JP6197821B2 - Ethylene-α-olefin copolymer - Google Patents

Description

  The present invention relates to an ethylene-α-olefin copolymer, a resin composition containing the copolymer, and a film comprising the resin composition.

  An ethylene-α-olefin copolymer is molded into a film, a sheet, a bottle, or the like by various molding methods such as inflation molding, T-die casting molding, blow molding, injection molding and the like, and is used for various applications. Such an ethylene-α-olefin copolymer includes, for example, a promoter support formed by contacting pentazinc with diethylzinc, then contacting silica treated with hexamethyldisilazane, and then contacting water. , A method of polymerizing using a catalyst formed from triisobutylaluminum and racemic-ethylenebis (1-indenyl) zirconium diphenoxide (Patent Document 1), and contacting diethylzinc with silica treated with hexamethyldisilazane Then, polymerization is carried out using a catalyst formed from a cocatalyst carrier which is contacted with pentafluorophenol and then contacted with water, and triisobutylaluminum and racemic-ethylenebis (1-indenyl) zirconium diphenoxide. Methods (Patent Documents 2 and 3) are known.

Japanese Patent Laid-Open No. 2003-171212 JP 2004-149760 A JP 200597481 A

However, the above-mentioned ethylene-α-olefin copolymer has an insufficient balance of extrusion load during processing, transparency of the film, melt tension, and mechanical strength.
Under such circumstances, the problem to be solved by the present invention is to provide an ethylene-α-olefin copolymer excellent in the balance of extrusion load during processing, transparency of film, melt tension, and mechanical strength. is there.

That is, the first of the present invention has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and a melt flow rate (MFR) of 0.01 to 100 g / 10 minutes, density is 860-970 kg / m ³ , molecular weight distribution (Mw / Mn) is 4.5-13, activation energy (Ea) is 40-100 kJ / mol, measured by NMR The long chain branching amount is 0.10 to 0.24 per 1000 carbon atoms, and the characteristic relaxation time (τ) is applied to the ethylene-α-olefin copolymer satisfying the relationship of the formula (1). is there.
τ <2.95 × MFR ^−0.6675 (1)
The second of the present invention has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and a melt flow rate (MFR) of 0.01 to 100 g. / 10 minutes, the density is 860-970 kg / m ³ , the molecular weight distribution (Mw / Mn) is 4.5-13, the activation energy (Ea) is 40-100 kJ / mol, and by NMR This is for an ethylene-α-olefin copolymer having a long chain branching amount of 0.25 to 0.50 per 1000 carbon atoms.

  According to the present invention, it is possible to provide an ethylene-α-olefin copolymer excellent in the balance of extrusion load during processing, transparency of film, melt tension, and mechanical strength.

It is the figure which plotted the value of (tau) (S) with respect to the value of MFR (g / 10min) about the ethylene-alpha-olefin copolymer of Examples 1-12 and Comparative Examples 1-5. It is the figure which plotted the value of (eta) ^* ₁₀₀ (Pa ^* s) with respect to the value of MFR (g / 10min) about the ethylene-alpha-olefin copolymer of Examples 1-12 and Comparative Examples 1-5. . It is the figure which plotted the value of melt tension (cN) with respect to the value of MFR (g / 10min) about the ethylene-alpha-olefin copolymer of Examples 14-18 and Comparative Examples 6 and 7. FIG.

  Hereinafter, the present invention will be described in detail.

  The first and second ethylene-α-olefin copolymers of the present invention are copolymers 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 units based on ethylene in the first and second ethylene-α-olefin copolymers of the present invention is based on the total weight (100% by weight) of the ethylene-α-olefin copolymer. Usually, it is 50% by weight or more. 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.

  The first and second ethylene-α-olefin copolymers of the present invention include, in addition to the monomer units based on ethylene and the monomer units based on α-olefins having 3 to 20 carbon atoms, As long as the effect is not impaired, the monomer unit may be based on a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms. Conjugated dienes such as 2-methyl-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 and acrylic acid Examples thereof include unsaturated carboxylic acid esters such as ethyl, butyl acrylate, methyl methacrylate and ethyl methacrylate; vinyl ester compounds such as vinyl acetate.

  The first and second ethylene-α-olefin copolymers of the present invention include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, 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 -Butene-1-octene copolymer and the like. 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 first and second ethylene-α-olefin copolymers 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 10 g / 10 min or less, more preferably 5 g / 10 min or less, still more preferably 3 g / 10 or less, and even more preferably. Is 2 g / 10 or less, and most preferably 1.5 g / 10 or less. Moreover, from a workability viewpoint, Preferably it is 0.05 g / 10min or more, More preferably, it is 0.1 g / 10min 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 first and second ethylene-α-olefin copolymers of the present invention is 860 to 970 kg / m ³ . Said seal degree, in view of enhancing the mechanical strength, is preferably 940 kg / m ³ or less, more preferably 930 kg / m ³ or less, more preferably 925 kg / m ³ or less. The density is preferably 890 kg / m ³ or more, more preferably 900 kg / m ³ or more, and further preferably 910 kg / m ³ or more, from the viewpoint of increasing rigidity. 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.

First ethylene-α-olefin copolymer Hereinafter, the first ethylene-α-olefin copolymer will be described.
The molecular weight distribution (Mw / Mn) of the first ethylene-α-olefin copolymer of the present invention is 4.5-13. In order to obtain a molded article having good mechanical strength, the molecular weight distribution of the ethylene-α-olefin copolymer is preferably 10 or less, more preferably 8 or less. Moreover, from a workability viewpoint, Preferably it is 5.0 or more, More preferably, it is 5.5 or more. The molecular weight distribution (Mw / Mn) is a value obtained by calculating a polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) by gel permeation chromatography, and dividing Mw by Mn (Mw / Mn). Mn).

  The flow activation energy (Ea, unit is kJ / mol) of the first ethylene-α-olefin copolymer of the present invention is 40 kJ / mol to 100 kJ / mol. From the viewpoint of fluidity, Ea of the ethylene-α-olefin copolymer of the present invention is preferably 45 kJ / mol or more, more preferably 50 kJ / mol or more, further preferably 55 kJ / mol or more, Even more preferably, it is 60 kJ / mol or more. Further, from the viewpoint of obtaining sufficient moldability at high temperatures, the Ea of the ethylene-α-olefin copolymer of the present invention is preferably 90 kJ / mol or less.

  The long chain branching amount (LCB amount) per 1000 carbon atoms of the first ethylene-α-olefin copolymer of the present invention is 0.10 to 0.24. The amount of LCB per 1000 carbon atoms is preferably 0.13 or more, more preferably 0.15 or more, still more preferably 0.16 or more, and still more preferably 0.13 or more from the viewpoint of improving processability. 17 or more, most preferably 0.18 or more. Moreover, from a viewpoint of raising mechanical strength, Preferably it is 0.22 or less, More preferably, it is 0.20 or less.

It is preferable that (eta) ^* _0.1 / (eta) ^* ₁₀₀ of the 1st ethylene-alpha-olefin copolymer of this invention is 5-100. η ^* _0.1 / η ^* ₁₀₀ is preferably 6 or more, more preferably 11 or more, and still more preferably 12 or more, from the viewpoint of improving workability. Moreover, from a viewpoint of improving mechanical strength, Preferably it is 80 or less, More preferably, it is 70 or less, More preferably, it is 60 or less. Η ^* _0.1 and η ^* ₁₀₀ are measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics).

