JP5302498B2 - Easy tear film, method for producing the same, and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an easily tearable film which is excellent in moldability and mechanical strength, is excellent in a balance between a tear strength in MD direction and a tear strength in TD direction, and has good tearableness in random directions. <P>SOLUTION: This easily tearable film is produced from a composition comprising an ethylenic resin which is a copolymer of ethylene with a 4 to 10C &alpha;-olefin and simultaneously satisfies specific requirements. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to an easily tearable film obtained from an ethylene-based resin excellent in easy tearability in a random direction as compared with known ethylene-based resins and excellent in mechanical strength, a method for producing the same, and an application thereof.

Ethylene-based resins are molded by various molding methods and used for various applications. Depending on these molding methods and applications, the characteristics required for ethylene resins also differ. For example, when a cast film is formed in T-die molding, a neck-in in which the film end portion shrinks in the center direction occurs. When neck-in occurs, the film width becomes smaller and the thickness of the film end becomes thicker than the center of the film, so that the yield of products deteriorates. In order to minimize neck-in, it is necessary to select an ethylene resin having a high melt tension for the molecular weight. Similar properties are necessary to prevent sagging or tearing in hollow molding, or to prevent bubble swaying or tearing in blown film.

Also, when casting cast film in T-die molding, “take-off surging” (“
Sometimes called “Draw Resonance”. It is known that regular thickness fluctuations that occur in the direction of film take-up are called. When take-up surging occurs, thickness unevenness occurs in the film, and as a result, the mechanical strength varies from place to place. For this reason, in order to stably produce a film having a uniform film thickness, it is necessary to avoid the occurrence of take-up surging. In order to suppress the occurrence of this take-up surging, it is considered that resin properties are required such that the strain hardening degree of elongational viscosity increases as the strain rate increases (for example, Toshitaka Kanai, Akira Funaki, Fiber Academic Journal, 41, T-1 (1986)).

A known ethylene polymer obtained using a metallocene catalyst is excellent in mechanical strength such as tensile strength, tear strength or impact strength, but has a low melt tension, so that a neck-in in T-die molding becomes large or Since the extensional viscosity does not show strain rate curability, there arises a problem that take-up surging occurs or the stability of bubbles in inflation molding deteriorates. Further, if the molecular weight is designed to be high in order to increase the melt tension, the extrusion load becomes high and molding becomes difficult.

The high-pressure method low-density polyethylene has a higher melt tension than an ethylene polymer obtained using a metallocene catalyst, and thus has excellent moldability such as neck-in in T-die molding or bubble stability in inflation molding. Further, since the extension viscosity shows strain rate curability, take-up surging does not occur. However, the high-pressure low-density polyethylene has a complicated long-chain branched structure, and therefore is inferior in mechanical strength such as tensile strength, tear strength or impact strength.

  Therefore, an ethylene polymer obtained using a metallocene catalyst and a high pressure method as an ethylene polymer having mechanical strength while maintaining moldability such as neck-in, take-up surging, and bubble stability. Compositions with low-density polyethylene have been proposed in Patent Document 1, Patent Document 2, and the like. However, when the content of the high pressure method low density polyethylene is large, it is expected that the mechanical strength such as tensile strength, tear strength or impact strength is inferior. Further, when the content of the high-pressure method low-density polyethylene is small, the melt tension is not sufficiently improved, so that the neck-in is large, the bubble stability is poor, and the moldability such as the extrusion load is expected to deteriorate.

In order to solve such problems, various ethylene polymers in which long chain branching is introduced by a metallocene catalyst have been disclosed. Patent Document 3 discloses an ethylene polymer obtained by solution polymerization in the presence of a catalyst composed of ethylenebis (indenyl) hafnium dichloride and methylalumoxane. Patent Document 3 discloses ethylenebis (indenyl) supported on silica. An ethylene polymer obtained by gas phase polymerization in the presence of a catalyst comprising zirconium dichloride and methylalumoxane is disclosed in Patent Document 4, and an ethylene polymer obtained by solution polymerization in the presence of a constrained geometric catalyst is disclosed in Patent Document 4. Patent Document 5 discloses an ethylene-based polymer obtained by gas phase polymerization in the presence of a catalyst comprising racemic and meso isomers of Me ₂ Si (2-Me-Ind) ₂ supported on silica and methylalumoxane. Is disclosed. Although these ethylene polymers are described as having improved melt tension and excellent moldability compared to linear ethylene polymers without long-chain branching, the neck-in is still large, so moldability This improvement is expected to be insufficient. In addition, unlike the high-pressure low-density polyethylene, these ethylene-based polymers are not expected to improve take-up surging because the extensional viscosity does not exhibit strain rate curability.

