JP2015010103A - Ethylene-based polymer composition, extrusion-laminated film, and packaging bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene-based polymer composition which has excellent processing properties (such as neck-in (shrinkage) resistance, tear resistance and surge resistance) when subjected to injection molding and from which an extrusion-laminated film, which has high seal strength and is excellent in boiling water resistance, content resistance and low-temperature sealability, or the like can be produced.SOLUTION: The ethylene-based polymer composition contains an ethylene-C4-10 α-olefin copolymer satisfying required items I)-VII) and another ethylene-C4-10 α-olefin copolymer satisfying required items 1)-3). The required item I) is that MFR=0.01-30 g/10 minutes. The required item II) is that the density is 890-970 kg/m. The required item III) is that MT/η=1.00×10-9.00×10. The required item IV) is that ((Me branches+Et branches)/1000C))≤1.80. The required item V) is that η/Mw=0.03×10-7.50×10. The required item VI) is that peak top M=1.0×10-1.0×10. The required item VII) is that η/Mw=0.80×10-1.65×10. The required item 1)is that MFR=7.0-30 g/10 minutes. The required item is that the density is 880-915 kg/m. The required item 3) is that η/Mw=1.90×10-2.80×10.

Description

  The present invention relates to an ethylene polymer composition and the like, and more particularly to an ethylene polymer composition suitable for uses such as an extruded laminate film and a packaging bag for storing liquid.

  For packaging liquids and mucilages, and liquids and mucilages containing solids such as fibers and powders as insoluble substances, an intermediate layer is laminated on the base film as necessary, and a sealant layer is further formed thereon. A laminated film obtained by laminating is used. As such a laminated film, a film made of polypropylene resin, polyamide resin, polyethylene terephthalate resin, paper, aluminum foil or the like is used as a surface base material, and a sealant layer is provided thereon, and the heat sealability of this sealant layer is improved. Films that use and package are known.

  As resins used for this sealant layer, ethylene / C4-10α-olefin random copolymer (hereinafter also referred to as “LLDPE”) having specific physical properties and high-pressure low-density polyethylene (hereinafter referred to as “HPLD”). (Abbreviated)) has been proposed.

  The food packaged using the above laminated film may be subjected to heat treatment (boil treatment) after packaging to ensure its hygiene, and the heating temperature at that time is year after year to cope with various bacteria. It tends to be high, and the packaging film is required to have heat resistance. Moreover, since many foods contain not only moisture but also oil, content resistance typified by oil resistance is also required.

  On the other hand, the rate at which food is packaged in order to reduce costs tends to increase year by year, so that it is possible to perform sealing with a small amount of heat, that is, sealing properties at low temperatures. In addition, cost reduction at the stage of film production is also required, and many laminated films are often subjected to extrusion lamination processing, so that the neck-in of the molten film of the extruded resin is small, and further, surging surging and It is required that the melted film called no sag occurs.

  With regard to such a laminated film, Patent Documents 1 and 2 disclose a composition containing specific LLDPE and HPLD, and by using this composition, liquid can be filled at a high speed with a wide range of sealing temperatures from low to high. There is a description that a simple film can be manufactured. Patent Document 3 proposes a film that improves the leakage of contents by improving the seal strength. Patent Document 4 describes a film using a composition containing long-chain branched LLDPE and HPLD. Patent Document 5 describes that a container formed from a film containing long-chain branched LLDPE is excellent in film strength and seal strength. Patent Document 6 discloses an ethylene / α-olefin copolymer having specific physical properties or a composition containing the same, a film obtained by extrusion lamination molding of these, a bag using the film as a sealant, and the like. Has been.

JP 2006-321986 A JP 2007-204628 A Japanese National Patent Publication No. 11-513345 JP 2004-115663 A JP 2012-207150 A JP 2009-197225 A

However, with conventional laminated films, it has been difficult to satisfy all of the film processability, boil resistance, low temperature sealability, and content resistance (including oil resistance) at the same time.
For example, Patent Documents 1 and 2 do not describe the resistance of the film to oil and the resistance to boil processing. Since the films of Patent Documents 1 and 2 contain HPLD, they are considered to be inferior in oil resistance.

  The film of the specific example of patent document 3 is an inflation film, and since an antiblocking agent and a slip agent are required, the filling property in the case of a low temperature seal is not enough. Moreover, there is no description about the tolerance to boil processing.

Since the film of patent document 4 contains HPLD, it is thought that it is inferior to oil resistance similarly to the film of patent documents 1 and 2.
Resistance to contents such as oil in the container of Patent Document 5 and resistance to boil processing are unknown. Further, although the composition has excellent sealing strength and film strength, it is presumed that the motor load and the resin pressure become high and extrusion lamination cannot be performed because the composition has an extremely low MFR.

  Further, the oil resistance and the like of a film formed by extrusion lamination from an ethylene / α-olefin copolymer described in Patent Document 6 is also unknown. Furthermore, since the sealing layer does not have a wide melting point distribution, it is presumed that this container is not sufficiently resistant to boil processing while maintaining a low temperature sealing property.

  The present invention has been made in view of such problems in the prior art, has excellent processing characteristics during extrusion molding (neck-in resistance, film breakage resistance, surging resistance), high sealing strength, Provided is a resin composition capable of producing an extruded laminated film or packaging bag having excellent boil resistance, excellent content resistance (water resistance, oil resistance), excellent low-temperature sealability (high hot tack strength). For the purpose.

The ethylene-based polymer composition (γ) of the present invention is
An ethylene copolymer (α) that is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms and simultaneously satisfies the following requirements (I) to (VII):
A copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms which simultaneously satisfies the following requirements (1) to (3):
The weight fraction [Wα] of the ethylene polymer (α) is 0.01 or more and 0.99 or less, and the weight fraction [Wβ] of the ethylene polymer (β) is 0.01 or more and 0.99. The ethylene-based polymer composition is as follows (the sum of Wα and Wβ is 1.00).

Requirements for ethylene polymer (α):
(I) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 0.01 g / 10 min or more and 30 g / 10 min or less.
(II) The density (d) is 890 kg / m ³ or more and 970 kg / m ³ or less.
(III) The ratio [MT / η ^* (g / P)] of the melt tension [MT (g)] at 190 ° C. and the shear viscosity [η * (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec. It is 1.00 × 10 ⁻⁴ or more and 9.00 × 10 ⁻⁴ or less.
(IV) Sum of methyl branch number [Me (/ 1000C)] and ethyl branch number [Et (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR [(Me + Et) (/ 1000C )] Is 1.80 or less.
(V) Ratio of zero shear viscosity at 200 ° C. [η ₀ (P)] and weight average molecular weight measured by GPC-viscosity detector method (GPC-VISCO) to the 6.8th power (Mw ^6.8 ), η ₀ / Mw ^6.8 is 0.03 × 10 ⁻³⁰ or more and 7.5 × 10 ⁻³⁰ or less.
(VI) The molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is 1.0 × 10 ^4.30 or more and 1.0 × 10 ^4.50 or less.
(VII) Intrinsic viscosity measured in decalin at 135 ° C. [[η] (dl / g)] and weight average molecular weight measured by GPC-viscosity detector method (GPC-VISCO) to the 0.776th power (Mw ^0.776 ), [Η] / Mw ^0.776 is 0.80 × 10 ⁻⁴ or more and 1.65 × 10 ⁻⁴ or less.

Requirements for ethylene polymer (β):
(1) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 7.0 g / 10 min or more and 30 g / 10 min or less.
(2) The density (D) is 880 kg / m ³ or more and 915 kg / m ³ or less.
(3) Intrinsic viscosity [[η] (dl / g)] measured in 135 ° C. decalin and 0.776 of the weight average molecular weight measured by GPC-viscosity detector method (GPC-VISCO) (Mw ^0.776 ) Ratio [η] / Mw ^0.776 is 1.90 × 10 ⁻⁴ or more and 2.80 × 10 ⁻⁴ or less.
The ethylene polymer (β) preferably further satisfies the following requirements (4) to (6).

(4) The ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight measured by GPC is 1.50 or more and 3.00 or less.
(5) In the elution curve obtained by temperature rising elution fractionation (TREF), the ratio of the peak height (H) with the strongest peak intensity to the width (W) at half the peak height (H) / W) and the density (D) (kg / m ³ ) satisfy the following relational expression (Eq-5-1).
0.0163 x D-14.10 ≤ Log ₁₀ (H / W) ≤ 0.0163 x D-13.40 (Eq-5-1)

(6) Sum of the number of methyl branches [Me (/ 1000C)] and the number of ethyl branches [Et (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR [(Me + Et) (/ 1000C )] Is 1.80 or less.

The ethylene polymer composition (γ) of the present invention may further contain a thermoplastic resin that is neither the ethylene polymer (α) nor the ethylene polymer (β).
The extruded laminate film of the present invention is a film having a base film and an ethylene copolymer composition layer obtained by extrusion laminating the ethylene polymer composition (γ) of the present invention to the base film. is there.

The packaging bag of the present invention is a packaging bag formed from the extruded laminate film of the present invention.
A preferred embodiment of the packaging bag of the present invention is a packaging bag for containing a liquid, the packaging bag in which the contact surface with the liquid is the ethylene polymer composition layer, and the extruded laminated film as the ethylene Folding the copolymer composition layers to face each other, heat-sealing a part of the ethylene copolymer composition layers, and forming the two extruded laminate films into the ethylene copolymer Examples thereof include a packaging bag formed by overlapping the composition layers so as to face each other and heat-sealing a part of the ethylene copolymer composition layers.

  The ethylene polymer composition (γ) of the present invention is excellent in processing characteristics (neck-in resistance, film breakage resistance, surging resistance) during extrusion molding, and is formed from the ethylene polymer composition (γ). Extruded laminated films or packaging bags have high sealing strength, excellent boil resistance, excellent content resistance (water resistance, oil resistance), and excellent low temperature sealing properties (high hot tack strength). .

  Hereinafter, the ethylene polymer composition (γ) and its use according to the present invention will be specifically described together with the ethylene polymer (α) and the ethylene polymer (β) which are constituent components thereof.

<Constituents>
Ethylene polymer (α);
The ethylene polymer (α) used in the present invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 6 to 10 carbon atoms. When using an α-olefin having 4 carbon atoms, it is preferable to also use an α-olefin having 6 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.
The ethylene polymer (α) has the characteristics shown in the following requirements (I) to (VII).

Requirement (I);
The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 0.1 g / 10 min or more and 30 g / 10 min or less. The lower limit is preferably 0.3 g / 10 minutes, more preferably 0.5 g / 10 minutes, and the upper limit is preferably 25 g / 10 minutes, more preferably 20 g / 10 minutes. When the melt flow rate (MFR) is not less than the above lower limit, the shear viscosity is not too high in the ethylene polymer composition (γ), and the extrusion characteristics and thin film processability are good. When the melt flow rate (MFR) is not more than the above upper limit, the ethylene polymer composition (γ) has good mechanical strength such as tensile strength and heat seal strength, and is excellent in neck-in resistance.

  The melt flow rate (MFR) strongly depends on the molecular weight. The smaller the melt flow rate (MFR), the larger the molecular weight, and the larger the melt flow rate (MFR), the smaller the molecular weight. In addition, it is known that the molecular weight of an ethylene polymer is determined by the composition ratio (hydrogen / ethylene) of hydrogen and ethylene in the polymerization system (for example, Kazuo Soga et al., “Catalytic Olefin Polymerization”, Kodansha Scientific, 1990, p.376). For this reason, it is possible to increase / decrease the melt flow rate (MFR) of an ethylene-type polymer ((alpha)) by increasing / decreasing hydrogen / ethylene.

