JP2017061653A - Polyethylene-based resin composition and film made of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene-based resin composition having excellent molding processability, from which a molded body having an excellent balance in impact strength and rigidity can be manufactured.SOLUTION: The polyethylene-based resin composition comprises a high-pressure polyethylene (A) and an ethylene α-olefin copolymer (B) satisfying the following conditions (B-1) to (B-5). The conditions are: (B-1) an MFR of the copolymer is over 0.1 g/10 minutes and 10 g/10 minutes or less; (B-2) a density is 0.895 to 0.940 g/cm; (B-3) a molecular weight distribution Mw/Mn measured by gel permeation chromatography (GPC) is 3.0 to 5.5; (B-4) a minimum (gc) of a branch index g' in the molecular weight range from 100000 to 1000000 is 0.40 to 0.85; and (B-5) a (W+W) value obtained from an integrated elution curve measured by cross-fractionation chromatography (CFC) is 40 wt.% or more and 80 wt.% or less.SELECTED DRAWING: None

Description

  The present invention relates to a polyethylene resin composition capable of producing a molded article having excellent molding processability and excellent balance between impact strength and rigidity, and injection molding, compression injection molding, rotational molding, and extrusion molding of the polyethylene resin composition. The present invention relates to a molded body obtained by hollow molding, blow molding, T-die molding, or inflation molding, and a product using the molded body, particularly a film.

In general, high-pressure polyethylene having a large number of branched and branched chains and linear low-density polyethylene having a linear molecular structure are mainly known as polyethylene resins widely used for packaging materials. Molding processing of polyethylene resin is carried out in a molten state, but high-pressure polyethylene (hereinafter also referred to as HPLD) having a large number of branched and branched chains is known to be easy to mold because of its excellent fluidity and extensional viscosity. ing. However, since the molecular weight distribution is wide, improvement in strength has been demanded.
In addition, the demand for reducing the thickness of molded products is increasing from the viewpoint of the need to reduce the amount of raw material resin used in the recent implementation of the Container Recycling Law and the trend toward resource saving. It is necessary to improve (elastic modulus).
On the other hand, in recent years, linear low-density polyethylene has been improved to improve molding processability and resin strength at the same time by utilizing a polymerization design technique using a metallocene catalyst capable of forming a long-chain branched structure in an ethylene polymer. Development of quality ethylene-based polymers has been reported. For example, an example of using an ethylene polymer containing a long-chain branch expressing a specific elongational viscosity behavior as a modifier for linear low-density polyethylene and blended with the target linear low-density polyethylene (Patent Document 1) And an example of a resin composition using a low-density ethylene / propylene copolymer having a long-chain branched structure defined by a specific polymer molecular structure index and an intrinsic viscosity ratio as a modifier (see Patent Document 2) An example in which a long-chain branched polyethylene having a high molecular weight distribution and high molecular weight distribution is used as a modifier (see Patent Document 3) is known. According to these methods, the impact strength of the polyolefin resin, which is conventionally caused by the modification by adding HPLD to the linear low density polyethylene, is not drastically reduced, but the long chain branched ethylene polymer is Since the design is insufficient, the strength and transparency are inevitably lowered, and the improvement level is still insufficient (see Patent Documents 4 to 7). Furthermore, research on metallocene polymerization catalysts capable of controlling a long-chain branched structure useful for the development of ethylene-based polymers having these characteristics has been continued (see Patent Document 8).

  Under these circumstances, a polyethylene resin that eliminates the problems associated with conventional ethylene resin compositions, is capable of producing a molded article that is excellent in molding processability, and has a balance between impact strength and rigidity and transparency. Development of a composition has been desired.

JP 2012-214781 A JP 09-031260 A JP 2007-119716 A International Publication No. 97/10295 JP 2006-63325 A JP 2006-124567 A JP 2007-197722 A JP 2013-227271 A

An object of the present invention is to provide a polyethylene resin composition that is excellent in balance between impact resistance and rigidity and also excellent in moldability, in view of the above-described problems of the prior art, and further, the polyethylene resin composition To provide a molded article excellent in the balance between impact strength and rigidity obtained by injection molding, compression injection molding, rotational molding, extrusion molding, hollow molding, blow molding, inflation molding, and use of the molded article is there.
In particular, a polyethylene resin obtained by blending an ethylene / α-olefin copolymer having a long-chain branched structure with a specific physical property range, which has been developed mainly for the modification of linear low density polyethylene, into high-pressure polyethylene. Surprisingly, in the composition, the present inventors have found that a resin composition excellent in the balance between impact strength and rigidity can be obtained by dramatically improving the physical properties inherent to the high-pressure low-density polyethylene.

That is, the first invention of the present application is a high-pressure polyethylene (A) and an ethylene / α-olefin copolymer (B) characterized by satisfying the following conditions (B-1) to (B-5): ) In the polyethylene-based resin composition.
(B-1) MFR exceeds 0.001 g / 10 min and is 20 g / 10 min or less (B-2) Density is 0.895-0.940 g / cm ³ (B-3) Gel permeation The molecular weight distribution Mw / Mn measured by chromatography (GPC) is 3.0 to 7.0. (B-4) Measured by a GPC measuring apparatus combining a differential refractometer, a viscosity detector and a light scattering detector. (B-5) Integral elution curve measured by cross-fractionation chromatography (CFC) having a molecular weight of 100,000 to 1,000,000 (gc) between 0.40 and 0.85. Of the components eluted at a temperature below the temperature at which the elution amount determined from 50% by weight, the ratio (W ₂ ) of the component having a molecular weight equal to or higher than the weight average molecular weight, and the elution amount determined from the integral elution curve is 50% by weight. The sum (W ₂ + W ₃ ) of the proportion (W 3) of the components whose molecular weight is less than the weight average molecular weight out of the components eluting at a temperature higher than the temperature is more than 40 wt% and less than 80 wt%

The second invention resides in the polyethylene-based resin composition according to the first invention, wherein the ethylene / α-olefin copolymer (B) further satisfies the following condition (B-6): .
(B-6) Ratio of components having a molecular weight equal to or higher than the weight average molecular weight among the components eluted at a temperature higher than the temperature at which the elution amount obtained from the integral elution curve measured by W ₂ and CFC is 50 wt% (W ₄ ) Sum (W ₂ + W ₄ ) is more than 25 wt% and less than 50 wt%

According to a third invention, in the polyethylene resin composition according to the first or second invention, the ethylene / α-olefin copolymer (B) satisfies the following condition (B-7): Exist.
(B-7) The difference between W ₂ and W ₄ (W ₂ −W ₄ ) is more than 0% by weight and less than 20% by weight.

According to a fourth aspect of the present invention, the ethylene / α-olefin copolymer (B) further satisfies the following condition (B-8): Resists in resin composition.
(B-8) The ratio (X) of the component that elutes at 85 ° C. or higher by temperature rising elution fractionation (TREF) is 2 to 15% by weight.

According to a fifth aspect of the present invention, the ethylene / α-olefin copolymer (B) satisfies the following condition (B-5 ′), and the polyethylene system according to any one of the first to fourth aspects Resists in resin composition.
(B-5 ′) The sum of W ₂ and W ₃ (W ₂ + W ₃ ) is more than 40% by weight and less than 56% by weight.

  The sixth invention is the polyethylene according to any one of the first to fifth inventions, wherein the α-olefin of the ethylene / α-olefin copolymer (B) has 3 to 10 carbon atoms. Resists in resin composition.

  In the seventh invention, the content of the ethylene / α-olefin copolymer (B) in the resin composition is 1 to 59% by weight, and the content of the high-pressure polyethylene (A) is 41 to 99% by weight. It exists in the polyethylene-type resin composition as described in any one of the 1st-6th invention characterized by being.

According to an eighth invention, the high-pressure polyethylene (A) satisfies the following conditions (A-1) and (A-2), and the polyethylene system according to any one of the first to seventh inventions Resists in resin composition.
(A-1) MFR is 0.1 to 20 g / 10 min. (A-2) Density is 0.910 to 0.940 g / cm ³ .

According to a ninth invention, in the polyethylene resin composition according to any one of the first to eighth inventions, the high-pressure polyethylene (A) further satisfies the following condition (A-3): Exist.
(A-3) The molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC) is 2.0 to 5.0.

A tenth invention resides in a film obtained from the resin composition according to any one of the first to ninth inventions.
The eleventh invention is characterized by using the ethylene / α-olefin copolymer (A) produced by an olefin polymerization catalyst containing the following catalyst components (X), (Y) and (Z): It exists in the manufacturing method of the polyethylene-type resin composition as described in any one of 1st-9th invention.
Catalyst component (X): a bridged cyclopentadienylindenyl compound containing a transition metal element.
Catalyst component (Y): A compound that reacts with the compound of component (X) to form a cationic metallocene compound.
Catalyst component (Z): inorganic compound carrier.

The polyethylene-based resin composition of the present invention is excellent in molding processing characteristics, and at the same time, excellent in the balance between impact strength and rigidity. In addition, the polyethylene-based resin composition is injection molded, compression injection molded, rotational molded, extruded, A molded product obtained by hollow molding, blow molding or inflation molding is also excellent in the balance between impact strength and rigidity and transparency, so that it is possible to provide a thin molded product economically advantageously. .

