B · Mwε Equation (3)
Strongly suggests that Substituting this equation (3) into equation (2), the following equation (4) can be derived.
τ = C · MFRε Equation (4)
In order to define the range of τ of the ethylene-α-olefin copolymer of the present invention, the inequality of formula (5) was used.
τ <C ₁ · MFRε ₁ formula (5)

The plot of τ and MFR of Examples in which the polymerization conditions other than the hydrogen concentration were made almost constant was fitted using the formula (4) using Microsoft Excel. The MFR and relaxation time of Examples 1 to 4 were used for fitting. In view of data accuracy and the like, equation (1-4) was obtained from equation (1-1) which is an inequality obtained by multiplying C1 by a constant in the following manner.
The value of C obtained at the time of fitting was multiplied by 1.484 to obtain Formula (1-1) as C1. The value of C obtained at the time of fitting was multiplied by 1.391 to obtain Formula (1-2) as C1. The value of C obtained at the time of fitting was multiplied by 1.298 to obtain C1 as a formula (1-3). The value of C obtained at the time of fitting was multiplied by 1.206 to obtain the expression (1-4) as C1.

Τ of the ethylene-α-olefin copolymer of the present invention satisfies the following relational expression (2-1). From the viewpoint of the extrusion load during processing, the relational expression of the formula (2-2) is preferable. More preferably, the relational expression (2-3) is satisfied.
τ> 3.0 × MFR ^−0.9654 formula (2-1)
τ> 3.5 × MFR ^−0.9654 formula (2-2)
τ> 4.0 × MFR ^−0.9654 (2-3)

  The plot of τ and MFR of Examples in which the polymerization conditions other than the hydrogen concentration were made almost constant was fitted using the formula (4) using Microsoft Excel. The MFR and relaxation time of Examples 1 to 4 were used for fitting. In view of data accuracy and the like, Equation (2-3) was obtained from Equation (2-1), which is an inequality obtained by multiplying C1 by a constant in the following manner. The value of C obtained at the time of fitting was multiplied by 0.556 to obtain the formula (2-1) as C1. The value of C obtained at the time of fitting was multiplied by 0.649 to obtain Formula (2-2) as C1. The value of C obtained at the time of fitting was multiplied by 0.742 to obtain a formula (2-3) as C1.

  The characteristic relaxation time (τ) of the ethylene-α-olefin copolymer of the present invention is preferably from 0.1 seconds to 15 seconds. From the viewpoint of the surface appearance of the molded article, it is preferably 12 seconds or less, more preferably 10 seconds or less, still more preferably 8 seconds or less, still more preferably 4 seconds or less, and most preferably 3 seconds or less. Further, from the viewpoint of moldability, it is preferably 0.2 seconds or longer, more preferably 0.3 seconds or longer, and further preferably 0.4 seconds or longer.

  The long chain branching amount (LCB amount) and short chain branching amount (SCB amount) per 1000 carbon atoms of the ethylene-α-olefin copolymer of the present invention are measured by the following methods.

The number of long chain branches (LCB) or short chain branches (SCB) per 1000 carbon atoms is determined by the carbon nuclear magnetic resonance ( ¹³ C-NMR) method according to the following measurement conditions. ¹³ C-NMR) spectrum was measured, and the number of long chain branches or short chain branches per 1000 carbon atoms in the polymer was determined by the following calculation method.

(Measurement condition)
Apparatus: AVANCE600 manufactured by Bruker
Measurement probe: 10 mm cryoprobe Measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4
= 75/25 (volume ratio) mixed solution measurement temperature: 130 ° C.
Measurement method: proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Tetramethylsilane window function: Exponential or Gaussian integration number: 2500

Method for calculating the number of long chain branches (LCB) In the NMR spectrum obtained by treating the window function with Gaussian, the sum of the peak areas of all peaks having a peak top at 5 to 50 ppm is 1000, and branches having 7 or more carbon atoms are present. The number of long chain branches (number of branches having 7 or more carbon atoms) was determined from the peak area of the peak derived from the bound methine carbon. Under the present measurement conditions, the number of long chain branches (the number of branches having 7 or more carbon atoms) was determined from the peak area of a peak having a peak top in the vicinity of 38.22 to 38.27 ppm. 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 this measurement condition, in the measurement of the ethylene-1-octene copolymer, the peak top position of the peak derived from the methine carbon to which the hexyl branch was bonded was 38.21 ppm.

  The ethylene polymer of the present invention has a long chain branching amount (LCB amount) per 1000 carbon atoms of 0.20 to 1.00. The amount of LCB per 1000 carbon atoms is preferably 0.22 or more, more preferably 0.23 or more, and further preferably 0.24 or more from the viewpoint of improving the workability during melt processing. Moreover, from a viewpoint of raising mechanical strength, Preferably it is 0.80 or less, More preferably, it is 0.60 or less, More preferably, it is 0.50 or less.

Method for calculating the number of short chain branches (SCB) When the comonomer is hexene In the NMR spectrum in which the window function is treated with an exponential, the branch having 4 carbon atoms is bonded when the sum of the peak areas of all peaks having a peak top at 5 to 50 ppm is 1000 The number of short chain branches was calculated from the peak area derived from the methine carbon. In this measurement condition, it calculated | required from the total value of the area of a peak of 38.0-38.21 ppm and the area of a peak of 35.85-36.00 ppm.
2. When the comonomer is hexene and butene In the NMR spectrum in which the window function is treated with the exponential, the branch of 2 carbon atoms when the sum of the peak areas of all peaks having a peak top at 5 to 50 ppm is 1000 The number of short-chain branches was calculated from the peak area derived from the methine carbon bonded to and the peak area derived from the methine carbon bonded to the branch having 4 carbon atoms. In this measurement condition, it calculated | required from the total value of the area of 39.60-39.85 ppm, the area of the peak of 38.00-38.21 ppm, and the area of the peak of 35.85-36.00 ppm.

The shrinkage factor g * of the ethylene polymer of the present invention is 0.500 to 0.800, and is preferably 0.790 or less, more preferably from the viewpoint of imparting sufficient processing characteristics, particularly strain hardening characteristics. Is 0.780 or less. When g * is large, long chain branching is not sufficiently contained, so that sufficient strain hardening characteristics cannot be obtained. Further, g * of the ethylene polymer is preferably 0.600 or more, more preferably 0.650 or more, still more preferably 0.700 or more, and still more preferably, from the viewpoint of improving mechanical strength. Is 0.730 or more. 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.
(For g *, reference was made to the following document: Developments in Polymer Characterization-4, .JV V. Dawkins, .Ed., Applied Science, London, .1983, Chapter.I, .z.f. Long Chain Branching in Polymers, '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 is the intrinsic viscosity (unit: dl / g) of a polymer that is assumed to have the same molecular weight distribution as that of the ethylene-α-olefin copolymer and that the molecular chain is linear. And defined by the following formula (I-II). g _SCB * represents a contribution to g * caused by introducing a short chain branch into the ethylene-α-olefin copolymer, and is defined by the following formula (I-III).
[Η] = 23.3 × log (η _rel ) (II)
(In the formula, η _rel 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 is calculated from the content of short chain branches in the ethylene-α-olefin copolymer, and can be directly determined from the measurement of the content of short chain branches in 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 L. H. Tung was used.

The relative viscosity (η _rel ) of the ethylene-α-olefin copolymer was obtained by dissolving 100 mg of the olefin polymer at 135 ° C. in 100 ml of tetralin containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor. And is calculated from the falling time of the sample solution and a blank solution made of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor using an Ubbelohde viscometer.

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

And a = 0.725.