The dynamic complex viscosity (η ^* ₁₀₀ , unit: Pa · sec) at a temperature of 190 ° C. and an angular frequency of 100 rad / sec of the first ethylene-α-olefin copolymer of the present invention is 1500 Pa · sec or less. preferable. From the viewpoint of improving workability, η ^* ₁₀₀ is preferably 1400 Pa · sec or less, more preferably 1350 Pa · sec or less, further preferably 1300 Pa · sec or less, and most preferably 1200 Pa · sec or less. Further, from the viewpoint of increasing mechanical strength, it is preferably 300 Pa · second or more, more preferably 400 Pa · second or more, further preferably 500 Pa · second or more, still more preferably 600 Pa · second or more, Preferably, it is 700 Pa · sec or more. The angular frequency of 100 rad / sec is an angular frequency close to the shear rate when an ethylene-α-olefin copolymer is processed with a general processing machine, and can be used as an index of workability.

The melt tension at 150 ° C. of the first ethylene-α-olefin copolymer of the present invention is 4 to 30 cN. From the viewpoint of stably producing a film or a blow bottle, it is preferably 5 cN or more, more preferably 6 cN or more, and further preferably 7 cN or more.
Moreover, from a viewpoint of production efficiency at the time of manufacturing a film or a blow bottle, it is preferably 25 cN or less, more preferably 20 cN or less.

  The ratio (Mz / Mw) of z-average molecular weight (Mz) and weight-average molecular weight (Mw) in terms of polystyrene of the first ethylene-α-olefin copolymer of the present invention is 2.0 to 3.0. Is preferred. In order to obtain a molded article having good mechanical strength, the Mz / Mw of the ethylene-α-olefin copolymer is preferably 2.6 or less, more preferably 2.5 or less, and still more preferably 2 .4 or less. Moreover, from a workability viewpoint, Preferably it is 2.1 or more, More preferably, it is 2.2 or more.

G * defined by the following formula (I) of the first ethylene-α-olefin copolymer of the present invention is 0.500 to 0.880.
(For g *, reference was made to the following document: Developments in Polymer Characterization-4, .JV V. Dawkins, .Ed., Applied Science, London, .1983, Chapter.I,. 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 LH 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 characteristic relaxation time (hereinafter sometimes referred to as “τ”) of the first ethylene-α-olefin copolymer of the present invention is expressed by the following relational expression (1-1).
τ <2.95 × MFR ^−0.6675 (1-1)
From the viewpoint of optical physical properties of a film formed using the first ethylene-α-olefin copolymer of the present invention, preferably satisfies the relational expression of formula (1-2), and more Preferably, the relational expression of the formula (1-3) is satisfied, more preferably the relational expression of the formula (1-4) is satisfied, and still more preferably the formula (1-5) is satisfied.
τ <2.90 × MFR ^−0.6675 (1-2)
τ <2.80 × MFR ^−0.6675 (1-3)
τ <2.70 × MFR ^−0.6675 (1-4)
τ <2.65 × MFR ^−0.6675 (1-5)

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. It is reported that this is a polyethylene containing long chain branches and the following formula η ₀ = B · Mw ^ε formula (3)
Strongly suggests that Substituting this equation (3) into equation (2), the following equation (4) can be derived.
τ = C · MFR ^ε1 formula (4)
In order to define the range of τ of the first ethylene-α-olefin copolymer of the present invention, the inequality of formula (5) was used.
τ <C ₁ · MFR ^ε1 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 1-7 were used for fitting. Etc. In view of the accuracy of the data, to obtain a formula (1-5) from the equation (1-1) is the inequality that a constant multiple of the C ₁ in the following manner.
To give equation (1-1) as a _{C 1} to 1.053 times the value of Motoma' was C during fitting. To give equation (1-2) as a _{C 1} to 1.073 times the value of Motoma' was C during fitting. To give equation (1-3) as a _{C 1} to 1.113 times the value of Motoma' was C during fitting. To give equation (1-4) as a _{C 1} to 1.153 times the value of Motoma' was C during fitting. To give equation (1-5) as a _{C 1} to 1.172 times the value of Motoma' was C during fitting.

Τ of the first ethylene-α-olefin copolymer of the present invention is the following relational expression (2-1)
τ> 1.00 × MFR ^−0.6675 (2-1)
From the viewpoint of the extrusion load during processing, the relational expression (2-2) is preferably satisfied, and the relational expression (2-3) is more preferably satisfied.
τ> 1.50 × MFR ^−0.6675 (2-2)
τ> 2.00 × MFR ^−0.6675 (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 1-7 were used for fitting. Etc. In view of the accuracy of the data, to obtain a formula (2-3) from the equation (2-1) is the inequality that a constant multiple of the C ₁ in the following manner.
To give equation (2-1) as a _{C 1} to 0.397 times the value of Motoma' was C during fitting. To give equation (2-2) as a _{C 1} to 0.596 times the value of Motoma' was C during fitting. To give equation (2-3) as a _{C 1} to 0.795 times the value of Motoma' was C during fitting.

  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). When the long chain branching is long (or the long chain branching amount is large), the characteristic relaxation time is large. In order to obtain a high melt tension and a high strain hardening property, it is necessary that a long chain branch having a sufficient amount or a sufficient length is introduced into the molecular chain, and preferably has a certain relaxation time or more. On the other hand, a polymer having a too long relaxation time 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 can be changed by, for example, polymerization conditions such as hydrogen concentration, ethylene pressure, and polymerization temperature, and the characteristic relaxation time of the ethylene-α-olefin copolymer can be changed.

The characteristic relaxation time is calculated from a master curve showing the dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. on the angular frequency (unit: rad / sec), which is created based on the temperature-time superposition principle. It is a numerical value. Specifically, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at each temperature (T, unit: ° C.) at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (unit of melt complex viscosity is (Pa · sec, unit of angular frequency is rad / sec.) Is superposed on the melt complex viscosity-angular frequency curve at 190 ° C based on the temperature-time superposition principle, and a master curve is obtained. It is a value calculated by approximating the master curve by the following formula (5).
η = η ₀ / [1+ (τ × ω) ⁿ ] (5)
η: Complex melt viscosity (unit: Pa · sec)
ω: angular frequency (unit: rad / sec)
τ: Characteristic relaxation time (unit: sec)
η ₀ : Constant determined for each ethylene-α-olefin copolymer (unit: Pa · sec)
n: Constant determined for each ethylene-α-olefin copolymer For the above calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics, Inc. may be used. 4.4.4.

  The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate interval: 1.5. ˜2 mm, strain: 5%, angular frequency: 0.1-100 rad / sec. The measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount of an antioxidant (for example, 1000 ppm) is blended in advance with the measurement sample.

Second ethylene-α-olefin copolymer Hereinafter, the second ethylene-α-olefin copolymer will be described.
The molecular weight distribution (Mw / Mn) of the second ethylene-α-olefin copolymer of the present invention is 4.5-13. In order to obtain a molded article having good mechanical strength, the molecular weight distribution of the ethylene-α-olefin copolymer is preferably 12 or less, more preferably 10 or less.
Further, from the viewpoint of workability, it is preferably 5.0 or more, more preferably 5.5 or more, still more preferably 6.0 or more, and still more preferably 6.3 or more. The molecular weight distribution (Mw / Mn) is a value obtained by calculating a polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) by gel permeation chromatography, and dividing Mw by Mn (Mw / Mn). Mn).

  The flow activation energy (Ea, unit is kJ / mol) of the second ethylene-α-olefin copolymer of the present invention is 40 kJ / mol to 100 kJ / mol. From the viewpoint of fluidity, Ea of the ethylene-α-olefin copolymer of the present invention is preferably 55 kJ / mol or more, more preferably 60 kJ / mol or more, and further preferably 65 kJ / mol or more. Further, from the viewpoint of obtaining sufficient moldability at high temperatures, the Ea of the ethylene-α-olefin copolymer of the present invention is preferably 90 kJ / mol or less.

