JP6690168B2 - Polyethylene resin composition and film - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a polyethylene-based resin composition, and more particularly to a polyethylene-based resin composition for a film having a high balance of mechanical strength and moldability for a film, and a film obtained thereby.

  Conventional ethylene polymers, which are widely used as packaging materials, are strongly demanded to have further improved physical properties as well as moldability suitable for any of various molding methods. The melt flow characteristics that control the molding processability are roughly classified into extrudability related to molten resin pressure under shear stress and molding stability related to melt elasticity during elongation deformation. Specifically, for example, extrusion molding Low viscosity under high shear stress, stable bubble under high-speed inflation molding, small neck-in in extrusion laminate molding T-die, etc. Each molding processability is required according to various molding methods. However, it is very difficult to satisfy all of them.

  Conventionally, so-called linear low-density polyethylene (LLDPE or metallocene PE) has a linear molecular structure, and is therefore known to be superior in strength to conventional high-pressure polyethylene having many branched and branched chains. However, in general, the molding of polyethylene resin is carried out in a molten state, but it is necessary to increase the amount of resin extruded per unit time, and in the case of a single LLDPE or metallocene PE, its melting characteristics are Is insufficient or the extensional viscosity is insufficient, so that it is difficult to secure sufficient moldability.

As a measure for supplementing these, blending of high-pressure polyethylene having excellent moldability and blending of ethylene-based polymers having different molecular weights and densities have been carried out to improve melting characteristics and solid physical properties ( (For example, see Patent Documents 1 to 3)
However, these blends (ethylene-based resin compositions) have a problem in that although the molding processability is obtained, the impact strength is lowered due to the blending of the high-pressure polyethylene.

In addition, due to 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 conservation, there is an increasing demand for thinner molded products. It is necessary to improve (elastic modulus).
As a method of improving the impact strength, a method of decreasing the density of the ethylene polymer is well known, but it is not preferable because the rigidity also decreases (becomes softer), and for the purpose of thinning the thickness. Is, for example, a three-component blend composition in which a specific HPLD is added to a combination of two specific ethylene / α-olefin copolymers having different densities to further improve molding processability and transparency. Attempts have been made to use it (see Patent Document 4).
According to this method, a polyethylene resin composition having a better balance of impact strength and rigidity than conventional ones and excellent molding processing characteristics can be obtained, but the impact strength is inevitably decreased due to the blending of high-pressure polyethylene. Furthermore, the blend of three kinds of ethylene-based polymers is considered to be economically more disadvantageous than the conventional one in stably supplying a product of constant quality at an industrial level.
As described above, in the conventional technique, it was difficult to sufficiently satisfy the basic performance required for the film of the packaging bag.

  In recent years, an ethylene polymer for modifying a polyolefin resin for simultaneously improving molding processability and resin strength by utilizing a polymerization design technology using a metallocene catalyst capable of forming a long-chain branched structure in an ethylene polymer. Development has been reported. For example, an example of blending an ethylene-based polymer containing a long chain branch that exhibits a specific extensional viscosity behavior with a target polyolefin-based resin as a modifier for a polyolefin-based resin (see Patent Document 5), or a specific example Of a resin composition using a low-density ethylene / propylene copolymer having a long-chain branched structure defined by the polymer molecular structure index and the intrinsic viscosity ratio as described above (see Patent Document 6) and high fluidization activation There is known an example (see Patent Document 7) in which long-chain branched polyethylene having a wide molecular weight distribution showing energy is used as a modifier. According to these methods, the impact strength of the polyolefin-based resin is not significantly reduced as in the conventional modification by HPLD, but since the design of the long-chain-branch-containing ethylene polymer is insufficient, the strength and The decrease in transparency was unavoidable, and the improvement level was still insufficient.

  Under such circumstances, the polyethylene-based resin capable of solving the problems of the conventional ethylene-based resin composition, and capable of producing a molded product having excellent molding processability, a balance of impact strength and rigidity, and excellent transparency. Development of the film was desired.

  Under these circumstances, the ethylene-based polymer for reforming that solves the problems of conventional ethylene-based polymers for reforming, is excellent in imparting moldability, and is also excellent in imparting a balance between impact strength and rigidity and transparency. Studies on metallocene polymerization catalysts capable of controlling long-chain branched structures, which are useful for the development of combined polymers and the development of ethylene-based polymers having these properties, have been continued (see Patent Documents 8 to 11).

JP-A-7-149962 JP, 9-31260, A JP, 2006-312753, A JP, 2010-31270, A JP 2012-214781 A JP, 09-031260, A JP, 2007-119716, A JP, 2004-217924, A JP 2004-292772 A JP-A-2005-206777 JP, 2013-22771, A

  In view of the problems of the above-mentioned conventional techniques, the object of the present invention is to provide a polyethylene-based resin composition having excellent balance between impact resistance and rigidity, transparency and molding processability, and particularly a polyethylene-based resin composition for films. The present invention further provides a film obtained by T-die molding and inflation molding of the polyethylene-based resin composition, which is excellent in balance of impact strength and rigidity and transparency, and use of the film. is there.

  As a result of intensive studies to solve such problems, ethylene having a specific long chain branching structure, that is, a specific branching index and a relatively narrow inverse comonomer composition distribution index, and a specific MFR and density Based on these findings, it was found that a resin composition obtained by blending an α-olefin copolymer with another ethylene / α-olefin copolymer has an excellent effect of improving the balance between impact strength and rigidity. As a result, the present invention has been completed. The gist of the present invention is as follows.

That is, the first invention is characterized by satisfying the following conditions (1) to (5): 1 to 59% by weight of an ethylene / α-olefin copolymer (A), and at least one (A) Other than the above), an ethylene / α-olefin copolymer (B) is contained in an amount of 99 to 41% by weight.
(1) MFR is more than 0.1 g / 10 min and 10 g / 10 min or less (2) Density is 0.895 to 0.940 g / cm ³ (3) By gel permeation chromatography (GPC) The measured molecular weight distribution Mw / Mn is 3.0 to 5.5. (4) The molecular weight of the branching index g'measured by a GPC measuring device in which a differential refractometer, a viscosity detector and a light scattering detector are combined. The minimum value (gc) between 10,000 and 1,000,000 is 0.40 to 0.85 (5) The elution amount obtained from the integrated elution curve measured by cross fractionation chromatography (CFC) is 50 wt%. Of a component having a molecular weight of not less than the weight average molecular weight (W ₂ ) among components that elute at a temperature equal to or lower than the above The sum (W ₂ + W ₃ ) of the proportions (W ₃ ) of the components having a molecular weight of less than the weight average molecular weight is more than 40% by weight and less than 56% by weight.

A second invention resides in the polyethylene-based resin composition according to the first invention, characterized in that the ethylene / α-olefin copolymer (A) further satisfies the following condition (6).
(6) The proportion (W ₄ ) of the components having a molecular weight of not less 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 integrated elution curve measured by W ₂ and CFC becomes 50 wt%. The sum (W ₂ + W ₄ ) is more than 25% by weight and less than 50% by weight.

A third invention provides the polyethylene-based resin composition according to the first or second invention, wherein the ethylene / α-olefin copolymer (A) further satisfies the following condition (7). Exist.
(7) The proportion (W ₄ ) of the components having a molecular weight of not less 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 integrated elution curve measured by W ₂ and CFC becomes 50 wt%. the difference _(W 2 -W ₄₎ is greater than 0 wt%, less than 20 wt%

A fourth invention is the polyethylene resin composition according to any one of the first to third inventions, wherein the ethylene / α-olefin copolymer (A) further satisfies the following condition (8): It exists in things.
(8) The proportion (X) of components that elute at 85 ° C. or higher by temperature rising elution fractionation (TREF) is 2 to 15% by weight.

  A fifth invention is the polyethylene according to any one of the first to fourth inventions, wherein the α-olefin of the ethylene / α-olefin copolymer (A) has 3 to 10 carbon atoms. System resin composition.

A sixth invention is the invention according to any one of the first to fifth inventions, characterized in that the ethylene / α-olefin copolymer (B) satisfies the following conditions (B-1) and (B-2). The polyethylene-based resin composition described in 1.
(B-1) MFR is 0.01 to 20 g / 10 minutes. (B-2) Density is 0.880 to 0.970 g / cm ³ .

A seventh invention is the polyethylene according to any one of the first to sixth inventions, wherein the ethylene / α-olefin copolymer (B) further satisfies the following condition (B-2 ′). System resin composition.
(B-2 ′) density is 0.890 to 0.940 g / cm ³ .

An eighth invention is the polyethylene described in any one of the first to seventh inventions, characterized in that the ethylene / α-olefin copolymer (B) further satisfies the following condition (B-3). System resin composition.
(B-3) The molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC) is 2.0 to 5.0.

A ninth invention is characterized in that the ethylene / α-olefin copolymer (A) and the ethylene / α-olefin copolymer (B) satisfy any one or more of the following conditions. The polyethylene resin composition according to any one of the inventions 1 to 8 exists.
(AB-1) MFR _B > MFR _A
(AB-2) [Mw / Mn] _B <[Mw / Mn] _A
(In the formula, MFR _A and [Mw / Mn] _A represent the MFR of the ethylene / α-olefin copolymer (A) and the molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC), respectively, MFR _B and [Mw / Mn] _B represent the MFR of the ethylene / α-olefin copolymer (B) and the molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC), respectively.)

  A tenth invention is a Ziegler linear low-density polyethylene having an MFR of 0.1 to less than 5.0, or a metallocene having an MFR of 0.1 to 10 inclusive, wherein the ethylene / α-olefin copolymer (B) is. The polyethylene-based resin composition according to any one of the first to ninth inventions is characterized by being a polyethylene-based resin.

An eleventh invention resides in the polyethylene resin composition according to any one of the first to tenth inventions, characterized in that the resin composition is a resin composition for a film.
A twelfth invention resides in a film obtained from the resin composition according to any one of the first to eleventh inventions.

  A thirteenth invention resides in a sealant film for a standing pouch obtained from the resin composition according to any one of the first to eleventh inventions.

A fourteenth invention is the ethylene / α-olefin copolymer (A), wherein the ethylene / α-olefin copolymer (A) is produced by an olefin polymerization catalyst containing catalyst components (X), (Y) and (Z). The method for producing a polyethylene resin composition according to any one of the first to twelfth aspects of the invention is characterized by being a united body.
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.

INDUSTRIAL APPLICABILITY The polyethylene-based resin composition of the present invention is excellent in molding processing characteristics, at the same time, has an excellent balance of impact strength and rigidity, and further has an effect of excellent transparency. Since the molded product obtained by die molding or inflation molding also has excellent impact strength and rigidity balance and transparency, it is possible to economically advantageously provide a thin molded product.

It is a graph which shows the baseline and the area | region of the chromatogram used by the gel permeation chromatography (GPC) method. It is a graph which shows the relationship between the branching index (g ') calculated from GPC-VIS measurement (branching structure analysis), and the molecular weight (M). It is a graph which shows the elution temperature distribution by temperature rising elution fractionation (TREF). It is a graph which shows as a contour map the elution amount regarding the elution temperature and the molecular weight measured by the cross fractionation chromatography (CFC) method. It is a graph which shows the relationship between the elution temperature measured by the cross fractionation chromatography (CFC) method and the elution ratio (wt%) at each elution temperature. It is a schematic view of W ₁ to _W-4. In this case, the horizontal axis is the logarithm of the molecular weight (logM), and the horizontal axis is the elution temperature (Temp.). It is a graph which shows the relationship of the elastic modulus and impact strength obtained about the film which blended the copolymerization of the Example of Experimental example a of this invention, and a comparative example. It is a graph which shows the relationship of the elastic modulus and impact strength obtained about the film which blended the copolymer of the Example and the comparative example of the experimental example B of this invention. It is a graph which shows the relationship of the film impact and impact strength obtained about the film which blended the copolymer of the Example and the comparative example of Experimental example C of this invention.