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 When the number of short chain branches per 1000 carbon atoms required is y,
A = ((12 × n + 2n + 1) × y) / ((1000−2y−2) × 14 + (y + 2) × 15 + y × 13)
As estimated.

  The amount of oligomer (the amount of oligomer component derived from n-C12 to C38 polyethylene) contained in the ethylene-α-olefin copolymer of the present invention is 1000 ppm or less. Since the amount of the oligomer is small, the volatile component is reduced, and it becomes difficult to generate smoke due to the volatile component at the time of melt processing at a high temperature. From the viewpoint of moldability during melt processing, it is preferably 800 ppm or less, more preferably 700 ppm or less, and even more preferably 600 ppm or less.

The amount of oligomer (the amount of oligomer component derived from polyethylene of n-C12 to C38) contained in the ethylene-α-olefin copolymer of the present invention can be measured using gas chromatography. The oligomer can be extracted by an ultrasonic method. The GPC measurement device and each measurement condition are as follows.
GC measuring device manufactured by SHIMADZU GC-2010
DB-1 made by J & W
(Thickness 0.15μm, length 15m, inner diameter 0.53mm)
Detector (FID) temperature 310 ℃
Measurement column temperature Hold at 100 ° C for 1 minute, then heat up to 310 ° C at 10 ° C / minute

  The melt tension (MT) of the ethylene-α-olefin copolymer of the present invention is preferably 1 cN or more and 20 cN or less. From the viewpoint of making it difficult to break when the molten resin is stretched during melt molding, it is more preferably 2 cN or more. Moreover, from a viewpoint of making it easy to extend | stretch molten resin at the time of melt molding, More preferably, it is 15 cN or less, More preferably, it is 12 cN or less, Most preferably, it is 10 cN or less.

  The maximum take-off speed (MTV) of the ethylene-α-olefin copolymer of the present invention is preferably 4 m / min or more and 50 m / min or less. From the viewpoint of facilitating stretching of the molten resin during melt molding, it is more preferably 5 m / min or more, and further preferably 6 m / min. Further, from the viewpoint of making it difficult to break when the molten resin is stretched during melt molding, it is more preferably 40 m / min or less, still more preferably 30 m / min or less, and particularly preferably 20 m / min.

  The melt tension (MT, unit: cN) and the maximum take-off speed (MTV, unit: m / min) of the ethylene-α-olefin copolymer of the present invention are 150 ° C using a melt tension tester manufactured by Toyo Seiki Seisakusho. A molten resin filled in a 9.55 mmφ barrel under the condition of ° C was extruded from an orifice having a diameter of 2.09 mmφ and a length of 8 mm at a piston lowering speed of 5.5 mm / min, and the extruded molten resin was Is taken up at a take-up speed of 40 rpm / min using a take-up roll of 50 mmφ, the tension immediately before the molten resin breaks is defined as melt tension (MT), and the take-up speed immediately before the molten resin breaks is the maximum take-up speed. (MTV).

<Manufacturing method>
The ethylene-α-olefin copolymer of the present invention uses a polymerization catalyst obtained by contacting the following transition metal compound (A), the following transition metal compound (B) and the activation promoter component (C). It is obtained by copolymerizing ethylene and α-olefin.

（式中、Ｍ¹は元素周期律表第４族の遷移金属原子を表す。Ｒ¹及びＲ^２は、それぞれ独立して、水素原子、置換基を有し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。少なくとも一つのＲ^１および／または少なくとも一つのＲ^２は、置換基を有していてもよい炭素原子数６〜２０のアリール基である。複数のＲ^１および複数のＲ^２は互いに同じであっても異なってもよい。Ｘ¹は、水素原子、ハロゲン原子、置換基を有していてもよい炭素原子数１〜２０のハイドロカルビル基、置換基を有し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、置換シリル基、又は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。ｎは１〜５の整数を表し、Ｊ¹は炭素原子、又はケイ素原子を表し、Ｊ¹が複数ある場合、それら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、又は置換基を有し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。） Transition metal compound (A): transition metal compound represented by the general formula (1)

(In the formula, M ¹ represents a transition metal atom of Group 4 of the Periodic Table of Elements. R ¹ and R ² are each independently a hydrogen atom or an optionally substituted carbon atom having 1 to 1 carbon atoms. represents a hydrocarbyl group of 20. at least one of R ¹ and / or at least one of R ² is substituted aryl group which may having 6 to 20 carbon atoms. plurality of R ¹ and A plurality of R ² may be the same or different from each other, and X ¹ represents a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. It represents a hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group, or a substituted amino group which may have, and two X ^{1 s} may be the same or different from each other, and n is 1. represents an integer of to 5, J ¹ is carbon atom or silicon atom table , If J ¹ there are a plurality, they may be different be the same as each other, R ⁵ is a hydrogen atom, or a hydrocarbyl group optionally having 1 to 20 carbon atoms which may have a substituent And a plurality of R ⁵ may be the same as or different from each other.)

（式中、Ｍ²は元素周期律表第４族の遷移金属原子を表す。Ｒ⁶は、水素原子、置換基を有し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Ｒ⁶はそれぞれ互いに同じであっても異なっていてもよい。）Ｘ²は、水素原子、ハロゲン原子、置換基を有していてもよい炭素原子数１〜２０のハイドロカルビル基、置換基を有し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、置換シリル基、又は置換アミノ基を表し、２つのＸ^２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^２は炭素原子、又はケイ素原子を表し、Ｊ^２が複数ある場合、それらは互いに同じであっても異なっていてもよい。Ｒ^７は、水素原子、又は置換基を有し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^７は互いに同じであっても異なっていてもよい。） Transition metal compound (B): transition metal compound represented by the general formula (2)

(In the formula, M ² represents a transition metal atom of Group 4 of the Periodic Table of Elements. R ⁶ represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent. And a plurality of R ⁶ may be the same or different from each other.) X ² is a hydrogen atom, a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent. Represents a hydrocarbyloxy group having 1 to 20 carbon atoms which may have a substituent, a substituted silyl group, or a substituted amino group, and two X ^{2 s} may be the same or different from each other. . m represents an integer of 1 to 5, J ² represents a carbon atom or a silicon atom, if J ² there is a plurality, they may be different from one another the same. R ⁷ represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, and the plurality of R ⁷ may be the same as or different from each other. )

Hereinafter, the transition metal compound (A) and the transition metal compound (B) will be described in detail.

M ¹ in the general formula (1) represents a transition metal atom of Group 4 of the periodic table of the elements, preferably a titanium atom, a zirconium atom, or a hafnium atom, and more preferably a zirconium atom.

The hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R ¹ and R ^{2 includes} an alkyl group having 1 to 20 carbon atoms and a substituent which may have a substituent. A cycloalkyl group having 1 to 20 carbon atoms which may have an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and 6 carbon atoms which may have a substituent. -20 aryl groups and the like.

Examples of the alkyl group having 1 to 20 carbon atoms that may have a substituent of R ¹ and R ² include an alkyl group having 1 to 20 carbon atoms and a carbon atom having 1 to 20 carbon atoms substituted with a halogen atom. An alkyl group, an alkyl group having 1 to 20 carbon atoms substituted with a substituted silyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a substituted amino group having 1 to 20 carbon atoms And an alkyl group having 1 to 20 carbon atoms substituted with a hydrocarbyloxy group having 1 to 20 carbon atoms.