  The long chain branching amount (LCB amount) per 1000 carbon atoms of the second ethylene-α-olefin copolymer of the present invention is 0.25 to 0.50. The LCB amount per 1000 carbon atoms is preferably 0.29 or more, more preferably 0.30 or more, still more preferably 0.32 or more, and still more preferably 0.000 from the viewpoint of improving processability. 33 or more, most preferably 0.34 or more. Moreover, from a viewpoint of raising mechanical strength, Preferably it is 0.45 or less, More preferably, it is 0.42 or less.

It is preferable that (eta) ^* _0.1 / (eta) ^* ₁₀₀ of the 2nd ethylene-alpha-olefin copolymer of this invention is 5-100. η ^* _0.1 / η ^* ₁₀₀ is preferably 10 or more, more preferably 15 or more, and still more preferably 17 or more, from the viewpoint of improving workability. Moreover, from a viewpoint of improving mechanical strength, Preferably it is 80 or less, More preferably, it is 70 or less, More preferably, it is 60 or less. Η ^* _0.1 and η ^* ₁₀₀ are measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics).

The dynamic complex viscosity (η ^* ₁₀₀ , unit: Pa · sec) at a temperature of 190 ° C. and an angular frequency of 100 rad / sec of the second ethylene-α-olefin copolymer of the present invention is 1500 Pa · sec or less. preferable. From the viewpoint of improving workability, η ^* ₁₀₀ is preferably 1300 Pa · sec or less, more preferably 1200 Pa · sec or less, further preferably 1150 Pa · sec or less, and most preferably 1100 Pa · sec or less. Further, from the viewpoint of increasing mechanical strength, it is preferably 300 Pa · second or more, more preferably 400 Pa · second or more, and further preferably 500 Pa · second or more. The angular frequency of 100 rad / sec is an angular frequency close to the shear rate when an ethylene-α-olefin copolymer is processed with a general processing machine, and can be used as an index of workability.

  The melt tension at 150 ° C. of the second ethylene-α-olefin copolymer of the present invention is 4 to 30 cN. From the viewpoint of stably producing a film or a blow bottle, the transparency of a film produced from a composition comprising the second ethylene-α-olefin copolymer of the present invention and linear low density polyethylene (LLDPE) is also demonstrated. From the viewpoint, it is preferably 6 cN or more, more preferably 7 cN or more, still more preferably 8 cN or more, and even more preferably 10 cN or more. Moreover, from a viewpoint of production efficiency at the time of manufacturing a film or a blow bottle, it is preferably 25 cN or less, more preferably 20 cN or less.

  The ratio (Mz / Mw) of z-average molecular weight (Mz) and weight-average molecular weight (Mw) in terms of polystyrene of the second ethylene-α-olefin copolymer of the present invention is 2.3 to 3.5. Is preferred. In order to obtain a molded article having good mechanical strength, the Mz / Mw of the ethylene-α-olefin copolymer is preferably 3.0 or less, more preferably 2.9 or less, and still more preferably 2 .7 or less. Moreover, from a workability viewpoint, Preferably it is 2.4 or more, More preferably, it is 2.5 or more.

  The amount of oligomers contained in the second ethylene-α-olefin copolymer of the present invention is 1500 ppm or less. From the viewpoint of cleanliness, it is preferably 1200 ppm or less, more preferably 1000 ppm or less, still more preferably 800 ppm or less, and even more preferably 700 ppm or less.

The amount of oligomer (an oligomer component derived from polyethylene of n-C12 to C18) contained in the second 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 g * of the second ethylene-α-olefin copolymer of the present invention is 0.500 to 0.880. From the viewpoint of imparting sufficient processing characteristics, particularly strain hardening characteristics, it is preferably 0.850 or less, more preferably 0.840 or less, still more preferably 0.830 or less, and even more preferably 0.8. 825 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-α-olefin copolymer is preferably 0.600 or more, more preferably 0.650 or more, and further preferably 0.700 or more, from the viewpoint of improving mechanical strength. Even more preferably, it is 0.750 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.

Process for Producing Ethylene-α-Olefin Copolymer As a process for producing the first and second ethylene-α-olefin copolymers of the present invention, for example, diethyl zinc (hereinafter referred to as component (a)) is used. 3,4,5-trifluorophenol (hereinafter referred to as component (b)), water (hereinafter referred to as component (c)), and inorganic compound particles (hereinafter referred to as component (d)). ) In a toluene solvent, and has two ligands having a cyclopentadienyl skeleton, the two-dimensional promoter support (hereinafter referred to as component (A)), A metallocene complex (hereinafter referred to as component (B)) having a structure in which two ligands are bonded by a crosslinking group such as an alkylene group or a silylene group, and an organoaluminum compound (hereinafter referred to as component (C)). Polymerization catalyst used as a catalyst component Examples thereof include a method of copolymerizing ethylene and an α-olefin in the presence of a medium.

Component (d) is 1,1,1,3,3,3-hexamethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH) (hereinafter referred to as component (e)) as necessary. You may carry out contact processing with.

  The inorganic compound particles of component (d) are preferably silica gel.

The amount of component (a), component (b), and component (c) used is not particularly limited, but the molar ratio of the amount of each component used is component (a): component (b): component (c) = 1: When the molar ratio of y: z is used, it is preferable that y and z substantially satisfy the following formula (1).
0.5 <y + 2z <5 (1)
In the above formula (1), y is preferably a number of 0.5 to 4, more preferably a number of 0.6 to 3, further preferably a number of 0.8 to 2.5, and most preferably. Is a number from 1 to 2. Z in the above formula (1) is a positive number larger than 0, and can arbitrarily take a range determined by y and the above formula (1).

Examples of the order in which the component (a), the component (b), the component (c), the component (d), and the component (e) are brought into contact include the following orders.
<1> After contacting component (d) and component (e), contact component (b), then contact component (a), and then contact component (c).
<2> After contacting component (d) and component (e), contact component (a), then contact component (b), and then contact component (c).
<3> Component (d) and component (a) are contacted, then component (b) is contacted, and then component (c) is contacted.
<4> Component (d) and component (b) are contacted, then component (a) is contacted, and then component (c) is contacted.
The contact order is preferably <1>.

  The contact treatment of component (a), component (b), component (c), component (d) and component (e) is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  As a metal atom (M) of the metallocene complex of the said component (B), a periodic table group IV atom is preferable, and a zirconium atom and a hafnium atom are more preferable.

  As a crosslinking group of the metallocene complex of the said component (B), a methylene group, a dimethylmethylene group, and an ethylene group are preferable, More preferably, it is an ethylene group.

  As the remaining substituents that the metal atom of the metallocene complex of the component (B) has, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, a carbon atom number of 3 10 cycloalkyl groups, aralkyl groups having 7 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, carbon atoms 6-20 aryloxy group, silyl group optionally having 1-20 carbon atoms hydrocarbyl group as a substituent, hydrocarbyl group having 1-20 carbon atoms as a substituent The amino group which may be sufficient is mentioned. Preferably, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms An amino group optionally having a hydrocarbyl group as a substituent, particularly preferably a chlorine atom, a bromine atom, an iodine atom, an alkoxy group having 1 to 10 carbon atoms, or an aryl having 6 to 10 elementary atoms An amino group which may have an oxy group or a hydrocarbyl group having 1 to 6 carbon atoms as a substituent. Specifically, phenoxy group, 4-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6- Examples include trimethylphenoxy group, 3,4,5-trimethylphenoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, dimethylamino group, and diethylamino group. Particularly preferred are a phenoxy group and a dimethylamino group.