It is a graph which shows the base line and area of a chromatogram used by gel permeation chromatography (GPC) method. It is a graph which shows the relationship between the molecular weight distribution curve computed from GPC-VIS measurement (branch structure analysis), and a branching index (g '), and molecular weight (M). It is a graph which shows elution temperature distribution by temperature rising elution fractionation (TREF). It is a graph which shows the elution amount regarding the elution temperature and molecular weight which are measured by the cross fractionation chromatography (CFC) method of the polymer (B) used in the Example as a contour map. It is a graph which shows the relationship between the elution temperature measured by the cross fractionation chromatography (CFC) method of the polymer (B) used in the Example, and the elution ratio (wt%) in each elution temperature. It is a schematic view of W ₁ to _W-4. In the figure, the horizontal axis represents the logarithm of molecular weight (log M), and the horizontal axis represents the elution temperature (Temp.). It is a graph which shows the relationship of the elastic modulus and impact strength which were obtained about the film which blended the copolymer of the Example and comparative example of this invention.

Hereinafter, the present invention will be described in detail for each item.
[1] Components of polyethylene resin composition High pressure polyethylene (A)
The high pressure polyethylene (hereinafter also referred to as “HPLD”) (A) used in the present invention is a polyethylene having a large number of branched long chain branches produced by polymerizing ethylene by a high pressure radical polymerization method. For example, ethylene monomer, radical pressure polymerization using oxygen or organic peroxide as a polymerization initiator in a pressure range of 500-3500 Kg / cm ² G, polymerization temperature in a range of 100-400 ° C., autoclave type or tubular type It can be produced in a mold reactor. It is also called high pressure method low density polyethylene or high pressure radical polymerization method low density polyethylene. Since the high-pressure method low-density polyethylene has many branched long-chain branches, a low value of about 0.26 or less is detected when gc defined in the present invention is measured.
The physical properties of the high-pressure polyethylene (A) in the present invention are not particularly defined, and conventionally known high-pressure low-density polyethylene can be used. Among them, the conditions (A-1) to (A-) described below can be used. It is preferable to use high-pressure polyethylene that satisfies all 3). The high-pressure polyethylene (A) used is not limited to one type, and two or more types may be used.

1-1. Condition (A-1)
The melt flow rate (MFR _A ) of the high-pressure polyethylene (A) is 0.1 to 20.0 g / 10 minutes, and preferably 0.1 to 5.0 g / 10 minutes. If MFR _A is too low, molding processability is inferior. On the other hand, if MFR _A is too high, impact resistance, mechanical strength and the like may be reduced.
Here, the MFR _A of the high-pressure polyethylene (A) is 190 ° C., 21 in accordance with JIS K7210 “Testing method for melt mass flow rate (MFR) and melt volume rate (MVR) of plastic-thermoplastic plastic”. The value when measured under the condition of .18N (2.16 kg) load.

1-2. Condition (A-2)
The density _A of the high-pressure polyethylene (A) is a 0.910~0.940g / cm ^3, preferably 0.915~0.935g / cm ^3, is 0.915~0.930g / cm ³ More preferred. When the density _A is within this range, the balance between impact resistance and rigidity is excellent. Moreover, when the density _A is too low, rigidity will fall. On the other hand, if the density _A is too high, impact resistance may be impaired.

Here, the density _A of the high pressure polyethylene (A) refers to a value measured by the following method.
The pellets were hot-pressed to prepare a press sheet having a thickness of 2 mm. The sheet was placed in a beaker having a capacity of 1000 ml, filled with distilled water, capped with a watch glass, and heated with a mantle heater. After boiling boiling water for 60 minutes, the beaker was placed on a wooden table and allowed to cool. This time was adjusted not to be less than 60 minutes. In addition, the test sheet was immersed in a substantially central portion in water so as not to contact the beaker and the water surface. After annealing the sheet at a temperature of 23 ° C. and a humidity of 50% within a period of 16 hours to 24 hours, the sheet was punched out to 2 mm in length and width, and the test temperature was 23 ° C. And measurement method of specific gravity ”.

1-3. Condition (A-3)
Furthermore, the ratio [Mw / Mn] _A (hereinafter also referred to as Q value) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high-pressure polyethylene (A) is 2.0 to 10.0. . When the Q value is less than 2.0, the high-pressure polyethylene (A) and other polymer components may not be mixed easily. When the Q value exceeds 10.0, the effect of improving impact resistance is not sufficient, and the balance between impact resistance and rigidity is impaired. In view of the balance between impact resistance and rigidity, the upper limit of the Q value is preferably 7.5 or less, more preferably 5.0 or less. The lower limit of the Q value is preferably 2.3 or more, more preferably 2.5 or more.
In addition, the ratio [Mw / Mn] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high pressure polyethylene (A) _A may be referred to as the following condition (hereinafter referred to as “method for measuring molecular weight distribution”). It is the value when measured in (Yes). Mw / Mn is defined by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC).

Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical value is used for the viscosity formula [η] = K × Mα used in that case.
PS: K = 1.38 × 10 −4, α = 0.7
PE: K = 3.92 × 10 −4, α = 0.733

The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as illustrated in FIG.

Ethylene / α-olefin copolymer (B)
The ethylene / α-olefin copolymer (B) used in the polyethylene resin composition of the present invention is a copolymer of ethylene and one or more α-olefins, and has a special long-chain branched structure. It is an α-olefin copolymer.
That is, it is essential that the ethylene / α-olefin copolymer (B) of the present invention satisfies all the conditions (B-1) to (B-5) described below. Preferably, the condition (B-6), (B-7), (B-8) or (B-9) is further satisfied. That is, in a specific, relatively low MFR (B-1) and relatively low density (B-2), the molecular weight distribution is narrow (B-3), and an appropriate range of long chain branching is introduced ( B-4), a polymer having a relatively narrow inverse comonomer composition distribution (B-5), which has a new characteristic not seen in a conventionally marketed polymer.

2-1. Condition (B-1) MFR
The melt flow rate (MFR) of the ethylene / α-olefin copolymer of the present invention is 0.001 g / 10 min or more and 20 g / 10 min or less. Among them, one preferred embodiment is more than 0.1 g / 10 min and 10 g / 10 min or less, preferably more than 0.1 g / 10 min and 5.0 g / 10 min or less, more preferably 0.1 g / min. Examples include a copolymer that exceeds 10 minutes and is 2.0 g / 10 minutes or less.
When the MFR is within this range, the copolymer can be obtained by a relatively easy manufacturing process, with excellent processing characteristics when processed into a film and excellent impact strength of the processed film, and excellent balance between the two. .
On the other hand, another preferred embodiment is an ethylene / α-olefin copolymer having an MFR of 0.001 g / 10 min or more and 0.1 g / 10 min or less. Preferably, it is 0.005-0.1g / 10min, More preferably, it is 0.009-0.09g / 10min.
When the MFR is in this range, a markedly excellent effect can be achieved in the balance between the impact strength and rigidity of the film blended with the copolymer.
If the MFR is too low, the production is difficult and may not be preferable in terms of molding processability, and if the MFR is too large, the molding processability when processing into a film deteriorates and the impact strength of the processed film is low. It is not preferable because it is difficult to express sufficiently.
In the present invention, the MFR of the ethylene / α-olefin copolymer is in accordance with JIS K7210 “Testing method of melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic”. , 190 ° C., 21.18N (2.16 kg) when measured under load conditions.
The MFR can be adjusted by changing the amount of chain transfer agent (hydrogen, etc.) coexisting during ethylene polymerization or by changing the polymerization temperature, increasing the amount of hydrogen or increasing the polymerization temperature. By doing so, it can be enlarged.

2-2. Condition (B-2) Density The density of the ethylene / α-olefin copolymer of the present invention is 0.895 to 0.940 g / cm ³ , preferably 0.898 g / cm ³ or more and 0.934 g / cm ^3. less, more preferably 0.900~0.930g / cm ^3, further preferably not 0.910~0.930g / cm ^3, particularly preferably 0.915~0.930g / cm ^3.
If the density is less than 0.895 g / cm ³ , the rigidity of the polyolefin-based resin is lowered, the product is too soft, and an unnecessarily thick design is required, which is not preferable. In addition, the stickiness is so bad that it is difficult to handle, which is not preferable. On the other hand, if the density is greater than 0.940 g / cm ³ , the impact strength of the processed film is hardly exhibited, which is not preferable.
In the present specification, the density of the ethylene / α-olefin copolymer can be measured by JIS K7112 (1999 edition): Method A (submersion method in water).
The density can be adjusted by the amount of α-olefin during polymerization of ethylene / α-olefin.

2-3. Condition (B-3) Molecular Weight Distribution The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer in the present invention is 3.0 to 7.0, Preferably it is 3.0-5.5, More preferably, it is 3.2-5.5, More preferably, it is 3.2 or more and less than 5.3, Most preferably, it is 3.2 or more and less than 5.1, Especially preferably, 3 3 to 5.0. If Mw / Mn is too low, the processability at the time of extrusion molding is inferior and causes appearance defects such as melt fracture, and therefore should be avoided.
If Mw / Mn is too large, the impact strength of the polyethylene-based resin composition and its molded product will be reduced. Moreover, since it becomes easy to stickiness, it is not preferable.