  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 cycloalkyl group having 1 to 20 carbon atoms which may have a substituent of R ¹ and R ² include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-phenylcyclohexyl group, 1-indanyl group, 2-indanyl group, norbornyl group, bornyl group, menthyl group, 1-adamantyl group, 2-adamantyl group Preferably, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-indanyl group, 2-indanyl group, norbornyl group, bornyl group, menthyl group, 1- Adamantyl group, 2-adamantyl group, etc. A cycloalkyl group having 5 to 10 carbon atoms constituting the ring, more preferably a cyclohexyl group, a 1-methylcyclohexyl group, a norbornyl group, a bornyl group, a 1-adamantyl group, a 2-adamantyl group, etc. It is a cycloalkyl group having 6 to 10 carbon atoms constituting the ring. These cycloalkyl groups may have a hydrocarbyl group having 1 to 10 carbon atoms as a substituent.

The aryl group having 6 to 20 carbon atoms which may have a substituent of R ¹ and R ² in the general formula (1) includes an aryl group having 6 to 20 carbon atoms and a carbon substituted with a halogen atom. Number of carbon atoms substituted with an aryl group having 6 to 20 atoms, an aryl group having 6 to 20 carbon atoms substituted with a substituted silyl group having 1 to 20 carbon atoms, and a substituted amino group having 1 to 20 carbon atoms And an aryl group having 6 to 20 carbon atoms and 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.

The aryl group having 6 to 20 carbon atoms which may have a substituent of R ¹ and R ² is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms which may have a substituent 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.

R ¹ and R ² are preferably a hydrogen atom or an aryl group having 6 to 20 carbon atoms which may have a substituent.

X ^{1 in the} general formula (1) is a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 1 substituent which may have a substituent. Represents a ˜20 hydrocarbyloxy 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 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.

The hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of X ¹ is a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R ¹ and R ^2. The same thing as what was illustrated as a building group can be mention | raise | lifted.

The hydrocarbyloxy group having 1 to 20 carbon atoms which may have a substituent of X ¹ has an alkoxy group having 1 to 20 carbon atoms which may have a substituent or a substituent. And an aralkyloxy group having 7 to 20 carbon atoms which may be present, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, 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 aralkyloxy group having 7 to 20 carbon atoms which may have a substituent 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. Can be given.

  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 aryloxy group having 6 to 20 carbon atoms which may have a substituent 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. Can be given.

  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 are preferable, a chlorine atom, a methyl group, a phenoxy group, and a benzyl group are more preferable, and a chlorine atom is more preferable.

  N of General formula (1) is an integer of 1-5. n is preferably 1 or 2.

J ^{1 in the} general formula (1) represents a carbon atom or a silicon atom, and when there are a plurality of J ^{1 s} , they may be the same as or different from each other.

R ^{5 in the} general formula (1) is each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent.

The hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R ⁵ is a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R ¹ and R ^2. The same thing as what was illustrated as a building group can be mention | raise | lifted.

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、シリレン基、ジシリレン基、トリシリレン基、テトラシリレン基、ジメチルシリレン基、ビス（ジメチルシラン）ジイル基、ジエチルシリレン基、ジプロピルシリレン基、ジブチルシリレン基、ジフェニルシリレン基、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、ジビニルシリレン基、ジアリルシリレン基、（メチル）（ビニル）シリレン基、（アリル）（メチル）シリレン基等があげられる。 As the crosslinking group represented by the following general formula (3) in 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, silylene group, disilylene group, trisilylene group, tetrasilylene group, dimethylsilylene group, bis (dimethylsilane) diyl group, diethyl Silylene group, dipropylsilylene group, dibutylsilylene group, diphenylsilylene group, silacyclobutanediyl group, silacyclohexanediyl group, divinylsilylene group, diallylsilylene group, (methyl) (vinyl) silylene group, Allyl) (methyl) silylene group and the like.

  The cross-linking group represented by the general formula (3) is preferably methylene group, ethylene group, isopropylidene group, bis (cyclohexyl) methylene group, diphenylmethylene group, dimethylsilylene group, bis (dimethylsilane) diyl group, diphenylsilylene. More preferably an isopropylidene group or a dimethylsilylene group.

  Examples of the transition metal compound (A) represented by the general formula (1) 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, dimethylsilane Renbis (2,3,5-triphenylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (tetraphenylcyclopentadienyl) zirconium dichloride, and “dimethylsilylene” of these compounds as “methylene”, “ethylene” , “Isopropylidene”, “bis (cyclohexyl) methylene”, “diphenylmethylene”, “dimethylsilylene”, “bis (dimethylsilane) diyl”, or “diphenylsilylene”, “difluoride” , “Dibromide”, “diaiodide”, “dimethyl,“ diethyl ”,“ diisopropyl ”,“ diphenyl ”,“ dibenzyl ”,“ dimethoxide ”,“ diethoxide ”,“ di (n-propoxide) ”,“ 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) is preferably dimethylsilylene bis (3-phenylcyclopentadienyl) dichloride.

The transition metal compound represented by the general formula (1) may be used alone or in combination of two or more. Also, isomers may exist depending on the position and number of substituents on the cyclopentadienyl ring, but even if one of those isomers is used alone, it can be used as a mixture of isomers in an arbitrary ratio. Also good.

M ² in the general formula (2) represents a transition metal atom of Group 4 of the Periodic Table of Elements, preferably a titanium atom, a zirconium atom, or a hafnium atom, and more preferably a zirconium atom.

R ^{6 in the} general formula (2) represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, and a plurality of R ⁶ may be the same or different from each other. May be.

The hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R ^{6 in} the general formula (2) has a substituent in R ¹ and R ² in the general formula (1). Examples thereof may be the same as those exemplified as the hydrocarbyl group having 1 to 20 carbon atoms.

R ^{6 in the} general formula (2) is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and more preferably a hydrogen atom.

X ^{2 in the} general formula (2) is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 1 carbon atom. Represents 20 hydrocarbyloxy groups, substituted silyl groups, or substituted amino groups, and two X ^{2 s} may be the same or different from each other.

X ^{2 in the} general formula (2) can be the same as those exemplified as X ^{1 in the} general formula (1).

X ^{2 in the} general formula (2) is preferably a chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Butoxy group, trifluoromethoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6 -A tetrafluoro-4-pentafluorophenylphenoxy group and a benzyl group, more preferably a chlorine atom, a methyl group, a phenoxy group, and a benzyl group, and still more preferably a phenoxy group.

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

J ^{2 in the} general formula (2) represents a carbon atom or a silicon atom, and when there are a plurality of J ^{2 s} , they may be the same as or different from each other.

R ^{7 in the} general formula (2) is each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent.

R ^{7 in the} general formula (2) can be the same as those exemplified as R ^{5 in the} general formula (1).

As the crosslinking group represented by the following general formula (4) in the general formula (2), the same as those exemplified as the crosslinking group represented by the general formula (3) in the general formula (1). I can give you.

  The cross-linking group represented by the general formula (4) is preferably a methylene group, a diphenylmethylene group, a methylphenylmethylene group, an ethylene group, a tetramethylethylene group, or a dimethylsilylene group, more preferably an ethylene group or dimethylsilylene. It is a group.

  Examples of the transition metal compound (B) represented by the general formula (2) include dimethylsilylene bis (indenyl) zirconium dichloride, dimethylsilylene bis (2-methylindenyl) zirconium dichloride, and dimethylsilylene bis (2-tert- Butylindenyl) zirconium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) zirconium dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-isopropyl) Indenyl) zirconium dichloride, dimethylsilylene bis (4,5-benzindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4,5-benzindenyl) zirconium dichloride, dimethyl Silylene bis (2-phenylindenyl) zirconium dichloride, dimethylsilylene bis (4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-5) -Phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, and “ Dichloride is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxy , “Di (n-propoxide)”, “di (isopropoxide)”, “diphenoxide”, or “di (pentafluorophenoxide)”, and “zirconium” in each of the above compounds Compound changed to “titanium” or “hafnium”, “dimethylsilylene” replaced with “methylene”, “ethylene”, “dimethylmethylene (isopropylidene)”, “diphenylmethylene”, “diethylsilylene”, “diphenylsilylene”, or “Dimethoxysilylene” can be exemplified.