On the other hand, in recent years, films having easy tearability are preferred as packaging materials and the like. Packaging materials include packaging bags for foods, confectionery, medicines, etc., and cut tapes, standing pouches, tubes, and the like. If a film having easy tearability is used, opening, incision, etc. are facilitated. In the case of blown film molding or T-die molding, the film take-up direction is the MD direction, and the direction perpendicular to the film take-up direction is the TD direction. Usually, the formed film has a higher tear strength in the TD direction.

  On the other hand, Patent Document 6 proposes a film having excellent processability and mechanical strength and having an easy tear property in the MD direction. At the time of opening / cutting a packaging material or the like obtained from the film Is not necessarily torn in one direction. Moreover, when easy tearability is limited to one direction, it will be necessary to shape | mold in consideration of the direction of a film in manufacturing processes, such as a packaging material. Therefore, a film having an easy tear property in any direction (random direction) that can solve these problems has been desired.

However, from the conventional technology, it has excellent bubble stability in inflation molding, moldability such as neck-in / take-out surging and low extrusion load in T-die molding, and excellent mechanical strength, and random direction when filmed. It was difficult to efficiently obtain an ethylene-based resin having easy tearability.
JP-A-6-65443 JP 7-26079 A JP-A-4-213309 International Publication No. 93/08221 Pamphlet JP-A-8-311260 JP 2006-168225 A

The present invention solves the above-mentioned problems, is excellent in moldability such as bubble stability in inflation molding, low neck-in / take-off sirjin and low extrusion load in T-die molding, and excellent in mechanical strength It aims at obtaining the easy tear film which consists of a composition and is easy to tear in any direction (random direction).

As a result of diligent research in view of such circumstances, the present inventors have found that an ethylene-based resin having a specific molecular structure and melting characteristics is suitable for bubble stability in inflation molding and low neck-in / take-up surging in T-die molding. It is excellent in moldability such as low extrusion load and mechanical strength, and by making an ethylene resin excellent in the balance of tear strength in the MD direction and TD direction, an easily tearable film can be formed from the composition containing this. The inventors have found that it can be manufactured, and have completed the present invention.

That is, the film according to the present invention is an ethylene-based resin which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms and simultaneously satisfies the following requirements [1] to [ 6 ]. Ri Do a resin composition containing, divided by Elmendorf tear strength in the vertical direction (TD direction) Elmendorf tear strength (according to ASTM D1922) in the take-up direction of the take-up direction at the time of film molding (MD direction) value, characterized in der Rukoto 0.3 to 1.0.
[1] Melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 50 g / 10 min.
[2] The density (d) is in the range of 875 to 970 kg / m ³ .
[3] 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. The range is from 1.50 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ .
[4] Sum [(A + B) (/ 1000C) of methyl branch number [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR )] Is 1.8 or less.
[5] Zero shear viscosity [η ₀ (P)] at 200 ° C. and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01 × 10 ^-13 × Mw ^3.4 ≦ η ₀ ≦ 4.5 × 10 ^-13 × Mw ^3.4 ----- (Eq-1)
[6] The intrinsic viscosity ([η] (dl / g)) measured in decalin at 135 ° C. and the weight average molecular weight Mw measured by GPC-viscosity detector method (GPC-VISCO) 7) Satisfies.
0.80 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.65 × 10 ^-4 × Mw ^0.776 ----- (Eq-7)