  The present invention provides an ethylene / α-olefin copolymer having a specific long chain branching index and a relatively narrow inverse comonomer composition distribution index, and having a specific MFR and density, which is good as an olefin resin modifier. The present invention relates to an olefin resin composition containing it. Hereinafter, the present invention will be described in detail for each item.

1. Ethylene / α-olefin copolymer (A) of the present invention
The ethylene / α-olefin copolymer of the present invention satisfies the following conditions (1) to (4) and (6), preferably condition (5) or / and further conditions (7) and (8).

1-1. Condition (1) MFR
The ethylene / α-olefin copolymer of the present invention has a melt flow rate (MFR) of 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 / min. It is 10 minutes or less, more preferably more than 0.1 g / 10 minutes and 2.0 g / 10 minutes or less.
When the MFR is in this range, the molding processability when blended with a polyolefin resin and the effect of improving the balance between impact strength and rigidity are excellent. On the other hand, if the MFR is 0.1 g / 10 minutes or less, it may be unfavorable in terms of moldability and the like, and if the MFR is more than 10 g / 10 minutes, the effect of improving impact strength and rigidity may not be sufficiently exhibited, which is not preferable. . In the present invention, the MFR of the ethylene / α-olefin copolymer is in accordance with JIS K7210 “Plastic-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR) test method”. , 190 ° C., 21.18 N (2.16 kg) load.

1-2. Condition (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 less than 0.934 g / cm ³ . more preferably 0.900~0.930g / cm ^3, more preferably 0.905~0.930g / cm ^3, particularly preferably 0.910~0.925g / cm ^3.
When the density is within this range, the effect of improving the balance between impact strength and rigidity when blended with the polyolefin resin to be modified is excellent. On the other hand, when the density is less than 0.895 g / cm ³ , it may not be preferable in terms of rigidity, and when the density is more than 0.940 g / cm ^{3, the} effect of improving impact strength and the like is not sufficient, which is not preferable.
In the present invention, the density of the ethylene / α-olefin copolymer means a value measured by the following method.

  The pellets were hot-pressed to prepare a pressed sheet having a thickness of 2 mm, the sheet was placed in a beaker having a capacity of 1000 ml, filled with distilled water, covered with a watch glass and heated with a mantle heater. After boiling the distilled 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, and the time required to reach room temperature was adjusted not to be less than 60 minutes. Further, the test sheet was immersed in substantially the center of water so as not to contact the 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, and then punched to have a length and width of 2 mm, and at a test temperature of 23 ° C., JIS K7112 “Plastics-Density of non-foamed plastic” And the measuring method of specific gravity ".

1-3. Condition (3) Molecular Weight Distribution The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the ethylene / α-olefin copolymer in the present invention is 3.0 to 5.5, preferably It is 3.0 to 5.3, more preferably 3.3 or more and less than 5.3, and further preferably 3.5 or more and less than 5.3. If the Mw / Mn is less than 3.0, the molding processability when blended with a polyolefin resin, particularly the melt fluidity, is poor, and it is difficult to mix with other polymer components, so it should be avoided. If the Mw / Mn is larger than 5.5, the effect of improving the rigidity and impact strength of the polyolefin resin or its molded product becomes insufficient, the transparency deteriorates, and stickiness tends to occur, which is not preferable.
Mw / Mn is one of the indices showing the molecular weight distribution in the copolymer, and the number is small when the polymerization reaction on the catalyst is carried out at a relatively uniform site, and it is carried out at a relatively multi-site. And the numerical value becomes large. It can be roughly and appropriately controlled by selecting the catalyst species used for the polymerization and the catalyst adjustment conditions.
In addition, in this invention, Mw and Mn of an ethylene / alpha-olefin copolymer refer to what was measured by the gel permeation chromatography (GPC) method.

The conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance using 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 prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each has a concentration of 0.5 mg / mL. For the calibration curve, a cubic expression obtained by approximation by the least square method is used. For the conversion to the molecular weight, a general-purpose calibration curve is used with reference to “Size Exclusion Chromatography” by Sadao Mori (Kyoritsu Shuppan). For the viscosity formula [η] = K × M ^α used at that time, the following numerical values are used.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733

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

1-4. Condition (4) gc
The ethylene / α-olefin copolymer in the present invention has a branch measured by a GPC measuring device in which a differential refractometer, a viscosity detector and a light scattering detector are combined in addition to the above-mentioned conditions (1) to (3). The lowest value (gc) of the index g'with a molecular weight of 100,000 to 1,000,000 is 0.40 to 0.85, preferably 0.45 to 0.85 or 0.50 to 0.85, and more preferably 0.50 to 0.77, particularly preferably 0.51 to 0.75. When the g _C value is larger than 0.85, the effect of improving the molding processability when blended with the polyolefin resin is not sufficiently exhibited, which is not preferable. When the g _C value is less than 0.40, the moldability of the polyolefin resin is improved, but the impact strength is lowered and the transparency is deteriorated, which is not preferable.
In the present invention, the g _C value of the ethylene / α-olefin copolymer is a physical property value indicating the degree of development of long chain branching introduced into the copolymer, and when the g _C value is large, the long chain When the number of branches is small and the g _C value is small, the amount of long-chain branch introduced is large. The value of g _C can be roughly controlled by selecting the catalyst used for the polymerization. The g _C value of the ethylene / α-olefin copolymer is an evaluation method of long chain branching amount using a molecular weight distribution curve or branching index (g ′) calculated from the following GPC-VIS measurement.

[Branch structure analysis by GPC-VIS]
An Alliance GPCV2000 manufactured by Waters was used as a GPC device equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). Further, as the light scattering detector, a multi-angle laser light scattering detector (MALLS) Wyatt Technology DAWN-E was used. The detector was connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (antioxidant Irganox 1076 added at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As a column, two Tohso GMHHR-H (S) HTs were connected and used.
The temperature of the column, sample injection part 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 radius of gyration (Rg) and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation was performed with reference to the following documents.

References:
1. Developments in polymer characterisation, vol. 4. Essex: Applied Science; 1984. Chapter1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4. Macromolecules, 33, 6945-6952 (2000).

[Calculation of branching index (g _C )]
The branching index (g ′) is calculated as a ratio (ηbranch / ηlin) between the intrinsic viscosity (ηbranch) obtained by measuring the sample with the Viscometer and the intrinsic viscosity (ηlin) separately obtained by measuring the linear polymer. To do.
The introduction of long chain branching into the polymer molecule results in a smaller radius of gyration as compared to a linear polymer molecule of the same molecular weight. Since the intrinsic viscosity becomes smaller as the radius of gyration becomes smaller, 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 becomes smaller (ηbranch / ηlin) as the long chain branching is introduced. It will become. Therefore, when the branching index (g '= ηbranch / ηlin) becomes a value smaller than 1, it means that branching is introduced, and as the value becomes smaller, the number of long-chain branching introduced increases. Means that. Particularly, in the present invention, as the absolute molecular weight obtained from MALLS, the lowest value of the above-mentioned g ′ in the 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. The left side of FIG. 2 shows a molecular weight distribution curve measured based on the molecular weight (M) obtained from MALLS and the concentration obtained from RI, and the right side of FIG. 2 shows the branching index (g ′) in the molecular weight (M). . As the linear polymer, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used.

1-5. Condition (5) W ₂ + W ₃
The ethylene / α-olefin copolymer of the present invention has an elution amount of 50 wt% obtained from an integrated elution curve measured by cross fractionation chromatography (CFC) in addition to the above conditions (1) to (4). Of the components having a molecular weight of not less than the weight average molecular weight (W ₂ ) among the components that elute at a temperature equal to or lower than the temperature at which The sum (W ₂ + W ₃ ) of the proportions (W ₃ ) of components having a weight average molecular weight of less than 40% by weight is less than 56% by weight. It is preferably more than 41% by weight and less than 56% by weight, more preferably more than 43% by weight and less than 56% by weight, particularly preferably more than 45% by weight and less than 56% by weight.

The above-mentioned numerical values such as W ₁ obtained from the integrated elution curve measured by cross fractionation chromatography (CFC) are indicators that collectively show the distributions of the comonomer amount and the molecular weight of the individual polymers contained in the entire copolymer. This is a method used to show the "comonomer composition distribution". That is, a polymer with a large amount of comonomer and a small molecular weight (W ₁ ), a polymer with a large amount of comonomer and a large molecular weight (W ₂ ), a polymer with a small amount of comonomer and a small molecular weight (W ₃ ), and a polymer with a small amount of comonomer. Shows that the polymer (W ₄ ) having a large ratio accounts for the whole copolymer. FIG. 6 shows a schematic view of W _{1 to} W ₄ .

When the W ₂ + W ₃ value is 40% by weight or less, the proportion of the low-density high-molecular-weight component effectively acting to improve the impact strength of the polyolefin-based resin contained in the ethylene / α-olefin copolymer decreases, The high-density low-molecular weight component effectively acting to improve the rigidity of the polyolefin-based resin is reduced, and a larger amount of a blend of ethylene / α-olefin copolymer is required to exert the physical property-improving effect. It is not economical, so it is not preferable. On the other hand, when the W ₂ + W ₃ value is 56% by weight or more, the balance between the contents of the high-density low-molecular weight component and the low-density high-molecular weight component contained in the ethylene / α-olefin copolymer is disturbed, and the polyolefin type It is not preferable because the effect of modifying the physical properties of the resin does not appear as expected, or the dispersibility of the high-density low-molecular weight component and the low-density high-molecular weight component deteriorates, resulting in poor transparency and gel formation.

[CFC measurement conditions]
Cross fractionation chromatography (CFC) consists of a temperature-rising elution fractionation (TREF) section for performing crystalline fractionation and a gel permeation chromatography (GPC) section for performing molecular weight fractionation.
The analysis using this CFC is performed as follows.
First, a polymer sample was completely dissolved in ortho-dichlorobenzene (ODCB) containing 0.5 mg / mL of BHT at 140 ° C., and this solution was passed through a sample loop of the apparatus to a TREF column (inactive). It is injected into a column filled with glass bead carriers) and gradually cooled to a predetermined first elution temperature to crystallize the polymer sample. After holding at a predetermined temperature for 30 minutes, by passing ODCB through the TREF column, 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 at a measurement wavelength of 3.42 μm. Meanwhile, in the TREF section, the temperature is raised to the next elution temperature, a chromatogram at the first elution temperature is obtained, and then the elution component at the second elution temperature is injected into the GPC section. Hereinafter, by repeating the same operation, a chromatogram of the eluted components at each elution temperature can be obtained.