（式中、

Ｒ^１およびＲ^２は、同一または相異なり、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数３〜１０のシクロアルキル基、ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルケニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルキニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、または
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基を表し、Ｒ^３およびＲ^４は、同一または相異なり、水素原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数３〜１０のシクロアルキル基、ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルケニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルキニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、または
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基を表し、Ｒ^５からＲ^８は、同一または相異なり、水素原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数３〜１０のシクロアルキル基、ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルケニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルキニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、炭素原子数１〜２０のハイドロカルビル基もしくはハロゲン化ハイドロカルビル基を置換基として有していてもよいシリル基、
炭素原子数１〜２０のハイドロカルビル基もしくはハロゲン化ハイドロカルビル基を置換基として有していてもよいアミノ基、または
ヘテロ環式化合物残基を表し、
Ｒ^１およびＲ^３、Ｒ^２およびＲ^４、Ｒ^５およびＲ^６、Ｒ^５およびＲ^７、Ｒ^７およびＲ^８は、連結して環を形成してもよく、該環は置換基を有していてもよい。） As a ligand having a cyclopentadienyl skeleton of the metallocene complex of the component (B)

(Where

R ¹ and R ² are the same or different,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
A cycloalkyl group having 3 to 10 carbon atoms which may have a halogen atom as a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkynyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, R ³ and R ⁴ is the same or different and is a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
A cycloalkyl group having 3 to 10 carbon atoms which may have a halogen atom as a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkynyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
Aralkyl group optionally having 7 to 20 carbon atoms which may have a halogen atom as a substituent or a halogen atom represent an aryl group having 6 to 20 carbon atoms which may have a substituent, a R ^5, R ⁸ is the same or different and is a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
A cycloalkyl group having 3 to 10 carbon atoms which may have a halogen atom as a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkynyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
The aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, the hydrocarbyl group or halogenated hydrocarbyl group having 1 to 20 carbon atoms as a substituent Good silyl group,
An amino group optionally having a hydrocarbyl group having 1 to 20 carbon atoms or a halogenated hydrocarbyl group as a substituent, or a heterocyclic compound residue;
R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁷ , R ⁷ and R ⁸ may be linked to form a ring, and the ring has a substituent. It may be. )

Preferred examples of the metallocene complex of the component (B) include the following compounds (B-1) and (B-2). From the viewpoint of mechanical strength such as tensile impact strength, more preferably (B-1 ).

  Moreover, the compound which changed the phenoxy group of these compounds into the dimethylamino group or the diethylamino group, and the compound which changed the zirconium atom into the hafnium atom are also mentioned preferably.

  The organoaluminum compound of component (C) is preferably triisobutylaluminum, trinormal octylaluminum, triethylaluminum, or trimethylaluminum.

The amount of the metallocene complex used as the component (B) is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol with respect to 1 g of the promoter support of the component (A). The amount of the organoaluminum compound used as the component (C) is preferably a ratio of the number of moles of aluminum atoms in the organoaluminum compound as the component (C) to the number of moles of metal atoms in the metallocene complex as the component (B) (Al / M ) And 1 to 5000.

  In the polymerization catalyst obtained by contacting the promoter support (A), the metallocene complex (B) and the organoaluminum compound (C), the promoter support (A) and the metallocene complex (B ) And the organoaluminum compound (C) may be a polymerization catalyst obtained by contacting the electron donating compound (D). Specific examples of the electron donating compound (D) include tertiary amines and secondary amines. Tertiary amines are preferable, and specific examples include triethylamine and trinormaloctylamine.

  From the viewpoint of increasing the molecular weight distribution of the obtained ethylene-α-olefin copolymer, the electron donating compound (D) is preferably used, and the amount of the electron donating compound (D) used is an organoaluminum compound. The amount is more preferably 0.1 mol% or more, still more preferably 1 mol% or more, relative to the number of moles of aluminum atoms in (C). In addition, from the viewpoint of increasing the polymerization activity, the amount used is preferably 30 mol% or less, and more preferably 20 mol% or less.

  The first ethylene-α-olefin copolymer of the present invention is a continuous slurry polymerization method or a continuous bulk polymerization method, and can be preferably polymerized by a continuous slurry polymerization method.

  The second ethylene-α-olefin copolymer of the present invention can be polymerized by a continuous gas phase polymerization method. The gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method of supplying each component of the polymerization catalyst used for the production of the first and second ethylene-α-olefin copolymers of the present invention to the reaction vessel, usually, an inert gas such as nitrogen or argon, hydrogen, A method in which ethylene or the like is used to supply in a state free from moisture, or a method in which each component is dissolved or diluted in a solvent and supplied in a solution or slurry state is used. Each component of the catalyst may be supplied individually, or arbitrary components may be supplied in contact in advance in an arbitrary order.

  In the production of the first ethylene-α-olefin copolymer of the present invention, prepolymerization is performed before the main polymerization, and the prepolymerized prepolymerized catalyst component is used as the catalyst component or catalyst for the main polymerization. May be used. In the production of the second ethylene-α-olefin copolymer of the present invention, prepolymerization is carried out, and the prepolymerized prepolymerized catalyst component is used as a catalyst component or catalyst for the main polymerization.

  The polymerization temperature of the first ethylene-α-olefin copolymer of the present invention is preferably 0 to 150 ° C, more preferably 30 to 100 ° C, still more preferably 65 to 90 ° C, still more preferably 70 to 90. ° C. By increasing the polymerization temperature, the molecular weight distribution can be narrowed.

  The polymerization temperature of the second ethylene-α-olefin copolymer of the present invention is preferably 60 to 100 ° C, more preferably 65 to 90 ° C, still more preferably 70 to 90 ° C, and even more preferably 75 to 90. It is 80 degreeC, Most preferably, it is 80-90 degreeC. By increasing the polymerization temperature, the molecular weight distribution can be narrowed.

  In order to adjust the melt fluidity of the first and second ethylene-α-olefin copolymers of the present invention, hydrogen may be added as a molecular weight regulator in the polymerization reactor.

An inert gas may be added into the polymerization reactor. From the viewpoint of increasing η ^* _0.1 / η ^* ₁₀₀ , it is preferable to reduce the hydrogen concentration, and from the viewpoint of decreasing η ^* _0.1 / η ^* ₁₀₀ , it is preferable to increase the hydrogen concentration.

  Multi-stage polymerization may be performed for the purpose of broadening the molecular weight distribution of the first and second ethylene-α-olefin copolymers of the present invention.

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

The ethylene-α-olefin copolymer (A) of the present invention can be used together with other resins. Examples of other resins include ethylene resins different from the ethylene-α-olefin copolymer (A) of the present invention, and olefin resins such as propylene resins.
In the resin composition containing the ethylene-α-olefin copolymer (A) and the ethylene copolymer (B) of the present invention, the ethylene-α-olefin copolymer (A) and the ethylene copolymer ( As the content of B), the total of the ethylene-α-olefin copolymer (A) and the ethylene-based copolymer (B) is 100% by weight, and from the viewpoint of improving optical properties, ethylene-α-olefin copolymer is used. The content of the coalescence (A) is 5% by weight or more (the content of the ethylene copolymer (B) is 95% by weight or less), preferably the content of the ethylene-α-olefin copolymer (A) is 10% by weight or more (component (B) content is 90% by weight or less). Further, from the viewpoint of enhancing optical properties, the content of the ethylene-α-olefin copolymer (A) is 95% by weight or less (the content of the ethylene copolymer (B) is 5% by weight or more), Preferably, the content of the ethylene-α-olefin copolymer (A) is 70% by weight or less (the content of the ethylene copolymer (B) is 30% by weight or more), more preferably the ethylene-α-olefin. The content of the copolymer (A) is 50% by weight or less (the content of the ethylene copolymer (B) is 50% by weight or more).