Furthermore, the method for producing the film according to the present invention is an ethylene resin that is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms and simultaneously satisfies the following requirements [1] to [ 6 ]. It is characterized by processing the resin composition containing.
[1] Melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 50 g / 10 min.
[2] The density (d) is in the range of 875 to 970 kg / m ³ .
[3] 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. The range is from 1.50 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ .
[4] Sum [(A + B) (/ 1000C) of methyl branch number [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR )] Is 1.8 or less.
[5] Zero shear viscosity [η ₀ (P)] at 200 ° C. and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01 × 10 ^-13 × Mw ^3.4 ≦ η ₀ ≦ 4.5 × 10 ^-13 × Mw ^3.4 ----- (Eq-1)
[6] The intrinsic viscosity ([η] (dl / g)) measured in decalin at 135 ° C. and the weight average molecular weight Mw measured by GPC-viscosity detector method (GPC-VISCO) 7) Satisfies.
0.80 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.65 × 10 ^-4 × Mw ^0.776 ----- (Eq-7)
Moreover, the packaging material of this invention consists of the said film .

  The easily tearable film of the present invention is an ethylene resin composition excellent in moldability and mechanical strength, excellent in the balance of tear strength in the MD and TD directions, and easily tearable in the random direction. It is.

Moreover, according to the manufacturing method of this invention, the said easily tearable film excellent in the tearability to a random direction can be manufactured.
Furthermore, according to this invention, the packaging material which consists of the said easily tearable film excellent in the tearability to a random direction can be obtained.

Hereinafter, the easy tear film of this invention is demonstrated concretely.
The easy tear film of the present invention has a specific ethylene resin (hereinafter referred to as “ethylene resin [R]”).
A resin composition (hereinafter also referred to as “resin composition [R]”).

The ethylene resin [R] is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms.
The ethylene-based resin [R] may be composed of only one ethylene-based polymer, or may be composed of two or more ethylene-based polymers, but the above-mentioned requirements [1] to [5] ] To satisfy all of the above. When the ethylene resin [R] is composed of only one kind of ethylene polymer, the ethylene polymer [R1] is efficiently produced by a polymerization method described later. When the ethylene resin [R] is composed of two or more kinds of ethylene polymers, the ethylene polymer [R1] is preferably included, and an ethylene polymer other than the ethylene polymer [R1] [ Examples of R2] include, for example, a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms obtained by using a metallocene catalyst or a Ziegler catalyst, and a high pressure method low density polyethylene produced by a high pressure radical polymerization method. be able to. When composed of two or more ethylene polymers, the composition ratio of the ethylene polymer [R1] and the ethylene polymer [R2] and the type of the ethylene polymer [R2] are [R1] and [R2]. R2] can be blended, and is not particularly limited as long as the blended resin satisfies the above requirements [1] to [5] at the same time. Usually, ethylene in the ethylene-based resin [R] is used. The composition ratio of the system polymer [R1] is set to 99% by weight or less, preferably 70% by weight or less, and more preferably 30% by weight or less.

However, from the viewpoint that ethylene resin [R] can omit processing steps such as blending,
Usually, it is composed only of an ethylene polymer [R1]. On the other hand, if you want to further promote the specific performance of the ethylene polymer [R1], or if you want to add new performance that the ethylene polymer [R1] does not originally possess, The polymer [R2] is used in combination as a blend form.

The ethylene-based resin [R] satisfies the above-mentioned requirements [1] to [5] at the same time.
Hereinafter, these requirements [1] to [5] will be specifically described.
Requirement [1]
The melt flow rate (MFR) of ethylene resin [R] at 190 ° C and 2.16 kg load is 0.1
-100 g / 10 min, preferably 1.0-50 g / 10 min, more preferably 4.0-30. When the MFR is 0.1 g / 10 min or more, the shear viscosity of the ethylene-based resin is not too high and the moldability is excellent. For example, the appearance of a film is good. When the MFR is 100 g / 10 min or less, the tensile strength and heat seal strength of the ethylene-based resin are good. The MFR is a value measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89.

In general, MFR is strongly dependent on molecular weight. That is, the smaller the MFR, the larger the molecular weight, and the larger the MFR, the smaller the molecular weight. It is known that the molecular weight of the ethylene resin [R] is determined by the composition ratio (hydrogen / ethylene) of hydrogen and ethylene in the polymerization system when the ethylene polymer constituting the ethylene resin [R] is produced ( For example, Kazuo Soga, KODANSHA “CATALYTIC OLEFIN POLYMERIZATION”, p376 (1990)). Therefore, by increasing / decreasing hydrogen / ethylene, it is possible to produce an ethylene-based resin [R] having an MFR in the upper limit to lower limit range of the claims.