In the present invention, Mw and Mn of the ethylene / α-olefin copolymer are those measured by a gel permeation chromatography (GPC) method.
Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical value is used for the viscosity formula [η] = K × M ^α used in this case.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733

The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as illustrated in FIG.
The molecular weight distribution (Mw / Mn) can be set to a predetermined range mainly by selecting a polymerization catalyst and polymerization conditions, and can be set to a predetermined range by mixing a plurality of components having different molecular weights. be able to.

2-4. Condition (B-4) Branch index gc
In addition to the above conditions (B-1) to (B-3), the ethylene / α-olefin copolymer in the present invention is further obtained by a GPC measurement device that combines a differential refractometer, a viscosity detector, and a light scattering detector. The minimum value (gc) of the measured branching index (g ′) between 100,000 and 1,000,000 is 0.40 to 0.85, preferably 0.45 to 0.80, more preferably 0.00. It is 45 to 0.77, particularly preferably 0.45 to 0.75. When the g _C value is larger than 0.85, the molding processability is not sufficiently exhibited, which is not preferable. If the g _C value is less than 0.40, the moldability of the polyethylene resin composition is improved, but the impact strength is lowered and the transparency is deteriorated.
In the present invention, the g _C value of the ethylene / α-olefin copolymer is an evaluation method for the amount of long chain branching using a molecular weight distribution curve or branching index (g ′) calculated from the following GPC-VIS measurement. is there.

[Branch structure analysis by GPC-VIS]
Waters Alliance GPCV2000 was used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As the light scattering detector, DAWN-E manufactured by Multi-angle Laser Light Scattering Detector (MALLS) Wyatt Technology can be used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with the antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. The column can be used by connecting two Tosoh Corporation GMHHR-H (S) HT. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration is 1 mg / mL and the injection volume (sample loop volume) is 0.2175 mL. In order to obtain the absolute molecular weight (M) obtained from MALLS, the inertial square radius (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, data processing software ASTRA (version 4.73.04) attached to MALLS was used. The calculation can be performed with reference to the following documents.

References:
1. Developments in polymer characterization, vol. 4). Essex: Applied Science; 1984. Chapter 1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

[Calculation of branching index (g _C ), etc.]
The branching index (g ′) is calculated as a ratio (ηbranch / ηlin) between the intrinsic viscosity (ηbranch) obtained by measuring the sample with the above Viscometer and the intrinsic viscosity (ηlin) obtained separately by measuring a linear polymer. To do.
When long chain branching is introduced into a polymer molecule, the radius of inertia is reduced compared to a linear polymer molecule of the same molecular weight. Since the intrinsic viscosity decreases as the radius of inertia decreases, the ratio of the intrinsic viscosity (ηbranch) of the branched polymer to the intrinsic viscosity (ηlin) of the linear polymer having the same molecular weight decreases as the long chain branching is introduced (ηbranch / ηlin). It will become. Therefore, when the branching index (g ′ = ηbranch / ηlin) is smaller than 1, it means that a branch is introduced, and the introduced long chain branching increases as the value decreases. Means that. In particular, in the present invention, as the absolute molecular weight obtained from MALLS, the minimum value of the above g ′ at a molecular weight of 100,000 to 1,000,000 is calculated as g _C. FIG. 2 shows an example of the analysis result by the GPC-VIS. FIG. 2 represents the branching index (g ′) in molecular weight (M). Here, as the linear polymer, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) can be used.
The minimum value (gc) of the molecular weight between 100,000 and 1,000,000 of the branching index g ′ can be set within a predetermined range mainly by selecting a polymerization catalyst and polymerization conditions. By using a metallocene catalyst, a predetermined range can be obtained.

2-5. Condition (B-5) W ₂ + W ₃
In addition to the said conditions (B-1)-(B-4), the ethylene-alpha-olefin copolymer in this invention is further integrated integral elution curve measured by (B-5) cross fractionation chromatography (CFC). Of the components that elute below the temperature at which the elution amount determined from 50% by weight is obtained, the proportion (W ₂ ) of the component having a molecular weight equal to or greater than the weight average molecular weight of the ethylene / α-olefin copolymer and the integral elution curve are obtained. The sum (W ₂ + W ₃ ) of the proportion (W ₃ ) of the components whose molecular weight is less than the weight average molecular weight of the ethylene / α-olefin copolymer among the components eluted at a temperature higher than the temperature at which the elution amount becomes 50 wt% Is more than 40% by weight and less than 80% by weight. More preferably, the range is more than 40% by weight and less than 56% by weight. It is particularly preferably more than 43% by weight and less than 56% by weight, more preferably more than 45% by weight and less than 56% by weight.
The above-mentioned numerical values such as W ₁ obtained from the integral elution curve measured by cross-fractionation chromatography (CFC) are an index that combines the distribution of comonomer amount and molecular weight of each polymer contained in the entire copolymer. This is a technique used to show “comonomer composition distribution”. That is, a polymer having a large amount of comonomer and a small molecular weight (W ₁ ), a polymer having a large amount of comonomer and a large molecular weight (W ₂ ), a polymer having a small amount of comonomer and a small molecular weight (W ₃ ), and a molecular weight having a small amount of comonomer The ratio of the polymer (W ₄ ) having a large value in the entire copolymer is shown. FIG. 6 shows a schematic diagram of W _{1 to} W ₄ .
If the W ₂ + W ₃ value is too small, the ratio of the low density high molecular weight component that effectively acts to improve the impact strength of the polyolefin-based resin contained in the ethylene / α-olefin copolymer is reduced, or the ethylene / α -It is not preferable because the high density low molecular weight component which effectively acts on the rigidity improvement of the olefin copolymer is reduced. On the other hand, if the W ₂ + W ₃ value is too large, the balance between the content of the high-density low-molecular weight component and the content of the low-density high-molecular weight component contained in the ethylene / α-olefin copolymer is lost, resulting in deterioration of transparency and gel. Is not preferable. In particular, the ethylene / α-olefin copolymer in a range where (B-5 ′) W ₂ + W ₃ is more than 40% by weight and less than 56% by weight has a remarkable effect in improving the rigidity and impact strength. Is preferable.

[CFC measurement conditions]
Cross fractionation chromatography (CFC) consists of a temperature rising elution fractionation (TREF) part for performing crystalline fractionation and a gel permeation chromatography (GPC) part for molecular weight fractionation.
The analysis using the CFC is performed as follows.
First, a polymer sample was completely dissolved in orthodichlorobenzene (ODCB) containing 0.5 mg / mL BHT at 140 ° C., and this solution was passed through a sample loop of the apparatus, and a TREF column (inert) maintained at 140 ° C. The polymer sample is crystallized by slowly cooling to a predetermined first elution temperature. After maintaining at a predetermined temperature for 30 minutes, ODCB is passed through a TREF column, whereby the eluted component is injected into the GPC section to perform molecular weight fractionation, and an infrared detector (MIRAN 1A IR detector manufactured by FOXBORO, A chromatogram is obtained with a measurement wavelength of 3.42 μm. Meanwhile, in the TREF part, the temperature is raised to the next elution temperature, and after obtaining the chromatogram of the first elution temperature, the elution component at the second elution temperature is injected into the GPC part. Hereinafter, by repeating the same operation, a chromatogram of the eluted components at each elution temperature is obtained.

The CFC measurement conditions are as follows.
Equipment: CFC-T102L manufactured by Dia Instruments
GPC column: Showa Denko AD-806MS (3 connected in series)
Solvent: ODCB
Sample concentration: 3 mg / mL
Injection volume: 0.4mL
Crystallization rate: 1 ° C / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stabilization time after GPC measurement: 5 minutes Elution temperature: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 102, 120, 140

[Data analysis]
From the chromatogram of the eluted components at each elution temperature obtained by the measurement, the eluted amount (proportional to the area of the chromatogram) normalized so that the sum is 100% is obtained.
In addition, an integrated elution curve for the elution temperature is calculated. The integrated elution curve is differentiated with temperature to obtain a differential elution curve.
Moreover, molecular weight distribution is calculated | required by the following procedure from each chromatogram. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is created by injecting 0.4 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL.
The calibration curve uses a cubic equation obtained by approximation by the least square method.
Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical value is used for the viscosity formula [η] = K × M ^α used in this case.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733
In the chromatogram at the first elution temperature, the peak due to BHT added to the solvent may overlap with the low molecular weight side of the elution component. In this case, the baseline is drawn as shown in FIG. Define the desired section.
Further, as shown in Table 1 below, the weight average molecular weight of the whole (whole) is obtained from the elution ratio (wt% in the table) and the weight average molecular weight (Mw in the table) at each elution temperature.