Melt flow rate (MFR) is measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89.
The MFR for the ethylene polymer (α) may be described as “MFRα” for the purpose of distinguishing from the MFR for the ethylene polymer (β) described later.

Requirement (II);
The density is 890 kg / m ³ or more and 970 kg / m ³ or less. The lower limit is preferably 900 kg / m ^3, more preferably 905 kg / m ^3, the upper limit is preferably 964kg / m ^3, more preferably 940 kg / m ^3, particularly preferably a 935 kg / m ^3. When the density is not less than the above lower limit, the film formed from the ethylene polymer composition (γ) has less surface stickiness and excellent blocking resistance, and the packaging bag formed from the ethylene polymer composition (γ) is voile resistant. Excellent in properties. When the density is less than or equal to the above upper limit value, the film formed from the ethylene polymer composition (γ) has good impact strength, mechanical strength such as heat seal strength and bag breaking strength, and low temperature seal. Excellent in properties.

  The density depends on the α-olefin content of the ethylene polymer. The smaller the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. Further, it is known that the α-olefin content in an ethylene polymer is determined by the composition ratio of α-olefin and ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p.606 (1992)). For this reason, the ethylene polymer which has the density of the said range can be manufactured by increasing / decreasing (alpha) -olefin / ethylene.

  The density can be measured by a density gradient tube method after the strand obtained at the time of MFR measurement is heat-treated at 100 ° C. for 1 hour and further left at room temperature for 1 hour in accordance with JIS K7112.

Requirement (III);
The ratio [MT / η ^* (g / P)] of the melt tension [MT (g)] at 190 ° C. to the shear viscosity [η ^* (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec is 1.00. × 10 ⁻⁴ or more and 9.00 × 10 ⁻⁴ or less. That is, in the ethylene polymer (α) used in the present invention, MT and η ^* are represented by the following formula (Eq-III):
1.00 × 10 ^-4 ≦ MT / η ^* ≦ 9.00 × 10 ^-4 -------- (Eq-III)
Meet. Here, the upper limit is preferably 8.00 × 10 ⁻⁴ , more preferably 7.00 × 10 ⁻⁴ .

[MT / η ^* (g / P)] indicates the melt tension per unit shear viscosity. When this value is large, the melt tension increases with respect to the shear viscosity.
[MT / η ^* (g / P)] is considered to depend on the long chain branching content of the ethylene polymer, and the larger the long chain branching content, the larger [MT / η ^* (g / P)]. [MT / η ^* (g / P)] tends to decrease as the long chain branching content decreases.

It is generally known that there is a correlation between melt tension and neck-in and drawdown (Masayoshi Araki, latest laminating manual, processing technology workshop, 1989, p.266-p.267).
Melt tension tends to increase as the molecular weight (shear viscosity) increases. In extrusion laminate molding, the balance between extrudability, neck-in resistance, and draw-down resistance is important. Resins with high tension are preferred. In addition to molecular weight (shear viscosity), the content of long chain branching can be cited as an example of increasing the melt tension, and [MT / η ^* (g / P)] depends on the long chain branching content of the ethylene polymer. [MT / η ^* (g / P)] increases as the long-chain branch content increases, and [MT / η ^* (g / P)] decreases as the long-chain branch content decreases. Therefore, in the ethylene polymer composition (γ) of the present invention containing the ethylene polymer (α), [MT / η ^* (g / P)] of the ethylene polymer (α) is not less than the above lower limit value. Therefore, in comparison with the composition containing an ethylene polymer that does not satisfy the requirement (III) and has the same shear viscosity instead of the ethylene polymer (α), it has excellent neck-in resistance, and [MT / η ^* (G / P)] is not more than the above upper limit value, and therefore has excellent drawdown resistance (surging resistance).

  Here, long-chain branching is defined as a branched structure having a length equal to or greater than the molecular weight (Me) between the entanglement points contained in the ethylene-based polymer. By introducing long-chain branching, the melt properties of the ethylene-based polymer, and molding It is known that processability changes significantly (for example, Kazuo Matsuura et al., “Polyethylene Technology Reader”, Industrial Research Committee, 2001, p. 32, 36).

As will be described later, the ethylene-based polymer (α) is composed of ethylene and α 4 -C 10 in the presence of an olefin polymerization catalyst comprising the component (A), the component (B), and the component (C). It can be produced by polymerizing olefins. In the mechanism in which the ethylene polymer (α) is produced, the present inventors are present in the presence of a catalyst component for olefin polymerization containing components (A) and (C), and optionally component (S). A terminal vinyl having a number average molecular weight of about 4000 to 20000, preferably 4000 to 15000 by polymerizing ethylene or ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 4 to 10 carbon atoms. And then a catalyst component for olefin polymerization containing component (B) and component (C) and optionally component (S) to produce ethylene and a carbon number of 4 to By copolymerizing the macromonomer competitively with the polymerization of 10 α-olefin, long chain branching is generated in the ethylene polymer (α). I believe. The long chain branching content in the ethylene polymer (α) depends on the composition ratio ([macromonomer] / [ethylene]) of the macromonomer and ethylene in the polymerization system, and [macromonomer] / [ethylene ] Is higher, the long chain branching content in the ethylene polymer is increased. Since the ratio of component (A) in the olefin polymerization catalyst ([A] / [A + B]) can be increased, [macromonomer] / [ethylene] can be increased, so [A] / [A + B] By increasing or decreasing, an ethylene polymer (α) having MT / η ^* in the above range can be produced.

The value of melt tension (MT) is measured by the following method or an equivalent method.
Melt tension (MT) is determined by measuring the stress when the molten polymer is stretched at a constant rate. Capillary rheometer manufactured by Toyo Seiki Seisakusho Co., Ltd .: Capillograph 1B, resin temperature 190 ° C., melting time 6 minutes, barrel diameter 9.55 mmφ, extrusion speed 15 mm / min, take-up speed 24 m / min (if the molten filament breaks) In this case, the winding speed is decreased by 5 m / min), the nozzle diameter is 2.095 mmφ, and the nozzle length is 8 mm.

Also, 200 ° C., the angular velocity 1.0 rad / shear viscosity in seconds (eta ^*) is the angular velocity of the shear viscosity at a measurement temperature of 200 ° C. (eta ^*) [omega (rad / sec)] dispersed 0.01 ≦ ω ≦ 100 Measure in the range of. For the measurement, an Anton Paar viscoelasticity measuring device Physica MCR301 or an equivalent device is used. The sample holder uses a 25 mmφ parallel plate and the sample thickness is about 2.0 mm. The number of measurement points is 5 points per ω digit. The amount of strain is appropriately selected within a range of 3 to 10% so that the torque in the measurement range can be detected and torque is not exceeded. The sample used for the measurement of the shear viscosity uses a molding machine (for example, a press molding machine manufactured by Shinto Metal Industry), preheating temperature 190 ° C., preheating time 5 minutes, heating temperature 190 ° C., heating time 2 minutes, heating pressure 100 kgf / It is prepared by press-molding the measurement sample to a thickness of 2 mm under the conditions of cm ² , cooling temperature 20 ° C., cooling time 5 minutes, and cooling pressure 100 kgf / cm ² .

Requirement (IV);
The sum [(Me + Et) (/ 1000C)] of the number of methyl branches [Me (/ 1000C)] per 1000 carbon atoms and the number of ethyl branches [Et (/ 1000C)] measured by ¹³ C-NMR is 1.80 or less, preferably 1.30 or less, more preferably 0.80 or less, and even more preferably 0.50 or less. The number of methyl branches and the number of ethyl branches defined in the present invention are defined by the number per 1000 carbons as described later.

  If there are short chain branches such as methyl branch and ethyl branch in the ethylene-based polymer, the short chain branch is incorporated into the crystal and the interplanar spacing of the crystal widens, which may reduce the mechanical strength of the resin. It is known (eg, supervised by Zenjiro Osawa et al., “Technology for predicting and extending the life of polymers”, NTS Corporation, 2002, p. 481). Therefore, when the sum of the number of methyl branches and the number of ethyl branches (Me + Et) is 1.80 or less, the mechanical strength and seal strength of the ethylene polymer composition (γ) are good. Moreover, since the packaging bag formed from the ethylene polymer composition (γ) includes the ethylene polymer (α) that satisfies the requirement (IV), the packaging bag is excellent in content resistance such as oil resistance. When the sum of the number of methyl branches and the number of ethyl branches (Me + Et) is within the above range, a “tie molecule” that connects the crystals to each other is easily generated, and thus the ethylene polymer composition (γ) is used. In the film, crystals existing in the film are efficiently connected. Since the film breakage is supposed to occur when the crystal is torn, the connection between the crystals increases the film strength and the seal strength. The failure of the seal part due to oil is thought to be caused by the oil soaking in between the crystals and tearing off the connection of the crystals, so there is a strong connection between the crystals due to the presence of tie molecules. It is estimated that the oil resistance is improved.

  The number of methyl branches and the number of ethyl branches in the ethylene polymer depend strongly on the polymerization method of the ethylene polymer, and the ethylene polymer obtained by high-pressure radical polymerization is obtained by coordination polymerization using a Ziegler type catalyst. The number of methyl branches and the number of ethyl branches are larger than the obtained ethylene polymer. In the case of coordination polymerization, the number of methyl branches and the number of ethyl branches in the ethylene polymer strongly depend on the composition ratio of propylene, 1-butene and ethylene (propylene / ethylene, 1-butene / ethylene) in the polymerization system. To do. For this reason, it is possible to increase / decrease the sum (Me + Et) of the number of methyl branches and the number of ethyl branches of an ethylene-type polymer by increasing / decreasing 1-butene / ethylene.

^The number of methyl branches and the number of ethyl branches measured by ¹³ C-NMR can be determined as follows.
The measurement is performed using an ECP500 type nuclear magnetic resonance apparatus ( ¹ H: 500 MHz) manufactured by JEOL Ltd. at a total number of 10,000 to 30,000. The main chain methylene peak (29.97 ppm) is used as the chemical shift standard. In a commercial NMR measurement quartz glass tube having a diameter of 10 mm, 3 ml of a mixed solution of 250 to 400 mg of sample and special grade o-dichlorobenzene manufactured by Wako Pure Chemical Industries, Ltd .: benzene-d6 = 5: 1 (volume ratio) manufactured by ISOTEC Is carried out by heating at 120 ° C. and uniformly dispersing. The attribution of each absorption in the NMR spectrum is as follows: Chemical Domain No. 141 NMR-Review and Experiment Guide [I], p. It carries out according to 132-133. The number of methyl branches per 1,000 carbons, that is, the number of methyl branches per 1000 carbon atoms constituting the polymer chain of the ethylene-based polymer is derived from methyl branches with respect to the integral sum of absorption appearing in the range of 5 to 45 ppm. It is calculated from the integrated intensity ratio of the methyl group absorption (19.9 ppm). The number of ethyl branches is calculated from the ratio of the integrated intensity of the absorption of ethyl groups (10.8 ppm) derived from ethyl branches to the integrated total of absorption appearing in the range of 5 to 45 ppm.