The CFC measurement conditions are as follows.
Equipment: Dia Instruments CFC-T102L
GPC column: Showa Denko AD-806MS (three connected in series)
Solvent: ODCB
Sample concentration: 3mg / mL
Injection volume: 0.4 mL
Crystallization rate: 1 ° C / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stability 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 chromatograms of the elution components at each elution temperature obtained by the measurement, the elution amount (proportional to the area of the chromatogram) normalized so that the total sum becomes 100% can be obtained.
In addition, the integrated elution curve for the elution temperature is calculated. The differential elution curve is obtained by differentiating this integrated elution curve with temperature.
Further, the molecular weight distribution is obtained from each chromatogram by the following procedure. The conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance using 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 prepared by injecting 0.4 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each of them has a concentration of 0.5 mg / mL.
For the calibration curve, a cubic expression obtained by approximation by the least square method is used.
For the conversion to the molecular weight, a general-purpose calibration curve is used with reference to “Size Exclusion Chromatography” by Sadao Mori (Kyoritsu Shuppan). For the viscosity formula [η] = K × M ^α used at that time, the following numerical values are used.
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 and the low molecular weight side of the elution component may overlap, but in that case, the baseline is drawn as shown in FIG. Determine the desired section.
Further, as shown in Table 1 below, the weight average molecular weight of the whole (total) is determined 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 the elution amount at each elution temperature, S. Nakano, Y. Goto, “Development of automatic Cross Fractionation: Combination of Fractionation Jr. 26, pp. 4217-4231 (1981)), a graph (contour diagram) showing the elution amount with respect to elution temperature and molecular weight as contour lines is obtained.
The following component amounts are obtained using the above contour map.
W ₁ : Ratio of components having a molecular weight less than the weight average molecular weight of the ethylene / α-olefin copolymer, of the components eluted at a temperature at which the amount of elution obtained from the integrated elution curve is 50 wt% or less.
W _2: ratio of the weight average molecular weight or more components having a molecular weight of component elution volume as determined from integral elution curve is eluted with the following temperature at which 50 wt% is the ethylene · alpha-olefin copolymer.
W _3: ratio of components having a weight average molecular weight less than the molecular weight of the ethylene · alpha-olefin copolymer of the component elution volume as determined from integral elution curve is eluted at a temperature higher than the temperature at which 50 wt%.
W _4: ratio of weight average molecular weight or more components having a molecular weight of component elution volume as determined from integral elution curve is eluted at a temperature higher than the temperature at which 50 wt% is the ethylene · alpha-olefin copolymer.
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. You can

1-6. Condition (6) W ₂ + W ₄
In the ethylene-α-olefin copolymer according to the present invention, the sum (W ₂ + W ₄ ) of W ₂ and W ₄ described in (1-5) is more than 25% by weight and less than 50% by weight, preferably It is more than 29% by weight and less than 50% by weight, more preferably more than 29% by weight and less than 45% by weight, further 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 of the polyolefin-based resin contained in the ethylene / α-olefin copolymer is decreased, which is not preferable. It is not preferable because the high molecular weight long chain branching components that act particularly effectively in improving the molding processability of the polyolefin-based resin contained in the α-olefin copolymer are reduced, or the ratio of those high molecular weight components and long chain branching components However, since a large amount of blending is required due to the modification of the polyolefin resin, the economical efficiency is deteriorated. On the other hand, when the W ₂ + W ₄ value is 50% by weight or more, the proportion of the high molecular weight component and the high molecular weight long-chain branched component contained in the ethylene / α-olefin copolymer is high, and therefore the dispersibility in the polyolefin resin is high. Is deteriorated, the transparency is deteriorated, and gel is generated, which is not preferable.

1-7. Condition ₍₇₎ W 2 -W ₄
In the ethylene / α-olefin copolymer according to the present invention, the difference (W ₂ −W ₄ ) between W ₂ and W ₄ described in (1-6) is more than 0% by weight and less than 20% by weight, preferably More than 0% by weight, less than 15% by weight, more preferably more than 1% by weight, less than 15% by weight, further preferably more than 2% by weight, less than 14% by weight, particularly preferably more than 2% by weight, 13% by weight It is less than%. When W ₂ -W ₄ is 0 wt% or less, since the low density high molecular weight component is reduced to act particularly effectively in impact strength improvement of the polyolefin resin contained in the ethylene · alpha-olefin copolymer unfavorably . On the other hand, if W ₂ -W ₄ value is 20 wt% or more, imbalance of the amount of high density and high molecular weight component and a low-density high-molecular weight component contained in the ethylene · alpha-olefin copolymer, the polyolefin resin This is not preferable because the effect of modifying the physical properties does not appear as expected, or the dispersibility in the polyolefin resin deteriorates, resulting in poor transparency and gel formation.

1-5. Condition (5) X
In the ethylene / α-olefin copolymer according to the present invention, the proportion (X value) of the component eluted at 85 ° C. or higher by temperature rising elution fractionation (TREF) is 2 to 15% by weight, preferably 3 to 14% by weight. Is. More preferably, it is 4 to 14% by weight. When the X value is more than 15% by weight, the proportion of low density component effectively acting to improve the impact strength of the polyolefin-based resin contained in the ethylene / α-olefin copolymer is decreased, and a large amount is added to improve the impact strength. It is not preferable because a blend of the ethylene / α-olefin copolymer is required, which is not economical. If the X value is less than 2% by weight, the compatibility at the time of blending with the polyolefin resin may be deteriorated or the rigidity of the polyolefin resin may be deteriorated, which is not preferable in some cases. The amount of X value is a numerical value that indicates the ratio of a relatively high molecular weight component contained in the copolymer, and can be adjusted by adjusting the catalyst and controlling the polymerization conditions.

[TREF measurement conditions]
A sample is dissolved in orthodichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to form a solution. After introducing this into a 140 ° C TREF column, it is cooled to 100 ° C at a cooling rate of 8 ° C / min, subsequently cooled to 40 ° C at a cooling rate of 4 ° C / min, and subsequently to a cooling rate of 1 ° C / min. And cool to −15 ° C. and hold for 20 minutes. Then, ortho-dichlorobenzene (containing 0.5 mg / mL BHT) as a solvent was passed through the column at a flow rate of 1 mL / min, and the components dissolved in ortho-dichlorobenzene at -15 ° C in the TREF column were eluted for 10 minutes, Next, the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve. At this time, the amount of the component eluted between 85 ° C. and 140 ° C. is X (unit: wt%).

The equipment used is as follows.
(TREF section)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 100 μm surface inert 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 Co., Ltd. Digital Program Controller KP1000
(Bulb oven)
Heating method: Air bath type Oven temperature: 140 ℃
Temperature distribution: ± 1 ℃
Valve: 6-way valve, 4-way valve (sample injection part)
Injection method: Loop injection method Injection volume: Loop size 0.1 ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ℃
(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 x 4 mm oblong, synthetic sapphire window plate Measuring temperature: 140 ° C
(Pump part)
Liquid feeding pump: SSC-3461 pump manufactured by Senshu Scientific Co., Ltd. Measurement conditions Solvent: Ortho-dichlorobenzene (containing 0.5 mg / mL BHT)
Sample concentration: 5mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min 1-9. Composition of ethylene / α-olefin copolymer (A) of the present invention

  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, heptene. -1, octene-1, nonene-1, decene-1 and the like. Further, 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, and specifically, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, pentene-1, hexene-1. , Heptene-1, Octene-1 and the like. More preferable α-olefins are those having 4 or 6 carbon atoms, and specific examples thereof include butene-1, 4-methylpentene-1 and hexene-1. A particularly preferred α-olefin is hexene-1.

The ratio of ethylene and α-olefin in the ethylene / α-olefin copolymer of the present invention is about 75 to 99.8 wt% ethylene and about 0.2 to 25 wt% α-olefin, preferably about ethylene. 80 to 99.6% by weight, α-olefin is about 0.4 to 20% by weight, more preferably ethylene is about 82 to 99.2% by weight, α-olefin is about 0.8 to 18% by weight, and It is preferably about 85 to 99% by weight of ethylene and about 1 to 15% by weight of α-olefin, and particularly preferably about 88 to 98% by weight of ethylene and about 2 to 12% by weight of α-olefin. When 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, it is also possible to use a small amount of a comonomer other than ethylene or α-olefin, and in this case, styrenes such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1,5- It has a polymerizable double bond 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 a diene is used, it must be used within a range where the long-chain branched structure and the molecular weight distribution satisfy the above conditions.

2. Method for Producing Ethylene / α-Olefin Copolymer (A) 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 with the above-mentioned α-olefin using a catalyst for olefin polymerization.
As an example of a suitable production method for simultaneously realizing the 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 (Z) can be used.
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.

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

[However, 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 is a bridge between 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 containing an oxygen atom or a nitrogen atom, and a carbon atom having 1 to 20 carbon atoms. A hydrogen group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. ]

[However, in the formula [2], M represents a transition metal of Ti, Zr, or Hf. Q ¹ represents a bonding group bridging 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 containing an oxygen atom or a nitrogen atom, and a carbon atom having 1 to 20 carbon atoms. A hydrogen group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. 10 R's 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 containing 1 to 6 silicon atoms, and 1 to 1 carbon atoms. 20 represents a halogen-containing hydrocarbon group, a C 1-20 hydrocarbon group containing an oxygen atom, or a C 1-20 hydrocarbon group-substituted silyl group. ]

  A particularly preferable catalyst component (X) for producing the ethylene / α-olefin copolymer of the present invention is a metallocene compound represented by the general formula (1c) described in JP2013-22727A.

[However, in the formula (1c), all explanations of abbreviations follow those described in JP 2013-22771 A. That is, M ^1c represents a transition metal of Ti, Zr, or Hf. X ^1c and X ^2c 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 containing an oxygen atom or a nitrogen atom, and 1 to 20 carbon atoms. Represents 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 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1c are bonded to each other to form a ring together with Q ^1c and Q ^2c. Good. m ^c is 0 or 1, and when m ^c is 0, Q ^1c is directly bonded to the 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 containing 1 to 6 silicon atoms, or 1 carbon atom. To a halogen-containing hydrocarbon group having 20 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. 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族又は１６族の原子を示す。Ｒ^５ｃ、Ｒ^６ｃ、Ｒ^７ｃ、Ｒ^８ｃ及び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、又は炭素数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及び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又は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又は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。］

[However, in formula (1-ac), Y ^1c represents an atom of Group 14, Group 15 or Group 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, or 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 C1-C6, 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 is shown, and R ^5c , R ^6c , R ^7c , R ^8c and R ^9c are bonded to each other by adjacent groups. , May form a ring together with the atom bonded to them. n ^c is 0 or 1, and when n ^c is 0, the substituent R ^5c does not exist in Y ^1c . p ^c is 0 or 1, and when p ^c is 0, the carbon atom to which R ^7c is bonded and the carbon atom to which R ^9c is 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 preferable catalyst component (X) for producing the ethylene / α-olefin copolymer of the present invention is a metallocene compound represented by the general formula (2c) described in JP2013-22771A.

In the metallocene compound represented by the above general formula (2c), M ^1c , X ^1c , X ^2c , Q ^1c , R ^1c , R ^2c and R ^4c are the metallocene compounds represented by the above general formula (1c). Structures similar to the atoms and groups shown in can be selected. Further, R ^10c can be selected from the same structures 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). .

Specific examples of the metallocene compound include the compounds described in Table 1c of JP2013-22771A, but the invention is not limited thereto.
The compound of the above specific examples is preferably a zirconium compound or a hafnium compound, and more preferably a zirconium compound.
As the catalyst component (X) preferable for producing the ethylene / α-olefin copolymer of the present invention, two or more kinds of the above-mentioned bridged cyclopentadienylindenyl compounds may be used.

2-2. Catalyst component (Y)
A preferred catalyst component (Y) for producing the ethylene / α-olefin copolymer of the present invention is a compound which reacts with the compound of component (X) to form a cationic metallocene compound, and more preferably The component (Y) described in JP-A-2013-22727, [0064] to [0083], and more preferably the organoaluminum oxy compound described in [0065] to [0069].

2-3. Catalyst component (Z)
The preferred catalyst component (Z) for producing the ethylene / α-olefin copolymer of the present invention is an inorganic compound carrier, and more preferably, it is described in JP-A-2013-22727 [0084] to [0088]. It is an inorganic compound. At this time, the metal oxides described in the publication [0085] are preferable as the inorganic compound.

2-4. Method for Producing Olefin Polymerization Catalyst The ethylene / α-olefin copolymer of the present invention copolymerizes ethylene with the above α-olefin using the olefin polymerization catalyst containing the catalyst components (X) to (Z). It is preferably manufactured by the method. The method of contacting each component when obtaining the catalyst for olefin polymerization from the catalyst components (X) to (Z) of the present invention is not particularly limited, and, for example, the following methods (I) to (III) are optional. Can be used for.

(I) A catalyst component (X) which is a bridged cyclopentadienylindenyl compound containing the above transition metal element, and a catalyst component which is a compound which reacts with the compound of the above catalyst component (X) to form a cationic metallocene compound. After contacting with (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.

  Among these contacting methods, (I) and (III) are preferable, and (I) is most preferable. In any contacting method, generally, in an inert atmosphere such as nitrogen or argon, aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, pentane, heptane, hexane, decane are generally used. , Dodecane, cyclohexane, etc., a method of bringing the respective components into contact with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) . This contact is usually at a temperature of -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, and further preferably It is desirable to carry out for 30 minutes to 12 hours.