In addition, from the molecular weight distribution and elution amount at each elution temperature, literature (S. Nakano, Y. Goto, “Development of Automatic Cross Fractionation: Combination of Crystallization Fractionation and Molecule Fractionation and Molecular Pul. .26, pp. 4217-4231 (1981)), a graph (contour map) is obtained which shows the elution amount related to the elution temperature and molecular weight as contour lines.
The following component amounts are determined using the above contour map.
W ₁ : The proportion of components whose molecular weight is less than the weight average molecular weight of the ethylene / α-olefin copolymer among components eluted at or below the temperature at which the elution amount determined from the integral elution curve is 50 wt%.
W ₂ : Ratio of components having a molecular weight equal to or higher than the weight average molecular weight of the ethylene / α-olefin copolymer among components eluted at or below the temperature at which the elution amount determined from the integral elution curve is 50 wt%.
W ₃ : The proportion of components having a molecular weight less than the weight average molecular weight of the ethylene / α-olefin copolymer among components eluted at a temperature higher than the temperature at which the elution amount determined from the integral elution curve is 50 wt%.
W ₄ : Ratio of components having a molecular weight equal to or higher than the weight average molecular weight of the ethylene / α-olefin copolymer among components eluted at a temperature higher than the temperature at which the elution amount obtained from the integral elution curve is 50 wt%.
Note that W ₁ + W ₂ + W ₃ + W ₄ = 100.
The value of W ₂ + W ₃ can be set within a predetermined range mainly by selecting a polymerization catalyst and polymerization conditions, and preferably within a predetermined range by using a specific metallocene catalyst. Can do.

2-6. Condition (B-6) W ₂ + W ₄
In the ethylene / α-olefin copolymer of the present invention, the sum of W ₂ and W ₄ (W ₂ + W ₄ ) described in (2-5) is more than 25% by weight and less than 50% by weight, preferably 29 More than 50% by weight, more preferably more than 29% by weight, less than 45% by weight, still more preferably 30 to 43% by weight, particularly preferably 30 to 42% by weight. When W ₂ + W ₄ is 25% by weight or less, the high molecular weight component that effectively acts to improve the impact strength contained in the ethylene / α-olefin copolymer is decreased, and this is not preferable. This is not preferable because the high molecular weight long-chain branching component that acts particularly effectively on the molding processability contained in the polymer is reduced, and the ratio of the high molecular weight component and the long-chain branching component is not preferable. On the other hand, if the W ₂ + W ₄ value is 50% by weight or more, since the ratio of the high molecular weight component and the high molecular weight long-chain branched component contained in the ethylene / α-olefin copolymer is large, deterioration of transparency and gel Is not preferable.

2-7. Conditions _{(B-7) W 2 -W} 4
In the ethylene / α-olefin copolymer of the present invention, the difference (W ₂ −W ₄ ) between W ₂ and W ₄ described in (2-6) exceeds 0% by weight, preferably less than 20% by weight, More than 0%, less than 15%, more preferably more than 1%, less than 15%, still more preferably more than 2%, less than 14%, particularly preferably more than 2%, 13% %. When W ₂ -W ₄ is 0% by weight or less, the low density high molecular weight component that acts particularly effectively on the impact strength improvement contained in the ethylene / α-olefin copolymer is decreased, which is not preferable. On the other hand, if the W ₂ -W ₄ value is 20% by weight or more, the balance of the content of the high density high molecular weight component and the low density high molecular weight component contained in the ethylene / α-olefin copolymer is lost, and the transparency Deterioration or gel generation is not preferable.

2-8. Condition (B-8) X
In the ethylene / α-olefin copolymer in the present invention, the proportion (X) of the component that elutes at 85 ° C. or higher by the temperature rising elution fractionation (TREF) is preferably 2 to 15% by weight, preferably 3 to 14% by weight. More preferably, it is 4 to 13% by weight. When the X value is larger than 15% by weight, the ratio of the low density component that effectively acts to improve the impact strength contained in the ethylene / α-olefin copolymer is decreased, which is not preferable. If the X value is less than 2% by weight, the rigidity may deteriorate, which may not be preferable.
[TREF measurement conditions]
A sample is dissolved in orthodichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to obtain a solution. This was introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to 40 ° C. at a rate of 4 ° C./min, and then cooled at a rate of 1 ° C./min. To -15 ° C and hold for 20 minutes. Thereafter, orthodichlorobenzene (containing 0.5 mg / mL BHT) as a solvent is passed through the column at a flow rate of 1 mL / min, and the components dissolved in orthodichlorobenzene at −15 ° C. are eluted in the TREF column for 10 minutes. Next, the column is linearly heated to 140 ° C. at a temperature increase rate of 100 ° C./hour to obtain an elution curve. At this time, the amount of components eluted between 85 ° C. and 140 ° C. is X (unit: wt%).

The equipment used is as follows.
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 100 μm surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000
(Valve oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve, 4-way valve (sample injection part)
Injection method: Loop injection method Injection amount: Loop size 0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High-temperature flow cell: LC-IR micro flow cell, optical path length 1.5 mm, window shape 2φ × 4 mm oval, synthetic sapphire window Measurement temperature: 140 ° C.
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co., Ltd. Measurement conditions Solvent: Orthodichlorobenzene (with 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

2-9. Melt tension (MT)
The ethylene / α-olefin copolymer in the present invention has a high melt tension (melt tension: MT), preferably 40 mN or more. When MT is less than 40 mN, molding process characteristics, particularly stability during T-die molding or inflation molding tend to be lowered.
MT is a value determined by measuring a stress when a melted ethylene / α-olefin copolymer is stretched at a constant speed, and can be measured under the following conditions. 3. Capillograph 1B manufactured by Toyo Seiki Co., Ltd. was used as a testing machine, orifice: L / D = 8.0 / 2.095, inflow angle flat, set temperature: 190 ° C., piston speed: 10 mm / min, take-up speed It is measured under the condition of 0 m / min.
In particular, MT can be prepared by appropriately selecting the minimum value (gc) of the molecular weight between 100,000 and 1,000,000 of the branching index (g ′) of polyethylene.

2-10. Composition of ethylene / α-olefin copolymer (B) The ethylene / α-olefin copolymer of the present invention is a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. Examples of the α-olefin which is a copolymerization component used here include propylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, pentene-1, hexene-1 and heptene. -1, octene-1, nonene-1, decene-1, and the like. These α-olefins may be used alone or in combination of two or more. Among these, more preferable α-olefins are those having 3 to 8 carbon atoms, specifically, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, pentene-1, and hexene-1. , Heptene-1, octene-1, and the like. More preferable α-olefins have 4 or 6 carbon atoms, and specific examples include butene-1, 4-methylpentene-1, and hexene-1. A particularly preferred α-olefin is hexene-1.

The proportion of ethylene and α-olefin in the ethylene / α-olefin copolymer of the present invention is about 75 to 99.8% by weight of ethylene and about 0.2 to 25% by weight of α-olefin, preferably about ethylene. 80 to 99.6% by weight, α-olefin of about 0.4 to 20% by weight, more preferably ethylene of about 82 to 99.2% by weight, α-olefin of about 0.8 to 18% by weight, Preferred are about 85 to 99% by weight of ethylene and about 1 to 15% by weight of α-olefin, and particularly preferred are about 88 to 98% by weight of ethylene and about 2 to 12% by weight of α-olefin. If the ethylene content is within this range, the effect of modifying the polyethylene resin is high.
The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. Of course, a small amount of a comonomer other than ethylene or α-olefin may be used. In this case, styrenes such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1,5- It has polymerizable double bonds such as dienes such as hexadiene, 1,4-hexadiene and 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, oxygen-containing compounds such as hexenol, hexenoic acid and methyl octenoate. A compound can be mentioned. However, it goes without saying that when diene is used, it must be used within the range where the long-chain branched structure and molecular weight distribution satisfy the above conditions.

Production Method of Ethylene / α-Olefin Copolymer (B) of the Present Invention The ethylene / α-olefin copolymer of the present invention is produced and used so as to satisfy all the above conditions. The production is carried out by a method of copolymerizing ethylene and the above-mentioned α-olefin using an olefin polymerization catalyst.

As an example of a suitable production method for simultaneously realizing a specific long chain branched structure, composition distribution structure, MFR, and density of the ethylene / α-olefin copolymer of the present invention, a specific catalyst component (X ), (Y) and a method using an olefin polymerization catalyst containing (Z).
Component (X): Bridged cyclopentadienylindenyl compound containing a transition metal element Component (Y): Compound that reacts with the compound of component (X) to form a cationic metallocene compound Component (Z): Inorganic compound carrier

3-1. Catalyst component (X)
A preferred catalyst component (X) for producing the ethylene / α-olefin polymer (B) of the present invention is a bridged cyclopentadienylindenyl compound containing a transition metal element, more preferably the following general formula [ 1], more preferably a metallocene compound represented by the following general formula [2].

[In the formula [1], M represents a transition metal of Ti, Zr, or Hf. A ¹ is a ligand having a cyclopentadienyl ring (conjugated five-membered ring) structure, A ² is a ligand having an indenyl ring structure, and Q ¹ bridges A ¹ and A ² at an arbitrary position. A binding group is shown. X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, or a carbon atom having 1 to 20 carbon atoms. A hydrogen-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ]

[In the formula [2], M represents any transition metal of Ti, Zr or Hf. Q ¹ represents a binding group that bridges the cyclopentadienyl ring and the indenyl ring. X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, or a carbon atom having 1 to 20 carbon atoms. A hydrogen-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. 10 Rs are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, 20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing an oxygen atom or a C1-C20 hydrocarbon group-substituted silyl group. ]
A particularly preferable catalyst component (X) for producing the ethylene / α-olefin copolymer (B) of the present invention is a metallocene compound represented by the general formula (1c) described in JP2013-227271A. It is.