Requirement [2]
The density (d) of the ethylene-based resin [R] is in the range of 875 to 970 kg / m ³ , preferably 885 to 964 kg / m ³ , more preferably 905 to 960 kg / m ³ . The density (d) according to the present invention is a value measured with a density gradient tube after the measurement sample is heat-treated at 120 ° C. for 1 hour and linearly cooled to room temperature over 1 hour.

When the density (d) is 875 kg / m ³ or more, the heat resistance of the ethylene resin is good, and the film surface formed from the ethylene resin is less sticky. On the other hand, when the density (d) is 970 kg / m ³ or less, the low temperature sealing property of the ethylene-based resin is good.

In general, 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. In addition, 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)). Therefore, when producing an ethylene polymer constituting the ethylene resin [R], it is possible to control the density of the polymer by increasing or decreasing α-olefin / ethylene. By the method, the density of the ethylene-based resin [R] can be made to satisfy the range of the lower limit to the upper limit of the claims.

Requirement [3]
Ratio [MT / η * (g / g) of melt tension [MT (g)] at 190 ° C. and shear viscosity [η * (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec. P)] is in the range of 1.50 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ , preferably 2.00 × 10 ^{−4 to} 7.00 × 10 ⁻⁴ , more preferably 2.60 × 10 ^{−4 to} 5.00 × 10 ⁻⁴ . is there. An ethylene resin having MT / η * of 1.50 × 10 ⁻⁴ or more has good neck-in and bubble stability and extrudability.

MT / η near the lower limit of the claims by manufacturing under the conditions described in Manufacturing Example 31 to be described later.
An ethylene-based polymer having ^* can be obtained, and an ethylene-based polymer having MT / η ^* near the upper limit of the claim can be obtained by producing under the conditions described in Production Example 19.

In the present invention, the melt tension (MT) was determined by measuring the stress when the molten polymer was stretched at a constant speed. An MT measuring machine manufactured by Toyo Seiki Seisakusho was used for the measurement. Measurement conditions are: resin temperature 190 ° C, melting time 6 minutes, barrel diameter 9.55 mmφ, extrusion speed 15 mm / minute, winding speed 24 m / minute (if the molten filament breaks, the winding speed is 5 m / minute. The nozzle diameter is 2.095 mmφ and the nozzle length is 8 mm.

The shear viscosity (η ^* ) at 200 ° C and angular velocity of 1.0 rad / sec is the angular velocity [ω (rad / sec)] dispersion of shear viscosity (η ^* ) at a measurement temperature of 200 ° C in the range of 0.02512 ≦ ω ≦ 100. Determined by measuring. A dynamic stress rheometer SR-5000 manufactured by Rheometrics was used for the measurement. The sample holder was a 25 mmφ parallel plate, and the sample thickness was about 2.0 mm. The number of measurement points was 5 per ω digit. The amount of strain was appropriately selected within a range of 3 to 10% so that the torque in the measurement range could be detected and torque was not exceeded. The sample used for the shear viscosity measurement is a pre-heating temperature using a press molding machine manufactured by Shinto Metal Industry.
190 ° C, preheating time 5 minutes, heating temperature 190 ° C, heating time 2 minutes, heating pressure 100 kgf / cm ² , cooling temperature 20 ° C, cooling time 5 minutes, cooling pressure 100 kgf / cm ² Was prepared by press molding to a thickness of 2 mm.

Requirement [4]
Sum of the number of methyl branches [A (/ 1000C)] and the number of ethyl branches [B (/ 1000C)] measured by ¹³ C-NMR of ethylene resin [R] [(A + B) (/ 1000C) ] Is 1.8 or less, preferably 1.3 or less, more preferably 0.8 or less, and particularly preferably 0.5 or less. The number of methyl branches and the number of ethyl branches defined in the present invention are defined by the number per 1,000 carbons as described later.