  The transition metal compound represented by the general formula (2) is preferably racemic-ethylenebis (indenyl) zirconium diphenoxide.

The transition metal compound represented by the general formula (2) may be used alone or in combination of two or more. Further, although isomers may exist depending on the position and number of substituents on the indenyl ring, they may be used alone or as a mixture of isomers in an arbitrary ratio.

Co-catalyst component for activation (C)
The activation promoter component is not particularly limited as long as it activates the transition metal compound (A) and the transition metal compound (B) to enable polymerization,
(C-1) Organoaluminum compound (C-2) There can be mentioned at least one compound selected from the group consisting of boron compounds.

The organoaluminum compound (C-1) may be a known compound, preferably a compound represented by the following formula or a mixture thereof:
(C-1-1) A compound represented by E ¹ _c AlY ¹ _3-c .
(C-1-2) {-Al (E ² ) —O—} A cyclic aluminoxane represented by _d .
(C-1-3) E ³ {—Al (E ³ ) —O—} _e Linear aluminoxane represented by AlE ³ ₂ .
(In the formula, E ¹ , E ² , and E ³ are hydrocarbyl groups having 1 to 8 carbon atoms, and all E ¹ , all E ^2, and all E ³ are the same or different, and Y ¹ is a hydrogen atom. Or a halogen atom, all Y ¹ are the same or different, c is a number of 0 <c ≦ 3, d is an integer of 2 or more, and e is an integer of 1 or more.

  As organoaluminum compound (C-1-1), trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, Dialkylaluminum chlorides such as diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride; and dimethylaluminum hydride, diethyl Rumi bromide hydride, dipropyl aluminum hydride, can be mentioned dialkyl aluminum hydride such as diisobutyl aluminum hydride, and dihexyl aluminum hydride. Among them, preferred is trialkylaluminum, and more preferred is triethylaluminum or triisobutylaluminum.

Examples of E ² and E ³ in the above formula include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. Among these, a methyl group or an isobutyl group is preferable. d is an integer of 2 or more, preferably an integer of 2 to 40, and e is an integer of 1 or more, preferably an integer of 1 to 40.

The method for producing the above aluminoxane is not particularly limited, and may be a known method. As a production method, a method in which a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (for example, benzene or aliphatic hydrocarbyl) is contacted with water, or a trialkylaluminum (for example, trimethylaluminum) is used. A method of bringing aluminum) into contact with a metal salt containing crystal water (for example, copper sulfate hydrate) can be exemplified.

Examples of the boron compound (C-2) include the following compounds:
(C-2-1) A boron compound represented by the formula BR ¹³ R ¹⁴ R ¹⁵ .
(C-2-2) A boron compound represented by the formula M ^{3 +} (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ⁻ .
(C-2-3) A boron compound represented by the formula (M ⁴ —H) ⁺ (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ^— .
Wherein R ^{13 to} R ¹⁶ are halogen atoms, hydrocarbyl groups containing 1 to 20 carbon atoms, halogenated hydrocarbyl groups containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms. A substituted silyl group containing, an alkoxy group containing 1-20 carbon atoms or a disubstituted amino group containing 2-20 carbon atoms, which are the same or different, preferably a halogen atom, 1-20 A hydrocarbyl group containing 1 carbon atom or a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, M ³⁺ is an inorganic or organic cation, M ⁴ is a neutral Lewis base (M ⁴ -H) ⁺ is a Bronsted acid.)

Examples of the compound represented by the above formula (C-2-1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5- Examples include tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, and phenylbis (pentafluorophenyl) borane. Of these, tris (pentafluorophenyl) borane is most preferable.

Examples of M ^{3+ in the} above formula (C-2-2) include a ferrocenium cation, an alkyl-substituted ferrocenium cation, a silver cation, and a triphenylmethyl cation. Further, as (BR ¹³ R ¹⁴ R ¹⁵ R ¹⁶ ) ⁻ in the above formula (C-2-2), tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) Examples include borate and tetrakis (3,5-bistrifluoromethylphenyl) borate.

Compounds of formula (C-2-2) include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri Examples thereof include phenylmethyltetrakis (pentafluorophenyl) borate and triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate. Of these, triphenylmethyltetrakis (pentafluorophenyl) borate is most preferable.

Examples of (M ⁴ —H) ^{+ in the} above formula (C-2-3) include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, and triarylphosphonium, and (BR ¹³ R Examples of ¹⁴ R ¹⁵ R ¹⁶ ) ⁻ are the same as those described above. Compounds of formula (C-2-3) include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal) Butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- 2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate , Diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (Dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate can be exemplified. Among these, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate is most preferable.

As the activation promoter component (C), preferably the organoaluminum compound (C-1-2), organoaluminum compound (C-1-3), organoaluminum compound (C-1-2), and organoaluminum compound. A combination of (C-1-3), a boron compound (C-2), or an organoaluminum compound (C-1-1) and a boron compound (C-2).

When the olefin polymer according to the present invention is produced by polymerization (e.g., slurry polymerization, gas phase polymerization, bulk polymerization, etc.) accompanied by the formation of polymer particles, as the activation co-catalyst component (C), the following ( It is preferable to use the modified particles of I) or (II) below, and it is more preferable to use in combination with the organoaluminum compound (C-1-1), but it is not intended to be limited thereto. As another example, a clay mineral or an ion-exchange layered compound that may be subjected to chemical treatment or physical treatment can also be used.

(I) Modified particles obtained by bringing the following (a), (b), (c) and particles (d) into contact with each other.
(A): Compound represented by the following general formula (5) M ⁵ L ¹ _f (5)
(B): Compound represented by the following general formula (6) R ¹⁷ _t-1 TH (6)
(C): Compound represented by the following general formula (7) R ¹⁸ _t-2 TH ₂ (7)
(In the above general formulas (5) to (7), M ⁵ represents a typical metal atom of Group 1, 2, 12, 14 or 15 of the periodic table, and f represents a valence of M ⁵ , L ^1. Represents a hydrogen atom, a halogen atom or a hydrocarbyl group, and when a plurality of L ¹ are present, they may be the same or different from each other, and R ¹⁷ represents an electron-withdrawing group or an electron-withdrawing group. In the case where a plurality of R ¹⁷ are present, they may be the same as or different from each other, R ¹⁸ represents a hydrocarbyl group or a halogenated hydrocarbyl group, and T represents each independently. (Represents a group 15 or group 16 atom of the periodic table, t represents the valence of T of each compound, and H represents a hydrogen atom.)

(II) Modified particles obtained by contacting aluminoxane (e) and particles (d).
Hereinafter, these will be further described sequentially.

  A specific example of the compound (a) is dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, dinormalbutylzinc, diisobutylzinc, or dinormalhexylzinc.

  Specific examples of the compound (b) include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) ) Phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, or 3,4,5-tris (trifluoromethyl) phenol.

  Specific examples of the compound (c) include water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2, 6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoro Methyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4,6-tris (trifluoromethyl) aniline Or 3,4,5-tris (trifluoromethyl) anily , And the most preferably is water or pentafluoroaniline.

  As the particles (d), those generally used as carriers are preferably used, and porous inorganic oxides having a uniform particle size are preferred.

Specific examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , and mixtures thereof, for example, SiO ₂ − Examples thereof include MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and silica is particularly preferable.