[However, in the formula (1c), all of the abbreviations are described in JP 2013-227271 A. That is, M ^1c represents a transition metal of Ti, Zr, or Hf. X ^1c and X ^2c each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, or 1 to 20 carbon atoms. A hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ^1c and Q ^2c each independently represent a carbon atom, a silicon atom, or a germanium atom. R ^1c independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1cs are bonded to form a ring together with Q ^1c and Q ^2c. Also good. ^mc is 0 or 1, and when ^mc is 0, Q ^1c is directly bonded to a conjugated 5-membered ring containing R ^2c . R ^2c and R ^4c are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 carbon atom. -20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing an oxygen atom, or a C1-C20 hydrocarbon group-substituted silyl group. R ^3c represents a substituted aryl group represented by the following general formula (1-ac). ]

［但し、式（１−ａｃ）中、Ｙ^１ｃは、周期表１４族、１５族または１６族の原子を示す。Ｒ^５ｃ、Ｒ^６ｃ、Ｒ^７ｃ、Ｒ^８ｃおよびＲ^９ｃは、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、炭素数１〜２０の炭化水素基、酸素若しくは窒素を含む炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０のアルコキシ基、ケイ素数１〜６を含む炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、または炭素数１〜２０の炭化水素基置換シリル基を示し、Ｒ^５ｃ、Ｒ^６ｃ、Ｒ^７ｃ、Ｒ^８ｃおよびＲ^９ｃは隣接する基同士で結合して、それらに結合している原子と一緒に環を形成していてもよい。ｎ^ｃは、０または１であり、ｎ^ｃが０の場合、Ｙ^１ｃに置換基Ｒ^５ｃが存在しない。ｐ^ｃは、０または１であり、ｐ^ｃが０の場合、Ｒ^７ｃが結合する炭素原子とＲ^９ｃが結合する炭素原子は直接結合している。Ｙ^１ｃが炭素原子の場合、Ｒ^５ｃ、Ｒ^６ｃ、Ｒ^７ｃ、Ｒ^８ｃ、Ｒ^９ｃのうち少なくとも１つは水素原子ではない。］

[In the formula (1-ac), Y ^1c represents an atom of Group 14, 15 or 16 of the periodic table. R ^5c , R ^6c , R ^7c , R ^8c and R ^9c are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon number containing oxygen or nitrogen 1-20 hydrocarbon group, C1-C20 hydrocarbon group-substituted amino group, C1-C20 alkoxy group, C1-C18 silicon-containing hydrocarbon group containing 1-6 silicon atoms, carbon A halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, wherein R ^5c , R ^6c , R ^7c , R ^8c, and R ^9c are bonded together in adjacent groups; And may form a ring together with atoms bonded to them. n ^c is 0 or 1, if ^{n c} is ^0, there is no substituent ^{R 5c} to ^{Y 1c. pc} is 0 or 1, and when ^pc is 0, the carbon atom to which R ^7c is bonded and the carbon atom to which R ^9c are bonded are directly bonded. When Y ^1c is a carbon atom, at least one of R ^5c , R ^6c , R ^7c , R ^8c , and R ^9c is not a hydrogen atom. ]

The most preferred catalyst component (X) for producing the ethylene / α-olefin copolymer (B) of the present invention is a metallocene compound represented by the general formula (2c) described in JP2013-227271A It is.

In the metallocene compound represented by the general formula (2c), M ^1c , X ^1c , X ^2c , Q ^1c , R ^1c , R ^2c, and R ^4c are the descriptions of the metallocene compound represented by the general formula (1c). The structure similar to the atom and group shown by can be selected. R ^10c can be selected from the same structure as the atoms and groups of R ^5c , R ^6c , R ^7c , R ^8c , and R ^9c shown in the description of the metallocene compound represented by the general formula (1c). .

  As specific examples of the metallocene compounds, in general formulas (4c) and 1c-1 to 5 of Table 1c and general formulas (5c) and (6c) and Tables 1c-6 to 9 of JP2013-227271A The compounds described can be mentioned, but are not limited to these.

  The compound of the above specific example is preferably a zirconium compound or a hafnium compound, and more preferably a zirconium compound.

  As a preferable catalyst component (X) for producing the ethylene / α-olefin copolymer (B) of the present invention, two or more of the above-mentioned crosslinked cyclopentadienylindenyl compounds can be used.

3-2. Catalyst component (Y)
A preferred catalyst component (Y) for producing the ethylene / α-olefin copolymer (B) of the present invention is a compound that reacts with the compound of component (X) to form a cationic metallocene compound, and more preferably. Is the component (B) described in JP 2013-227271 A [0064] to [0083], and more preferably the organoaluminum oxy compound described in [0065] to [0069].

3-3. Catalyst component (Z)
A preferred catalyst component (Z) for producing the ethylene / α-olefin copolymer (B) of the present invention is an inorganic compound carrier, and more preferably, JP2013-227271A [0084] to [0088]. It is an inorganic compound described in 1. At this time, the metal oxide described in the publication [0085] is preferable as the inorganic compound.

3-4. Ethylene / α-Olefin Copolymer (B) Production Method of Polymerization Catalyst The ethylene / α-olefin copolymer of the present invention is produced by using an olefin polymerization catalyst containing the above catalyst components (X) to (Z) with ethylene. It is preferably produced by a method of copolymerizing with the above-mentioned α-olefin. The contact method of each component when obtaining the olefin polymerization catalyst from the catalyst components (X) to (Z) of the present invention is not particularly limited. For example, the following methods (I) to (III) are optional. Can be adopted.

(I) The catalyst component (X) which is a bridged cyclopentadienylindenyl compound containing the transition metal element and the catalyst component which is a compound which reacts with the compound of the catalyst component (X) to form a cationic metallocene compound After contacting (Y), the catalyst component (Z), which is an inorganic compound carrier, is contacted.
(II) After contacting the catalyst component (X) and the catalyst component (Z), the catalyst component (Y) is contacted.
(III) After contacting the catalyst component (Y) and the catalyst component (Z), the catalyst component (X) is contacted.

  Of these contact methods, (I) and (III) are preferred, and (I) is most preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), pentane, heptane, hexane and decane. , A method in which each component is brought into contact with stirring or non-stirring in the presence of a liquid inert hydrocarbon such as aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as dodecane or cyclohexane. . This contact is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C., for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  When contacting the catalyst component (X), the catalyst component (Y), and the catalyst component (Z), as described above, an aromatic hydrocarbon solvent in which a certain component is soluble or hardly soluble, and a certain component Any insoluble or hardly soluble aliphatic or alicyclic hydrocarbon solvent can be used.

  In the case where the contact reaction between the components is performed stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid or once or part of the soluble solvent is removed by means such as drying. After removing the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In this invention, it does not prevent performing contact reaction of each component in multiple times.

  In the present invention, the use ratio of the catalyst component (X), the catalyst component (Y) and the catalyst component (Z) is not particularly limited, but the following ranges are preferable.

  When an organoaluminum oxy compound is used as the catalyst component (Y), the atomic ratio (Al / M) of the aluminum of the organoaluminum oxy compound to the transition metal (M) in the catalyst component (X) is usually 1 to 100, 000, preferably 100 to 1000, more preferably 210 to 800, particularly preferably 250 to 500 is desirable. When a borane compound or a borate compound is used, it is based on the transition metal (M) in the catalyst component (X). The boron atomic ratio (B / M) is usually selected in the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10. Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the catalyst component (Y), the same use as described above for the transition metal (M) for each compound in the mixture It is desirable to select by percentage.

The catalyst component (Z) is used in an amount of 0.0001-5 mmol, preferably 0.001-0.2 mmol, more preferably 0.005-0.1 mmol of transition metal in the catalyst component (X). Especially preferably, it is 1 g per 0.01 to 0.04 mmol.
In the present invention, the ratio of the number of moles of the metal of the catalyst component (Y) to 1 g of the catalyst component (Z) is preferably more than 0.005 and 0.020 (mol / g) or less, more preferably 0. More than 0.006 to 0.015 (mol / g) or less, more preferably more than 0.006 and 0.012 (mol / g) or less, particularly preferably 0.007 to 0.010 (mol / g). It is.

  The catalyst component (X), the catalyst component (Y), and the catalyst component (Z) are brought into contact with each other by appropriately selecting the contact methods (I) to (III) described above, and then the solvent is removed, An olefin polymerization catalyst can be obtained as a solid catalyst. Removal of the solvent is performed at normal pressure or reduced pressure at 0 to 200 ° C., preferably 20 to 150 ° C., more preferably 20 to 100 ° C. for 1 minute to 100 hours, preferably 10 minutes to 50 hours, more preferably 30 minutes. It is desirable to perform in ~ 20 hours.

The ethylene / α-olefin copolymer (B) polymerization catalyst can also be obtained by the following methods (IV) and (V).
(IV) The catalyst component (X) and the catalyst component (Z) are contacted to remove the solvent, which is used as a solid catalyst component, and an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof under polymerization conditions Make contact.
(V) The catalyst component (Y), which is an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof, is contacted with the catalyst component (Z) to remove the solvent, and this is used as a solid catalyst component. In contact with the catalyst component (X).
In the case of the contact methods (IV) and (V), the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

Further, as an ethylene / α-olefin copolymer (B) polymerization catalyst suitable for obtaining the ethylene / α-olefin copolymer (B) of the present invention, it reacts with the catalyst component (X) to form a cationic metallocene. As a component that serves as both the catalyst component (Y) and the catalyst component (Z) for generating the compound, a layered silicate that is well known as described in JP-A Nos. 05-301917 and 08-127613 is used. You can also The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with a weak binding force. Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to natural ones and may be artificially synthesized.
Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite and the like, smectite group, vermiculite group and mica group are preferable.