It is known that when a short chain branch such as methyl branch or ethyl branch is present in an ethylene-based resin, the short chain branch is incorporated into the crystal and the interplanar spacing of the crystal widens, so that the mechanical strength of the resin decreases. (For example, Zenjiro Osawa et al., “Prediction and extension of polymer life”, p481, NTS (2002)). Therefore, when the sum (A + B) of the number of methyl branches and the number of ethyl branches (A + B) is 1.8 or less, the mechanical strength of the obtained ethylene-based resin is good.

The number of methyl branches and the number of ethyl branches in the ethylene resin strongly depend on the polymerization method of the ethylene polymer constituting the ethylene resin, and the ethylene polymer obtained by high-pressure radical polymerization is a Ziegler type catalyst system. The number of methyl branches and the number of ethyl branches are larger than the ethylene polymer obtained by the coordination polymerization used. In the case of coordination polymerization, the number of methyl branches and the number of ethyl branches in an 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. Therefore, by increasing or decreasing 1-butene / ethylene, it is possible to produce an ethylene-based resin having the sum of the number of methyl branches and the number of ethyl branches (A + B) that satisfies the claims.

The number of methyl branches and the number of ethyl branches measured by ¹³ C-NMR are determined as follows. The measurement was carried out using an ECP500 type nuclear magnetic resonance apparatus (1H; 500 MHz) manufactured by JEOL Ltd. at a cumulative number of 10,000 to 30,000. The main chain methylene peak (29.97 ppm) was used as the chemical shift standard. In a commercially available quartz glass tube with a diameter of 10 mm, a sample of 250 to 400 mg, Wako Pure Chemical Industries, Ltd. special grade o-dichlorobenzene: ISOTEC benzene-d ₆ = 5: 1 (volume ratio) 3 ml of the mixed solution was added, heated at 120 ° C., and uniformly dispersed. The assignment of each absorption in the NMR spectrum was carried out in accordance with “Chemical Region Special Issue 141 NMR-Review and Experiment Guide [I], p132-p133. The number of methyl branches per 1,000 carbons was in the range of 5-45 ppm. Calculated from the integrated intensity ratio of the absorption of methyl groups derived from methyl branching (19.9 ppm) to the integrated sum of the appearing absorption, and the number of ethyl branches is the ethyl branching relative to the integrated sum of absorption appearing in the range of 5 to 45 ppm. It was calculated from the integrated intensity ratio of the absorption (10.8 ppm) of the ethyl group derived therefrom.

Requirement [5]
The weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) and the zero shear viscosity [η ₀ (P)] at 200 ° C. of the ethylene-based resin [R] are expressed by the following equation (Eq -1) is satisfied.

0.01 × 10 ^-13 × Mw ^3.4 ≦ η ₀ ≦ 4.5 × 10 ^-13 × Mw ^3.4 ----- (Eq-1)
Preferably, the following relational expression (Eq-2) is satisfied.
0.05 × 10 ^-13 × Mw ^3.4 ≦ η ₀ ≦ 4.5 × 10 ^-13 × Mw ^3.4 ----- (Eq-2)
More preferably, the following relational expression (Eq-3) is satisfied.

0.10 × 10 ^-13 × Mw ^3.4 ≦ η ₀ ≦ 3.5 × 10 ^-13 × Mw ^3.4 ----- (Eq-3)
Particularly preferably, the following relational expression (Eq-4) is satisfied.
0.15 × 10 ^-13 × Mw ^3.4 ≦ η ₀ ≦ 1.8 × 10 ^-13 × Mw ^3.4 ----- (Eq-4)
When the zero shear viscosity [η ₀ (P)] is log-log plotted against the weight average molecular weight (Mw), the extensional viscosity is strain-hardening like a linear ethylene polymer without long chain branching. The resin with no slope follows the power law of 3.4, whereas the low shear viscosity resin with elongation viscosity like the high pressure method low density polyethylene has lower zero shear viscosity [η ₀ (P)] than the power law (C Gabriel, H. Munstedt, J. Rheol., 47 (3), 619 (2003)). When the zero shear viscosity [η ₀ (P)] at 200 ° C. is 4.5 × 10 ⁻¹³ × Mw ^3.4 or less, the elongational viscosity of the resulting ethylene polymer exhibits strain rate curability, so that take-up surging does not occur.