  When the catalyst component (X), the catalyst component (Y) and the catalyst component (Z) are brought into contact with each other, as described above, an aromatic hydrocarbon solvent in which a certain component is soluble or hardly soluble, and a certain component Any of insoluble or sparingly soluble aliphatic or alicyclic hydrocarbon solvents can be used.

  When the contact reaction between the components is carried out stepwise, it may be used as it is as a solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the first stage catalytic reaction using a soluble solvent, a liquid inert hydrocarbon in which a certain component is insoluble or sparingly soluble (for example, pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, and other aliphatic hydrocarbons). Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) to recover the desired product as a solid, or once the soluble solvent is partially or entirely removed by a means such as drying to obtain the desired product. After removing the product as a solid, a subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In the present invention, the catalytic reaction of each component may be carried out 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 range is preferable.

  When an organoaluminum oxy compound is used as the catalyst component (Y), the aluminum atomic ratio (Al / M) 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, and particularly preferably 250 to 500. When a borane compound or a borate compound is used, the transition metal (M) in the catalyst component (X) is used. 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. Furthermore, when a mixture of an organoaluminum oxy compound, a borane compound and a borate compound is used as the catalyst component (Y), each compound in the mixture is used in the same manner as described above for the transition metal (M). It is desirable to select in proportion.

  The amount of the catalyst component (Z) used is 0.0001 to 5 mmol, preferably 0.001 to 0.2 mmol, and more preferably 0.005 to 0.1 mmol of the transition metal in the catalyst component (X). Per gram, particularly preferably 0.01 to 0.04 mmol per gram.

  Further, 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). 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 above-mentioned contact methods (I) to (III), and then the solvent is removed. The olefin polymerization catalyst can be obtained as a solid catalyst. The solvent is removed under 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 carry out in about 20 hours.

The olefin polymerization catalyst can also be obtained by the following methods (IV) and (V).
(IV) The catalyst component (X) and the catalyst component (Z) are brought into contact with each other to remove the solvent, and this is used as a solid catalyst component, and under polymerization conditions, an organoaluminumoxy compound, a borane compound, a borate compound, or a mixture thereof. Contact.
(V) The catalyst component (Y), which is an organoaluminum oxy compound, a borane compound, a borate compound or a mixture thereof, is brought into contact with the catalyst component (Z) to remove the solvent, which is used as a solid catalyst component under polymerization conditions. And contact with the catalyst component (X).
Also in the case of the contact methods (IV) and (V), the same component ratios, contact conditions and solvent removal conditions as described above can be used.

  Further, a catalyst component (Y) which reacts with the catalyst component (X) to produce a cationic metallocene compound, as an olefin polymerization catalyst suitable for obtaining the ethylene / α-olefin copolymer (A) of the present invention. A well-known layered silicate described in JP-A Nos. 05-301917 and 08-127613 can be used as a component that also serves as the catalyst component (Z). A layered silicate is a silicate compound that has a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces. Most of the layered silicates are naturally produced mainly as the main components of clay minerals, but these layered silicates are not limited to those of natural origin, and may be synthetic products.

  Among these, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite, vermiculite, and mica 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, and 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 preliminarily polymerizing the monomer, if necessary.

2-5. Polymerization Method of Ethylene / α-Olefin Copolymer (A) The ethylene / α-olefin copolymer of the present invention preferably uses the olefin polymerization catalyst prepared by the production method described in 2-4 above. , Ethylene and the above-mentioned α-olefin are copolymerized.

  As described above, as the α-olefin which is a comonomer, an α-olefin having 3 to 10 carbon atoms can be used, and it is also possible to copolymerize two or more types of α-olefins with ethylene. It is also possible to use small amounts of comonomers other than olefins.

  In the present invention, the above 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 a comonomer is introduced, circulated or circulated while oxygen and water are 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 preferable 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 atmospheric pressure to 10 MPa, preferably atmospheric 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.

In order to obtain a copolymer having a relatively narrow inverse comonomer composition distribution having long-chain branching in an appropriate range and a low density high molecular weight component in an appropriate ratio, which is one of the features of the present invention, the catalyst component ( X) and the type of catalyst component (Y), as well as the molar ratio of catalysts (X) and (Y), the molar ratio of (X) and (Z), and the molar ratio of (Y) and (Z). , The polymerization temperature, the ethylene partial pressure, the H2 / C2 ratio, the comonomer / ethylene ratio, and other polymerization conditions can be appropriately adjusted.
Specifically, for example, when the complex described in Example 1 of the present application is used, as a method for adjusting the catalyst, complex / silica = 10 to 40 μmol / g, organoaluminum oxy compound / silica = 7 to 10 mmol / g, adjustment The use of the agent is optional, polymerization conditions are 60 to 90 ° C., ethylene partial pressure is 0.3 to 2.0 MPa, H2 / C2% = 0.2 to 2.0%, C6 / C2 = 0.1 to 0. It is appropriately set within the range of 8%.
In addition, it can be carried out without any trouble even if a component for the purpose of removing water, that is, a scavenger is added to the polymerization system.
Examples of the scavenger include trimethylaluminum, triethylaluminum, organoaluminum compounds such as triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, diethylzinc, organozinc compounds such as dibutylzinc, and diethyl. Organomagnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.

The long-chain branched structure (that is, g _C ) and the comonomer copolymerization composition distribution (that is, W _{1 to} W _4, etc.) of the produced copolymer are determined by the types of the catalyst component (X) and the catalyst component (Y), 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 species that easily forms a long chain branched structure is selected, it is possible to produce a copolymer having a small long chain branched structure, for example, by lowering the polymerization temperature or increasing the ethylene pressure. Further, even if a catalyst component species having a wide molecular weight distribution or copolymer composition distribution is selected, for example, a copolymer having a narrow molecular weight distribution or copolymer composition distribution can be produced by changing the catalyst component molar ratio, the polymerization conditions or the polymerization process. It is also possible.

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

3. Other Resins The ethylene / α-olefin copolymer (A) of the present invention (hereinafter, referred to as “ethylene / α-olefin copolymer (A)”) has its remarkable reforming effect, It can be used in a polyethylene resin composition by containing it together with an ethylene / α-olefin copolymer (B) other than A).
The content of the ethylene / α-olefin copolymer (A) in the resin composition is 1 to 59% by weight, more preferably 1 to 49% by weight, and further preferably 3 to 39% by weight based on 100% by weight of the resin composition. % Is preferred for modification purposes.

3-1. Other ethylene / α-olefin copolymers (B)
The other ethylene / α-olefin copolymer (B) does not substantially have a long-chain branched structure and has a linear molecular structure, for example, a linear molecular structure obtained by a Ziegler catalyst. And so-called linear low-density polyethylene (LLDPE) having a relatively wide molecular weight distribution, or metallocene-based polyethylene having a linear molecular structure and a narrower molecular weight distribution obtained by a metallocene catalyst. As described above, a linear low-density polyethylene having substantially no long-chain branched structure and a linear molecular structure has a gc value defined in the present invention of a value exceeding 0.85. Therefore, it is different from the ethylene / α-olefin copolymer (A).
It is particularly preferable to use an ethylene / α-olefin copolymer that satisfies the following physical properties (B-1) and (B-2), because the modification effect of the copolymer (A) is exhibited.
(B-1) MFR = 0.01 to 20 g / 10 minutes (B-2) Density = 0.880 to 0.970 g / cm ^3.
Furthermore, when a metallocene-based polyethylene satisfying the following physical properties (B-3) is used as another ethylene / α-olefin copolymer (B), the modification effect by the copolymer (A) is more effective, preferable.
(B-3) Mw / Mn = 2.0 to 5.0
The definitions of MFR, density and Mw / Mn are the same as the above-mentioned definition of the copolymer (A).

3-2-1. Condition (B-1) MFR
The melt flow rate (MFR _B ) of the ethylene / α-olefin copolymer (B) is 0.01 to 20.0 g / 10 minutes, preferably 0.1 to 5.0 g / 10 minutes. Further, as (B), a Ziegler-based linear low-density polyethylene copolymer obtained with a Ziegler-based catalyst having a relatively wide molecular weight distribution (often showing a value of more than 3.0 in terms of Q value described later). When used, the range of 0.3 to 3.0 g / 10 minutes is more preferable, and on the other hand, as (B), the molecular weight distribution obtained with a metallocene catalyst is relatively narrow (2. In the case of using a copolymer which often exhibits a value of 0 or more and 3.0 or less), the range of 0.3 to 4.0 g / 10 minutes is more preferable. If the MFR _B is too low, the molding processability will be poor, while if the MFR _B is too high, the impact resistance, mechanical strength, etc. may decrease.

3-2-2. Condition (B-2) Density The density _B of the ethylene · alpha-olefin copolymer (B) is a 0.880~0.970g / cm ^3, preferably 0.880~0.950g / cm ³ , 0.890 to 0.940 g / cm ³ is more preferable. When the density _B is within this range, the balance between impact resistance and rigidity is excellent. On the other hand, if the density _B is too low, the rigidity is lowered and the suitability for automatic bag making may be impaired. On the other hand, if the density _B is too high, impact resistance may be impaired.

3-2-3. Condition (B-3) Molecular weight distribution Furthermore, the ratio [Mw / Mn] _B of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer (B) (hereinafter, also referred to as Q value). Is 2.0 to 10.0. When the Q value is less than 2.0, it may be difficult to mix the ethylene / α-olefin copolymer (B) with other polymer components. 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 terms 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.
As the component (B), when a copolymer obtained with a Ziegler-based catalyst is used, a Q value is more than 3.0 to 5.0 g / 10 minutes, and when a copolymer obtained with a metallocene-based catalyst is used. Preferably has a Q value of 2.0 to 4.0 g / 10 minutes. The ratio [Mw / Mn] _B of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer (B) is measured under the following conditions (hereinafter, “method of measuring molecular weight distribution”). Sometimes referred to as "). 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).

3-2-4. Composition of ethylene / α-olefin copolymer (B) The ethylene / α-olefin copolymer (B) component is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. The α-olefin as a copolymerization component used here is the same as that used in the above-mentioned ethylene / α-olefin copolymer (A).

  The ratio of ethylene and α-olefin in the ethylene / α-olefin copolymer (B) is about 80 to 100% by weight of ethylene and about 0 to 20% by weight of α-olefin, preferably about 85 to 99.% of ethylene. 9% by weight, about 0.1 to 15% by weight of α-olefin, more preferably about 90 to 99.5% by weight of ethylene, about 0.5 to 10% by weight of α-olefin, and even more preferably about ethylene. 90 to 99% by weight and about 1 to 10% by weight of α-olefin. When the ethylene content is within this range, the polyethylene resin composition and the molded article have a good balance of rigidity and impact strength.

3-2-5. Method for producing ethylene / α-olefin copolymer (B) The ethylene / α-olefin copolymer (B) is produced by homopolymerizing ethylene with the catalyst for olefin polymerization or by copolymerizing with ethylene as described above. To be done.
Various kinds of olefin polymerization catalysts are known today, and the above-mentioned ethylene / α-olefin copolymer (B) is used within the scope of the constitution of the catalyst component and the devising conditions of polymerization and post-treatment. There is no limitation as long as it can be prepared, but as a technical example suitable for the production of the ethylene / α-olefin copolymer (B) and satisfying the economical efficiency at the industrial level, the following (i) to ( Specific examples of the olefin polymerization catalyst containing a transition metal described in ii) can be given.
(I) Ziegler catalyst As an example of an olefin polymerization catalyst suitable for producing the ethylene / α-olefin copolymer (B), an olefin coordination polymerization catalyst comprising a combination of a transition metal compound and a typical metal alkyl compound, etc. Ziegler-Natta catalyst is included. In particular, a so-called Mg-Ti-based Ziegler catalyst in which a solid catalyst component in which a titanium compound is supported on a magnesium compound and an organoaluminum compound are combined (for example, "catalyst utilization dictionary; published by the 2004 Industrial Research Board", "application system diagram-olefin"). Transition of Polymerization Catalyst—; Issued by The Invention Association of 1995 ”) is preferable because it is inexpensive, highly active, and excellent in polymerization process suitability.