Requirement (V);
Zero shear viscosity [η ₀ (P)] at 200 ° C. and GPC-viscosity detector method (GP
The ratio η ₀ / Mw ^{6.8 of} the weight average molecular weight measured by C-VISCO to the 6.8th power (Mw ^6.8 ) is 0.03 × 10 ⁻³⁰ or more and 7.5 × 10 ⁻³⁰ or less. That is, in the ethylene polymer (α) used in the present invention, η ₀ and Mw are represented by the following formula (Eq-V-1)
0.03 × 10 ^-30 ≦ η ₀ / Mw ^6.8 ≦ 7.5 × 10 ^-30 -------- (Eq-V-1)
Meet. Here, the lower limit is preferably 0.05 × 10 ⁻³⁰ , more preferably 0.1 × 10 ⁻³⁰ , and the upper limit is preferably 6.0 × 10 ⁻³⁰ , more preferably 5.0 × 10 ⁻³⁰ .

It eta ₀ / Mw ^6.8 is at 0.03 × 10 ^-30 over 7.5 × 10 ^-30 or less, upon log-log plot of the eta ₀ and Mw, log (η ₀₎ and logMw the following formula (the eq- It is synonymous with existing in the area specified in V-2).
6.8Log (Mw) -31.523 ≦ Log (η ₀ ) ≦ 6.8Log (Mw) -29.125 -------- (Eq-V-2)

When the zero-shear viscosity [η ₀ (P)] is plotted logarithmically with respect to the weight average molecular weight (Mw), the ethylene-based polymer having no long-chain branching and linear, and the extensional viscosity does not exhibit strain hardening is According to the power law with a slope of 3.4. On the other hand, an ethylene polymer having many relatively short long-chain branches and having an extensional viscosity exhibiting strain rate curability exhibits a zero shear viscosity [η ₀ (P)] lower than the power law, and its slope is It is known that the value is larger than 3.4 (C. Gabriel, H. Munstedt, J. Rheol., 47 (3), 619 (2003), H. Munstedt, D. Auhl, J. Non -Newtonian Fluid Mech. 128, 62-69, (2005)), slope 6.8 can be chosen empirically. Taking the ratio between η ₀ and Mw ^6.8 is also disclosed in Japanese Patent Laid-Open No. 2011-1545.

When the zero shear viscosity [η ₀ (P)] at 200 ° C. of the ethylene polymer (α) is 20 × 10 ⁻¹³ × Mw ^6.8 or less, the occurrence of take-up surging is suppressed in the ethylene polymer composition (γ). Is done.

The relationship between the zero shear viscosity [η ₀ (P)] and the weight average molecular weight (Mw) is considered to depend on the long chain branch content and the length of the long chain branch in the ethylene polymer. The greater the chain branch content and the shorter the long chain branch length, the closer the zero shear viscosity [η ₀ (P)] is to the lower limit of the above range. The smaller the long chain branch content, the longer the long chain branch. The longer the length, the zero shear viscosity [η ₀ (P)] is considered to show a value closer to the upper limit of the above range. As described above, the long chain branching content is increased by increasing the ratio ([A] / [A + B]) of the component (A) in the olefin polymerization catalyst. Further, in the ethylene polymer of the present invention, when the composition ratio of hydrogen and ethylene (hydrogen / ethylene) in the polymerization system is increased, the molecular weight of the macromonomer is decreased, so that a long chain introduced into the ethylene polymer. The length of the branch is shortened. From this, an ethylene polymer having zero shear viscosity [η ₀ (P)] in the above range can be produced by increasing or decreasing [A] / [A + B] and hydrogen / ethylene.

The zero shear viscosity [η ₀ (P)] at 200 ° C. is determined as follows or by an equivalent method.
The angular velocity [ω (rad / sec)] dispersion of the shear viscosity (η ^* ) at a measurement temperature of 200 ° C. is measured in the range of 0.02512 ≦ ω ≦ 100. For the measurement, a dynamic stress rheometer SR-5000 manufactured by Rheometrics is used. The sample holder was a 25 mmφ parallel plate, and the sample thickness was about 2.0 mm. The number of measurement points is 5 points per ω digit. The amount of strain is appropriately selected within a range of 3 to 10% so that the torque in the measurement range can be detected and torque is not exceeded. The sample used for the shear viscosity measurement is a press molding machine manufactured by Shinto Metal Industry, with a preheating temperature of 190 ° C., a preheating time of 5 minutes, a heating temperature of 190 ° C., a heating time of 2 minutes, a heating pressure of 100 kg weight / cm ² , and a cooling temperature. The measurement sample is prepared by press molding to a thickness of 2 mm under the conditions of 20 ° C., cooling time of 5 minutes and cooling pressure of 100 kg weight / cm ² .

The zero shear viscosity η ₀ is calculated by fitting the Carreau model of the following formula (Eq-V-3) to the measured rheological curve [angular velocity (ω) dispersion of shear viscosity (η ^* )] by the nonlinear least square method. .

ここで、λは時間の次元を持つパラメーター、ｎは材料の冪法則係数（power law index）を表す。なお、非線形最小二乗法によるフィッティングは下記数式（Eq-V-4）におけるｄが最小となるよう行われる。

Here, λ represents a parameter having a time dimension, and n represents a power law index of the material. The fitting by the nonlinear least square method is performed so that d in the following mathematical formula (Eq-V-4) is minimized.

ここで、η_exp（ω）は実測のせん断粘度、η_calc（ω）はCarreauモデルより算出したせん断粘度を表す。

Here, η _exp (ω) represents the measured shear viscosity, and η _calc (ω) represents the shear viscosity calculated from the Carreau model.

  The weight average molecular weight (Mw) by GPC-VISCO method is measured as follows using, for example, GPC / V2000 manufactured by Waters. The guard column uses Shodex AT-G, the analytical column uses two AT-806MS, the column temperature is 145 ° C., the mobile phase uses o-dichlorobenzene and BHT 0.3 wt% as an antioxidant, 1. The sample is moved at 0 ml / min, the sample concentration is 0.1% by weight, and a differential refractometer and 3-capillary viscometer are used as detectors. Standard polystyrene used was manufactured by Tosoh Corporation. In the molecular weight calculation, an actual viscosity is calculated from a viscometer and a refractometer, and a weight average molecular weight (Mw) is calculated from an actual universal calibration.

Requirement (VI);
The molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is 1.0 × 10 ^4.30 or more and 1.0 × 10 ^4.50 or less.

It is known that low molecular weight components have a strong influence on the mechanical strength of ethylene polymers. The presence of low molecular weight components is thought to decrease the mechanical strength due to an increase in molecular ends that are considered to be the starting point of destruction (edited by Kazuo Matsuura and Naotaka Mikami, “Polyethylene Technology Reader”, Inc. Industrial Research Committee, 2001, p.45). When the molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is 1.0 × 10 ^4.30 or more, there are few low molecular weight components that adversely affect the mechanical strength. A film formed from the ethylene polymer composition (γ) of the present invention containing the coalescence (α) is excellent in mechanical strength and sealing strength.

  It is known that the molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is determined by the composition ratio (hydrogen / ethylene) of hydrogen and ethylene in the polymerization system. (For example, Kazuo Soga et al., “Catalytic Olefin Polymerization”, Kodansha Scientific, 1990, p.376). Therefore, by increasing / decreasing hydrogen / ethylene, it is possible to increase / decrease the molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve.

  The molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve is calculated as follows using, for example, a gel permeation chromatograph alliance GPC2000 (high temperature size exclusion chromatograph) manufactured by Waters.

[Devices and conditions]
Analysis software: Chromatography data system Empower (Waters)
Column: TSKgel GMH ₆ -HT x 2 + TSKgel GMH _6- HTL x 2
(Inner diameter 7.5mm x length 30cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene (Wako Pure Chemicals special grade reagent)
Detector: Differential refractometer (built-in device)
Column temperature: 140 ° C
Flow rate: 1.0 mL / min Injection volume: 500 μL
Sampling time interval: 1 second Sample concentration: 0.15% (w / v)
Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation) / Molecular weight 495 ~ Molecular weight 20.6 million

A molecular weight distribution curve is prepared in terms of polyethylene molecular weight according to the general calibration procedure described in Z. Crubisic, P. Rempp, H. Benoit, J. Polym. Sci., B5 , 753 (1967). From this molecular weight distribution curve, the molecular weight (peak top M) at the maximum weight fraction is calculated.

Requirement (VII);
Ratio of intrinsic viscosity [[η] (dl / g)] measured in decalin at 135 ° C. to 0.776th power (Mw ^0.776 ) of weight average molecular weight measured by GPC-viscosity detector method (GPC-VISCO) [Η] / Mw ^0.776 is 0.80 × 10 ⁻⁴ or more and 1.65 × 10 ⁻⁴ or less. That is, in the ethylene polymer (α) used in the present invention, [η] and Mw are represented by the following formula (Eq-VII-1)
0.80 × 10 ^-4 ≦ [η] / Mw ^0.776 ≦ 1.65 × 10 ^-4 -------- (Eq-VII-1)
Meet. Here, the lower limit is preferably 0.85 × 10 ⁻⁴ , more preferably 0.90 × 10 ⁻⁴ , and the upper limit is preferably 1.55 × 10 ⁻⁴ , more preferably 1.45 × 10 ⁻⁴ .

  It is known that when long chain branching is introduced into an ethylene polymer, the intrinsic viscosity [η] (dl / g) is smaller for the molecular weight than a straight chain ethylene polymer without long chain branching. (For example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p.137 (1999)).

  Further, based on the Mark-Houwink-Sakurada equation, [η] of polyethylene is Mv to the 0.7th power, [η] of polypropylene is Mw to the 0.80th power, and [η] of poly-4-methyl-1-pentene is 0.81 of Mn. It has been reported to be proportional to the power (eg R. Chiang, J. Polym. Sci., 36, 91 (1959): P. 94, R. Chiang, J. Polym. Sci., 28, 235 (1958 ): P.237, AS Hoffman, BA Fries and PC Condit, J. Polym. Sci. Part C, 4, 109 (1963): P.119 Fig. 4).

  Then, as a typical index of a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, Mw is set to 0.776 power, and the molecular weight compared to the conventional ethylene polymer [η ] Is a requirement (VII) described above, and this idea is disclosed in International Publication WO2006 / 80578.

Therefore, since the ethylene polymer composition (γ) includes an ethylene polymer (α) having [η] / Mw ^0.776 equal to or less than the above upper limit and having a large number of long chain branches, the ethylene polymer ( It has excellent melt tension as compared with a composition containing an ethylene polymer that does not satisfy the requirement (VII) in place of α) and has the same MFR, and can suppress neck-in when producing a film by extrusion, In addition, it has excellent balance between high-speed moldability and resistance to drawdown. Further, since [η] / Mw ^{0.776 of} the ethylene-based polymer (α) is not less than the above lower limit value, it is considered that the film strength and the seal strength are not reduced due to the presence of ^excessive long chain branching. .

  Since the long chain branching content is increased by increasing the ratio ([A] / [A + B]) of the component (A) in the olefin polymerization catalyst as described above, [A] / [A + B ] Can be increased or decreased to produce an ethylene polymer (α) having an intrinsic viscosity [η] in the above range.

The intrinsic viscosity [η] (dl / g) is measured using a decalin solvent as follows.
About 20 mg of sample is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner. This dilution operation is further repeated twice, and the ηsp / C value when the concentration (C) is extrapolated to 0 is defined as the intrinsic viscosity [η]. (See the following formula (Eq-VII-2))
[Η] = lim (ηsp / C) (C → 0) --------- (Eq-VII-2)

Ethylene polymer (β);
The ethylene-based polymer (β) used in the present invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 6 to 10 carbon atoms. When using an α-olefin having 4 carbon atoms, it is preferable to also use an α-olefin having 6 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.