The use ratio of the catalyst component (X) and the layered silicate support is not particularly limited, but the following range is preferable. The supported amount of the catalyst component (X) is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 1 g of the layered silicate support.
The olefin polymerization catalyst thus obtained may be used after the prepolymerization of the monomer if necessary.

3-5. Polymerization Method of Ethylene / α-Olefin Copolymer (B) The ethylene / α-olefin copolymer of the present invention preferably uses an olefin polymerization catalyst prepared by the production method described in 3-4 above. It is produced by copolymerizing ethylene and the above-mentioned α-olefin.

  As the α-olefin as a comonomer, [2-12. As described in [Composition of ethylene / α-olefin copolymer (B)], α-olefins having 3 to 10 carbon atoms can be used, and two or more types of α-olefins may be copolymerized with ethylene. It is possible to use a small amount of a comonomer other than the α-olefin.

  In the present invention, the copolymerization reaction can be preferably carried out by a gas phase method or a slurry method. In the case of gas phase polymerization, ethylene or the like is polymerized in a reactor in which a gas flow of ethylene or comonomer is introduced, circulated, or circulated with oxygen and water substantially cut off. In the case of slurry polymerization, an inert hydrocarbon selected from aliphatic hydrocarbons such as isobutane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Ethylene or the like is polymerized in the presence or absence of a solvent. Needless to say, liquid monomers such as liquid ethylene and liquid propylene can also be used as the solvent. In the present invention, more preferred polymerization is gas phase polymerization. The polymerization conditions are such that the temperature is 0 to 250 ° C., preferably 20 to 110 ° C., more preferably 60 to 100 ° C., and the pressure is normal pressure to 10 MPa, preferably normal pressure to 4 MPa, more preferably 0.5 to 2 MPa. The polymerization time is usually 5 minutes to 20 hours, preferably 30 minutes to 10 hours.

The molecular weight of the resulting copolymer can be adjusted to some extent by changing the polymerization conditions such as the type of catalyst component (X) and catalyst component (Y), the molar ratio of the catalyst, and the polymerization temperature. The molecular weight can be adjusted more effectively by adding. Moreover, even if a component for the purpose of removing moisture, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble.
Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and grinier compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.
The long-chain branched structure (ie, g _C ) and comonomer copolymer composition distribution (ie, X and W _{1 to} W ₄ ) of the produced copolymer are the types of catalyst component (X) and catalyst component (Y), and the molar ratio of the catalyst. It can be adjusted by changing the polymerization conditions such as polymerization temperature, pressure and time and the polymerization process. Even if a catalyst component type that easily forms a long-chain branched structure is selected, a copolymer having a small long-chain branched structure can be produced, for example, by lowering the polymerization temperature or increasing the ethylene pressure. Even if a catalyst component species having a broad molecular weight distribution or copolymer composition distribution is selected, a copolymer having a narrow molecular weight distribution or copolymer composition distribution is produced by changing the catalyst component molar ratio, polymerization conditions or polymerization process, for example. It is also possible.

  The ethylene / α-olefin copolymer of the present invention can be used as long as the polymerization conditions are appropriately set even in a multi-stage polymerization system having two or more stages in which polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature are different from each other. Although it may be possible to produce (B), the ethylene / α-olefin copolymer (B) of the present invention sets complex polymerization operating conditions when produced by a one-step polymerization reaction. Therefore, it is preferable because it can be produced more economically.

4). Next, the blending ratio of the resin component in the polyethylene resin composition of the present invention will be described.
The weight ratio of the high pressure polyethylene (A) / ethylene / α-olefin copolymer (B) is (41 to 99% by weight) / (1 when the total of (A) and (B) is 100% by weight. -59 wt%), preferably (51-99 wt%) / (1-49 wt%), more preferably (61-99 wt%) / (1-39 wt%). If the high-pressure polyethylene (A) is too much, the impact resistance is lowered, and if it is too little, the resin pressure is increased and the productivity is lowered. On the other hand, if the ethylene / α-olefin copolymer (B) is too much, the resin pressure increases and the productivity is lowered, and if it is too little, the impact resistance is lowered.

4-1. MFR
The MFR of the polyethylene resin composition of the present invention comprising the components (A) and (B) is preferably in the range of 0.1 to 20 g / 10 minutes, more preferably 0.05 to 10 g / 10. Min, more preferably 0.10 to 5 g / 10 min.
If the MFR is lower than 0.1 g / 10 min, the fluidity is poor and the motor load of the extruder becomes too high. On the other hand, if the MFR is higher than 20 g / 10 min, the bubbles are not stable and difficult to mold. The strength of the film is lowered.
In addition, although MFR of a polyethylene resin composition is a value measured on condition of 190 degreeC and 21.18N (2.16kg) load based on JISK7210, approximate MFR is component (A), ( It can be calculated according to the additivity rule from each MFR and the ratio of B).

4-2. Density The density of the polyethylene resin composition of the present invention comprising the components (A) and (B) needs to be in the range of 0.910 to 0.940 g / cm ³ , preferably 0.910. was 0.935 g / cm ^3, more preferably 0.915~0.930g / cm ^3.
When the density of the polyethylene resin composition is lower than 0.910 g / cm ³ , the rigidity of the film is lowered, and the suitability of the automatic bag making machine is deteriorated. Moreover, when the density of the polyethylene resin composition is higher than 0.940 g / cm ³ , the strength of the film is lowered.
The density of the polyethylene resin composition is in accordance with JIS K 7112. The resin composition comprising components (A) and (B) is hot-pressed to produce a 2 mm-thick press sheet, and the sheet has a capacity of 1000 ml. The beaker was filled with distilled water, covered with a watch glass and heated with a mantle heater. After boiling boiling water for 60 minutes, the beaker was placed on a wooden table and allowed to cool. At this time, the boiling distilled water after boiling for 60 minutes was adjusted to 500 ml so that the time until reaching room temperature was not more than 60 minutes. Moreover, the test sheet was immersed in the substantially center part in water so that it might not contact a beaker and the water surface. The sheet was annealed at a temperature of 23 ° C. and a humidity of 50% for 16 hours or more and within 24 hours, then punched out to 2 mm in length and width, and measured at a test temperature of 23 ° C. The approximate density can be calculated according to the additivity rule from the respective densities and ratios of the components (A) and (B).

4-3. Other formulations etc. In the present invention, as long as the characteristics of the present invention are not impaired, an antistatic agent, an antioxidant, an antiblocking agent, a nucleating agent, a lubricant, an antifogging agent, an organic or inorganic pigment, an ultraviolet ray, and the like. Known additives such as an inhibitor and a dispersant can be added.

  The polyethylene resin composition of the present invention comprises the above-described high-pressure polyethylene (A), ethylene / α-olefin copolymer (B), and various additives and resin components that are added or blended as necessary. After mixing using a mixer, super mixer, tumbler mixer or the like, the mixture may be kneaded by heating with a single-screw or twin-screw extruder, a kneader, etc., and pelletized.

5. 3. Use of polyethylene resin composition The molded article of the polyethylene resin composition of the present invention is the above-mentioned 4. It is manufactured by molding the polyethylene resin composition of the present invention described in 1. The molding method is conventionally known injection molding, compression injection molding, rotational molding, extrusion molding, hollow molding, blow molding, It is possible to refer to all of the molding methods of polyolefin resin and polyolefin resin composition, such as inflation molding.
As specific uses of the molded article of the polyethylene resin composition of the present invention, a standard bag with a dimensional standard such as an inner bag or a garbage bag of a paper bag, a heavy bag, a wrap film, a sugar bag, Food packaging film for water packaging bags such as rice bags, oil packaging bags, pickles, etc., packaging materials that require automatic filling, infusion bags, agricultural films, nylon, polyester, metal foil, ethylene-vinyl acetate copolymer Used as laminates with various base materials such as saponified coal products, standing pouches, foams and molded products thereof, see applications of molded products of known polyethylene resins and polyethylene resin compositions such as bag-in-boxes I can do it.

  The molding method of the molded body of the present invention is not particularly limited as long as it is a method that can effectively utilize the excellent molding processing characteristics, mechanical characteristics, and transparency of the polyethylene resin composition of the present invention. In the case of films, bags, and sheets which are examples of mainly intended uses of the polyethylene resin composition of the present invention, preferred molding methods, molding conditions, and uses thereof include, for example, Japanese Patent Application Laid-Open No. 2007-197722. Various inflation molding methods and T-die film molding as described in detail in Japanese Patent Application Publication No. 2007-177168, Japanese Patent Application Publication No. 2007-177187, Japanese Patent Application Publication No. 2010-31270, etc. , Calendering method, multilayer coextrusion molding machine, multilayer film forming method by laminating process, etc. That. Needless to say, in inflation molding, a gas other than air or a liquid can be used as a refrigerant, and can also be used for special inflation molding such as stretch (inflation simultaneous biaxial stretching) molding or multistage blow.

  The thickness of the film (or sheet) of the product thus obtained is not particularly limited, and the preferred thickness varies depending on the molding method and conditions. For example, in the case of inflation molding, it is about 5 to 300 μm, and in the case of T-die molding, it can be a film (or sheet) of about 5 μm to 5 mm.