The amount of each compound (a), (b), (c) used is not particularly limited, but the molar ratio of the amount of each compound used is (a) :( b) :( c) = 1: y: z Then, it is preferable that y and z substantially satisfy the following formula (U).
| F−y−2z | ≦ 1 (U)
(In the above formula (U), f represents the valence of M ^5. )
In the above formula (U), y is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably a number of 0.20 to 1.50. Yes, most preferably a number from 0.30 to 1.00, and a similar preferred range of z in the above formula (U) is determined by d, y and the above formula (U).

The amount of the compounds (a), (b) and (c) used is more preferably such that the following formulas (U), (V) and (W) are substantially satisfied.
| F−y−2z | ≦ 1 (U)
z ≧ −2.5y + 2.48 (V)
y <0.5f (W)
Specifically, when f is 2, y usually takes a value of 0.5 to 0.99, more preferably 0.55 to 0.95, and even more preferably 0.6 to 0.9. Yes, most preferably 0.7 to 0.8. In this case, the normal ratio, more preferable ratio, further preferable ratio, and most preferable ratio of z are the valence of M ⁵ , the molar ratio of the amount of the compound (b) used, and the above formulas (V) to (X) Each is calculated.

  The aluminoxane (e) is preferably the organoaluminum compounds (C-1-2) and (C-1-3).

The method for bringing the aluminoxane (e) into contact with the particles (d) is not particularly limited. Examples of the method include a method in which aluminoxane (e) is added to a solvent in which particles (d) are dispersed. Examples of the solvent include the solvents described above, preferably a solvent that does not react with the aluminoxane (e), and more preferably a solvent that dissolves the aluminoxane (e). The solvent is preferably an aromatic hydrocarbyl solvent such as benzene, toluene and xylene, or an aliphatic hydrocarbyl solvent such as hexane, heptane and octane, more preferably toluene or xylene.

The temperature and time for contacting the aluminoxane (e) and the particles (d) are not particularly limited, and the temperature is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 150 ° C., more preferably −20 ° C. to 120 ° C. It is. In particular, at the initial stage of contact, it is preferable to contact them at a low temperature in order to suppress heat generation due to the reaction. The amount of aluminoxane (e) and particles (b) used is not particularly limited. The aluminoxane (e) is usually 0.01 to 100 mmol, preferably 0.1 to 20 mmol, more preferably 1 to 10 mmol per unit gram of the particles (d) in terms of aluminum atoms in the aluminoxane used.

<Olefin polymer production method>
The ethylene-α-olefin copolymer of the present invention is formed by bringing a transition metal compound (A), a transition metal compound (B), and an activating co-catalyst component (C) into contact with each other to form a catalyst. It can manufacture by polymerizing.
The contact treatment of the transition metal compound (A), the transition metal compound (B), and the activation promoter component (C) is carried out by subjecting the transition metal compound (A), the transition metal compound (B), and the activation promoter component ( As long as the catalyst is formed by contact with C), any means may be used. The transition metal compound (A) and the transition metal compound (B) may be prepared by diluting each component with a solvent in advance or without dilution. A method in which the co-catalyst component for activation (C) is mixed and brought into contact, and the transition metal compound (A), the transition metal compound (B), and the co-catalyst component for activation (C) are separately supplied to the polymerization tank. Then, a method of bringing them into contact in a polymerization tank can be taken. Here, a plurality of types of co-catalyst components for activation (C) may be used in combination, but some of them may be mixed in advance and used separately or supplied to the polymerization tank. May be used.

The molar ratio of transition metal compound (A) to transition metal compound (B) ([A] / [B]) is not particularly limited, but is preferably 0.1 to 200, more preferably 1 to 100. is there.

  When the organoaluminum compound (C-1) is used as the activation promoter component (C), the molar ratio of (C-1) to the total amount of the transition metal compound (A) and the transition metal compound (B) used is It is 0.01-10000, Preferably it is 1-5000. When the boron compound (C-2) is used as the activating co-catalyst component (C), the molar ratio of (C-2) to the total amount of the transition metal compound (A) and the transition metal compound (B) used is 0. 0.01 to 100, preferably 1 to 50.

When the catalyst is produced in the polymerization reaction vessel before the polymerization reaction, the concentration when each component is supplied in a solution state or suspended or slurried in a solvent is determined depending on the performance of the apparatus for supplying each component to the polymerization reaction vessel. It is appropriately selected depending on the conditions.
In general, the concentration of the transition metal compound (A) or the transition metal compound (B) is usually 0.0001 to 10000 mmol / L, more preferably 0.001 to 1000 mmol / L, still more preferably 0.00. 01 to 100 mmol / L. When the organoaluminum compound (C-1) is used, the concentration is usually 0.01 to 10000 mol / L, more preferably 0.05 to 5000 mol / L, and even more preferably in terms of Al atoms. 0.1 to 2000 mol / L. The density | concentration of a boron compound (C-2) is 0.001-500 mol / L normally, More preferably, it is 0.01-250 mol / L, More preferably, it is 0.05-100 mol / L.

When the transition metal compound (A), the transition metal compound (B), and the organoaluminum compound (C-1) are brought into contact with each other, the organoaluminum compound (C-1) may be the above cyclic aluminoxane (C-1- 2) and / or linear aluminoxane (C-1-3) are preferred.
When the transition metal compound (A), the transition metal compound (B), the organoaluminum compound (C-1) and the boron compound (C-2) are contacted, the organoaluminum compound (C-1) The organoaluminum compound (C-1-1) is preferable, and the boron compound (C-2) is preferably a boron compound (C-2-1) or a boron compound (C-2-2).

  Further, when the ethylene-α-olefin copolymer of the present invention is produced, in addition to the transition metal compound (A), the transition metal compound (B), and the activating co-catalyst component (C), an electron donating property is also provided. A compound may be used. As such an electron-donating compound, a compound containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom is preferable, and examples thereof include an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound and a sulfur-containing compound. Compounds or nitrogen-containing compounds are preferred. Examples of oxygen-containing compounds include alcohols, phenols, alkoxysilicones, ethers, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, acid amides of organic or inorganic acids, acid anhydrides Among them, alkoxysilicones or ethers are preferable. Examples of the nitrogen-containing compound include amines, nitriles, isocyanates, and the like, and amines are preferable. In addition, the electron donating compound may be used alone or in combination of two or more.

  As the method for producing the ethylene-α-olefin copolymer of the present invention, the above-mentioned transition metal compound (A), the above-mentioned transition metal compound (B), and the activation promoter component (C) are further provided as necessary. A prepolymerized solid component obtained by polymerizing a small amount of olefin (hereinafter referred to as prepolymerization) using a catalyst obtained by contacting with a functional compound, as a polymerization catalyst component or a polymerization catalyst, You may copolymerize ethylene and an alpha olefin. At this time, it is preferable to use the modified particles as the activation site catalyst component (C).

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

  The 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 type slurry polymerization method, and a continuous type gas phase polymerization method.

  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.

The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed. Moreover, the partial pressure of olefins in the gas phase part during 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.

  The method for producing an olefin polymer of the present invention uses a transition metal compound (A), a transition metal compound (B), an activation co-catalyst component (C), and, if necessary, an electron donating compound. Alternatively, the olefin having 2 to 20 carbon atoms is homopolymerized or copolymerized using the prepolymerized prepolymerized solid catalyst component.

  The type of olefin to be polymerized may be single or plural. If a single olefin is polymerized, a homopolymer is obtained, and if a plurality of olefins are polymerized, a copolymer is obtained. In the case of copolymerization, for example, a combination of ethylene and an α-olefin having 3 to 20 carbon atoms such as ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene, 1-butene and 1-hexene. Can be mentioned.

  Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-alkene (branched) having 2 to 20 carbon atoms such as 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene Or cyclopentene, cyclohexene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloun Decene, pentacyclopentadecene, pentacyclohex Decene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene And cyclic alkene such as 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene, and the like.