  The ethylene-α-olefin copolymer of the present invention is excellent in the balance of extrusion load during processing, film transparency, melt tension, and mechanical strength. The ethylene-α-olefin copolymer of the present invention can be produced by various moldings (such as an extrusion molding method such as an inflation film molding method or a T-die film molding method, an injection molding method, a compression molding method). Film, sheet, bottle, tray, etc.). As the molding method, an inflation film molding method is suitably used, and the resulting molded body is used for various applications such as food packaging and surface protection.

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

  The 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) 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.

(3) 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

(4) η ^* _0.1 / η ^* ₁₀₀
Using a strain-controlled rotational viscometer (rheometer), after measuring the dynamic complex viscosity from an angular frequency of 0.1 rad / sec to 100 rad / sec under the following conditions, the angular frequency at 0.1 rad / sec. A value (η ^* _0.1 / η ^* ₁₀₀ ) obtained by dividing the dynamic complex viscosity (η ^* _0.1 ) by the dynamic complex viscosity (η ^* ₁₀₀ ) at an angular frequency of 100 rad / sec was obtained. Examples of the strain control type rotational rheometer include ARES manufactured by TA Instruments.
Temperature: 190 ° C
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(5) Activation energy (Ea, unit: kJ / mol)
The activation energy Ea is obtained by measuring dynamic viscoelasticity data at each temperature T (K) measured under the following conditions (a) to (d) using a strain-controlled rotary viscometer (rheometer). -Arrhenius equation of shift factor (aT) when shifting based on the time superposition principle: log (aT) = Ea / R (1 / T-1 / T0) (R is gas constant, T0 is reference temperature 463K) The index of formability calculated from the above. Calculation software includes Rohms V. from Reometrics. 4.4.4 is used, and the Ea value when the correlation coefficient r2 at the time of linear approximation in the Arrhenius plot log (aT) − (1 / T) is 0.99 or more is adopted. The measurement is performed under nitrogen.
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

(6) 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.

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

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 rougher the surface of the film using the resin. .
Accordingly, from the viewpoint of transparency of the film, it is preferable that the characteristic relaxation time of the resin is short (see, for example, H. Zhu et. Al. Polymer 48, (2007) 5098-5106).

(8) Haze, unit:%
The measurement was performed according to the method defined in ASTM D1003. It shows that transparency is excellent, so that this value is small.

(9) Internal haze, unit:%
The measurement was performed according to the method defined in ASTM D1003. It shows that transparency is so good that this value is small. Further, in order to suppress the scattering of light on the film surface unevenness, a quartz glass cell was filled with dimethyl phthalate, and the internal haze was measured in a state where the film was submerged in the cell.

(9) External haze, unit:%
The value obtained by subtracting the internal haze from the above haze was defined as the external haze. The roughness of the film surface affects the external haze and gloss. Generally, the larger the surface roughness, the greater the external haze value.

(10) 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

Method for calculating the number of long chain branches (LCB) In an 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 the branch has 7 or more carbon atoms. The number of long chain branches (the number of branches having 7 or more carbon atoms) was determined from the peak area of the peak derived from methine carbon bonded with. 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.

Method for calculating the number of short chain branches (SCB) When the comonomer is hexene, a branch having 4 carbon atoms is bound when the sum of the peak areas of all peaks having a peak top at 5 to 50 ppm is 1000 in the NMR spectrum obtained by treating the window function with an exponential. 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 processed with the exponential, the branching with 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.

(11) Melt tension (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, molten resin filled in a 9.55 mmφ barrel at a temperature of 150 ° 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.

(12) Contractile factor g *
The contraction factor g * was determined by the formula (I).
[Η] represents the relative viscosity (η _rel ) of the ethylene-α-olefin copolymer in 100 ml of tetralin containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor, and the ethylene-α-olefin copolymer. A sample solution is prepared by dissolving 100 mg of polymer at 135 ° C., and the sample solution is dropped using a Ubbelohde viscometer with a blank solution composed of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor. Calculated from time and determined by formula (II), [η] _GPC is determined by formula (I-II) from measurement of molecular weight distribution of ethylene-α-olefin copolymer of (6), g _SCB * Was determined by the formula (I-III) from the measurement of the number of short chain branches of the ethylene-α-olefin copolymer of (2).

Example 1
(1) Treatment of silica In a reactor equipped with a nitrogen-replaced stirrer, 500 ml of toluene as a solvent and silica heat-treated at 300 ° C. under a nitrogen stream (Sypolol 948 manufactured by Devison; average particle size = 55 μm; pore volume) = 1.67 ml / g; specific surface area = 325 m ² / g) was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 28.5 ml of 1,1,1,3,3,3-hexamethyldisilazane and 38.3 ml of toluene was maintained while keeping the temperature in the reactor at 5 ° C. It was dripped in 30 minutes. After completion of the dropping, the mixture was stirred at 5 ° C. for 1 hour and then at 95 ° C. for 3 hours and filtered. The obtained solid component was washed 6 times with 500 ml of toluene and twice with 500 ml of hexane. Thereafter, the solid component was dried at 23 ° C. under reduced pressure for 1 hour to obtain 52.2 g of surface-treated silica gel.

(2) Preparation of cocatalyst carrier After drying under reduced pressure, in a 300 ml four-necked flask purged with nitrogen, 16.2 g of the surface-treated silica gel obtained in Example 1 (1) above, 112.5 ml of toluene, Was introduced.
Next, 40.5 ml of a diethylzinc hexane solution having a diethylzinc concentration of 2 mmol / ml was added and stirred. Then, after cooling to 5 ° C., 16.7 ml of a 3,4,5-trifluorophenol toluene solution having a concentration of 3,4,5-trifluorophenol of 2.42 mmol / ml was added to the reactor. While maintaining the temperature at 5 ° C., the solution was added dropwise over 180 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 1.08 ml of water was added dropwise over 4.5 hours while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. After the stirring was stopped, the mixture was allowed to stand, 90 ml of the supernatant liquid was extracted, 90 ml of toluene was added, the temperature was raised to 95 ° C., the mixture was stirred for 4 hours, and after stirring, the supernatant liquid was extracted to obtain a solid component. The obtained solid component was washed 4 times with 90 ml of toluene and 3 times with 90 ml of hexane. Thereafter, the solid component (hereinafter referred to as a promoter support (A1)) was obtained by drying.