The ethylene polymer (β) has the characteristics shown in the following requirements (1) to (3).
Requirement (1);
The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 7.0 g / 10 min or more and 30 g / 10 min or less. Here, the lower limit is preferably 25 g / 10 minutes, and the upper limit is preferably 20 g / 10 minutes. When the melt flow rate (MFR) is at least the above lower limit, the ethylene polymer composition (γ) shear viscosity is not too high, and the extrudability and thin film processability are good. When the melt flow rate (MFR) is not more than the above upper limit, the tensile strength and heat seal strength of the ethylene polymer composition (γ) are good, and the neck-in and mechanical strength are excellent.
The MFR for the ethylene polymer (β) may be described as “MFRβ” for the purpose of distinguishing from the MFR for the ethylene polymer (α).

Requirement (2);
The density is 880 kg / m ³ or more and 915 kg / m ³ or less. The lower limit is preferably 885kg / m ^3, the upper limit is preferably 913kg / m ^3. When the density is not less than the above lower limit, the film formed from the ethylene polymer composition (γ) has less surface stickiness and excellent blocking resistance, and the packaging bag formed from the ethylene polymer composition (γ) is voile resistant. Excellent in properties. When the density is less than or equal to the above upper limit value, the film formed from the ethylene polymer composition (γ) has good impact strength, mechanical strength such as heat seal strength and bag breaking strength, and low temperature seal. Excellent in properties.

Requirement (3);
Ratio of intrinsic viscosity [[η] (dl / g)] measured in decalin at 135 ° C. to 0.776th power (Mw ^0.776 ) of weight average molecular weight measured by GPC-viscosity detector method (GPC-VISCO) [Η] / Mw ^0.776 is 1.90 × 10 ⁻⁴ or more and 2.80 × 10 ⁻⁴ or less. That is, in the ethylene polymer (β) used in the present invention, [η] and Mw are represented by the following formula (Eq-3-1)
1.90 × 10 ^-4 ≦ [η] / Mw ^0.776 ≦ 2.80 × 10 ^-4 -------- (Eq-3-1)
Meet.

[η] / Mw ^0.776 is 1.90 × 10 ⁻⁴ or more and 2.80 × 10 ⁻⁴ or less when logarithmic plotting of [η] and Mw is log ([η]) and log (Mw) It is synonymous with existing in the region defined by the following formula (Eq-3-2).

0.776Log (Mw) -3.721 ≦ Log ([η]) ≦ 0.776Log (Mw) -3.553 -------- (Eq-3-2)
As described above, when there is no long chain branching in the ethylene polymer, the intrinsic viscosity [η] (dl / g) may be larger for the molecular weight than the ethylene polymer having a long chain branch. Are known. Therefore, an ethylene polymer ^having [η] / Mw ^0.776 of 1.90 × 10 ⁻⁴ or more is a linear ethylene polymer substantially free of long chain branching. The ethylene polymer composition (γ) of the present invention containing such an ethylene polymer (β) does not have too high melt tension, and entanglement between molecules is likely to occur during melting by heat when performing heat sealing. Thus, sealing at a lower temperature becomes possible. The ethylene-based polymer composition (γ) is also excellent in low-temperature sealant performance because it also has high sealing strength.
The ethylene polymer (β) preferably further satisfies all of the following requirements (4) to (6) in addition to the above requirements (1) to (3).

Requirement (4);
The ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight measured by GPC is 1.50 or more and 3.00 or less. The lower limit is preferably 1.50, more preferably 1.60, and the upper limit is preferably 2.50, more preferably 2.20, and particularly preferably 2.10.

  The ethylene polymer composition (γ) of the present invention containing the ethylene polymer (β) is excellent in extrudability because Mw / Mn of the ethylene polymer (β) is not less than the above lower limit, and Mw / Mn Is less than the above upper limit value, it is difficult to dissolve in oil.

In the present invention, the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is measured using a GPC-150C manufactured by Waters as follows. The separation columns are TSKgel GMH6-HT and TSKgelGMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) ) And 0.025% by weight of BHT (Takeda Pharmaceutical) as the antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 μL, and the differential refraction as the detector A total was used. Standard polystyrenes are those manufactured by Tosoh Corporation for molecular weights of Mw ≦ 1000 and Mw ≧ 4 × 10 ⁶ , and those manufactured by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ . The molecular weight is universally calibrated and converted to polyethylene.

Requirement (5);
In the elution curve obtained by temperature rising elution fractionation (TREF), the ratio of the height (H) of the peak with the strongest peak intensity to the width (W) at half the height of the peak with the strongest peak intensity ( H / W) and the density (D (kg / m ³ )) satisfy the following relational expression (Eq-5-1), and preferably satisfy the following relational expression (Eq-5-2).
0.0163 x D-14.10 ≤ Log ₁₀ (H / W) ≤ 0.0163 x D-13.40 (Eq-5-1)
0.0163 x D-14.10 ≤ Log ₁₀ (H / W) ≤ 0.0163 x D-13.30 (Eq-5-2)

  In temperature rising elution fractionation (TREF), components with higher α-olefin content elute at lower temperatures, and components with lower α-olefin content elute at higher temperatures. H / W is the height (H) of the peak with the strongest peak intensity and the width (W) at half the height of the peak with the strongest peak in the elution curve obtained by temperature rising elution fractionation (TREF). Therefore, when compared with an ethylene polymer having the same density, the larger the H / W, the more uniformly the α-olefin is introduced into the molecular chain, and the composition distribution becomes narrower. For this reason, the ethylene polymer composition (γ) of the present invention containing the ethylene polymer (β) has less elution component and less oil when the H / W of the ethylene polymer (β) is not less than the lower limit. When the H / W is less than or equal to the above upper limit, the low-temperature melt component is not too small and the low-temperature sealability is excellent.

  The value of H / W can be adjusted by the method described in paragraph [0022] of Japanese Patent Application No. 2008-230068. The value of H / W can be determined by the procedure described in [0023] to [0025] of the publication.

Requirement (6);
The sum [(Me + Et) (/ 1000C)] of the number of methyl branches [Me (/ 1000C)] and the number of ethyl branches [Et (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR is 1.80 or less, preferably 1.30 or less, more preferably 0.80 or less, and even more preferably 0.50 or less. When the sum of the number of methyl branches and the number of ethyl branches (Me + Et) is not more than the above value, the mechanical strength of the ethylene polymer composition (γ) is good.

<Ethylene polymer composition (γ)>
The ethylene polymer composition (γ) according to the present invention is:
Including the ethylene polymer (α) and the ethylene polymer (β),
The total of the weight fraction [Wα] of the ethylene polymer (α) and the weight fraction [Wβ] of the ethylene polymer (β) is 1.00, and Wα is 0.01 or more and 0.99 or less. Wβ is 0.01 or more and 0.99 or less. Here, Wα is preferably 0.05 or more and 0.75 or less, more preferably 0.05 or more and 0.50 or less. Within this range, the balance between mechanical strength and moldability of the ethylene polymer composition (γ) is excellent.

  In addition, the ethylene polymer composition (γ) according to the present invention may be substantially composed of only the ethylene polymer (α) and the ethylene polymer (β). A thermoplastic resin that is not limited to the ethylene polymer (α) and the ethylene polymer (β), and is not the ethylene polymer (α) or the ethylene polymer (β). (Hereinafter also referred to as “other thermoplastic resin (ω)”). The ethylene polymer composition (γ) obtained as a thermoplastic resin composition by blending “other thermoplastic resin” with the ethylene polymer (α) and the ethylene polymer (β) is: Excellent moldability and mechanical strength. The blend ratio of the total of the ethylene polymer (α) and the ethylene polymer (β) to the “other thermoplastic resin (ω)” is the sum of ((α), (β) / (ω ) =) 99.9 / 0.1 to 0.1 / 99.9, preferably 99.0 / 1.0 to 1.0 / 99.0, more preferably 90/10 to 10/90.

Other thermoplastic resins (ω);
The “other thermoplastic resin (ω)” that can be blended in the ethylene polymer composition (γ) includes crystalline thermoplastic resins such as polyolefin, polyamide, polyester, and polyacetal; polystyrene, acrylonitrile / butadiene / styrene An amorphous thermoplastic resin such as a polymer (ABS), polycarbonate, polyphenylene oxide, or polyacrylate is used. Polyvinyl chloride is also preferably used.

  Specific examples of the polyolefin include ethylene polymers, propylene polymers, butene polymers, 4-methyl-1-pentene polymers, 3-methyl-1-butene polymers, hexene polymers, and the like. Is mentioned. Among these, an ethylene polymer, a propylene polymer, and a 4-methyl-1-pentene polymer are preferable. When the ethylene polymer is an ethylene polymer according to the present invention, the conventional ethylene Although it may be a polymer or an ethylene / polar group-containing vinyl copolymer, a conventional ethylene polymer is more preferred.

  Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycaprolactone, polyhydroxybutyrate, and the like.

  Specific examples of the polyamide include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46, and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. Can be mentioned.

  Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like. Among these, polyformaldehyde is particularly preferable.

The polystyrene may be a homopolymer of styrene, or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene.
The ABS includes a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and a structural unit derived from styrene. Is preferably used in an amount of 40 to 60 mol%.

  Examples of the polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl). ) A polymer obtained from butane or the like. Of these, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.

As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide) is preferably used.
As the polyacrylate, polymethyl methacrylate or polybutyl acrylate is preferably used.

The thermoplastic resins (ω) as described above may be used alone or in combination of two or more. A particularly preferable thermoplastic resin is polyolefin, and an ethylene polymer is more particularly preferable.
The melt flow rate (MFR) of other thermoplastic resin (ω) under a load of 2.16 kg at 190 ° C. is preferably 0.1 g / 10 min or more and 7.0 g / 10 min or less.

Other ingredients;
The ethylene-based polymer composition (γ) of the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent and a lubricant as long as the object of the present invention is not impaired. In addition, additives such as pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants may be further blended.

The total blending amount of these “other blending components” is generally 10 parts by weight or less, preferably 1 part by weight or less, more preferably 0.1 parts by weight, per 100 parts by weight of the ethylene polymer composition (γ). 5 parts by weight or less.
Next, the method for producing the ethylene polymer (α), the ethylene polymer (β) and the ethylene polymer composition (γ) in the present invention will be described.

<Method for producing ethylene polymer (α)>
The ethylene polymer (α) used in the present invention can be produced by polymerizing ethylene and an α-olefin having 4 to 10 carbon atoms in the presence of a catalyst for producing an ethylene polymer, which will be described later. .

In the present invention, a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a polymerization method such as a gas phase polymerization method is used, and a suspension polymerization method or a gas phase polymerization method is preferably used.
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methyl. And alicyclic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof. Moreover, alpha-olefin itself can also be used as a solvent.

Catalyst for producing ethylene polymer (α);
The ethylene-based polymer (α) of the present invention polymerizes ethylene and an α-olefin having 4 to 10 carbon atoms in the presence of a catalyst containing the component (A), the component (B) and the component (C). Can be manufactured efficiently.

The catalyst for producing an ethylene polymer (α) used in the present invention comprises a solid carrier (S) and a component (G) in addition to the components (A), (B) and (C) described below. May be included.
Each component used in the olefin polymerization catalyst will be described.

Component (A);
The component (A) that can be used in the present invention is a bridged metallocene compound represented by the following general formula (I).