In the following, the present invention will be described in more detail with reference to examples and comparative examples, and the superiority of the present invention and the superiority in the structure of the present invention will be demonstrated, but the present invention is limited by these examples. It is not a thing.
In addition, the measuring method used in the Example and the comparative example is as follows. The following catalyst synthesis step and polymerization step were all performed under a purified nitrogen atmosphere, and the solvent used was dehydrated and purified with molecular sieve 4A.

[Measurement method of physical properties]
(1) MFR
In accordance with JIS K7210 "Plastic-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR) test methods", measurement was performed under the conditions of 190 ° C. and 21.18 N (2.16 kg) load. .
(2) Density JIS K7112 (1999 edition): Measured by method A (submersion method in water).
(3) Molecular weight distribution measured by GPC (Mw / Mn)
It measured by the gel permeation chromatography (GPC) method. The measurement conditions of GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
In addition, the baseline and the section of the obtained chromatogram were performed as illustrated in FIG. Conversion from the retention capacity to the molecular weight was performed using a standard curve prepared in advance with standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. For the calibration curve, a cubic equation obtained by approximation by the least square method was used. For conversion to molecular weight, a general calibration curve was used with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical value was used for the viscosity formula [η] = K × Mα used at that time.
PS: K = 1.38 × 10 −4, α = 0.7
PE: K = 3.92 × 10 −4, α = 0.733

(4) Minimum value (gc) of molecular weight between 100,000 and 1,000,000 of the branching index (g ′) measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector
Waters Alliance GPCV2000 was used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). In addition, as a light scattering detector, a DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) was used. The detectors were connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with the antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As a column, two Tosoh Corporation GMHHR-H (S) HT were connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration was 1 mg / mL. The injection volume (sample loop volume) is 0.2175 mL. In order to obtain the absolute molecular weight (M) obtained from MALLS, the inertial square radius (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, data processing software ASTRA (version 4.73.04) attached to MALLS was used. The calculation was performed with reference to the above-mentioned literature.

[Calculation of branching index (gc), etc.]
The branching index (g ′) is calculated as a ratio (ηbranch / ηlin) between the intrinsic viscosity (ηbranch) obtained by measuring the sample with the above Viscometer and the intrinsic viscosity (ηlin) obtained separately by measuring a linear polymer. did.
As the absolute molecular weight obtained from MALLS, the minimum value of the above g ′ at a molecular weight of 100,000 to 1,000,000 was calculated as gC. Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used as the linear polymer.

(5) Ratio of components eluted at 85 ° C. or higher by temperature rising elution fractionation (TREF) (X)
A sample is dissolved in orthodichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to obtain a solution. This was introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to 40 ° C. at a rate of 4 ° C./min, and then cooled at a rate of 1 ° C./min. To -15 ° C and hold for 20 minutes. Thereafter, orthodichlorobenzene (containing 0.5 mg / mL BHT) as a solvent is passed through the column at a flow rate of 1 mL / min, and the components dissolved in orthodichlorobenzene at −15 ° C. are eluted in the TREF column for 10 minutes. Next, the column is linearly heated to 140 ° C. at a temperature increase rate of 100 ° C./hour to obtain an elution curve. At this time, the amount of components eluted between 85 ° C. and 140 ° C. is X (unit: wt%).

The equipment used is as follows.
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 100 μm surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000
(Valve oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve, 4-way valve (sample injection part)
Injection method: Loop injection method Injection amount: Loop size 0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High-temperature flow cell: LC-IR micro flow cell, optical path length 1.5 mm, window shape 2φ × 4 mm oval, synthetic sapphire window Measurement temperature: 140 ° C.
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co., Ltd. Measurement conditions Solvent: Orthodichlorobenzene (with 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

(6) W ₂ + W ₃ , W ₂ + W ₄ , W ₂ -W ₄ ,
This was carried out by cross-fractionation chromatography (CFC) comprising a temperature rising elution fractionation (TREF) portion for performing crystalline fractionation and a gel permeation chromatography (GPC) portion for carrying out molecular weight fractionation.
That is, after completely dissolving a polymer sample in orthodichlorobenzene (ODCB) containing 0.5 mg / mL BHT at 140 ° C., this solution was passed through a sample loop of the apparatus, and the TREF column (inert The polymer sample was crystallized by gradually cooling to a predetermined first elution temperature.
After maintaining at a predetermined temperature for 30 minutes, ODCB is passed through a TREF column, whereby the eluted component is injected into the GPC section to perform molecular weight fractionation, and an infrared detector (MIRAN 1A IR detector manufactured by FOXBORO, A chromatogram was obtained with a measurement wavelength of 3.42 μm. Meanwhile, in the TREF part, the temperature was raised to the next elution temperature, and after obtaining the chromatogram of the first elution temperature, the elution component at the second elution temperature was injected into the GPC part. Thereafter, by repeating the same operation, chromatograms of the eluted components at each elution temperature were obtained.

The CFC measurement conditions are as follows.
Equipment: CFC-T102L manufactured by Dia Instruments
GPC column: Showa Denko AD-806MS (3 connected in series)
Solvent: ODCB
Sample concentration: 3 mg / mL
Injection volume: 0.4mL
Crystallization rate: 1 ° C / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stabilization time after GPC measurement: 5 minutes Elution temperature: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 102, 120, 140

Data analysis From the chromatogram of the elution components obtained at each elution temperature obtained by measurement, the elution amount (proportional to the area of the chromatogram) normalized so that the sum total was 100% was determined.
Moreover, molecular weight distribution was calculated | required by the same procedure as the above-mentioned GPC from each chromatogram.
From the molecular weight distribution and the elution amount at each elution temperature, the literature (S. Nakano, Y. Goto, “Development of Automatic Cross Fractionation: Combination of Crystallization Fractionation and Molecular Weight. , Pp. 4217-4231 (1981)), a graph (contour map) showing the elution amount relating to the elution temperature and molecular weight as contour lines was obtained.

The following component amounts were determined using the above contour map.
W ₁ : The proportion of components whose molecular weight is less than the weight average molecular weight of the ethylene / α-olefin copolymer among components eluted at or below the temperature at which the elution amount determined from the integral elution curve is 50 wt%.
W ₂ : Ratio of components having a molecular weight equal to or higher than the weight average molecular weight of the ethylene / α-olefin copolymer among components eluted at or below the temperature at which the elution amount determined from the integral elution curve is 50 wt%.
W ₃ : The proportion of components having a molecular weight less than the weight average molecular weight of the ethylene / α-olefin copolymer among components eluted at a temperature higher than the temperature at which the elution amount determined from the integral elution curve is 50 wt%.
W ₄ : Ratio of components having a molecular weight equal to or higher than the weight average molecular weight of the ethylene / α-olefin copolymer among components eluted at a temperature higher than the temperature at which the elution amount obtained from the integral elution curve is 50 wt%.
Note that W ₁ + W ₂ + W ₃ + W ₄ = 100.

(7) Melt tension (MT)
The melt tension (MT) was evaluated under the following conditions.
Capillograph 1B manufactured by Toyo Seiki Co., Ltd. was used as a testing machine, orifice: L / D = 8.0 / 2.095, inflow angle flat, set temperature: 190 ° C., piston speed: 10 mm / min, take-up speed 4.0 m Melt tension (MT) was measured at / min.

[Film evaluation method]
(1) Tensile modulus:
Based on JIS K7127-1999, the tensile elastic modulus (MPa) when deformed by 1% in the film processing direction (MD direction) was measured.
(2) Dart drop impact strength (DDI)
It measured based on JIS K 7124 1 A method.

[Formation conditions for blown film]
An inflation film was molded and evaluated under the following molding conditions using an inflation film film forming machine (molding apparatus) having the following 50 mmφ extruder.
Equipment: Inflation molding equipment Extruder screw diameter: 50mmφ
Die diameter: 75mmφ
Extrusion amount: 15 kg / hr
Die lip gap: 1.0mm
Take-up speed: 20.0 m / min Blow-up ratio: 2.0
Molding resin temperature: 170 ° C
Film thickness: 30 μm

[Evaluation resin]
HPLD-1: Commercially available high-pressure radical method low-density polyethylene (LF440B manufactured by Nippon Polyethylene Co., Ltd .; MFR = 2.8 g / 10 min, density 0.924 g / cm ³ )
Sample 1: Ethylene / α-olefin copolymer having a long chain branch produced according to Production Example 1 below (MFR = 0.21 g / 10 min, density 0.920 g / cm ³ )
LL-1: Commercially available linear low density polyethylene (SF240 manufactured by Nippon Polyethylene Co., Ltd .; MFR = 2.0 g / 10 min, density 0.920 g / cm ³ )
LL-2: Commercially available linear low density polyethylene (NF464N manufactured by Nippon Polyethylene; MFR = 2.0 g / 10 min, density 0.918 g / cm ³ )
Comparative LCB: Commercially available ethylene polymer having a long chain branch (CU5001 manufactured by Sumitomo Chemical Co., Ltd .; MFR = 0.3 g / 10 min, density 0.922 g / cm ³ )