(Ii) Metallocene Catalyst As an example of a polymerization catalyst suitable for producing the ethylene / α-olefin copolymer (B), a metallocene catalyst which is an olefin polymerization catalyst composed of a metallocene-based transition metal compound and a cocatalyst component (for example, “metallocene”). Next-generation polymer industrialization technology using catalysts (upper and lower volumes); published by 1994 Interresearch Co., Ltd.) is relatively inexpensive, highly active, and has excellent suitability for polymerization processes, as well as molecular weight distribution and copolymer composition distribution. Is used because an ethylene-based polymer having a narrow range is obtained.
(Iii) Specific metallocene polyethylene In particular, in the present invention, as another ethylene / α-olefin copolymer (B) to be combined with the ethylene / α-olefin copolymer (A) of the present invention, for example, Japanese Patent No. 3562562. It is preferable to use the specific metallocene-based polyethylene having the following characteristic features described in 1. because the transparency of the resin composition is significantly improved.
Ethylene / α-olefin copolymer having the following physical properties (a) Density 0.86 to less than 0.945 g / cm ³ (b) Melt flow rate (MFR) 0.01 to 50 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) 1.5 to 4.5,
(D) Composition distribution parameter Cbl. 08-2.00,
(E) The amount W (wt%) of orthodichlorobenzene (ODCB) soluble content at 25 ° C. and the density d and MFR satisfy the following relationship (a) or (b): (b) Density d and MFR Is d−0.008 × log MFR ≧ 0.93, W <2.0
(B) When the values of the density d and MFR are d-0.008 × logMFR <0.93 W <9.8 × 103 × (0.9300-d + 0.008 × 10 gMFR) 2 + 2.0
(F) Multiple peaks on the elution temperature-elution volume curve by continuous temperature elution fractionation (TREF)

4. Polyethylene Resin Composition Below, 1 to 59% by weight of the ethylene / α-olefin copolymer (A) of the present invention and other olefin resins other than A (ethylene / α-olefin copolymer ( The resin composition containing 99 to 41% by weight of (B) and the like), which is mainly suitable for film applications, will be described in detail.
Specifically preferably, as the olefin resin composition for films and sheets, the specific ethylene / α-olefin copolymer (A) of the present invention is 1 to 49% by weight, other ethylene / α-olefins. The copolymer (B) is 99 to 51% by weight, preferably (A) is 3 to 35% by weight, the ethylene / α-olefin copolymer (B) is 75% to 97% by weight, and in some cases, more preferably A composition obtained by adding 1 to 30% by weight of another olefin resin (C) can be mentioned.

4-1. MFR
The MFR of the olefin resin composition for a film comprising the above components (A) and (B) needs to be in the range of 0.01 to 20 g / 10 minutes, preferably 0.05 to 10 g / It is 10 minutes, more preferably 0.10 to 5 g / 10 minutes.
If the MFR is lower than 0.01 g / 10 minutes, 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 minutes, the bubbles are unstable and difficult to mold. , The strength of the film becomes low.
The MFR of the olefin resin composition is a value measured according to JIS K 7210 under the conditions of 190 ° C. and 21.18 N (2.16 kg) load, but the approximate MFR is the component (A), It can be calculated from each MFR and the ratio in (B) according to the additive rule.

4-2. Density The density of the olefin resin composition of the present invention comprising the above components (A) and (B) needs to be in the range of 0.880 to 0.970 g / cm ³ , and preferably 0.910. It is -0.950 g / cm < ³ >, More preferably, it is 0.915-0.940 g / cm < ³ >.
When the density of the olefin resin composition is lower than 0.880 g / cm ³ , the rigidity of the film becomes low and the suitability for an automatic bag making machine deteriorates. Moreover, when the density of the olefin resin composition is higher than 0.970 g / cm ³ , the strength of the film decreases.
The density of the olefin resin composition can be calculated from the respective densities and proportions of the components (A) and (B) according to the additive rule.

4-3. Condition (AB-1) Relationship between MFR of components (A) and (B) In preparing the olefin resin composition of the present invention consisting of the above components (A) and (B), the above components (A) and As the relationship of MFR in (B), it is preferable that MFR _B > MFR _A or 20> MFR _B / MFR _A > 1.0, and more preferably 15.0> MFR _B / MFR _A > 1.0. Yes, and more preferably 10.0> MFR _B / MFR _A > 1.0.
When the relationship between the MFRs of the components (A) and (B) is MFR _B > MFR _A , the addition of the component (A) makes the bubbles more stable. Further, when 20> MFR _B / MFR _A > 1.0, bubbles are stabilized during the inflation molding by the addition of the component (B), and the processing characteristics are improved.

4-4. Condition (AB-2) Relationship between Molecular Weight Distributions of Components (A) and (B) In preparing the olefin resin composition of the present invention comprising the above components (A) and (B), the above component (A) As the relationship between [Mw / Mn] of (B) and (B), it is preferable that [Mw / Mn] _B <[Mw / Mn] _A.
When the relation of [Mw / Mn] of the components (A) and (B) is [Mw / Mn] _B <[Mw / Mn] _A , bubbles are stable during inflation molding due to addition of the component (B). However, the processing characteristics are improved.

5. Other compounds, etc. In the present invention, as long as the characteristics of the present invention are not impaired, if necessary, antistatic agents, antioxidants, antiblocking agents, nucleating agents, lubricants, antifogging agents, organic or inorganic pigments, and ultraviolet rays. Known additives such as an inhibitor, a weather resistance agent, and a dispersant can be added.

  The polyethylene-based resin composition of the present invention comprises the above-mentioned ethylene / α-olefin copolymer (A), other polyolefin-based resin, and if necessary, various additives and copolymer components added or blended. After mixing using a Henschel mixer, a super mixer, a tumbler type mixer or the like, the mixture may be heated and kneaded with a single-screw or twin-screw extruder, a kneader or the like to form pellets.

6. Molding method The molding method of a molded article using the polyethylene resin composition of the present invention is particularly limited as long as it is a method capable of effectively utilizing the excellent processing characteristics and mechanical properties of the polyethylene resin composition of the present invention. However, in the case of a film, a bag or a sheet which is an example of the intended purpose of the polyethylene resin composition of the present invention, various inflation molding methods and T-die film molding are preferable molding methods. Method, calender molding method, multi-layer co-extrusion molding machine, multi-layer film molding method by laminating treatment, and the like.

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

7. Uses As a use of the film (or sheet) using the ethylene resin composition for a film of the present invention, concrete examples are: a standard bag having a dimensional standard such as an inner bag of a paper bag or a dust bag, a heavy bag. , Wrapping film, sugar bags, rice bags, oil packaging bags, food packaging films for water packaging bags such as pickles, packaging materials that require automatic filling, infusion bags, agricultural films, nylon, polyester, metal foil , Laminates with various base materials such as saponified ethylene-vinyl acetate copolymer, standing pouches, use as foams and molded articles thereof, bag-in-boxes, detergent containers, edible oil containers, retort containers, medical containers , Containers for chemicals, containers for solvents, containers for agricultural chemicals, infusion bags, clean films and the like. Specific examples of the use of the clean film include foods / beverages such as supplements, medical products / medicines such as syringes and infusion bags, liquid crystal members, electronic / electrical parts, packaging bags for precision parts, and the like.

  In addition, a film using the resin composition of the present invention is used as a standing pouch sealant film used for a refilling pouch that has been required to improve impact strength of the sealant film itself in recent years with an increase in capacity of a container. And preferred. The sealant film for a standing pouch is usually used as a single film made of a polyethylene resin composition, or by laminating nylon, polyester film or the like with an adhesive such as urethane. Conventionally, a resin obtained by blending a copolymer of ethylene and 1-butene with low-density polyethylene of high-pressure method has been used, but when the thickness is increased, the impact strength is improved, but there is a demand for volume reduction of the container. Couldn't answer. On the other hand, when the resin composition of the present invention is used, it becomes possible to maintain the impact strength higher than the conventional level even if the volume of the container is reduced, that is, the film is thinned. Further, the film impact (strength resistance against piercing) required for a standing pouch sealant film is sufficiently satisfied.

Hereinafter, 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 constitution of the present invention will be demonstrated. However, the present invention is limited by these Examples. Not a thing.
The measuring methods used in Examples and Comparative Examples are as follows. Further, the following catalyst synthesis step and polymerization step were all carried out under a purified nitrogen atmosphere, and the solvent used was dehydrated and purified with molecular sieve 4A.

[Method of measuring physical properties]
(1) MFR
According to JIS K7210 "Plastics-Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics", measurement was performed under the conditions of 190 ° C and 21.18N (2.16 kg) load. .
(2) Density JIS K7112 (1999 version): Measured by method A (underwater substitution method).
(3) Molecular weight distribution (Mw / Mn) measured by GPC
It was measured by a gel permeation chromatography (GPC) method. The measurement conditions of GPC are as follows.
Device: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M / S (3)
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: The sample is prepared using ODCB (containing 0.5 mg / mL BHT) to prepare a 1 mg / mL solution, which is dissolved at 140 ° C. in about 1 hour.
The baseline and section of the obtained chromatogram were determined as illustrated in FIG.
The conversion from the retention capacity to the molecular weight was performed using a calibration curve prepared in advance using 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 prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each has a concentration of 0.5 mg / mL. For the calibration curve, a cubic expression obtained by approximation by the least square method was used. For the conversion to the molecular weight, a general-purpose calibration curve was used with reference to “Size Exclusion Chromatography” by Sadao Mori (Kyoritsu Publishing). For the viscosity formula [η] = K × Mα used at that time, the following numerical values were used.
PS: K = 1.38 × 10 −4, α = 0.7
PE: K = 3.92 × 10 −4, α = 0.733

(4) The lowest value (gc) of the branching index (g ') measured by a GPC measuring device which is a combination of a differential refractometer, a viscosity detector and a light scattering detector, in the molecular weight range of 100,000 to 1,000,000.
An Alliance GPCV2000 manufactured by Waters was used as a GPC device equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). Further, as the light scattering detector, a multi-angle laser light scattering detector (MALLS) Wyatt Technology DAWN-E was used. The detector was connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (antioxidant Irganox 1076 added at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As a column, two Tohso GMHHR-H (S) HTs were connected and used. The temperature of the column, the sample injection part, 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 radius of gyration (Rg) and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation was performed with reference to the above-mentioned documents.
[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 Viscometer and the intrinsic viscosity (ηlin) separately obtained by measuring the linear polymer. did.
As the absolute molecular weight obtained from MALLS, the lowest value of the above-mentioned g'at a molecular weight of 100,000 to 1,000,000 was calculated as gC. As the linear polymer, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used.