The fact that ethylene resin [R] satisfies the above relational expression (Eq-1) indicates that η ₀ and Mw of ethylene resin [R]
Is logarithmically plotted, this means that log (η ₀ ) and logMw are present in the region defined by the following relational expression (Eq-1 ′).

3.4Log (Mw) −15.0000 ≦ Log (η ₀ ) ≦ 3.4Log (Mw) −12.3468 -------- (Eq-1 ')
FIG. 1 shows a plot of log (η ₀ ) and logMw for all ethylene resins described in the production examples according to the present invention. By producing under the conditions described in Production Example 2, the relationship between the zero shear viscosity [η ₀ (P)] defined by the parameter inequality (Eq-1) and the weight average molecular weight (Mw) is the parameter inequality (Eq -1 ′), it is possible to obtain an ethylene-based resin close to the boundary line defined by the following formula (Eq-1 ″), while producing it under the conditions described in Reference Production Example 29, Among the parameter inequalities (Eq-1 ′), an ethylene resin close to the boundary line defined by the following formula (Eq-1 ′ ″) can be obtained.

Log (η ₀ ) = 3.4 Log (Mw) −15.0000 --------- (Eq-1``)
Log (η ₀ ) = 3.4Log (Mw) −12.3468 ---------- (Eq-1 ''')
The zero shear viscosity [η ₀ (P)] at 200 ° C. was determined as follows. 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. A dynamic stress rheometer SR-5000 manufactured by Rheometrics was used for the measurement. The sample holder uses a 25 mmφ parallel plate, and the sample thickness is approximately 2.0 mm.
It was. The number of measurement points was 5 per ω digit. The amount of strain was appropriately selected within a range of 3 to 10% so that the torque in the measurement range could be detected and torque was not exceeded. The sample used for shear viscosity measurement was a press molding machine manufactured by Shin-Fuji Metal Industry Co., Ltd., preheating temperature 190 ° C, preheating time 5 minutes, heating temperature 190 ° C, heating time 2 minutes, heating pressure 100 kg / cm ² , cooling temperature The measurement sample was 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 / cm ² .

The zero shear viscosity η ₀ was calculated by fitting the Carreau model of the following formula (Eq-5) to an actually measured rheological curve [angular velocity (ω) dispersion of shear viscosity (η *)] by a nonlinear least square method.

In the above formula (Eq-5), λ is a parameter having a time dimension, and n is a power law index of the material. Note that the fitting by the nonlinear least square method is performed so that d in the following equation (Eq-6) is minimized.

In the above formula (Eq-6), 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 was measured as follows using GPC / V2000 manufactured by Waters. The guard column uses Shodex AT-G, the analytical column uses two AT-806, the column temperature is 145 ° C, the mobile phase is o-dichlorobenzene and BHT 0.3 wt% as an antioxidant, 1.0 ml / The sample concentration was 0.1 wt%, and a differential refractometer and 3-capillary viscometer were used as detectors. Standard polystyrene used was manufactured by Tosoh Corporation. In the molecular weight calculation, the actually measured viscosity was calculated from a viscometer and a refractometer, and the weight average molecular weight (Mw) was calculated from the actually measured universal calibration.

As long as the above requirements [I] to [V] are satisfied, the ethylene-based resin [R] will exhibit the effects described later in most plastics industrial applications, but it will surely prevent sudden failures in moldability and fluidity. From the viewpoint that it can be prevented, it is preferable to satisfy the following requirement [VI] in addition to the above requirements [I] to [V].

Requirement [6]
The intrinsic viscosity ([η] (dl / g)) of ethylene resin [R] measured in 135 ° C decalin and the weight average molecular weight Mw measured by GPC-viscosity detector method (GPC-VISCO) The following relational expression (Eq-7) is satisfied.

0.80 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.65 × 10 ^-4 × Mw ^0.776 ----- (Eq-7)
More preferably, the following relational expression (Eq-8) is satisfied.
0.90 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.55 × 10 ^-4 × Mw ^0.776 ----- (Eq-8)
Particularly preferably, the following relational expression (Eq-9) is satisfied.