[Production Example 1 (Production Example of Long Chain Branched Ethylene / α-Olefin Copolymer (B))]
(1) Synthesis of a bridged cyclopentadienylindenyl compound;
Dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride was synthesized according to the method described in JP 2013-227271 A [0140] to [0143].
(2) Synthesis of olefin polymerization catalyst;
Under a nitrogen atmosphere, 30 grams of silica baked at 400 ° C. for 5 hours was placed in a 500 ml three-necked flask, and then 195 ml of dehydrated toluene was added to form a slurry. In a 200 ml two-necked flask prepared separately, 410 mg of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride synthesized in (1) above was placed in a nitrogen atmosphere and dehydrated toluene. After dissolving in 80.4 ml, 82.8 ml of 20% methylaluminoxane / toluene solution made by Albemarle was further added at room temperature and stirred for 30 minutes. While heating and stirring a 500 ml three-necked flask containing a silica slurry of toluene in a 40 ° C. oil bath, the entire amount of the toluene solution of the reaction product of the zirconocene complex and methylaluminoxane was added. After stirring at 40 ° C. for 1 hour, the mixture was allowed to settle for 15 minutes while being heated to 40 ° C. to remove 224 ml of the supernatant, and then the toluene solvent was distilled off under reduced pressure to obtain a powdered catalyst.
(3) Production of ethylene / 1-hexene copolymer;
Ethylene / 1-hexene gas phase continuous copolymerization was performed using the powdery catalyst obtained in (2) above. That is, a gas phase continuous polymerization apparatus (internal volume of 100 L, internal volume prepared at a temperature of 75 ° C., a hexene / ethylene molar ratio of 0.24%, a hydrogen / ethylene molar ratio of 0.72%, a nitrogen concentration of 26 mol%, and a total pressure of 0.8 MPa. Polymerization is carried out at a constant gas composition and temperature while intermittently supplying the powdered catalyst to a fluidized bed diameter of 10 cm and a fluidized bed species polymer (dispersant) of 1.8 kg) at a rate of 0.21 g / hour. It was. In order to maintain cleanliness in the system, 0.03 mol / L of a hexane diluted solution of triethylaluminum (TEA) was supplied to the gas circulation line at 15.7 ml / hr. As a result, the average production rate of the produced polyethylene was 370 g / hour. The MFR and density of the ethylene / 1-hexene copolymer obtained after producing a cumulative 5 kg or more of polyethylene were 0.21 g / 10 min and 0.920 g / cm ³ , respectively. The polymerization conditions are shown in Table 2 below. Table 3 below shows the physical properties of Sample 1 obtained in Production Example 1 and a commercially available long-chain ethylene polymer (Comparative LCB: CU5001) used for comparison.

※メタロセン１； ジメチルシリレン（４−（４−トリメチルシリル−フェニル）−インデニル）（シクロペンタジエニル）ジルコニウムジクロリド

* Metallocene 1; dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride

Example 1
The long chain produced in Production Example 1 above was compared with an example in which HPLD-1 (LF440B), which is a high pressure method low density polyethylene, was used alone (control example) and HPLD-1, which was a high pressure method, low density polyethylene. A branched ethylene / α-olefin copolymer (sample 1; MFR = 0.21 g / 10 min, density 0.920 g / cm ³ ) was dry blended at a ratio shown in Table 4 to form a film. Table 4 shows the measurement results of various physical properties.

(Comparative Example 1)
Example 1 except that a commercially available linear low-density polyethylene (SF240 manufactured by Nippon Polyethylene; MFR = 2.0 g / 10 min, density 0.920 g / cm ³ ) was used instead of Sample 1 above. A similar test was conducted. Table 4 shows the measurement results of various physical properties.

(Comparative Example 2)
Instead of the sample 1, a commercially available ethylene polymer having a long chain branch (LCB for comparison: CU5001 manufactured by Sumitomo Chemical Co., Ltd .; MFR = 0.3 g / 10 min, density 0.922 g / cm ³ ) was used. Except for this, the same test as in Example 1 was performed. Table 4 shows the measurement results of various physical properties.

(Comparative Example 3)
A commercially available linear low density instead of the ethylene / α-olefin copolymer having a long chain branch prepared in Production Example 1 (Sample 1; MFR = 0.3 g / 10 min, density 0.922 g / cm ³ ). The same test as in Example 1 was performed except that polyethylene (NF464N manufactured by Nippon Polyethylene Co., Ltd .; MFR = 2.0 g / 10 min, density 0.918 g / cm ³ ) was used. Table 4 shows the measurement results of various physical properties.

[Discussion]
FIG. 7 shows a graph illustrating the tensile modulus of the results of Example 1 and Comparative Examples 1, 2, and 3 and the results of DDI. As is apparent from this graph, Example 1 of the present invention shows the following advantageous effects compared to the comparative example.
Comparison between Example 1 and Comparative Example 1: In Example 1, both the elastic modulus and DDI increased as the prototype addition amount increased, but in Comparative Example 1, the change in elastic modulus was small and DDI decreased.
Comparison of Example 1 and Comparative Example 2: In Example 1, both the elastic modulus and DDI increase as the amount of prototype added increases, but in Comparative Example 2, although the elastic modulus increases, DDI does not improve.
Example 1 and Comparative Example 3: In Example 1, both the modulus of elasticity and DDI increased as the amount of prototype added increased, but in Comparative Example 3, the improvement in DDI was seen but the change in modulus of elasticity was small.

Therefore, the industrial value of the polyethylene resin composition of the present invention, which can economically advantageously provide a molded product having such desirable characteristics, is extremely large.

Claims (11)

High-pressure polyethylene (A) and polyethylene containing an ethylene / α-olefin copolymer (B) characterized by satisfying the following conditions (B-1) to (B-5) -Based resin composition.
(B-1) MFR exceeds 0.001 g / 10 min and is 20 g / 10 min or less (B-2) Density is 0.895-0.940 g / cm ³ (B-3) Gel permeation The molecular weight distribution Mw / Mn measured by chromatography (GPC) is 3.0 to 7.0. (B-4) Measured by a GPC measuring apparatus combining a differential refractometer, a viscosity detector and a light scattering detector. (B-5) Integral elution curve measured by cross-fractionation chromatography (CFC) having a molecular weight of 100,000 to 1,000,000 (gc) between 0.40 and 0.85. Of the components eluted at a temperature below the temperature at which the elution amount determined from 50% by weight, the ratio (W ₂ ) of the component having a molecular weight equal to or higher than the weight average molecular weight, and the elution amount determined from the integral elution curve is 50% by weight. The sum (W ₂ + W ₃ ) of the proportion (W ₃ ) of the components having a molecular weight less than the weight average molecular weight out of the components eluted at a temperature higher than the temperature exceeds 40% by weight and less than 80% by weight The polyethylene-based resin composition according to claim 1, wherein the ethylene / α-olefin copolymer (B) further satisfies the following condition (B-6).
(B-6) Ratio of components having a molecular weight equal to or higher than the weight average molecular weight among the components eluted at a temperature higher than the temperature at which the elution amount obtained from the integral elution curve measured by W ₂ and CFC is 50 wt% (W ₄ ) Sum (W ₂ + W ₄ ) is more than 25 wt% and less than 50 wt% The polyethylene-based resin composition according to claim 1 or 2, wherein the ethylene / α-olefin copolymer (B) satisfies the following condition (B-7).
(B-7) The difference between W ₂ and W ₄ (W ₂ −W ₄ ) is more than 0% by weight and less than 20% by weight. The polyethylene-based resin composition according to any one of claims 1 to 3, wherein the ethylene / α-olefin copolymer (B) further satisfies the following condition (B-8).
(B-8) The ratio (X) of the component that elutes at 85 ° C. or higher by temperature rising elution fractionation (TREF) is 2 to 15% by weight. The polyethylene resin composition according to any one of claims 1 to 4, wherein the ethylene / α-olefin copolymer (B) satisfies the following condition (B-5 ').
(B-5 ′) The sum (W ₂ + W ₃ ) of (W ₂ ) and (W ₃ ) is more than 40% by weight and less than 56% by weight.   The polyethylene resin composition according to any one of claims 1 to 5, wherein the α-olefin of the ethylene / α-olefin copolymer (B) has 3 to 10 carbon atoms.   The ethylene / α-olefin copolymer (B) content in the resin composition is 1 to 59% by weight, and the high pressure polyethylene (A) content is 41 to 99% by weight. The polyethylene resin composition according to any one of claims 1 to 6. The polyethylene resin composition according to any one of claims 1 to 7, wherein the high-pressure polyethylene (A) satisfies the following conditions (A-1) and (A-2).
(A-1) MFR is 0.1 to 20 g / 10 min. (A-2) Density is 0.910 to 0.940 g / cm ³ . The polyethylene resin composition according to any one of claims 1 to 8, wherein the high-pressure polyethylene (A) further satisfies the following condition (A-3).
(B-3) The molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC) is 2.0 to 5.0.   The film obtained from the resin composition as described in any one of Claims 1-9. The ethylene / α-olefin copolymer (A) produced by the olefin polymerization catalyst containing the following catalyst components (X), (Y) and (Z) is used. The manufacturing method of the polyethylene-type resin composition as described in any one.
Catalyst component (X): a bridged cyclopentadienylindenyl compound containing a transition metal element.
Catalyst component (Y): A compound that reacts with the compound of component (X) to form a cationic metallocene compound.
Catalyst component (Z): inorganic compound carrier.

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