(5) Proportion (X) of components that elute at 85 ° C or higher by temperature rising elution fractionation (TREF)
A sample is dissolved in orthodichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to form a solution. After introducing this into a 140 ° C TREF column, it is cooled to 100 ° C at a cooling rate of 8 ° C / min, subsequently cooled to 40 ° C at a cooling rate of 4 ° C / min, and subsequently to a cooling rate of 1 ° C / min. And cool to −15 ° C. and hold for 20 minutes. Then, ortho-dichlorobenzene (containing 0.5 mg / mL BHT) as a solvent was passed through the column at a flow rate of 1 mL / min, and the components dissolved in ortho-dichlorobenzene at -15 ° C in the TREF column were eluted for 10 minutes, Next, the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve. At this time, the amount of the component eluted between 85 ° C. and 140 ° C. is X (unit: wt%).
The equipment used is as follows.
(TREF section)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 100 μm surface inert 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 Co., Ltd. Digital Program Controller KP1000
(Bulb oven)
Heating method: Air bath type Oven temperature: 140 ℃
Temperature distribution: ± 1 ℃
Valve: 6-way valve, 4-way valve (sample injection part)
Injection method: Loop injection method Injection volume: Loop size 0.1 ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ℃
(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 x 4 mm oblong, synthetic sapphire window plate Measuring temperature: 140 ° C
(Pump part)
Liquid feeding pump: SSC-3461 pump manufactured by Senshu Scientific Co., Ltd. Measurement conditions Solvent: Ortho-dichlorobenzene (containing 0.5 mg / mL BHT)
Sample concentration: 5mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

(6) W2 + W3, W2 + W4, W2-W4
Cross-fractionation chromatography (CFC) consisting of a temperature-rising elution fractionation (TREF) part for performing crystalline fractionation and a gel permeation chromatography (GPC) part for performing molecular weight fractionation was performed.
That is, a polymer sample was completely dissolved in ortho-dichlorobenzene (ODCB) containing 0.5 mg / mL of BHT at 140 ° C., and this solution was passed through a sample loop of an apparatus to a TREF column (inert). It was injected into a column filled with a glass bead carrier) and gradually cooled to a predetermined first elution temperature to crystallize the polymer sample.
After holding at a predetermined temperature for 30 minutes, by passing ODCB through the TREF column, 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 at a measurement wavelength of 3.42 μm. Meanwhile, in the TREF section, the temperature was raised to the next elution temperature, a chromatogram at the first elution temperature was obtained, and then the elution component at the second elution temperature was injected into the GPC section. Hereinafter, by repeating the same operation, chromatograms of the eluted components at each elution temperature were obtained.
The CFC measurement conditions are as follows.
Equipment: Dia Instruments CFC-T102L
GPC column: Showa Denko AD-806MS (three connected in series)
Solvent: ODCB
Sample concentration: 3mg / mL
Injection volume: 0.4 mL
Crystallization rate: 1 ° C / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stability 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 chromatograms of the elution components at each elution temperature obtained by the measurement, the elution amount (proportional to the area of the chromatogram) normalized so that the sum total was 100% was obtained.
Further, the molecular weight distribution was determined from each chromatogram by the same procedure as the above-mentioned GPC.
From the molecular weight distribution and the elution amount at each elution temperature, S. Nakano, Y. Goto, "Development of automatic Cross Fractionation: Combining of Crystallization, Jpn. , Pp. 4217-4231 (1981)), a graph (contour map) showing the elution amount with respect to elution temperature and molecular weight as contour lines was obtained.
The following component amounts were obtained using the above contour map.
W ₁ : Ratio of components having a molecular weight less than the weight average molecular weight of the ethylene / α-olefin copolymer, of the components eluted at a temperature at which the amount of elution obtained from the integrated elution curve is 50 wt% or less.
W _2: ratio of the weight average molecular weight or more components having a molecular weight of component elution volume as determined from integral elution curve is eluted with the following temperature at which 50 wt% is the ethylene · alpha-olefin copolymer.
W _3: ratio of components having a weight average molecular weight less than the molecular weight of the ethylene · alpha-olefin copolymer of the component elution volume as determined from integral elution curve is eluted at a temperature higher than the temperature at which 50 wt%.
W _4: ratio of weight average molecular weight or more components having a molecular weight of component elution volume as determined from integral elution curve is eluted at a temperature higher than the temperature at which 50 wt% is the ethylene · alpha-olefin copolymer.
Note that W ₁ + W ₂ + W ₃ + W ₄ = 100.

[Molding conditions for blown film]
An inflation film was formed and evaluated under the following forming conditions using an inflation film forming machine (forming apparatus) having the following 50 mmφ extruder.
Equipment: Inflation molding equipment Extruder Screw diameter: 50mmφ
Die diameter: 75mmφ
Extrusion rate: 15kg / hr
Die lip gap: 1.0 mm or 3.0 mm (described in Examples)
Collection speed: 20.0 m / min Blow-up ratio: 2.0
Molding resin temperature: 170-190 ° C (described in Examples)
Film thickness: 30 μm

[Film evaluation method]
(1) Tensile modulus:
According to JIS K7127-1999, the tensile elastic modulus when the film was deformed by 1% in the processing direction (MD) and the width direction (TD) of the film was measured.
(2) Dirt drop impact strength (DDI)
It was measured according to the JIS K 7124 1 A method.

<Experimental example B>
[Production Example 1 of Polymer (A)]
(1) Synthesis of bridged cyclopentadienylindenyl compound;
Dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride was synthesized according to the method described in JP-A-2013-22727 [0140] to [0143].

(2) Synthesis of catalyst for olefin polymerization;
Under a nitrogen atmosphere, 30 g of silica calcined at 400 ° C. for 5 hours was placed in a 500 ml three-necked flask, and dried under reduced pressure with a vacuum pump for 1 hour while heating in an oil bath at 150 ° C. In a 200 ml two-necked flask prepared separately, under a nitrogen atmosphere, 410 mg of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride synthesized in the above (1) was put and dehydrated toluene After dissolving with 80.4 ml, 82.8 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was further added at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 500 ml three-necked flask containing vacuum dried silica in an oil bath at 40 ° C., the toluene solution of the reaction product of the zirconocene complex and methylaluminoxane was added in total amount. After stirring at 40 ° C. for 1 hour, the toluene solvent was distilled off under reduced pressure while heating at 40 ° C. to obtain a powdery catalyst.
(3) Production of ethylene / 1-hexene copolymer;
Ethylene / 1-hexene vapor phase continuous copolymerization was carried out using the powdery catalyst obtained in (2) above. That is, a gas phase continuous polymerization apparatus (internal volume 100 L, prepared at a temperature of 75 ° C., a hexene / ethylene molar ratio of 0.27%, a hydrogen / ethylene molar ratio of 0.53%, a nitrogen concentration of 26 mol% and a total pressure of 0.8 MPa. Polymerization was carried out while intermittently supplying the powdered catalyst to a fluidized bed polymer (dispersant 1.8 kg) having a fluidized bed diameter of 10 cm at a rate of 0.21 g / hour while maintaining a constant gas composition and temperature. It was Further, 0.03 mol / L of hexane diluted solution of triethylaluminum (TEA) was supplied to the gas circulation line at 15.7 ml / hr in order to maintain the cleanliness of the system. As a result, the average production rate of produced polyethylene was 330 g / hour. The MFR and density of the ethylene / 1-hexene copolymer obtained after the cumulative production of polyethylene of 5 kg or more were 0.23 g / 10 min and 0.921 g / cm ³ , respectively. The results are shown in Tables 3 and 4.

[Production Example 2]
(1) Synthesis of olefin polymerization catalyst;
Under a nitrogen atmosphere, 30 g of silica calcined 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, under a nitrogen atmosphere, 410 mg of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride synthesized in Production Example 1 (1) was placed, After dissolving in 80.4 ml of dehydrated toluene, 82.8 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was further added at room temperature, and the mixture was stirred for 30 minutes. 4 x 500 ml three-necked flask containing toluene slurry of silica
All the toluene solution of the reaction product of the zirconocene complex and methylaluminoxane was added while heating and stirring in an oil bath at 0 ° C. After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 15 minutes while heating at 40 ° C. to remove 224 ml of the supernatant liquid, and then the toluene solvent was distilled off under reduced pressure to obtain a powdery catalyst.
(2) Production of ethylene / 1-hexene copolymer;
Instead of the powdery catalyst of Production Example 1 (2), the powdery catalyst obtained in (1) above was used, and ethylene catalyst was produced in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. 1-Hexene vapor phase continuous copolymerization was performed. The results are shown in Tables 3 and 4.

[Production Example 3]
(1) Synthesis of olefin polymerization catalyst;
20 g of silica calcined at 400 ° C. for 5 hours was put in a 500 ml three-necked flask under a nitrogen atmosphere, and dried under reduced pressure by a vacuum pump for 1 hour while heating in an oil bath at 150 ° C. Under a nitrogen atmosphere, a separately prepared 200 ml two-necked flask was charged with 273 mg of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride synthesized in (1) above and dehydrated toluene. After dissolving with 53.6 ml, 55.2 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was further added at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 500 ml three-necked flask containing vacuum dried silica in an oil bath at 40 ° C., the toluene solution of the reaction product of the zirconocene complex and methylaluminoxane was added in total amount. After stirring at 40 ° C. for 1 hour, the toluene solvent was distilled off under reduced pressure while heating at 40 ° C. to obtain a powdery catalyst.
(2) Production of ethylene / 1-hexene copolymer;
Instead of the powdery catalyst of Production Example 1 (2), the powdery catalyst obtained in (1) above was used, and ethylene catalyst was produced in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. 1-Hexene vapor phase continuous copolymerization was performed. The results are shown in Tables 3 and 4.

[Production Example 4]
Production of ethylene / 1-hexene copolymer;
Using the powdery catalyst obtained in Production Example 2 (2), ethylene / 1-hexene vapor phase continuous copolymerization was carried out in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. The results are shown in Tables 3 and 4.

[Production Example 5]
Production of ethylene / 1-hexene copolymer;
Using the powdery catalyst obtained in Production Example 2 (2), ethylene / 1-hexene vapor phase continuous copolymerization was carried out in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. The results are shown in Tables 3 and 4.

[Production Example 6]
(1) Synthesis of olefin polymerization catalyst;
Under a nitrogen atmosphere, 30 g of silica calcined 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. Under a nitrogen atmosphere, a separately prepared 200 ml two-necked flask was charged with 412 mg of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride synthesized in Production Example 1 (1). After dissolved in 80.7 ml of dehydrated toluene, 78.9 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was further added at room temperature, and the mixture was stirred for 30 minutes. A toluene solution of the reaction product of the zirconocene complex and methylaluminoxane was added in total while heating and stirring a 500 ml three-necked flask containing a toluene slurry of silica in an oil bath at 40 ° C. After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 15 minutes while heating at 40 ° C. to remove 221 ml of the supernatant liquid, and then the toluene solvent was distilled off under reduced pressure to obtain a powdery catalyst.
(2) Production of ethylene / 1-hexene copolymer;
Instead of the powdery catalyst of Production Example 1 (2), the powdery catalyst obtained in (1) above was used, and ethylene catalyst was produced in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. 1-Hexene vapor phase continuous copolymerization was performed. The results are shown in Tables 3 and 4.

[Production Example 7]
(1) Treatment of Catalyst for Olefin Polymerization Under a nitrogen atmosphere, 32 g of the powdery catalyst obtained in Production Example 6 (1) was placed in a 500 ml three-necked flask, and 195 ml of dehydrated hexane and dehydrated liquid paraffin (manufactured by MORESCO; trade name) A mixture of 13.5 g of Moresco White P-120) was added at room temperature and stirred for 10 minutes, and then the solvent was distilled off under reduced pressure at 40 ° C. to obtain a powdery catalyst again.
(2) Production of ethylene / 1-hexene copolymer;
Instead of the powdery catalyst of Production Example 1 (2), the powdery catalyst obtained in (1) above was used, and ethylene catalyst was produced in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. 1-Hexene vapor phase continuous copolymerization was performed. The results are shown in Tables 3 and 4.

[Production Example 8]
(1) Treatment of Olefin Polymerization Catalyst Under a nitrogen atmosphere, into a 500 ml three-necked flask, 31 g of the powdery catalyst obtained in Production Example 6 (1) was placed, and 195 ml of dehydrated hexane and dehydrated liquid polybutene (JX Nippon Oil & Energy Corporation). Manufactured by Niseki Polybutene LV-7) (trade name) was added at room temperature and stirred for 10 minutes, and then the solvent was distilled off under reduced pressure at 40 ° C. to obtain a powdery catalyst again.
(2) Production of ethylene / 1-hexene copolymer;
Instead of the powdery catalyst of Production Example 1 (2), the powdery catalyst obtained in (1) above was used, and ethylene catalyst was produced in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. 1-Hexene vapor phase continuous copolymerization was performed. The results are shown in Tables 3 and 4.