  The olefin is preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, more preferably ethylene, propylene, 1-butene. 1-pentene, 1-hexene, 1-octene, 1-decene and 4-methyl-1-pentene, more preferably ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. is there.

  As a polymerization method, a solvent polymerization method using an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane, an aromatic hydrocarbon such as benzene and toluene, or a halogenated hydrocarbon such as methylene dichloride as a solvent, or slurry Examples thereof include a polymerization method, a gas phase polymerization method, and a bulk polymerization method. The gas phase polymerization reaction apparatus used in the gas phase 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. Either continuous polymerization or batch polymerization is possible.

  The temperature and time of the polymerization reaction can be determined in consideration of the desired polymerization average molecular weight, the activity of the catalyst and the amount used. The polymerization temperature can usually be in the range of −50 ° C. to 200 ° C., but the range of −20 ° C. to 100 ° C. is particularly preferable, and the polymerization pressure is usually preferably normal pressure to 50 MPa. In general, the polymerization time is appropriately determined depending on the type of the target polymer and the reaction apparatus, but can usually be in the range of 1 minute to 20 hours, preferably in the range of 5 minutes to 18 hours. However, it is not intended to be limited to these ranges. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.

When a solvent is used for the polymerization reaction, the concentration of each compound in the solvent is not particularly limited. The total concentration of the transition metal compound (A) and the transition metal compound (B) in the solvent can be selected, for example, in the range of 1 × 10 ⁻⁸ mmol / L to 10 mol / L, and the concentration of the activation promoter component For example, a range of 1 × 10 ⁻⁸ mmol / L to 10 mol / L can be selected. The olefin: solvent can be selected in a volume ratio of 100: 0 to 1: 1000. However, these ranges are examples and are not intended to be limited to them. Even when no solvent is used, the concentration can be appropriately set with reference to the above range.

  When using a prepolymerized prepolymerized solid catalyst component, the method for supplying to the polymerization reaction tank is usually a method of supplying in the absence of moisture using an inert gas such as nitrogen or argon, hydrogen, ethylene or the like. A method is used in which each component is dissolved or diluted in a solvent and supplied in a solution or slurry state.

  The ethylene-based polymer of the present invention may contain an additive as necessary. Examples of the additive include antioxidants, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, dripping agents, pigments, fillers, and the like.

  The ethylene polymer of the present invention can be used together with other resins. Examples of the other resin include an ethylene resin different from the ethylene polymer of the present invention and an olefin resin such as a propylene resin.

  The ethylene-based polymer of the present invention is excellent in the balance of extrusion load during processing, processability of the molded product, melt tension, and mechanical strength. The ethylene-based polymer of the present invention can be produced by various moldings (films, sheets, and the like) by a known molding method, for example, an extrusion molding method such as an inflation film molding method or a T-die film molding method, an injection molding method, or a compression molding method. Bottle, tray, etc.). As the molding method, a T-die film molding method and an inflation film molding method are suitably used, and the obtained molded body is used for various uses such as a laminate film, a food packaging film, and a surface protective film.

  Hereinafter, the present invention will be described with reference to examples and comparative examples.

  The measured value of each item in the examples and comparative examples was measured according to the following method. The sample was prepared by mixing an appropriate amount of 1000 ppm or more with an antioxidant such as Irganox 1076 in advance.

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

(2) Swell ratio (SR)
In the measurement of the melt flow rate, an ethylene-α-olefin copolymer strand extruded at a length of about 15 to 20 mm from an orifice under conditions of a temperature of 190 ° C. and a load of 21.18 N was cooled in air. A solid strand was obtained. Next, the diameter D (unit: mm) of the strand at a position 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.

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

(4) Mw / Mn, Mz / Mw
The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) measurement are calculated, and the value obtained by dividing Mw by Mn is the molecular weight distribution (Mw / Mn). did. Further, the polystyrene-equivalent Z-average molecular weight (Mz) and weight-average molecular weight (Mw) obtained by gel permeation chromatography (GPC) measurement were calculated, and the ratio of Mz to Mw was defined as Mz / Mw.
Apparatus: Waters 150C manufactured by Waters
Separation column: TOSOH TSKgelGMH-HT
Measurement temperature: 140 ° C
Carrier: Orthodichlorobenzene Flow rate: 1.0 mL / min Injection volume: 500 μL

(5) Long chain branch (LCB), short chain branch (SCB) amount, unit: number / number of long chain branches or short chain branches per 1000 carbon atoms is carbon nuclear magnetic resonance (13C-NMR) According to the method, the carbon nuclear magnetic resonance (13C-NMR) spectrum of the polymer is measured under the following measurement conditions, and the long chain branch or short chain branch per 1000 carbon atoms in the polymer is calculated by the following calculation method. I asked for a number.

(Measurement condition)
Apparatus: AVANCE600 manufactured by Bruker
Measurement probe: 10 mm cryoprobe Measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4
= 75/25 (volume ratio) mixed solution measurement temperature: 130 ° C.
Measurement method: proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Tetramethylsilane window function: Exponential or Gaussian integration number: 2500

Calculation method of the number of long chain branches (LCB) In the NMR spectrum in which the window function is processed with Gaussian, the sum of the peak areas of all peaks having a peak top at 5 to 50 ppm is 1000, and branches having 7 or more carbon atoms are present. The number of long chain branches (number of branches having 7 or more carbon atoms) was determined from the peak area of the peak derived from the bound methine carbon. Under the present measurement conditions, the number of long chain branches (the number of branches having 7 or more carbon atoms) was determined from the peak area of a peak having a peak top in the vicinity of 38.22 to 38.27 ppm. 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 this measurement condition, in the measurement of the ethylene-1-octene copolymer, the peak top position of the peak derived from the methine carbon to which the hexyl branch was bonded was 38.21 ppm.

Calculation method of the number of short chain branches (SCB) In the NMR spectrum which processed the window function with the exponential, carbon atom number when the sum total of the peak areas of all peaks having a peak top at 5 to 50 ppm is 1000 The number of short chain branches was calculated from the peak area derived from methine carbon to which 4 branches were bonded. In this measurement condition, it calculated | required from the total value of the area of a peak of 38.0-38.21 ppm and the area of a peak of 35.85-36.00 ppm.

(6) Melt tension (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a 9.55 mmφ barrel at a temperature of 190 ° C., a piston descending speed of 5.5 mm / min, a diameter of 2.09 mmφ, and a length of 8 mm The molten resin extruded from the orifice was wound up at a take-up rate of 40 rpm / min using a take-up roll having a diameter of 50 mmφ, and the tension immediately before the molten resin broke 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.

(7) Contractile factor g *
The contraction factor g * was determined by the formula (I).
[Η] is the relative viscosity (η _rel ) of the ethylene polymer dissolved in 100 ml of tetralin containing 5% by weight of butylhydroxytoluene (BHT) as a heat degradation inhibitor at 135 ° C. A sample solution was prepared using a Ubbelohde viscometer and calculated from the fall time of the sample solution and a blank solution made of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor. [Η] _GPC is determined by the formula (I-II) from the measurement of the molecular weight distribution of the ethylene polymer of (5), and g _SCB * is the value of the ethylene polymer of (8). It calculated | required by the formula (I-III) from the measurement of the number of short chain branches.