(3) Polymerization After drying under reduced pressure, the inside of a 5 liter autoclave equipped with a stirrer substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.029 MPa, and 230 mL of 1-hexene and 1046 g of butane were charged. After raising the temperature to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.50 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Then racemic-ethylene (indenyl) (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide concentration is 1 μmol / mL. ) 1.0 mL of a toluene solution of (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide was added, and the concentration of triethylamine was 0.1 mmol / mL 1.5 mL of a triethylamine toluene solution was added. Subsequently, 9.0 mg of the promoter support (A1) prepared in Example 1 (2) was added. Polymerization was carried out at 70 ° C. for 120 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.16 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 153.7 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 2
After drying under reduced pressure, the inside of an autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.026 MPa, 230 mL of 1-hexene and 1046 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.34 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Then racemic-ethylene (indenyl) (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide concentration is 1 μmol / mL. ) 1.0 mL of a toluene solution of (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide was added, and the concentration of triethylamine was 0.1 mmol / mL 1.5 mL of a triethylamine toluene solution was added. Subsequently, 10.5 mg of the promoter support (A1) prepared in Example 1 (2) was added. The polymerization was carried out at 70 ° C. for 170 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.14 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 237.0 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 3
After drying under reduced pressure, the inside of an autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.026 MPa, 230 mL of 1-hexene and 1046 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.33 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Then racemic-ethylene (indenyl) (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide concentration is 1 μmol / mL. ) 1.0 mL of a toluene solution of (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide was added, and the concentration of triethylamine was 0.1 mmol / mL 1.5 mL of a triethylamine toluene solution was added. Subsequently, 6.4 mg of the promoter support (A1) prepared in Example 1 (2) was charged. During the polymerization, polymerization was performed at 70 ° C. for 225 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.14 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 214.9 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 4
After drying under reduced pressure, the inside of an autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.026 MPa, 230 mL of 1-hexene and 1046 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.30 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Then racemic-ethylene (indenyl) (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide concentration is 1 μmol / mL. ) 1.0 mL of a toluene solution of (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide was added, and the concentration of triethylamine was 0.1 mmol / mL 1.5 mL of a triethylamine toluene solution was added. Subsequently, 8.4 mg of the promoter support (A1) prepared in Example 1 (2) was added. Polymerization was carried out at 70 ° C. for 153 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.15 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 228.1 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 5
After drying under reduced pressure, the inside of a 5 liter autoclave equipped with a stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.024 MPa, 250 mL of 1-hexene and 1032 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.23 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Then racemic-ethylene (indenyl) (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide concentration is 1 μmol / mL. ) 0.75 mL of a toluene solution of (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide was added and the concentration of triethylamine was 0.1 mmol / mL 1.5 mL of a triethylamine toluene solution was added. Subsequently, 6.7 mg of the promoter support (A1) prepared in Example 1 (2) was added. The polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.16 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 195.0 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 6
After drying under reduced pressure, the autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.021 MPa, 230 mL of 1-hexene and 1046 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.07 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Then racemic-ethylene (indenyl) (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide concentration is 1 μmol / mL. ) 1.0 mL of a toluene solution of (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide was added, and the concentration of triethylamine was 0.1 mmol / mL 1.5 mL of a triethylamine toluene solution was added. Subsequently, 9.0 mg of the promoter support (A1) prepared in Example 1 (2) was added. The polymerization was carried out at 70 ° C. for 140 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.11 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 241.0 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 7
After drying under reduced pressure, the inside of a 5 liter autoclave equipped with a stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.017 MPa, 250 mL of 1-hexene and 1032 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 0.84 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Then racemic-ethylene (indenyl) (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide concentration is 1 μmol / mL. ) (5,6,7,8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide in 0.5 mL was added, and the triethylamine concentration was 0.1 mmol / mL. 1.5 mL of a triethylamine toluene solution was added. Subsequently, 4.8 mg of the promoter support (A1) prepared in Example 1 (2) was added. The polymerization was carried out at 70 ° C. for 210 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.25 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene, and hydrogen were purged to obtain 48.1 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 8
(1) Preparation of prepolymerization catalyst component After introducing 837 g of butane into an autoclave with a stirrer having an internal volume of 5 liters, which had been previously purged with nitrogen, racemic-ethylene (indenyl) (5, 6, 7, 8-tetrahydro-5, 0.96 g of 5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide was added, and the autoclave was heated to 50 ° C. and stirred for 1.25 hours. Next, after the temperature of the autoclave was lowered to 30 ° C. and the system was stabilized, 2.0 g of ethylene was charged, and the promoter support (A1) 10.72 obtained in (2) of Example 1 was charged. Polymerization was started by adding 6 mmol of isobutylaluminum. After 30 minutes have elapsed while continuously supplying ethylene at 0.17 g / min, the temperature is raised to 50 ° C., and an ethylene / hydrogen mixed gas (hydrogen = 0.30 mol%) is continuously supplied for a total of 200 minutes. Polymerization was performed.
After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature, and the prepolymerized catalyst component (B1) containing 15.5 g of polyethylene per 1 g of the promoter support (A1) is added. Obtained.

(2) Main polymerization After drying under reduced pressure, the inside of an autoclave with a 5 liter stirrer substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.024 MPa, and 230 mL of 1-hexene and 1046 g of butane were charged. After the temperature in the system was raised to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.26 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 1.5 mL of a toluene solution of triethylamine having a triethylamine concentration of 0.1 mmol / mL was added. Subsequently, 157.6 mg of the prepolymerized catalyst component (B1) prepared in Example 9 (1) was added to initiate polymerization. The polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.197 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 120.3 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 9
After drying under reduced pressure, the inside of a 5 liter autoclave equipped with a stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.019 MPa, 230 mL of 1-hexene and 1046 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.01 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 1.5 mL of a toluene solution of triethylamine having a triethylamine concentration of 0.1 mmol / mL was added. Subsequently, 154.6 mg of the prepolymerized catalyst component (B1) prepared in Example 8 (1) was added to initiate polymerization. The polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.154 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene, and hydrogen were purged to obtain 153.6 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 10
After drying under reduced pressure, the autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.024 MPa, 180 mL of 1-hexene and 1080 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.25 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 1.5 mL of a toluene solution of triethylamine having a triethylamine concentration of 0.1 mmol / mL was added. Subsequently, 182.4 mg of the prepolymerized catalyst component (B1) prepared in Example 8 (1) was added to initiate polymerization. The polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.205 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 86.2 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 11
After drying under reduced pressure, the autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.024 MPa, 280 mL of 1-hexene and 1012 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.28 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 1.5 mL of a toluene solution of triethylamine having a triethylamine concentration of 0.1 mmol / mL was added. Subsequently, 150.3 mg of the prepolymerized catalyst component (B1) prepared in Example 8 (1) was added to initiate polymerization. The polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.170 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 173.8 g of an ethylene-1-hexene copolymer. The physical properties of the obtained first ethylene-α-olefin copolymer are shown in Table 1.

Example 12
After drying under reduced pressure, the inside of a 3 liter autoclave equipped with a stirrer substituted with argon was evacuated, hydrogen was added so that the partial pressure became 0.017 MPa, and 1-butene (71 g) and butane (679 g) were charged. After the temperature was raised to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.10 mol%. To this was added 0.9 mL of a triisobutylaluminum heptane solution having a triisobutylaluminum concentration of 1 mmol / mL. Next, ethylene bis (5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz-f-indenyl) zirconium diphenoxide concentration of 2 μmol / mL ethylene bis (5,5,8, 0.25 mL of a toluene solution of 8-tetramethyl-5,6,7,8-tetrahydrobenz-f-indenyl) zirconium diphenoxide was added, and a toluene solution of triethylamine having a triethylamine concentration of 0.1 mmol / mL was reduced to 0. .9 mL was charged. Subsequently, 6.3 mg of the promoter support (A1) prepared in Example 1 (2) was charged. During the polymerization, the polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.26 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 164.3 g of an ethylene-1-hexene copolymer. Table 2 shows the physical properties of the obtained first ethylene-α-olefin copolymer.