[Production Example 9]
(1) Synthesis of olefin polymerization catalyst;
Under a nitrogen atmosphere, 30 g of silica calcined at 600 ° C. for 5 hours was placed in a 500 ml three-necked flask, and dried under reduced pressure by a vacuum pump for 1 hour while heating in an oil bath at 150 ° C. Under a nitrogen atmosphere, a separately prepared 200 ml two-necked flask was charged with 412 mg of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride synthesized in (1) above and dehydrated toluene. After dissolving with 80.7 ml, 83.1 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was further added at room temperature, and the mixture was stirred for 30 minutes. While heating and stirring a 500 ml three-necked flask containing vacuum dried silica in an oil bath at 40 ° C., the toluene solution of the reaction product of the zirconocene complex and methylaluminoxane was added in total amount. After stirring at 40 ° C. for 1 hour, the toluene solvent was distilled off under reduced pressure while heating at 40 ° C. to obtain a powdery catalyst.
(2) Production of ethylene / 1-hexene copolymer;
Instead of the powdery catalyst of Production Example 1 (2), the powdery catalyst obtained in (1) above was used, and ethylene catalyst was produced in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. 1-Hexene vapor phase continuous copolymerization was performed. The results are shown in Tables 3 and 4.

[Production Example 10]
(1) Synthesis of olefin polymerization catalyst;
Dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride instead of dimethylsilylene (3-methyl-4- (4-trimethylsilyl-phenyl) -3-methyl-indenyl) A powdery olefin polymerization catalyst was obtained in the same manner as in Production Example 1 (2) except that 421 mg of (cyclopentadienyl) zirconium dichloride was used.
(2) Production of ethylene / 1-hexene copolymer;
Instead of the powdery catalyst of Production Example 1 (2), the powdery catalyst obtained in (1) above was used, and ethylene catalyst was produced in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. 1-Hexene vapor phase continuous copolymerization was performed. The results are shown in Tables 3 and 4.

[Production Example 11] Production of ethylene / 1-hexene copolymer;
Using the slurry catalyst obtained in 180 g of dehydrated liquid paraffin in Production Example 7 (1) instead of the powdered catalyst of Production Example 7 (2), except for the conditions shown in Table 2, Production Example 1 (3 In the same manner as in ()), ethylene / 1-hexene vapor phase continuous copolymerization was carried out. The results are shown in Tables 3 and 4.

[Production Example 12] Production of ethylene / 1-hexene copolymer;
In Production Example 11, ethylene / 1-hexene vapor phase continuous copolymerization was performed in the same manner as in Production Example 11 except for the conditions shown in Table 2. The results are shown in Tables 3 and 4.

[Comparative Polymer 1]
Production of ethylene / 1-hexene copolymer;
Ethylene / 1-hexene vapor phase continuous copolymerization was carried out in the same manner as in the method for producing the ethylene polymer (B-8) described in Example 8a (1) of JP2012-214781A. The results are shown in Tables 3 and 4.

[Comparative polymer 2]
(1) Synthesis of olefin polymerization catalyst;
Under a nitrogen atmosphere, 30 g of silica calcined 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. Under a nitrogen atmosphere, a separately prepared 200 ml two-necked flask was charged with 820 mg of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride synthesized in Production Example 1 (1). After dissolving with 161 ml of dehydrated toluene, 49.7 ml of 20% methylaluminoxane / toluene solution manufactured by Albemarle was further added at room temperature, and the mixture was stirred for 30 minutes. A toluene solution of the reaction product of the zirconocene complex and methylaluminoxane was added in total while heating and stirring a 500 ml three-necked flask containing a toluene slurry of silica in an oil bath at 40 ° C. After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand for 15 minutes while heating at 40 ° C. to remove 224 ml of the supernatant liquid, and then the toluene solvent was distilled off under reduced pressure to obtain a powdery catalyst.
(2) Production of ethylene / 1-hexene copolymer;
Instead of the powdery catalyst of Production Example 1 (2), the powdery catalyst obtained in (1) above was used, and ethylene catalyst was produced in the same manner as in Production Example 1 (3) except for the conditions shown in Table 2. 1-Hexene vapor phase continuous copolymerization was performed. The results are shown in Tables 3 and 4.

[Comparative Polymer 3]
Production of ethylene / 1-hexene copolymer;
Ethylene / 1-hexene vapor phase continuous copolymerization was carried out in the same manner as in the method for producing the ethylene polymer (B-5) described in Example 5a (1) of JP2012-214781A. The results are shown in Tables 2 and 3.

[Comparative Polymer 4]
Tables 3 and 4 show the analysis results of a 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 ).

[Reference Polymer 1]
Tables 3 and 4 show the analysis results of commercially available high-pressure radical method low-density polyethylene (LF240 manufactured by Japan Polyethylene Co., Ltd .; MFR = 0.7 g / 10 min, density 0.924 g / cm ³ ).

[Comparative Polymer 5]
Production of linear low density polyethylene (ethylene / 1-hexene copolymer) having no long chain branching;
As an example of a normal linear low-density polyethylene having no long chain branching, metallocene 3 shown in Table 2 was used as a metallocene compound, and under the conditions other than those shown in Table 1, the examples of JP2012-214781A were used. Ethylene / 1-hexene vapor phase continuous copolymerization was carried out in the same manner as in the method for producing ethylene polymer (A-1) described in 1a (1). The results are shown in Tables 3 and 4.

[Film forming experiment]
(Examples 1 to 13, Comparative Examples 1 to 11)
The following film forming experiment was conducted in order to confirm the effect of modifying the other ethylene / α-olefin copolymer (B) by the ethylene / α-olefin copolymer (A) of the present invention.
The fact that the ethylene / α-olefin copolymer (A) of the present invention has excellent performance as a polyolefin-based resin modifier means that a predetermined amount of the copolymer of the present invention and the copolymer of the present invention, which are commercially available, are commercially available. The polyethylene-based resin composition obtained by blending with the ethylene-based polymer can be blown into an inflation film, and the physical properties of the film thus obtained can be measured.
That is, the above Production Examples 1 to 12, Comparative Polymers 1 to 5 and Reference Polymer 1 were prepared by using a commercially available ethylene-based polymer (UF230 manufactured by Japan Polyethylene Corporation; MFR = 1. 1 g / 10 min, density 0.921 g / cm ^3, ethylene / 1-butene copolymer) were blended under the conditions shown in Table 4, and inflation film molding was carried out under the above conditions. The blend ratio of the copolymer of the present invention to be blended with a commercially available ethylene-based polymer and the copolymer of the present invention, the tensile elastic modulus (unit MPa), and the dirt drop impact strength (DDI; unit g) of the obtained film are , As shown in Table 4.

(Discussion based on the results of Tables 2 to 4)
Among the ethylene / α-olefin copolymers of Table 3 produced by the catalyst of Table 2 and the polymerization conditions, the copolymers of Production Examples 1 to 9 belonging to the ethylene / α-copolymer having the specific physical properties of the invention of the present application Since the physical properties of the films (Examples 1 to 11) in which the polymer was blended with the ethylene polymer PE-3 and the catalyst components (A), (B) and (C) were the same, but the use ratios were different, Physical properties of films (Comparative Examples 1 to 3) using copolymers of Comparative Polymer 1 and Comparative Polymer 2 in which W ₂ + W ₃ do not satisfy the condition (5), and other catalyst component (X) are used. Comparative polymer 3 (Comparative Example 4), which is a non-invention copolymer produced, is a commercially available ethylene / α-olefin copolymer containing long chain branches but not the polymer (A) of the present invention. Films using certain Comparative Polymers 4 (Comparative Examples 5-7), commercially available The comparison between using using reference polymer 1 is a high-pressure low-density polyethylene film (Comparative Example 8-10) were carried out. FIG. 7 shows a plot of the elastic modulus and the impact strength obtained in each Example and Comparative Example for the blend ratios of the copolymers of 5, 10, 20% and 30%.
The balance between the tensile elastic modulus and the impact strength of the film of the example is extremely better than that of the comparative example, and it will be understood that the resin composition of the present invention is superior. Similarly, the balance of the tensile elastic modulus and impact strength of the film obtained by blending a smaller amount of 10% of the copolymer of the above Production Example belonging to the present invention was the same amount of the copolymer of Comparative Polymer 1. It exceeds that of Comparative Example 2, and is almost the same as Comparative Example 1 and Comparative Example 3 in which the copolymer of Comparative Polymer 1 or Comparative Polymer 2 was used in a larger amount of 20% in spite of a small blending amount of 10%. The superiority of the copolymer of the present invention is also apparent by exhibiting the performance of 1.

  Further, the copolymer of Comparative Polymer 4 showed only a modification effect equal to or less than that of the copolymer of Comparative Example 1, and the tensile modulus and impact of the ethylene polymer PE-3 before modification were Although the balance of strength was slightly improved, even if the blending amount was increased, almost no improvement in impact strength was observed as in the example. From this it will be understood that none of the other copolymers are comparable to the copolymers of the invention.

Next, a film obtained by a method of blending high-pressure radical polyethylene as a modifier, which is well known as a practical method for improving the blown film molding processing characteristics of the ethylene polymer PE-3, By comparing the physical properties of the films blended with the copolymer according to the present invention, it is shown that the copolymer of the present invention has utility as a modifier.
That is, in Comparative Examples 8 to 10, ethylene-based polymer PE-3 was blended with commercially available high-pressure polyethylene to 0%, 10%, and 15% to form films. The film formability of Run 10 in which 15% of high-pressure polyethylene was blended was almost the same as in Examples 1, 4, and 6-8 in which 20 to 30% of the copolymer of the present invention was blended (melt tension was almost the same. However, the tensile elastic modulus and impact strength of the film were the same as those of Comparative Example 8 which is an ethylene-based polymer PE-3 alone film. However, the impact strength obtained by using the copolymer of the present invention cannot be significantly improved. Therefore, the resin composition of the present invention has made it possible to provide an excellent method for obtaining an ethylene-based film that has not been obtained by the conventional modification method.

  From the above, the rationality and significance of the constitutional requirements of the present invention and the superiority of the present invention over the prior art are apparent.

<Experimental example B>
[Example B-1]
(1) Synthesis of Bridged Cyclopentadienylindenyl Compound The same dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride as in Experimental Example A above was used.
(2) Synthesis of Olefin Polymerization Catalyst Under a nitrogen atmosphere, 30 g of silica calcined 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. Under a nitrogen atmosphere, a separately prepared 200 ml two-necked flask was charged with 412 mg of dimethylsilylene (4- (4-trimethylsilyl-phenyl) -indenyl) (cyclopentadienyl) zirconium dichloride synthesized in (1) above and dehydrated toluene. After dissolving with 80.7 ml, 78.9 ml of 20% methylaluminoxane / toluene solution manufactured by Albemarle was further added at room temperature, and the mixture was stirred for 30 minutes. A toluene solution of the reaction product of the zirconocene complex and methylaluminoxane was added in total while heating and stirring a 500 ml three-necked flask containing a toluene slurry of silica in an oil bath at 40 ° C. After stirring at 40 ° C. for 1 hour, the mixture was allowed to stand still for 15 minutes while heating at 40 ° C. to remove 221 ml of the supernatant, and dehydrated hexane was added to stir, settle and remove the supernatant. After substituting to 3% or less, it was distilled off under reduced pressure to obtain a powdery catalyst.
(3) Treatment of Olefin Polymerization Catalyst Under a nitrogen atmosphere, 32 g of the powdered catalyst obtained in (2) above was placed in a 500 ml three-necked flask, and 195 ml of dehydrated hexane and dehydrated liquid paraffin (trade name: Moresco). A mixture of 180 g of White P-120) was added at room temperature and stirred for 10 minutes, and then the solvent was distilled off under reduced pressure at room temperature until the hexane content in the solvent became 5% or less, to obtain a slurry catalyst.
(4) Production of ethylene / 1-hexene copolymer Ethylene / 1-hexene vapor phase continuous copolymerization was performed using the slurry catalyst obtained in (3) above. That is, 0.027 g / hour of the powdery catalyst in a gas phase continuous polymerization apparatus prepared at a temperature of 85 ° C., a hexene / ethylene molar ratio of 0.43%, a hydrogen / ethylene molar ratio of 0.52% and an ethylene pressure of 1.5 MPa. Polymerization was carried out while the gas composition and temperature were kept constant while intermittently supplying at a rate of. Further, in order to maintain cleanliness in the system, triethylaluminum (TEA) was supplied to the gas circulation line at 0.04 mmol / hr. As a result, the average production rate of the produced polyethylene was 180 g / hour (average residence time 10 hours). The MFR and density of the ethylene / 1-hexene copolymer obtained after the cumulative production of polyethylene of 5 kg or more were 0.36 g / 10 min and 0.921 g / cm ³ , respectively. The physical properties are shown in Table 2 and the results are shown in Table 3.
For the evaluation, 1000 ppm of antioxidant (Sumitomo Chemical's Sumilizer GP) was added to the polymer and extruded at a extrusion temperature of 180 ° C using a single-screw extruder (Union Plastics' USV 30φ extruder). Pelletized. (Hereinafter, the polymer obtained in this Production Example is referred to as "mLCB")

[Comparative Example Row 1]
Using low-density polyethylene (LF240 manufactured by Japan Polyethylene Co., Ltd .; density 0.924 g / cm ³ , MFR 0.7 g / 10 min, hereinafter also referred to as “LDPE”) produced by the high-pressure method, as in Example 1. The material properties and moldability were evaluated. The physical properties are shown in Table 5 and the results are shown in Table 6.
[Comparative example row 2]
Commercially available ethylene / α-olefin copolymer having long-chain branching (CU5001 manufactured by Sumitomo Chemical Co., Ltd .; density: 0.922 g / cm ³ , MFR: 0.3 g / 10 minutes; hereinafter also referred to as “other LCB”) Was used to evaluate the material properties and moldability in the same manner as in Example 1. The physical properties are shown in Table 5 and the results are shown in Table 6.