一般式（Ｉ）中、Ｍは周期表第４族遷移金属原子を示し、具体的には、チタン、ジルコニウムおよびハフニウムから選ばれる遷移金属原子であり、好ましくはジルコニウムである。

In general formula (I), M represents a group 4 transition metal atom in the periodic table, specifically a transition metal atom selected from titanium, zirconium and hafnium, preferably zirconium.

R ^{1 to} R ⁸ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing Selected from a group and a tin-containing group, which may be the same or different from each other, but not all are hydrogen atoms at the same time. Moreover, R < ¹ > -R < ⁸ > may combine an adjacent group mutually and may form an aliphatic ring.

  Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an arylalkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, Examples include n-octyl group, nonyl group, dodecyl group, and eicosyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group. The aryl group includes phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, Tetrahydronaphthyl, indanyl and biphenylyl. Arylalkyl groups include benzyl, phenylethyl and phenylpropyl.

A preferable group for R ^{1 to} R ⁸ is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, more preferably, 6 or more of R ^{1 to} R ⁸ substituents are hydrogen atoms, particularly preferably. 7 of the substituents R ^{1 to} R ⁸ are hydrogen atoms, and the remaining one is an alkyl group having 3 to 15 carbon atoms.

Q ¹ is a divalent group that binds two ligands, and includes a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group, and an alkylidene group, a halogen-containing group, a silicon-containing group, and a germanium-containing group. Group selected from a group and a tin-containing group, and a silicon-containing group is particularly preferable.

  Specific examples of the alkylene group, substituted alkylene group and alkylidene group include alkylene groups such as methylene, ethylene, propylene and butylene; isopropylidene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene Methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene and 1 A substituted alkylene group such as ethyl-2-methylethylene; cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, Kurohepuchiriden, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, cycloalkylidene group and ethylidene such tetrahydronaphthyl dust den and dihydroindolyl mites alkylidene, and the like alkylidene group such as propylidene and butylidene.

  Examples of silicon-containing groups include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolylsilylene, methyl Examples include naphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like, particularly preferably dimethylsilylene group and dibutyl And dialkylsilylene groups such as a silylene group.

X is each independently an atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and a phosphorus-containing group. Preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and particularly preferably chlorine. Examples of the hydrocarbon group include the same hydrocarbon groups as R ^{1 to} R ⁸ described above, and an alkyl group having 1 to 20 carbon atoms is particularly preferable.

  Specific examples of preferred compounds of the component (A) represented by the general formula (I) include dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene. Bis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, Dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopenta) Dienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, trifluoro Examples include butylbutylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, and more preferred specific examples include dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadiene). Enyl) zirconium dichloride and dimethylsilylene (3-n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride.

Component (B);
The component (B) that can be used in the present invention is a bridged metallocene compound represented by the following general formula (II).

一般式（ＩＩ）中、Ｍは周期表第４族遷移金属原子を示し、具体的には、チタン、ジルコニウムおよびハフニウムから選ばれる遷移金属原子であり、好ましくはジルコニウムである。

In the general formula (II), M represents a Group 4 transition metal atom in the periodic table, specifically a transition metal atom selected from titanium, zirconium and hafnium, preferably zirconium.

R ^{9 to} R ²⁰ are hydrogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups. And may be the same or different from each other, and two adjacent groups may be connected to each other to form a ring. Preferred groups for R ^{9 to} R ²⁰ are a hydrogen atom and a hydrocarbon group, more preferably R ^{9 to} R ¹² are a hydrogen atom, and R ^{13 to} R ²⁰ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. It is.

Q ² is a divalent group that binds two ligands, and includes a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group, and an alkylidene group, a halogen-containing group, a silicon-containing group, and germanium. And a group selected from a tin-containing group, preferably a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group and an alkylidene group, and a silicon-containing group, particularly preferably an alkylene group or a substituted group. It is a C1-C10 hydrocarbon group such as an alkylene group or an alkylidene group.

X may be the same as X in the above formula (I).
Specific examples of preferred compounds of the component (B) represented by the general formula (II) include isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di- t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydridodi Benzfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dibutylmethyle (Cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (cyclo Pentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6- Di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zyl Nium dichloride, dimethylsilyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (3,6-di-t-butylfluorenyl) Zirconium dichloride and dimethylsilyl (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride are mentioned, and more preferred specific examples include isopropylidene (cyclopentadienyl) (2,7-di-t -Butyl-9-fluorenyl) zirconium dichloride and the like.

Component (C);
Component (C) that can be used in the present invention is at least one compound selected from the group consisting of the following (c-1) to (c-3).

(C-1) an organometallic compound represented by the following general formula (III), (IV) or (V),
R ^a _m Al (OR ^b ) _n H _p X _q (III)
[In General Formula (III), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m represents 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a AlR ^a ₄ (IV)
[In General Formula (IV), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (V)
[In General Formula (V), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, M ^b represents Mg, Zn or Cd, and X represents Represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]

(C-2) an organoaluminum oxy compound, and
(C-3) a compound that reacts with component (A) and component (B) to form an ion pair,
At least one compound selected from the group consisting of

  Among the organometallic compounds (c-1) represented by the general formula (III), (IV) or (V), those represented by the general formula (III) are preferable, specifically, trimethylaluminum, triethyl Trialkylaluminums such as aluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum; and dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride and diiso Examples include alkyl aluminum hydrides such as hexyl aluminum hydride. These are used singly or in combination of two or more.

  As the organoaluminum oxy compound (c-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and an aluminoxane prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such organoaluminum oxy compounds are used singly or in combination of two or more.

  Examples of the compound (c-3) that reacts with the component (A) and the component (B) to form an ion pair include JP-A-1-501950, JP-A-1-502036, and JP-A-3-179005. Lewis acids, ionic compounds, borane compounds and carborane compounds, and heteropoly compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. Isopoly compounds can be used without limitation.

Solid carrier (S);
The solid carrier (S) that can be used as required in the present invention is an inorganic or organic compound, and is a granular or particulate solid.

Among these, examples of the inorganic compound include porous oxides, inorganic chlorides, clays, clay minerals, and ion-exchangeable layered compounds, and porous oxides are preferable.
Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO and ThO ₂ , or a composite or mixture containing these, specifically Natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O _3, SiO ₂ —TiO ₂ —MgO, etc. Used. Of these, those containing SiO ₂ as the main component are preferred.

Such porous oxides have different properties depending on the type and production method, but as a solid support used in the present invention, the particle size is usually 0.2 to 300 μm, preferably 1 to 200 μm, surface area usually 50~1200m ² / g, preferably in the range of 100~1000m ² / g, which pore volume is in the range of usually 0.3~30cm ³ / g are preferred. Such a carrier is used, for example, after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Component (G);
Examples of the component (G) that can be optionally used in the present invention include at least one compound selected from the group consisting of the following (g-1) to (g-6).

(G-1) polyalkylene oxide block,
(G-2) a higher aliphatic amide,
(G-3) polyalkylene oxide,
(G-4) polyalkylene oxide alkyl ether,
(G-5) alkyldiethanolamine, and (g-6) polyoxyalkylenealkylamine.

  In the present invention, such component (G) is present in the catalyst for producing the ethylene polymer (α) for the purpose of suppressing fouling in the reactor or improving the particle properties of the produced polymer. Can be made. Among the components (G), (g-1), (g-2), (g-3) and (g-4) are preferable, and (g-1) and (g-2) are particularly preferable. Here, examples of (g-2) include higher fatty acid diethanolamide.

A method for preparing a catalyst for producing an ethylene polymer (α);
It describes about the preparation method of the catalyst for ethylene-type polymer ((alpha)) used by this invention.
The catalyst for producing the ethylene-based polymer (α) is obtained by adding the component (A), the component (B) and the component (C) into an inert hydrocarbon or a polymerization system using an inert hydrocarbon. Can be prepared.

The order of adding each component is arbitrary, but as a preferred order, for example,
i) Method in which component (A) and component (B) are mixed and contacted, and then component (C) is contacted and added to the polymerization system. ii) Contact in which component (A) and component (C) are mixed and contacted And a method of adding a contact product obtained by mixing and contacting the component (B) and the component (C) into the polymerization system. Iii) Component (A), component (B) and component (C) are continuously added to the polymerization system. How to add to,
Etc.

When the solid carrier (S) is contained, at least one of the component (A), the component (B) and the component (C) is brought into contact with the solid carrier (S) in an inert hydrocarbon to obtain a solid. Catalyst component (X) can be prepared. The order of contacting the components is arbitrary, but as a preferred order, for example,
iv) Method of preparing solid catalyst component (X) by contacting component (C) and solid support (S) and then contacting component (A) and component (B) v) Component (A), component (B) Method in which component (C) is mixed and contacted and then contacted with solid carrier (S); vi) Component (C) and solid carrier (S) are contacted, and then component (A) ) And the solid catalyst component (X2) prepared by contacting the component (C) with the solid carrier (S) and then contacting with the component (B). How to use,
Iv) is more preferable.

  Specific examples of inert hydrocarbons include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof.

  The contact time between the component (C) and the solid carrier (S) is usually 0 to 20 hours, preferably 0 to 10 hours, and the contact temperature is usually -50 to 200 ° C, preferably -20 to 120 ° C. It is. The molar ratio of contact between the component (C) and the solid carrier (S) (component (C) / solid carrier (S)) is usually 0.2 to 2.0, particularly preferably 0.4 to. 2.0.

  The contact time of the contact product of the component (C) and the solid carrier (S) with the component (A) and the component (B) is usually 0 to 5 hours, preferably 0 to 2 hours. Usually, it is −50 to 200 ° C., preferably −50 to 100 ° C. The amount of contact between component (A) and component (B) largely depends on the type and amount of component (C). When component (c-1) is used, component (A) and component (B) The molar ratio [(c-1) / M] of all transition metal atoms (M) and component (c-1) is usually 0.01 to 100,000, preferably 0.05 to 50,000. When component (c-2) is used, the molar ratio of aluminum atoms in component (c-2) to all transition metal atoms (M) in components (A) and (B) [( c-2) / M] is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. When component (c-3) is used, component (c-3) and component (A) And the molar ratio [(c-3) / M] to all transition metal atoms (M) in the component (B) is usually 1 to 10, preferably 1 to Used in an amount to be. The ratio of component (C) to all transition metal atoms (M) in component (A) and component (B) is determined by inductively coupled plasma (ICP) emission spectroscopy.

  The amount ratio of the component (A) and the component (B) can be arbitrarily determined from the molecular weight and molecular weight distribution of the ethylene polymer, but as a preferred range, it is generated from the polymer produced from the component (A) and the component (B). (Hereinafter also referred to as “polymer production ratio derived from component (A) and component (B)”) [= the amount of polymer produced by component (A) / the amount of polymer produced by component (B)] Usually, it is 40/60 to 95/5, preferably 50/50 to 95/5, and more preferably 60/40 to 95/5.

The calculation method of the polymer production | generation ratio derived from a component (A) and a component (B) is demonstrated.
The molecular weight distribution curve of the ethylene polymer (α) obtained by GPC measurement is substantially composed of three peaks. Among these three peaks, the peak on the lowest molecular weight side is a peak attributed to the component (A) -derived polymer, the second peak is a peak attributed to the component (B) -derived polymer, and the third peak That is, the peak on the most polymer side is a peak generated only when both the component (A) and the component (B) are used. The ratio of the peak derived from the component (A) -derived polymer (that is, the peak on the lowest molecular weight side) and the peak derived from the component (B) -derived polymer (that is, the second peak) [= component (A) peak derived from the derived polymer / peak derived from the component (B) derived polymer] is the polymer production ratio derived from the component (A) and the component (B) [= the amount of produced polymer of the component (A) / component ( B) Production polymer amount].