(8) Oligomer content (ppm)
The amount of oligomer (an oligomer component derived from n-C12 to C38 polyethylene) contained in the ethylene-based polymer of the present invention was measured by gas chromatography. The oligomer can be extracted by an ultrasonic method. The GPC measurement device and each measurement condition are as follows.
GC measuring device manufactured by SHIMADZU GC-2010
DB-1 made by J & W
(Thickness 0.15μm, length 15m, inner diameter 0.53mm)
Detector (FID) temperature 310 ℃
Measurement column temperature Hold at 100 ° C for 1 minute, then heat up to 310 ° C at 10 ° C / minute

(9) Characteristic relaxation time (τ, unit: seconds)
The characteristic relaxation time τ was measured under the following conditions (a) to (d) using a strain-controlled rotary viscometer (rheometer). The characteristic relaxation time is calculated from a master curve showing the dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. on the angular frequency (unit: rad / sec), which is created based on the temperature-time superposition principle. It is a numerical value. Specifically, the melt complex viscosity-angular frequency curve of the ethylene polymer at each temperature (T, unit: ° C.) of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (unit of melt complex viscosity is Pa · sec, The unit of the angular frequency is rad / sec.) Is superposed on the melt complex viscosity-angular frequency curve at 190 ° C. based on the temperature-time superposition principle, and a master curve is obtained. It is a value calculated by approximating with the following formula. The measurement was performed under nitrogen. Calculation software includes Rohms V. from Reometrics. 4.4.4 was used, and a numerical value when the correlation coefficient r2 at the time of linear approximation in the Arrhenius type plot log (aT) − (1 / T) was 0.99 or more was adopted.
Condition (a) Geometry: Parallel plate, diameter 25 mm, plate interval: 1.5-2 mm
Condition (b) Strain: 5%
Condition (c) Shear rate: 0.1 to 100 rad / sec
Condition (d) Temperature: 190, 170, 150, 130 ° C
η = η ₀ / [1+ (τ × ω) ⁿ ]
η: Complex melt viscosity (unit: Pa · sec)
ω: angular frequency (unit: rad / sec)
τ: Characteristic relaxation time (unit: sec)
η ₀ : Constant determined for each ethylene polymer (unit: Pa · sec)
n: Constant determined for each ethylene-based polymer The characteristic relaxation time is related to the appearance of the molded body. The shorter the relaxation time is, the better the molded body is.

(10) Extension viscosity nonlinear index k
The elongational viscosity nonlinearity index k is a viscosity-time curve σ ₁ (t) of a molten resin when uniaxially stretched at a temperature of 130 ° C. and a strain rate of 1 s ⁻¹ , a temperature of 130 ° C. and 0.1 s ^−1. The following function α (t) = σ ₁ (t) / σ _0.1 (t) (obtained from the viscosity-time curve σ _0.1 (t) of the molten resin when uniaxially stretched under the condition of the strain rate of 5)
On the other hand, t is a value calculated as the slope of lnα (t) between 1.4 seconds and 3.0 seconds, and k when the correlation coefficient r2 at the time of linear approximation is 0.99 or more. Adopted. The measurement of the viscosity-time curve σ (t) of the molten resin was performed using a viscoelasticity measuring apparatus (for example, ARES manufactured by TA Instruments). The measurement was performed in a nitrogen atmosphere.
The larger the extensional viscosity nonlinearity index, the smaller the neck-in of the film during T-die film molding.

(11) Melt draw ratio t _H
Melt draw ratio t _H is the viscosity of the molten resin when uniaxially stretched at a strain rate conditions of temperature and 1s ^-1 of 130 ° C. - is a melt draw ratio t _H of melt fracture point in time curve σ _{1 (t)} .

(12) Melt tension (MT, unit: cN), maximum take-off speed (MTV, unit: m / min)
Melt tension (MT, unit: cN) and maximum take-off speed (MTV, unit: m / min) were filled in a 9.55 mmφ barrel at a temperature of 150 ° C. using a melt tension tester manufactured by Toyo Seiki Seisakusho. The molten resin was extruded through an orifice having a diameter of 2.09 mmφ and a length of 8 mm at a piston lowering speed of 5.5 mm / min. The extruded molten resin was extruded at 40 rpm / min using a winding roll having a diameter of 50 mmφ. The tension immediately before the molten resin broke was measured as melt tension (MT), and the take-up speed just before the molten resin broke was measured as the maximum take-up speed (MTV).

(13) Tensile impact strength (unit: kJ / m ² )
The tensile impact strength of a sheet having a thickness of 2 mm that was compression-molded under conditions of a molding temperature of 190 ° C., a preheating time of 10 minutes, a compression time of 5 minutes, and a compression pressure of 5 MPa was measured according to ASTM D1822-68. The larger this value, the better the mechanical strength.

[Reference Example 1] Production of modified particles GZ-4
JP, 2009-79180, A Modified particles were produced by the method described in Example 1 (1) and (2). As a result of elemental analysis, Zn = 11 wt% and F = 6.4 wt%.

[Reference Example 2] Production of modified particles
Silica heat-treated at 300 ° C. under nitrogen flow in a 50 L reactor equipped with a nitrogen-substituted agitator (Sypolol 948 manufactured by Devison; average particle size = 55 μm; pore volume = 1.67 mL / g; specific surface area = 325 m ^{2 /} g) 9.68 kg was added. After adding 100 L of toluene here, it cooled to 2 degreeC. To this, 26.3 L of methylalumoxane in toluene (Tosoh Finechem) (2.9 M) 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. Thereafter, 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 L 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 L of toluene and stirring, it filtered simultaneously with stopping stirring. After repeating this operation once more, 110 L of hexane was added, and filtration was performed in the same manner. This operation was repeated once more. Thereafter, 12.6 kg of modified particles were obtained by drying at 70 ° C. for 7 hours under a nitrogen flow. As a result of elemental analysis, it was Al = 4.4 mmol / g.

[Example 1]
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 at a partial pressure of about 0.002 MPa, and 1-hexene (130 mL) and butane (800 g) were charged. The temperature was raised to ° C. 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 hydrogen concentration in the gas phase portion was 0.18 mol%. Next, a hexane solution of triisobutylaluminum (1.5 mL, 1.0 mmol / L) was added. Here, a toluene solution (1.5 mL, 1.0 mmol / L) of dimethylsilylenebis (3-phenylcyclopentadienyl) zirconium dichloride (racemic: meso = 1: 1) and racemic-ethylenebis (indenyl) A mixed solution of zirconium diphenoxide in toluene (0.27 mL, 0.1 mmol / L) was added. Further, 37.9 mg of the modified particles produced in Reference Example 1 were added as an activation promoter component to initiate polymerization. Polymerization was carried out at 70 ° C. for 1 hour while supplying ethylene so as to keep the total pressure constant to obtain 221 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 0.19 mol%. The activity per 1 g of the promoter component for activation was 5800 g / g / h.

[Example 2]
The hydrogen partial pressure was about 0.003 MPa (in-system hydrogen concentration 0.18 mol%), and a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic: meso = 1: 1) (2. 0 mL, 1.0 mmol / L) and a mixed solution of racemic-ethylenebis (indenyl) zirconium diphenoxide in toluene (1.5 mL, 0.1 mmol / L) was used to produce in Reference Example 1. Polymerization was performed in the same manner as in Example 1 except that 38.6 mg of the modified particles were used to obtain 242 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 0.21 mol%. The activity per 1 g of the promoter component for activation was 6300 g / g / h.

[Example 3]
The hydrogen partial pressure was about 0.003 MPa (in-system hydrogen concentration 0.17 mol%), and a toluene solution (1. 1) of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic: meso = 1: 1). 5 mL, 1.0 mmol / L) and a mixed solution of racemic-ethylenebis (indenyl) zirconium diphenoxide in toluene (0.75 mL, 0.1 mmol / L) was used to produce in Reference Example 1. Polymerization was carried out in the same manner as in Example 1 except that 8.8 mg of the modified particles were used to obtain 62 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 0.18 mol%. The activity per gram of the promoter component for activation was 7000 g / g / h.