[Film forming experiment]
The following film forming experiment was conducted in order to confirm the effect of modifying the other ethylene / α-olefin copolymer (B) by the ethylene / α-olefin copolymer (A) of the present invention.
The fact that the ethylene / α-olefin copolymer of the present invention has excellent performance as a polyethylene-based resin modifier means that a predetermined amount of the copolymer of the present invention and the non-invention of the copolymer of the present invention are commercially available. It can be shown by molding a polyethylene resin composition obtained by blending with a polymer into an inflation film and measuring the physical properties of the film thus obtained.

That is, the commercially available ethylene polymer (UF230 manufactured by Japan Polyethylene Co., Ltd .; MFR = 1.1 g / 10 min) produced by using the magnesium / titanium composite type Ziegler catalyst was used in Examples B-1 and B-2. , Density 0.921 g / cm ^3, ethylene / 1-butene copolymer), and blown film molding was carried out under the above conditions. The blend ratio of the copolymer of the present invention to be blended with a commercially available ethylene-based polymer and the copolymer of the present invention, the tensile elastic modulus (unit MPa), and the dirt drop impact strength (DDI; unit g) of the obtained film are , As shown in Table 6. Further, the relationship between the tensile elastic modulus and the dirt drop impact strength shown in Table 6 is shown in a graph in FIG.

  As shown in Tables 5 and 6 and FIG. 8 above, the ethylene / α-olefin copolymer of Example b-1 of the present invention satisfying the specific physical properties (1) to (5), which is a feature of the present invention. The film made of the polyethylene-based resin composition blended with (mLCB) improves both tensile elastic modulus and impact strength, whereas Comparative Example B-1 blended with conventional high-pressure low-density polyethylene (LDPE). Then, the impact strength is remarkably lowered due to the increase in the addition amount, while also in Comparative Example B-2 using a conventionally known long chain branching introduced ethylene / α-olefin copolymer (other LCB), The increase in the addition amount causes a decrease in impact strength, and the balance between the elastic modulus and the impact strength of the obtained film is not preferable.

<Example C>
The following is an example in which a film was molded according to the specifications suitable for a standing pouch sealant film and required physical properties were confirmed.
[Molding conditions for blown film]
An inflation film was formed and evaluated under the following forming conditions using an inflation film forming machine (forming apparatus) having the following 50 mmφ extruder.
Equipment: Inflation molding equipment Extruder Screw diameter: 50mmφ
Die diameter: 75mmφ
Extrusion rate:
32kg / hr when the thickness is 150μm
When the thickness is 130 μm, 27 kg / hr
22kg / hr for 100μm thickness
Die lip gap: 3.0mm
Collection speed: 8.0 m / min Blow-up ratio: 2.0
Molding resin temperature: 190 ℃
Film thickness: 150 μm, 130 μm, 100 μm
[Film evaluation method]
(1) Tensile modulus:
According to JIS K7127-1999, the tensile elastic modulus when the film was deformed by 1% in the processing direction (MD) and the width direction (TD) of the film was measured.
(2) Dirt drop impact strength (DDI)
It was measured according to the JIS K 7124 1 A method.
(3) Film Impact Using a film impact tester (FILM / IMPACT / TESTER: hereinafter simply referred to as “testing machine”) manufactured by Toyo Seiki Seisaku-sho, Ltd., the amount of work required for penetration breakage per unit film thickness was measured.
Specifically, the test film was stored in an atmosphere of 23 ° C.-50%, the condition was adjusted, and then the test film was fixed to a tester with a holder having a diameter of 500 mm, and then a 1/2 inch (about 13.0 mm The hemispherical metal of 4) was hit from the inner layer surface of the test film at the penetrating portion, and the work amount required for penetrating fracture was measured. At that time, the load was removed so that the maximum scale (work load) was 30 kg · cm. Then, a value obtained by dividing the work amount by the film thickness was defined as a film impact value.
[Example C-1 to C-6] Film Forming Experiment Commercially-produced ethylene / α-olefin copolymer (A) (mLCB) prepared in Example B-1 above with a magnesium / titanium composite type Ziegler catalyst. Ethylene polymer (UF230 manufactured by Nippon Polyethylene Co., Ltd .; MFR = 1.1 g / 10 min, density 0.921 g / cm ³ , ethylene / 1-butene copolymer), and blown into an inflation film under the above conditions. Was carried out. Examples C-1 to C-3 show examples in which the film thickness was changed to 150 μm, 130 μm, and 100 μm at the same blend ratio, and Examples C-4 to C-6 were similar at a blend ratio different from C-1. It is an example in which the film thickness is changed.
The blend ratio of the copolymer of the present invention to be blended with a commercially available ethylene-based polymer, the thickness of the obtained film, the tensile elastic modulus (MPa), the dirt drop impact strength (DDI; g), and the film impact are shown in the table. It was as shown in 8.
When molding the film, the following master batches were used.
KMB05S manufactured by Nippon Polyethylene Co., Ltd .: master batch of 5 wt% slip agent MBN560B manufactured by Japan Polyethylene Co., Ltd .: master batch of 20 wt% of anti-blocking agent [Comparative Examples C-1 to C-3].
Instead of the ethylene / α-copolymer (A), low-density polyethylene (LF240 manufactured by Nippon Polyethylene Co., Ltd .; density 0.924 g / cm ³ , MFR 0.7 g / 10 min) produced by a high pressure method is used. When used, the material properties and moldability were evaluated in the same manner as in Example C-1. The material properties are shown in Table 7, and the results are shown in Table 8.

［結果の考察］
上記実施例ハ−１〜３、実施例ハ−４〜６、比較例ハ−１〜ハ−３の結果で得られた、引張弾性率とフィルムインパクトの関係を示したグラフを図９として示す。
いずれもフィルム厚みが小さくなると引張弾性率とフィルムインパクト値が下がるが、実施例の樹脂組成物の方が、比較例の樹脂組成物に比べていずれも良好な引張弾性率とダート落下衝撃強度を有していることがわかる。

[Discussion of results]
FIG. 9 is a graph showing the relationship between the tensile elastic modulus and the film impact, obtained as a result of Examples C-1 to C-3, Example C-4 to C-6, and Comparative Examples C-1 to C-3. .
In both cases, when the film thickness becomes small, the tensile elastic modulus and the film impact value decrease, but the resin composition of the example shows good tensile elastic modulus and dirt drop impact strength as compared with the resin composition of the comparative example. You can see that it has.

Claims (10)

1 to 59% by weight of an ethylene / α-olefin copolymer (A) characterized by satisfying the following conditions (1) to (5) and one or more kinds of ethylene other than (A): A standing pouch sealant film obtained from a polyethylene-based resin composition, which comprises 99 to 41% by weight of an α-olefin copolymer (B) .
(1) MFR is more than 0.1 g / 10 min and 10 g / 10 min or less (2) Density is 0.895 to 0.940 g / cm ³ (3) By gel permeation chromatography (GPC) The measured molecular weight distribution Mw / Mn is 3.0 to 5.5. (4) The molecular weight of the branching index g'measured by a GPC measuring device in which a differential refractometer, a viscosity detector and a light scattering detector are combined. The minimum value (gc) between 10,000 and 1,000,000 is 0.40 to 0.85 (5) The elution amount obtained from the integrated elution curve measured by cross fractionation chromatography (CFC) is 50 wt%. Of a component having a molecular weight of not less than the weight average molecular weight (W ₂ ) among components that elute at a temperature equal to or lower than the above The sum (W ₂ + W ₃ ) of the proportions (W ₃ ) of the components having a molecular weight of less than the weight average molecular weight is more than 40% by weight and less than 56% by weight. The standing pouch sealant film according to claim 1, wherein the ethylene / α-olefin copolymer (A) further satisfies the following condition (6) .
(6) The proportion (W ₄ ) of the components having a molecular weight of not less 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 integrated elution curve measured by W ₂ and CFC becomes 50 wt%. The sum (W ₂ + W ₄ ) is more than 25% by weight and less than 50% by weight. The standing pouch sealant film according to claim 1 or 2, wherein the ethylene / α-olefin copolymer (A) further satisfies the following condition (7) .
(7) the difference between the _{W 2} and _{W 4 (W} 2 -W ₄₎ is greater than 0 wt%, less than 20 wt% 4. The standing pouch sealant film according to any one of claims 1 to 3, wherein the ethylene / α-olefin copolymer (A) further satisfies the following condition (8) .
(8) The proportion (X) of components that elute at 85 ° C. or higher by temperature rising elution fractionation (TREF) is 2 to 15% by weight. The α-olefin of the ethylene / α-olefin copolymer (A) has 3 to 10 carbon atoms, and the sealant film for a standing pouch according to any one of claims 1 to 4 . The standing pouch according to any one of claims 1 to 5, wherein the ethylene / α-olefin copolymer (B) satisfies the following conditions (B-1) and (B-2). Sealant film for.
(B-1) MFR is 0.01 to 20 g / 10 minutes. (B-2) Density is 0.880 to 0.970 g / cm ³ . The standing pouch sealant film according to any one of claims 1 to 6, wherein the ethylene / α-olefin copolymer (B) further satisfies the following condition (B-2 ') .
(B-2 ′) density is 0.890 to 0.940 g / cm ³ . The standing pouch sealant film according to any one of claims 1 to 7, wherein the ethylene / α-olefin copolymer (B) further satisfies the following condition (B-3) .
(B-3) The molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC) is 2.0 to 5.0. 9. The ethylene / α-olefin copolymer (A) and the ethylene / α-olefin copolymer (B) satisfy any one or more of the following conditions. The sealant film for a standing pouch as described in 1 above .
(AB-1) MFR _B > MFR _A
(AB-2) [Mw / Mn] _B <[Mw / Mn] _A
(In the formula, MFR _A and [Mw / Mn] _A represent the MFR of the ethylene / α-olefin copolymer (A) and the molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC), respectively, MFR _B and [Mw / Mn] _B represent the MFR of the ethylene / α-olefin copolymer (B) and the molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC), respectively.) The ethylene / α-olefin copolymer (B) is a Ziegler linear low density polyethylene having an MFR of 0.1 to less than 5.0, or a metallocene polyethylene having an MFR of 0.1 to 10 or less. The standing pouch sealant film according to any one of claims 1 to 9 .

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