The ratio of each peak is
Molecular weight distribution curve (G1) of ethylene polymer (α),
Except for using a catalyst comprising component (A), component (C), and solid carrier (S) (that is, a catalyst not containing component (B)), the same as when obtaining an ethylene polymer (α) A molecular weight distribution curve (G2) of an ethylene polymer obtained by polymerization under the polymerization conditions of
Except for using a catalyst comprising component (B), component (C), and solid carrier (S) (that is, a catalyst that does not contain component (A)), the same as when obtaining an ethylene polymer (α) Using the molecular weight distribution curve (G3) of an ethylene polymer obtained by polymerization under the above polymerization conditions, the following method was used. In the present specification, the term “molecular weight distribution curve” refers to a differential molecular weight distribution curve unless otherwise specified, and the term “area” for the molecular weight distribution curve refers to a molecular weight distribution curve. The area of a region formed between the base line.

  [1] In each numerical data of (G1), (G2), and (G3), Log (molecular weight) is divided into 0.02 intervals, and each of (G1), (G2), and (G3) has an area of 1 The intensity [dwt / d (log molecular weight)] is normalized so that

  [2] A composite curve (G4) of (G2) and (G3) is created. At this time, the intensity at each molecular weight of (G2) and (G3) is arbitrarily set at a certain ratio so that the absolute value of the difference between the intensity of (G1) and the intensity of (G4) at each molecular weight is approximately 0.0005 or less. Change to On the high molecular weight side, the absolute value of the difference between the intensity of (G1) and the intensity of (G4) becomes larger than 0.0005 due to the influence of the generated third peak. The strengths of (G2) and (G3) are changed so that the absolute value of the difference between the strength and the strength of (G4) is 0.0005 or less.

  [3] When the molecular weight at the maximum weight fraction in (G1) is the peak top, the part where (G1) and (G4) do not overlap with each other on the high molecular weight side from the peak top, that is, (G1) When a difference curve (G5) with (G4) is created, a peak portion (P5) [(G1) appearing on the higher molecular weight side than the molecular weight at the maximum weight fraction in (G1) in the difference curve (G5) − (G4)] is defined as the third peak (that is, the “third peak”).

[4] The peak ratio Wa attributed to the component (A) -derived polymer and the peak ratio Wb attributed to the component (B) -derived polymer are calculated as follows.
Wa = S (G2) / S (G4)
Wb = S (G3) / S (G4)
Here, S (G2) and S (G3) are the areas of (G2) and (G3) after the intensity is changed, and S (G4) is the area of (G4).

For example, if (G4) is obtained by adding x times the intensity of (G2) to y times the intensity of (G3), the normalization is performed by the normalization described in [1] above. Since the areas of (G2) and (G3) are both 1, S (G2), S (G3), and S (G4) are x, y, and (x + y), respectively. Therefore, the above Wa and Wb can be expressed as follows using the above x and y, respectively.
Wa = x / (x + y)
Wb = y / (x + y)

  A higher production amount of the polymer derived from component (A) is advantageous for producing long-chain branching, and the molar ratio of component (A) and component (B) per transition metal compound is as described above. It can be arbitrarily selected within a range that satisfies the ratio.

  For the production of the ethylene polymer (α), the solid catalyst component (X) as described above can be used as it is, but the solid catalyst component (X) is prepolymerized with an olefin, and the prepolymerized catalyst component (XP) ) Can be used after forming.

  The prepolymerization catalyst component (XP) can be prepared by introducing an olefin in the presence of the solid catalyst component (X), usually in an inert hydrocarbon solvent, and is prepared in batch, semi-continuous and continuous modes. Any of these methods can be used, and it can be carried out under reduced pressure, normal pressure or increased pressure. By this prepolymerization, a polymer of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g is produced per 1 g of the solid catalyst component (X).

  The prepolymerization catalyst component prepared in the inert hydrocarbon solvent may be separated from the suspension, then suspended in the inert hydrocarbon again, and the olefin may be introduced into the resulting suspension. Further, olefin may be introduced after drying.

In the prepolymerization, the prepolymerization temperature is usually −20 to 80 ° C., preferably 0 to 60 ° C., and the prepolymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours.
As the form of the solid catalyst component (X) used for the prepolymerization, those already described can be used without limitation. Moreover, a component (C) is used as needed, and especially the organoaluminum compound shown by the said Formula (III) in (c-1) is used preferably. When the component (C) is used, the molar ratio of the aluminum atom (Al-C) and the transition metal compound in the component (C) (component (C) / transition metal compound) is usually 0.1 to 10,000. It is preferably used in an amount of 0.5 to 5000.

  The concentration of the solid catalyst component (X) in the prepolymerization system is usually 1 to 1000 grams / liter, preferably 10 to 500 grams / liter, in a ratio of solid catalyst component (X) / polymerization volume of 1 liter.

  Component (G) may coexist in any step in the preparation of the catalyst for producing the ethylene polymer (α), and the contact order is also arbitrary. Moreover, you may make it contact the prepolymerization catalyst component (XP) produced | generated by prepolymerization.

In the polymerization of ethylene or ethylene and an α-olefin having 4 to 20 carbon atoms using the above-described catalyst for producing an ethylene polymer (α), the component (A) and the component (B) are reacted. The amount used is usually 10 ⁻¹² to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol per liter of volume.

Moreover, superposition | polymerization temperature is -50-200 degreeC normally, Preferably it is 0-170 degreeC, Most preferably, it is the range of 60-170 degreeC. The polymerization pressure is usually from normal pressure to 100 kgf / cm ² , preferably from normal pressure to 50 kgf / cm ² , and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can do. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions.

  The molecular weight of the resulting ethylene polymer (α) can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Further, the component (G) can be present in the polymerization system for the purpose of suppressing fouling or improving particle properties.

  In order to suppress variations in physical property values, the ethylene polymer (α) particles obtained by the polymerization reaction and other components added as desired are melted by any method and subjected to kneading, granulation, or the like. .

<Method for producing ethylene polymer (β)>
The ethylene polymer (β) used in the present invention can be obtained by polymerizing ethylene and an α-olefin having 4 or more and 10 or less carbon atoms, and is used as long as a material satisfying the above requirements is obtained. A polymerization catalyst and polymerization conditions are not particularly limited. As the ethylene polymer (β), for example, commercially available products such as linear low density polyethylene, ethylene-α-olefin copolymer, and high density polyethylene can be used. As a specific example, a material satisfying the requirement can be selected from LLDPE Evolue (registered trademark), Ultozex (registered trademark), etc. made of prime polymer.

<Method for Producing Ethylene Polymer Composition (γ)>
The ethylene polymer composition (γ) can be produced by melt-kneading the ethylene polymer (α) and the ethylene polymer (β), or the ethylene polymer (α). It can also be produced by dry blending the pellets obtained by granulating the pellets and the pellets of the ethylene polymer (β). Preferably, a method of production by melt kneading can be used, and at this time, a continuous extruder or a closed kneader can be used. For example, apparatuses, such as a single screw extruder, a twin screw extruder, a mixing roll, a Banbury mixer, a kneader, can be mentioned. Among these, it is preferable to use a single screw extruder and / or a twin screw extruder from the viewpoints of economy, processing efficiency, and the like.

  Here, when the melt-kneading and dry blending are performed, in addition to the ethylene polymer (α) and the ethylene polymer (β), the “other thermoplastic resin (ω)” may be blended. it can. Further, in addition to “other thermoplastic resin (ω)” or instead of “other thermoplastic resin (ω)”, the above “other blending components” may be further blended.

  The order of adding the “other thermoplastic resin (ω)” and the “other blending component” is not particularly limited. For example, the “other thermoplastic resin” and the “other compounding component” may be blended simultaneously with one or both of the ethylene polymer (α) and the ethylene polymer (β). Alternatively, the ethylene polymer (α) and the ethylene polymer (β) may be added after kneading.

<Extruded laminate film>
The extruded laminate film of the present invention is a film obtained by extrusion laminating the ethylene polymer composition (γ) on a base film.

  The ethylene-based polymer composition layer (layer composed of the ethylene-based polymer composition (γ)) may be provided on one side of the base film, or may be provided on both sides. Further, the base film may be a single layer or a laminate.

The extruded laminate film of the present invention exhibits excellent low-temperature heat-sealability by having a layer made of the ethylene polymer composition (γ) as the outermost layer.
As the form of the substrate, a film or a sheet is preferable. The thickness of the film or sheet is usually 10 to 1,000 μm.

  Examples of the material for the base film include plastic, metal, glass, paper, and the like, and a plastic that can stably form a layer made of an ethylene polymer composition (γ) is preferable. A polymer, an acrylic polymer, a polyester polymer and the like are preferable.

When a plastic film is used as the base film, the plastic film may be non-oriented or may be stretched uniaxially or biaxially.
Further, in order to stably form a layer made of the ethylene polymer composition (γ) on the surface of such a base film, a surface activation treatment such as a corona discharge treatment may be applied. A layer may be provided.

The layer made of the ethylene-based polymer composition (γ) is preferably used as a seal layer because it exhibits low-temperature heat sealability.
When a layer made of an ethylene polymer composition (γ) is used as a seal layer, the thickness of the seal layer can be appropriately set, and is preferably about 5 to 100 μm. The seal layer made of the ethylene polymer composition (γ) is excellent in heat seal strength and exhibits high heat seal strength even when the heat seal temperature is relatively low. That is, it is excellent in low temperature heat sealability.

  The extruded laminate film according to the present invention can be produced, for example, by extrusion laminating the ethylene polymer composition (γ) on the base film. When performing extrusion lamination, the ethylene polymer composition (γ) may be directly extruded to the base film, and the adhesion between the base film and the ethylene polymer composition (γ) is increased. For this purpose, an ethylene polymer composition (γ) is extruded after a known method is applied to the base film in advance, for example, an anchor coating agent is applied, or an undercoat resin layer such as adhesive polyolefin or high pressure polyethylene is provided. You may laminate.

  The thickness of the layer composed of the ethylene polymer composition (γ) during extrusion lamination is not particularly limited, but is preferably 300 μm or less, more preferably 250 μm or less from the viewpoint of maintaining transparency and flexibility. More preferably, it is 200 μm or less. On the other hand, in consideration of mechanical properties and low-temperature heat sealability, the thickness of the layer is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more.

  When the extruded laminate film of the present invention is used as a liquid packaging film, the layer composed of the ethylene polymer composition (γ) is used as a sealing layer of the liquid packaging film. The thickness of the seal layer in this case can be set as appropriate, but is preferably about 5 to 100 μm.

  The configuration of the liquid packaging film is a configuration in which a sealing layer is formed on the base film and the base film, and the material for forming the base film is not particularly limited as long as it has film-forming ability. Any polymer or paper, aluminum foil, cellophane, etc. can be used.

  Examples of such polymers include high density polyethylene, medium and low density polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, ionomer, polypropylene, poly-1-butene, and poly-4. -Olefin polymers such as methyl-1-pentene, vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, polyacrylonitrile, nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, Polyamide polymers such as nylon 610 and polymetaxylylene adipamide, polyester polymers such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, polyvinyl alcohol, ethylene vinyl alcohol Copolymer, polycarbonate-based polymers and the like and mixtures thereof.