Comparative Example 1
After drying under reduced pressure, the autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.046 MPa, 280 mL of 1-hexene and 1012 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 2.41 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 1.25 mL of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide having a racemic-ethylenebis (1-indenyl) zirconium diphenoxide concentration of 1 μmol / mL was added, and the concentration of triethylamine was 0.1 mmol. 1.5 mL of a toluene solution of triethylamine / mL. Subsequently, 9.8 mg of the promoter support (A1) prepared in Example 1 (2) was added. During the polymerization, the polymerization was carried out at 70 ° C. for 100 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.24 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 215.3 g of an ethylene-1-hexene copolymer. Table 2 shows the physical properties of the obtained ethylene-1-hexene copolymer.

Comparative Example 2
After drying under reduced pressure, the autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.046 MPa, 280 mL of 1-hexene and 1012 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 2.40 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 1.25 mL of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide having a racemic-ethylenebis (1-indenyl) zirconium diphenoxide concentration of 1 μmol / mL was added, and the concentration of triethylamine was 0.1 mmol. 1.5 mL of a toluene solution of triethylamine / mL. Subsequently, 11.7 mg of the promoter support (A1) prepared in Example 1 (2) was added. The polymerization was carried out at 70 ° C. for 120 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.25 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 204.6 g of an ethylene-1-hexene copolymer. Table 2 shows the physical properties of the obtained ethylene-1-hexene copolymer.

Comparative Example 3
After drying under reduced pressure, the inside of an autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure becomes 0.019 MPa, 265 mL of 1-hexene and 1021 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.16 mol%. To this, 2.0 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 0.5 mL of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide having a racemic-ethylenebis (1-indenyl) zirconium diphenoxide concentration of 1 μmol / mL was added, and then the above Example 1 40.0 mg of the promoter support (A1) prepared in (2) was added. During the polymerization, the polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.18 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene, and hydrogen were purged to obtain 146.7 g of an ethylene-1-hexene copolymer. Table 2 shows the physical properties of the obtained ethylene-1-hexene copolymer.

Comparative Example 4
(1) Preparation of prepolymerization catalyst component Into an autoclave equipped with a stirrer with an internal volume of 5 liters previously purged with nitrogen, 835.3 g of butane was added, and then 0.75 g of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. The autoclave was heated to 50 ° C. and stirred for 1.25 hours.
Next, after the temperature of the autoclave was lowered to 30 ° C. and the system was stabilized, 2.0 g of ethylene was charged, and the promoter support (A1) 10.56 obtained in Example 1 (2) was charged, followed by triisobutyl. Polymerization was started by charging 5.6 mmol of aluminum. After 30 minutes have elapsed while continuously supplying ethylene at 0.17 g / min, the temperature is raised to 50 ° C., and an ethylene / hydrogen mixed gas (hydrogen = 0.30 mol%) is continuously supplied for a total of 200 minutes. Polymerization was performed. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature, and a prepolymerized catalyst component (B2) containing 17.0 g of polyethylene per 1 g of the promoter support (A1) is added. Obtained.

(2) Main polymerization After drying under reduced pressure, the inside of a 5 liter autoclave equipped with a stirrer substituted with argon was evacuated, hydrogen was added so that the partial pressure became 0.037 MPa, and 230 mL of 1-hexene and 1046 g of butane were charged. After the temperature in the system was raised to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 2.05 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 1.5 mL of a toluene solution of triethylamine having a triethylamine concentration of 0.1 mmol / mL was added. Subsequently, 176 mg of the prepolymerized catalyst component (B2) prepared in Comparative Example 4 (1) was added to initiate polymerization. The polymerization was carried out at 70 ° C. for 180 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.289 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 126.9 g of an ethylene-1-hexene copolymer. Table 2 shows the physical properties of the obtained ethylene-1-hexene copolymer.

Example 13
The first ethylene-1-hexene copolymer obtained in Example 4 was blended with 2000 ppm of an antioxidant (Sumilyzer GP manufactured by Sumitomo Chemical Co., Ltd.) and 2000 ppm of calcium stearate, and then a 15 mmφ extruder was used. Then, ethylene-1-hexene copolymer was pelletized under the processing conditions of a processing temperature of 150 ° C. and an extrusion rate of 1.0 kg / hr. A pellet blend was obtained by mixing 20 parts by weight of the above pellets with 80 parts by weight of FS250 (LLDPE manufactured by Sumitomo Chemical Co., Ltd., MFR = 2.0 g / 10 min, density = 922 Kg / m ³ ). The pellet blend was processed by an inflation film molding machine (manufactured by Landcastle, single screw extruder (diameter 0.5 inch φ), die (die diameter 0.625 inch φ, lip gap 0.03 inch)) at a processing temperature of 200. An inflation film having a thickness of 20 μm was formed under the processing conditions of ° C., extrusion amount 200 g / hr, frost line height 20 mm, blow ratio 2.0, and film take-off speed 2.0 m / min. Table 3 shows the evaluation results of the physical properties of the obtained film.

Comparative Example 5
The ethylene-1-hexene copolymer obtained in Comparative Example 2 was blended with 2000 ppm of an antioxidant (Sumilizer GP manufactured by Sumitomo Chemical Co., Ltd.) and 2000 ppm of calcium stearate, and then processed using a 15 mmφ extruder. The ethylene-1-hexene copolymer was pelletized under the processing conditions of a temperature of 150 ° C. and an extrusion rate of 1.0 kg / hr. A pellet blend was obtained by mixing 20 parts by weight of the above pellets with 80 parts by weight of FS250 (LLDPE manufactured by Sumitomo Chemical Co., Ltd., MFR = 2.0 g / 10 min, density = 922 Kg / m ³ ). The pellet blend was processed by an inflation film molding machine (manufactured by Landcastle, single screw extruder (diameter 0.5 inch φ), die (die diameter 0.625 inch φ, lip gap 0.03 inch)) at a processing temperature of 200. An inflation film having a thickness of 20 μm was formed under the processing conditions of ° C., extrusion amount 200 g / hr, frost line height 20 mm, blow ratio 2.0, and film take-off speed 2.0 m / min. Table 3 shows the evaluation results of the physical properties of the obtained film.

Example 14
(1) Preparation of solid component In a reactor equipped with a nitrogen-replaced stirrer, silica heat-treated at 300 ° C. under nitrogen flow (Sypolol 948 manufactured by Devison; 50% volume average particle size = 55 μm; pore volume = 1 .67 ml / g; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 1.73 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 1.02 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of 3,4,5-trifluorophenol and 1.44 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1 hour, then heated to 40 ° C, and stirred at 40 ° C for 1 hour. Thereafter, the mixture was cooled to 22 ° C., and 0.11 kg of H ₂ O was added dropwise over 1.5 hours while maintaining the reactor temperature at 22 ° C. After completion of dropping, the mixture was stirred at 22 ° C. for 1.5 hours, then heated to 40 ° C., stirred at 40 ° C. for 2 hours, further heated to 80 ° C., and stirred at 80 ° C. for 2 hours. After stirring, at room temperature, the supernatant was withdrawn to a residual amount of 16 L, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours. After stirring, the supernatant liquid was extracted at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, the solid component was obtained by drying (hereinafter referred to as promoter support (A2)).