[Example 4]
The same method as in Example 1 except that the hydrogen partial pressure was about 0.004 MPa (in-system hydrogen concentration 0.21 mol%), and 9.4 mg of the modified particles produced in Reference Example 1 were used. Polymerization was carried out to obtain 56 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 0.21 mol%. The activity per 1 g of the promoter component for activation was 5900 g / g / h.

[Example 5]
The hydrogen partial pressure was about 0.003 MPa (in-system hydrogen concentration 0.18 mol%), and a toluene solution of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic: meso = 1: 1) (2. 0 mL, 1.0 mmol / L) and a mixed solution of racemic-ethylenebis (indenyl) zirconium diphenoxide in toluene (1.5 mL, 0.1 mmol / L) was used to produce in Reference Example 1. Polymerization was performed in the same manner as in Example 1 except that 38.6 mg of the modified particles were used to obtain 242 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 0.21 mol%. The activity per 1 g of the promoter component for activation was 6300 g / g / h.
[Comparative Example 1]
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 at a partial pressure of about 0.0025 MPa, and 1-hexene (180 mL) and butane (650 g) were charged. The temperature was raised to ° C. 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 hydrogen concentration in the gas phase portion was 0.10 mol%. Next, a hexane solution of triisobutylaluminum (0.9 mL, 1.0 mol / L) was added. Here, a toluene solution of dimethylsilylenebis (cyclopentadienyl) zirconium dichloride (6.2 mL, 2 mmol / L) and a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (1.0 mL) , 1.0 mmol / L). Furthermore, 93.4 mg of the modified particles produced in Reference Example 2 were added as an activation promoter component to initiate polymerization. Polymerization was carried out at 70 ° C. for 1.5 hours while supplying ethylene so as to keep the total pressure constant, thereby obtaining 50 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 0.12 mol%. The activity per gram of the promoter component for activation was 400 g / g / h.

[Comparative Example 2]
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 at a partial pressure of about 0.03 MPa, and 1-hexene (180 mL) and butane (650 g) were charged. The temperature was raised to ° C. 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 hydrogen concentration in the gas phase portion was 1.79 mol%. Next, a hexane solution of triisobutylaluminum (0.9 mL, 1 mol / L) was added. Here, a toluene solution of dimethylsilylene bis (cyclopentadienyl) zirconium dichloride (3.1 mL, 2 mmol / L) and a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (0.50 mL) 1 mmol / L) was added. Further, 53.3 mg of the modified particles produced in Reference Example 1 were added as an activation promoter component to initiate polymerization. Polymerization was carried out at 70 ° C. for 1 hour while supplying ethylene so as to keep the total pressure constant, to obtain 58 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 1.78 mol%. The activity per 1 g of the promoter component for activation was 1100 g / g / h.

[Comparative Example 3]
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 at a partial pressure of about 0.02 MPa, and 1-hexene (180 mL) and butane (650 g) were charged. The temperature was raised to ° C. 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 hydrogen concentration in the gas phase portion was 1.1 mol%. Next, a hexane solution of triisobutylaluminum (0.9 mL, 1.0 mol / L) was added. Here, a toluene solution of dimethylsilylene bis (cyclopentadienyl) zirconium dichloride (1.5 mL, 2 mmol / L) and a toluene solution of racemic-ethylenebis (indenyl) zirconium diphenoxide (0.1 mL, 1. 0 mmol / L) was added. Furthermore, 30.4 mg of the modified particles produced in Reference Example 1 were added as an activation promoter component to initiate polymerization. Polymerization was carried out at 70 ° C. for 1 hour while supplying ethylene so as to keep the total pressure constant to obtain 87 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 1.2 mol%. The activity per gram of the promoter component for activation was 2800 g / g / h.

[Comparative Example 4]
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 at a partial pressure of about 0.004 MPa, and 1-hexene (100 mL) and butane (650 g) were charged. The temperature was raised to ° C. 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 hydrogen concentration in the gas phase portion in the system was 0.24 mol%. Next, a hexane solution of triisobutylaluminum (0.9 mL, 1.0 mol / L) was added. A toluene solution (1.0 mL, 1.0 mmol / L) of dimethylsilylene bis (3-phenylcyclopentadienyl) zirconium dichloride (racemic: meso = 1: 1) was added thereto. Further, 6.2 mg of the modified particles produced in Reference Example 1 were added as an activation promoter component to initiate polymerization. Polymerization was carried out at 70 ° C. for 1 hour while supplying ethylene so as to keep the total pressure constant, thereby obtaining 33 g of an ethylene-hexene copolymer. The average hydrogen concentration during the polymerization was 0.26 mol%. The activity per 1 g of the promoter component for activation was 5400 g / g / h.

Claims (6)

An ethylene-α-olefin copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, which satisfies all of the following requirements (A) to (G): Coalescence.
(A) The melt flow rate (MFR) is 0.01 to 100 g / 10 min.
(B) The density is 860 to 970 kg / m ³ .
(C) The swell ratio (SR) is 1.7 to 2.3.
(D) The ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is 2.5 to 6.0.
(E) The extensional viscosity nonlinear index k is 0.8 to 2.0.
(F) When stretched uniaxially at a temperature of 130 ° C. and a strain rate of 1 s ⁻¹ , the melt draw ratio until the molten resin breaks is 2.7 or more.
(G) The characteristic relaxation time (τ) and the melt flow rate (MFR) satisfy the relationship of the following formula.
3.0 × MFR ^−0.9654 <τ <8.0 × MFR ^−0.9654 The ethylene-α-olefin copolymer according to claim 1, which satisfies the following requirement (H).
(H) The characteristic relaxation time (τ) is 15 seconds or less. The resin composition containing the ethylene-alpha-olefin copolymer of Claim 1 or Claim 2. The molded object which consists of a resin composition of Claim 3. The manufacturing method of the olefin polymer characterized by using the polymerization catalyst obtained by making the following transition metal compound (A), the following transition metal compound (B), and the co-catalyst component for activation (C) contact.
Transition metal compound (A): transition metal compound represented by the general formula (1)

(In the formula, M ¹ represents a transition metal atom of Group 4 of the Periodic Table of Elements. R ¹ and R ² are each independently a hydrogen atom or an optionally substituted carbon atom having 1 to 1 carbon atoms. represents a hydrocarbyl group of 20. at least one of R ¹ and / or at least one of R ² is substituted aryl group which may having 6 to 20 carbon atoms. plurality of R ¹ and A plurality of R ² may be the same or different from each other, and X ¹ represents a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. It represents a hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group, or a substituted amino group which may have, and two X ^{1 s} may be the same or different from each other, and n is 1. represents an integer of to 5, J ¹ is carbon atom or silicon atom table , If J ¹ there are a plurality, they may be different be the same as each other, R ⁵ is a hydrogen atom, or a hydrocarbyl group optionally having 1 to 20 carbon atoms which may have a substituent And a plurality of R ⁵ may be the same as or different from each other.)
Transition metal compound (B): transition metal compound represented by the general formula (2)

(In the formula, M ² represents a transition metal atom of Group 4 of the Periodic Table of Elements. R ⁶ represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent. And a plurality of R ⁶ may be the same or different from each other.) X ² is a hydrogen atom, a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent. Represents a hydrocarbyloxy group having 1 to 20 carbon atoms which may have a substituent, a substituted silyl group, or a substituted amino group, and two X ^{2 s} may be the same or different from each other. . m represents an integer of 1 to 5, J ² represents a carbon atom or a silicon atom, if J ² there is a plurality, they may be different from one another the same. R ⁷ represents a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, and the plurality of R ⁷ may be the same as or different from each other. ) The production method according to claim 5, wherein the olefin polymer is an ethylene polymer.