  Moreover, when a base film consists of a polymer, this polymer film may be non-oriented and may be extended | stretched uniaxially or biaxially. Furthermore, the base film may be a single layer or a multilayer.

Such a liquid packaging film can be produced, for example, by performing the extrusion lamination described above.
After the liquid packaging film is cut to an appropriate size, the sealant surfaces (layers made of the above-mentioned ethylene polymer composition) are stacked so that they are in contact with each other, and the surroundings are heat sealed to form a liquid packaging container. Can do. Such a liquid packaging container is suitably used as a packaging container for products containing liquids such as various liquids such as liquid soup, liquid seasoning, juice, liquor, water, pickles and retort foods.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, the method which is not described in the above description in the analysis method and evaluation method of the ethylene-type polymer composition obtained in the Example etc. is as follows.

<Processing characteristics>
[Neck-in]
The ethylene-based polymer composition (however, in Comparative Example 5, an ethylene-based polymer, the same applies to the following) was used, using a Sumitomo Heavy Industries Laminator having a 65 mmφ extruder and a T die having a die width of 500 mm. Extrusion lamination was performed on 50 g / m ² kraft paper as a base material under the following conditions.
・ Air gap: 130mm
-Resin temperature under die: 295 ° C
・ Pickup speed: 80m / min ・ Film thickness: 20μm
The value of L ₀ -L when the width of the T die is L ₀ and the width of the film laminated on the kraft paper at each take-off speed is L is defined as neck-in.

[Membrane breakage speed, take-off surging generation speed]
Using an ethylene polymer composition, a laminator manufactured by Sumitomo Heavy Industries, Ltd. having a 65 mmφ extruder and a T die having a die width of 500 mm, an air gap of 130 mm, under the die, on a craft paper of 50 g / m ² as a base material. Extrusion lamination was performed under the condition of a resin temperature of 295 ° C. The amount of extrusion was set so that the film thickness was 20 μm when the take-up speed was 80 m / min.

The take-up speed was increased, and the take-off speed when the molten film was cut (including when only the end of the molten film was cut) was taken as the film-cut speed.
Also, increase the take-up speed by 10 m / min to 350 m / min, measure the neck-in at each take-up speed 5 times, and measure the value that becomes ± 1.5 mm or more with respect to the average value of the neck-in 2 times or more. The take-up surging speed was defined as the take-up surging speed.

<Physical properties of film>
Using an ethylene polymer composition, a Laminator manufactured by Sumitomo Heavy Industries, Ltd. having a 65 mmφ extruder and a T die having a die width of 500 mm, an air gap of 130 mm, a resin temperature under the die of 295 ° C., a take-off speed of 80 m / The film was extruded and laminated to a film thickness of 25 μm under the conditions of minutes.

  As a base material, a urethane anchor coating agent was applied to one side of a 15 μm-thick biaxially stretched nylon film (trade name: Emblem ONM, manufactured by Unitika Ltd.), and then manufactured using a Ziegler catalyst. Using a laminate obtained by extruding and laminating an ethylene-based mixed resin blended with 50 parts by weight of linear low-density polyethylene and high-pressure method low-density polyethylene at a thickness of 25 μm, an ethylene-based polymer is formed on the surface of the ethylene-based mixed resin layer. The composition was extrusion laminated.

[Heat seal strength]
The obtained extruded laminate films were overlapped so that the ethylene polymer composition layers were in contact with each other, and the heat seal strength between the ethylene polymer composition layers was measured or evaluated according to the following method.
Uses single-sided heating bar sealer Heat sealing temperature: 120 ° C
Heat seal pressure: 2 kg / cm ²
Heat sealing time: 0.5 seconds Seal bar width: 10 mm
Specimen width: 15mm
Peeling angle: 180 degrees Peeling speed: 300 mm / min.

[Hot tack test (low temperature sealability)]
Using a heating bar set at each temperature, the film was heat-sealed under the following conditions. A peel test was conducted at the same time as the heating bar was removed after heat sealing, and a peel strength of 0.25 seconds was recorded after the start of peeling.
Uses double-sided heating bar sealer Heat sealing temperature: 85 ° C, 95 ° C
Heat seal pressure: 0.42 MPa
Heat sealing time: 1.0 second Sealing area: 25 mm x 12.7 mm
Specimen width: 15mm
Peeling angle: 180 degrees Peeling speed: 400 mm / min.

[Bag break test]
The two extruded laminate films were superposed so that the ethylene polymer composition layers were in contact with each other, and this was heat-sealed at 160 ° C. to prepare a three-pack sealed bag of 90 mm × 120 mm. After 100 g of salad oil or tap water was put into the bag, the remaining side of the bag was heat-sealed in the same manner to obtain a four-pack sealed bag containing the contents. The obtained four-pack sealed bag was boiled for 30 minutes in a water bath at 90 ° C. or 95 ° C. Immediately after completion, a 100 kg load was applied to the bag in a direction perpendicular to the surface for 1 minute to confirm the receding state of the seal. . Specifically, the maximum distance (mm) of receding on each of the four sides was measured, and the average value thereof was calculated.

[Synthesis of metallocene compounds]
(A-1) represented by the following structural formula is synthesized based on the method described in JP-A-2009-144148, and (A-2) represented by the following structural formula is manufactured by STREM. It was used.

  (B-1) represented by the following structural formula is based on the method described in JP-A-4-69394, and (B-2) represented by the following structural formula is disclosed in Japanese Patent No. 2813057. Synthesis was based on the described method.

[Production Example 1 (Production of ethylene polymer (α-1))]
Preparation of the solid component (S-1);
In a reactor equipped with a stirrer with an internal volume of 270 liters, silica (SiO ₂ : average particle size 70 μm, specific surface area 340 m ² / g, pore volume 1 as a solid carrier (S) under a nitrogen atmosphere as a solid carrier (S) .3cm ³ / g, 250 ℃ baking) and cooled to 0 to 5 ° C. after suspending 10kg to 77 liters of toluene. To the obtained suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mmol / mL in terms of Al atom) was added dropwise as a component (C) over 30 minutes. At this time, the temperature in the system was kept at 0 to 5 ° C.

  Subsequently, the solid carrier (S) and the component (C) were reacted at 0 to 5 ° C. for 30 minutes, and then heated to 95 to 100 ° C. over about 1.5 hours. For 4 hours. Thereafter, the system was cooled to room temperature, the supernatant was removed by decantation, and the precipitate was washed twice with toluene, and then a total amount of 115 liters of a solid component (S-1) toluene slurry was prepared. When a part of the obtained slurry component was sampled and the concentration was examined, the slurry concentration was 122.6 g / L and the Al concentration was 0.62 mol / L.

Preparation of the solid catalyst component (X-1);
Charge 12.2 liters of toluene slurry of solid component (S-1) to a reactor (1) with an internal volume of 114 liters under a nitrogen atmosphere, and add toluene so that the total amount becomes 28 liters. did. Next, 2.58 g (Zr atom) of dimethylsilylene (3-n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride as a component (A) was placed in a glass reactor having an internal volume of 5 liters under a nitrogen atmosphere. 6.61 mmol in terms of conversion), and as component (B), isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride 16.40 g (in terms of Zr atoms, 30.10 mmol) (Molar ratio of component (A) / component (B) = 19/81), these were dissolved in 5.0 liters of toluene and pumped to the reactor (1). After the pumping, the toluene slurry and the toluene solution of component (A) and component (B) are reacted at a reactor internal temperature of 73 to 76 ° C. for 2 hours, the supernatant is removed by decantation, and the precipitate is further hexane. Then, hexane was added to the precipitate to make a total volume of 30 liters, and a hexane slurry of the solid catalyst component (X-1) was prepared.

Preparation of prepolymerization catalyst component (XP-1);
Subsequently, 3.7 mol of diisobutylaluminum hydride (DiBAl-H) was added to the hexane slurry of the solid catalyst component (X-1) cooled to 10 ° C. in the reactor (1). Further, ethylene was continuously fed into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Then 0.10 liter of 1-hexene was added. After the addition of 1-hexene, ethylene supply was started at 1.4 kg / hour, and prepolymerization was performed at a system temperature of 32 to 37 ° C. 0.06 liter of 1-hexene was added 5 times every 30 minutes after the start of prepolymerization, and when ethylene supply reached 4.3 kg 190 minutes after the start of prepolymerization, the ethylene supply was stopped. Thereafter, the supernatant was removed by decantation, and the precipitate was washed four times with hexane, and then hexane was added to the precipitate to make a total volume of 50 liters.

  Next, at a system temperature of 34 to 36 ° C., a hexane solution of Chemistat 2500 (coconut fatty acid diethanolamide: 60.8 g) as a component (G) as a component (G) is pumped to the reactor (1). Subsequently, the reaction was carried out at 34 to 36 ° C. for 2 hours. Thereafter, the supernatant was removed by decantation, and the precipitate was washed four times with hexane to obtain hexane slurry (1).

  Next, after the hexane slurry (1) was inserted into a 43 liter evaporative dryer with a stirrer under a nitrogen atmosphere, the pressure in the dryer was reduced to −68 kPaG over about 60 minutes, and reached −68 kPaG. Vacuum drying was performed for about 4.3 hours to remove volatile components in hexane and the prepolymerized catalyst component. The pressure was further reduced to −100 kPaG, and when the pressure reached −100 kPaG, vacuum drying was performed for 8 hours to obtain 6.1 kg of a prepolymerized catalyst component (XP-1). A part of the obtained prepolymerization catalyst component (XP-1) was collected and examined for its composition. As a result, 0.52 mg of Zr atom was contained per 1 g of the prepolymerization catalyst component.

Production of an ethylene-based polymer (α-1);
In a fluidized bed gas phase polymerization reactor having an internal volume of 1.7 m ³ , an ethylene / 1-hexene copolymer was produced using a prepolymerization catalyst component (XP-1).

  According to the conditions shown in Table 1, the prepolymerization catalyst component (XP-1), ethylene, nitrogen, 1-hexene and the like were continuously fed into the reactor. The polymerization reaction product was continuously withdrawn from the reactor and dried with a drying apparatus to obtain an ethylene polymer (α-1) powder.

  The obtained ethylene copolymer (α-1) was not blended with additives such as antioxidants, and the ethylene copolymer (α-1) was mixed into a biaxially different 20 mmφ made by Toyo Seiki Seisakusho Co., Ltd. Using an extruder, the mixture was melt-kneaded under the conditions of a preset temperature of 200 ° C. and a screw rotation speed of 100 rpm, and then extruded into a strand shape and cut to obtain pellets.

[Production Example 2 (Production of Ethylene Polymer β-1)]
An ethylene polymer (β-1) was produced according to Example 11 of International Publication WO2007 / 034920.

[Example 1]
These were blended in a proportion of 20 parts by weight of the pellets of ethylene polymer α-1 obtained in Production Example 1 and 80 parts by weight of ethylene polymer β-1 obtained in Production Example 2. Using a biaxially different direction 20 mmφ extruder manufactured by Seiki Seisakusho, melt kneading was performed under the conditions of a set temperature of 200 ° C. and a screw rotation speed of 100 rpm, and then extruded into a strand shape and cut to obtain pellets.

The obtained pellet is further mixed with 25 parts by weight of Tuffmer A-4085 (resin that does not satisfy requirement (III), requirement (1 ′), etc.) manufactured by Mitsui Chemicals as component ω-1, and an ethylene polymer composition A product was manufactured and used as a measurement sample.
Table 2 shows the results of extrusion lamination molding using this measurement sample.