(2) Preparation of pre-polymerization catalyst component (B3) 80 liters of butane was charged into an autoclave with a stirrer having an internal volume of 210 liters previously purged with nitrogen, and then racemic-ethylene (indenyl) (5, 6, 7, 8- Tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide (101 mmol) was added, and the autoclave was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature of the autoclave is lowered to 30 ° C. and the system is stabilized, 0.03 MPa of ethylene is charged at the gas phase pressure in the autoclave, and 0.7 kg of the promoter support (A2) is added, followed by triisobutyl. Polymerization was started by charging 158 mmol of aluminum. After 30 minutes while continuously supplying ethylene at 0.7 kg / Hr, the temperature was raised to 50 ° C., and ethylene and hydrogen were respectively 3.5 kg / Hr and 5.5 liters (room temperature and normal pressure volume) / Hr. A total of 4 hours of prepolymerization was carried out by continuous feeding. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature, and the prepolymerized catalyst component (B3) in which 23 g of polyethylene is prepolymerized per 1 g of the promoter support (a). Got.

(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component (B3) obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus, I got a powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.52%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.30%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the prepolymerization catalyst component (B3) and triisobutylaluminum were continuously supplied to maintain a constant total powder weight of 80 kg in the fluidized bed. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. The ethylene-1-hexene copolymer was obtained by granulation under the conditions of Table 4 shows the results of physical properties evaluation of the obtained second ethylene-α-olefin copolymer.

Example 15
(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component (B3) obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus, I got a powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.71%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.31%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the prepolymerization catalyst component (B3) and triisobutylaluminum were continuously supplied to maintain a constant total powder weight of 80 kg in the fluidized bed. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. The ethylene-1-hexene copolymer was obtained by granulation under the conditions of Table 4 shows the results of physical properties evaluation of the obtained second ethylene-α-olefin copolymer.

Example 16
(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component (B3) obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus, I got a powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.98%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.34%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the prepolymerization catalyst component (B3) and triisobutylaluminum were continuously supplied to maintain a constant total powder weight of 80 kg in the fluidized bed. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. The ethylene-1-hexene copolymer was obtained by granulation under the conditions of Table 4 shows the results of physical properties evaluation of the obtained second ethylene-α-olefin copolymer.

Example 17
(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component (B3) obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus, I got a powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.14%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.34%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the prepolymerization catalyst component (B3) and triisobutylaluminum were continuously supplied to maintain a constant total powder weight of 80 kg in the fluidized bed. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. The ethylene-1-hexene copolymer was obtained by granulation under the conditions of Table 4 shows the results of physical properties evaluation of the obtained second ethylene-α-olefin copolymer.

Example 18
(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component (B3) obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus, I got a powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.31%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.32%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the prepolymerization catalyst component (B3) and triisobutylaluminum were continuously supplied to maintain a constant total powder weight of 80 kg in the fluidized bed. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. The ethylene-1-hexene copolymer was obtained by granulation under the conditions of Table 4 shows the results of physical properties evaluation of the obtained second ethylene-α-olefin copolymer.

Comparative Example 6
(2) Preparation of pre-polymerization catalyst component (B4) 80 liters of butane was added to an autoclave with an internal volume of 210 liters previously purged with nitrogen, and then 101 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. The autoclave was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature of the autoclave is lowered to 30 ° C. and the system is stabilized, 0.03 MPa of ethylene is charged at the gas phase pressure in the autoclave, and 0.7 kg of the promoter support (A2) is added, followed by triisobutyl. Polymerization was started by charging 158 mmol of aluminum. After 30 minutes while continuously supplying ethylene at 0.7 kg / Hr, the temperature was raised to 50 ° C., and ethylene and hydrogen were respectively 3.5 kg / Hr and 5.5 liters (room temperature and normal pressure volume) / Hr. A total of 4 hours of prepolymerization was carried out by continuous feeding. After the completion of the polymerization, the pre-polymerized catalyst component (B4) in which ethylene, butane, hydrogen gas, etc. are purged and the remaining solid is vacuum-dried at room temperature, and 20 g of polyethylene is pre-polymerized per 1 g of the promoter support (a). Got.

(3) Production of ethylene-α-olefin copolymer Using the prepolymerized catalyst component (B4) obtained above, copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. I got a powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.53%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.36%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. In addition, the prepolymerized catalyst component (B4) and triisobutylaluminum were continuously supplied to keep the total powder weight of 80 kg in the fluidized bed constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. The ethylene-1-hexene copolymer was obtained by granulation under the conditions of The results of physical property evaluation of the obtained copolymer are shown in Table 4.

Comparative Example 7
(3) Production of ethylene-α-olefin copolymer Using the pre-polymerization catalyst component (B4) obtained above, copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. As a result, polymer powder was obtained. As polymerization conditions, the polymerization temperature was 84 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.82%, the 1-butene molar ratio to the total of ethylene, 1-butene and 1-hexene was 2.46%, The 1-hexene molar ratio was 0.78%, respectively. During the polymerization, ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. In addition, the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder weight of 80 kg in the fluidized bed was kept constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. By granulating under the conditions, an ethylene-1-hexene-1-butene copolymer (hereinafter referred to as PE (1)) was obtained. The results of physical property evaluation of the obtained copolymer are shown in Table 4.

Optical properties of blown film (Examples 19 and 20, Comparative Examples 8 and 9)
20 parts by weight of the ethylene-α-olefin copolymer of Examples 15 to 16 or Comparative Examples 6 to 7 and a commercially available ethylene-1-butene copolymer (Sumikasen L FS150 manufactured by Sumitomo Chemical Co., Ltd .; Ziegler-Natta polymerization) Production using a catalyst with 80 parts by weight of a drive lens, an inflation film molding machine (Placo, single screw extruder (diameter 50 mmφ, L / D = 28), die (die diameter 125 mmφ, lip gap) 2.0mm), single slit air ring with iris), processing temperature 200 ° C, extrusion rate about 25kg / hr, frost line height (FLD) 250mm, blow ratio 1.8, film take-up speed 20m / min An inflation film having a thickness of 30 μm was molded under the conditions. The haze (unit:%) of the obtained film was measured according to ASTM D1003. The smaller the haze, the better the optical properties of the film. Table 5 shows the evaluation results of the physical properties of the obtained film.

  FIG. 1 shows a plot of the value of τ (S) against the value of MFR (g / 10 minutes) for the ethylene-α-olefin copolymers of Examples 1 to 12 and Comparative Examples 1 to 5. ◆ is an example, and □ is a comparative example.

The figure which plotted the value of (eta) ^* ₁₀₀ (Pa ^* s) with respect to the value of MFR (g / 10min) about the ethylene-alpha-olefin copolymer of Examples 1-12 and Comparative Examples 1-5. It is shown in 2. ◆ is an example, and □ is a comparative example.

  FIG. 3 shows a plot of melt tension (cN) values against MFR (g / 10 minutes) values for the ethylene-α-olefin copolymers of Examples 14 to 18 and Comparative Examples 6 and 7. ◆ is an example, and □ is a comparative example.

Claims (3)

It has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, has a melt flow rate (MFR) of 0.01 to 5 g / 10 min, and a density of 860. ˜940 kg / m ³ , molecular weight distribution (Mw / Mn) is 4.5 to 13, activation energy (Ea) is 40 to 100 kJ / mol, and the number of carbon atoms is 7 or more as measured by NMR . Ethylene having a long chain branching amount of 0.25 to 0.50 per 1000 carbon atoms, g * defined by the following formula (I) of 0.750 to 0.850, and an oligomer amount of 1200 ppm or less -Α-olefin copolymer.
g * = [η] / ([η] _GPC × g _SCB *) (I)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is defined by the following formula (II). [Η] _GPC was defined by the following formula (I-II). g _SCB * is defined by the following formula (I-III).
[Η] = 23.3 × log (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 the short-chain branched portion in the ethylene-α-olefin copolymer.)] A resin composition comprising the ethylene-α-olefin copolymer according to claim 1. A film comprising the resin composition according to claim 2.

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