[Example 2]
These were blended in a proportion of 20 parts by weight of the pellets of ethylene polymer α-1 obtained in Production Example 1 and 80 parts by weight of ethylene polymer β-1 obtained in Production Example 2. Using a biaxially different 20 mmφ extruder manufactured by Seiki Seisakusho, melt-kneaded under the conditions of a set temperature of 200 ° C. and a screw rotation speed of 100 rpm, and then extruded into strands and cut to produce ethylene polymer composition pellets. This was used as a measurement sample.
Table 2 shows the results of extrusion lamination molding using this measurement sample.

[Production Example 3 (Production of ethylene polymer (α-3))]
Preparation of solid catalyst component (X-3);
Among the toluene slurry of the solid component (S-1) obtained in “Preparation of the solid component (S-1)” of Production Example 1 in a reactor (1) with an internal volume of 114 liters, 12.2 The liter was charged under a nitrogen atmosphere, and toluene was added so that the total amount was 28 liters. Next, 16.40 g (30.10 mmol in terms of Zr atom) of the metallocene compound (B-1) was collected in a glass reactor having an internal volume of 5 liters under a nitrogen atmosphere and dissolved in 5.0 liters of toluene. Pumped to reactor (1). After the toluene slurry and the toluene solution of the component (B-1) were reacted at a reactor system temperature of 20 to 25 ° C. for 1 hour, the system temperature was raised to 95 ° C. and further reacted for 2 hours. . After lowering the temperature to 30 ° C., 1.08 liters of a toluene solution of 2.58 g (6.61 mmol in terms of Zr atoms) of the metallocene compound (A-1) was added to the obtained slurry solution, and the system temperature was 20-30 ° C. For 1 hour. The supernatant was removed by decantation, and the precipitate was further washed three times with hexane, and then hexane was added to the precipitate to make a total volume of 30 liters to prepare a hexane slurry of the solid catalyst component (X-3).

Preparation of prepolymerized catalyst (XP-3);
The same operation as “Preparation of prepolymerized catalyst component (XP-1)” in Production Example 1 except that the hexane slurry of the solid catalyst component (X-1) was changed to the hexane slurry of the solid catalyst component (X-3). And 6.1 kg of a prepolymerized catalyst (XP-3) was obtained. A part of the obtained prepolymerized catalyst (XP-3) was collected and examined for its composition. As a result, 0.52 mg of Zr atom was contained per 1 g of the prepolymerized catalyst component.

Production of ethylene polymer α-3;
In a fluidized bed gas phase polymerization reactor having an internal volume of 1.0 m ³ , an ethylene / 1-hexene copolymer was produced using the prepolymerization catalyst (XP-3).

  According to the conditions shown in Table 1, the prepolymerization catalyst component (XP-3), ethylene, nitrogen, 1-hexene and the like were continuously fed into the reactor. The polymerization reaction product was continuously withdrawn from the reactor and dried with a drying apparatus to obtain an ethylene polymer (α-3) powder.

  The resulting ethylene copolymer (α-3) was not blended with additives such as antioxidants, and the ethylene copolymer (α-3) was mixed with a biaxially different 20 mmφ made by Toyo Seiki Seisakusho Co., Ltd. Using an extruder, the mixture was melt-kneaded under the conditions of a preset temperature of 200 ° C. and a screw rotation speed of 100 rpm, and then extruded into a strand shape and cut to obtain pellets.

[Example 3]
An ethylene-based polymer composition was produced in the same manner as in Example 1 except that the ethylene copolymer (α-1) pellets were changed to 20 parts by weight of the ethylene copolymer (α-3) pellets. This was used as a measurement sample.
Table 2 shows the results of extrusion lamination molding using this measurement sample.

[Comparative Example 1]
Example 1 except that the pellet of the ethylene polymer α-1 was changed to 20 parts by weight of a product pellet of polyethylene (trade name: Mirason 11) by a high-pressure radical polymerization method commercially available from Mitsui DuPont Polychemical Co., Ltd. The same procedure as in Example 1 was performed to produce an ethylene polymer composition, which was used as a measurement sample.

Table 2 shows the results of extrusion lamination molding using this measurement sample.
In Comparative Example 1, Mirason 11 did not satisfy the requirement (IV) (sum of the number of methyl branches and the number of ethyl branches) and the requirement (VII) ([η] / Mw ^0.776 ), and oil was added as a content. Bag breakage occurred in the boil test.

[Comparative Example 2]
Example 2 except that the pellet of the ethylene polymer α-1 was changed to 20 parts by weight of a product pellet of polyethylene (trade name: Mirason 11) by a high-pressure radical polymerization method commercially available from Mitsui DuPont Polychemical Co., Ltd. The same operation was performed to produce a pellet of an ethylene polymer composition, which was used as a measurement sample.

Table 2 shows the results of extrusion lamination molding using this measurement sample.
Also in Comparative Example 2, Mirason 11 did not satisfy the requirement (IV) (sum of the number of methyl branches and the number of ethyl branches) and the requirement (VII) ([η] / Mw ^0.776 ), and oil was added as a content. Bag breakage occurred in the boil test.

[Comparative Example 3]
The pellet of ethylene polymer α-1 was changed to 20 parts by weight of a product pellet of polyethylene (trade name: Mirason 11) by a high-pressure radical polymerization method commercially available from Mitsui DuPont Polychemical Co., Ltd. Example 1 except that -1 was changed to 80 parts by weight of product pellets of ethylene-4-methyl-1-pentene copolymer (trade name: Ultozex 20100J) by a solution polymerization method commercially available from Prime Polymer Co., Ltd. The same operation as in No. 2 was performed to produce an ethylene polymer composition pellet, which was used as a measurement sample.

Table 2 shows the results of extrusion lamination molding using this measurement sample.
In Comparative Example 3, Mirason 11 does not satisfy the requirement (IV) (the sum of the number of methyl branches and the number of ethyl branches) and the requirement (VII) ([η] / Mw ^0.776 ), and the density of ULTZEX 20100J is It was larger than the range of requirement (2), the hot tack strength was remarkably weak, and the hot tack property was inferior.

[Comparative Example 4]
20 weights of pellets of ethylene polymer α-1 and 20 weights of product pellets of ethylene-4-methyl-1-pentene copolymer (trade name: Ultozex 20100J) by a solution polymerization method commercially available from Prime Polymer Co., Ltd. Except having changed to the part, the same operation as Example 1 was performed, the ethylene-type polymer composition was manufactured, and this was made into the measurement sample.

Table 2 shows the results of extrusion lamination molding using this measurement sample.
In Comparative Example 4, the MT / η ^* value of ULTZEX 20100J is smaller than the range of requirement (III), and the relationship between zero shear viscosity [η ₀ (P)] and weight average molecular weight (Mw) is also the requirement (V). Therefore, since the neck-in was large and take-up surging occurred, an extruded laminate film could not be prepared.

[Comparative Example 5]
An ethylene polymer was produced according to the method described in Example 6 of JP-A-2009-197225, and this was used as a measurement sample. Table 2 shows the results of extrusion lamination molding using this measurement sample.

  In Comparative Example 5, significant seal retraction occurred in a boil test (95 ° C.) in which oil was added as the content, and the seal strength and low-temperature sealability after boil were inferior.

Claims (8)

An ethylene copolymer (α) that is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms and simultaneously satisfies the following requirements (I) to (VII):
A copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms which simultaneously satisfies the following requirements (1) to (3):
The weight fraction [Wα] of the ethylene polymer (α) is 0.01 or more and 0.99 or less, and the weight fraction [Wβ] of the ethylene polymer (β) is 0.01 or more and 0.99. The ethylene polymer composition (γ) is as follows (the sum of Wα and Wβ is 1.00).
Requirements for ethylene polymer (α):
(I) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 0.01 g / 10 min or more and 30 g / 10 min or less.
(II) The density (d) is 890 kg / m ³ or more and 970 kg / m ³ or less.
(III) The ratio [MT / η ^* (g / P)] of the melt tension [MT (g)] at 190 ° C. and the shear viscosity [η * (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec. It is 1.00 × 10 ⁻⁴ or more and 9.00 × 10 ⁻⁴ or less.
(IV) Sum of methyl branch number [Me (/ 1000C)] and ethyl branch number [Et (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR [(Me + Et) (/ 1000C )] Is 1.80 or less.
(V) Ratio of zero shear viscosity at 200 ° C. [η ₀ (P)] and weight average molecular weight measured by GPC-viscosity detector method (GPC-VISCO) to the 6.8th power (Mw ^6.8 ), η ₀ / Mw ^6.8 is 0.03 × 10 ⁻³⁰ or more and 7.5 × 10 ⁻³⁰ or less.
(VI) The molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is 1.0 × 10 ^4.30 or more and 1.0 × 10 ^4.50 or less.
(VII) Intrinsic viscosity measured in decalin at 135 ° C. [[η] (dl / g)] and weight average molecular weight measured by GPC-viscosity detector method (GPC-VISCO) to the 0.776th power (Mw ^0.776 ), [Η] / Mw ^0.776 is 0.80 × 10 ⁻⁴ or more and 1.65 × 10 ⁻⁴ or less.
Requirements for ethylene polymer (β):
(1) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 7.0 g / 10 min or more and 30 g / 10 min or less.
(2) The density (D) is 880 kg / m ³ or more and 915 kg / m ³ or less.
(3) Intrinsic viscosity [[η] (dl / g)] measured in 135 ° C. decalin and 0.776 of the weight average molecular weight measured by GPC-viscosity detector method (GPC-VISCO) (Mw ^0.776 ) Ratio [η] / Mw ^0.776 is 1.90 × 10 ⁻⁴ or more and 2.80 × 10 ⁻⁴ or less. The ethylene polymer composition (γ) according to claim 1, wherein the ethylene polymer (β) further satisfies the following requirements (4) to (6).
(4) The ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight measured by GPC is 1.50 or more and 3.00 or less.
(5) In the elution curve obtained by temperature rising elution fractionation (TREF), the ratio of the peak height (H) with the strongest peak intensity to the width (W) at half the peak height (H) / W) and the density (D) (kg / m ³ ) satisfy the following relational expression (Eq-5-1).
0.0163 x D-14.10 ≤ Log ₁₀ (H / W) ≤ 0.0163 x D-13.40 (Eq-5-1)
(6) Sum of the number of methyl branches [Me (/ 1000C)] and the number of ethyl branches [Et (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR [(Me + Et) (/ 1000C )] Is 1.80 or less.   The ethylene polymer composition (γ) according to claim 1 or 2, further comprising a thermoplastic resin that is neither the ethylene polymer (α) nor the ethylene polymer (β).   The extrusion which has a base film and the ethylene copolymer composition layer obtained by carrying out the extrusion lamination process of the ethylene copolymer composition ((gamma)) in any one of Claims 1-3 on the said base film. Laminate film.   A packaging bag formed from the extruded laminate film according to claim 4.   The packaging bag according to claim 5, which is a bag for containing a liquid, and a contact surface with the liquid is the ethylene polymer composition layer.   The extruded laminate film according to claim 4 is formed by bending the ethylene copolymer composition layers so that the ethylene copolymer composition layers face each other, and heat sealing a part of the ethylene copolymer composition layers. Packaging bag as described in.   Two extruded laminate films according to claim 4 are laminated so that the ethylene copolymer composition layers face each other, and a part of the ethylene copolymer composition layers is heat-sealed. Item 7. A packaging bag according to item 5 or 6.