0.90 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.40 × 10 ^-4 × Mw ^0.776 ----- (Eq-9)
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)). Therefore, even in the ethylene-based resin [R], when the intrinsic viscosity [η] (dl / g) is 1.65 × 10 ⁻⁴ × Mw ^0.776 or less, it has a large number of long-chain branches. Excellent in properties.

By producing under the conditions described in Production Example 31 to be described later, the parameter formula (Eq-7) that defines the relationship between the intrinsic viscosity [[η] (dl / g)] and the weight average molecular weight (Mw), 0.80 × 10 ⁻⁴ × Mw ^0.776 = Ethylene-based polymer close to the boundary line defined by [η] can be obtained, while by producing it under the conditions described in Production Example 21, the parameter formula (Eq− 7), [η] = 1.65 × 10 ^-4
X An ethylene polymer close to the boundary line defined by Mw ^0.776 can be obtained.

The intrinsic viscosity [η] (dl / g) was measured as follows using a decalin solvent. About 20 mg of sample is dissolved in 15 ml of decalin, and the specific viscosity η _sp 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 η _sp is measured in the same manner. This dilution operation was repeated two more times, and the η _sp / C value when the concentration (C) was extrapolated to 0 was calculated as the intrinsic viscosity [η].
It was. (Refer to the following formula (Eq-10))
[η] = lim (η _sp / C) (C → 0) ---------- (Eq-10)
The ethylene-based resin [R] may be composed of an essential ethylene-based polymer [R1], or the ethylene-based resin [R] satisfies the above-described requirements [1] to [5] at the same time. As described above, the coexistence of the ethylene-based polymer [R2] is allowed in the range. Hereinafter, a method for producing the ethylene polymer [R1], which is an essential component in the ethylene resin [R], will be described in detail.

The ethylene polymer [R1] according to the present invention is:
(S) with solid carrier
(A) Group 4 metallocene compound (a-1) represented by the following general formula (I) and the following general formula
At least one compound selected from group 4 transition metal compounds (a-2) of the periodic table represented by (II)
(B) a metallocene compound of Group 4 of the periodic table represented by the following general formula (III):
(C) (c-1) Organometallic compound
(c-2) an organoaluminum oxy compound, and
(c-3) at least one compound selected from the group consisting of compounds that react with component (A) and component (B) to form ion pairs;
(In the following description, the catalyst component may be abbreviated as “solid catalyst component (K)”), and as necessary
(D) It can be efficiently produced by polymerizing ethylene and an α-olefin having 4 to 10 carbon atoms in the presence of an organoaluminum compound.

The details of the contact order of the components when preparing the solid catalyst component (K) will be described later. Usually, from the viewpoint that the contact treatment operation is simple, the following method [a] and method [b] Is preferred.

[a] a method of preparing a solid catalyst component (K) by mixing and contacting the component (S) and the component (C) and then contacting the mixed components of the component (A) and the component (B);
[b] Component (S) and component (C) are mixed and contacted, and then component (A) is mixed and contacted to prepare a solid catalyst component (K-1). Separately, component (S) and component (C) Are mixed and contacted, and then component (B) is mixed and contacted to prepare a solid catalyst component (K-2), and the solid catalyst component (K-1) and the solid catalyst component (K2) are blended to obtain a solid catalyst. A method of preparing component (K).

Examples of the α-olefin having 4 to 10 carbon atoms include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. An α-olefin having 6 to 10 carbon atoms is preferable, and 1-hexene is more preferable. Two or more different kinds of α-olefins having 4 to 10 carbon atoms can be used. In addition, when 1-butene is used as the α-olefin, it is preferable to use an α-olefin having 6 to 10 carbon atoms.

Next, each component (A), (B), (C) and (D) will be specifically described.
Component (A) is composed of compound (a-1) alone, compound (a-2) alone, or a combination of compound (a-1) and compound (a-2) Is done.

The metallocene compound (a-1) is a metallocene compound belonging to Group 4 of the periodic table represented by the following general formula (I).

In the general formula (I), R ^{1 to} R ⁸ are groups selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms (alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group). Each may be the same or different, Q ¹ is an alkylene group having 1 to 20 carbon atoms, an alkylidene group or a silicon-containing group, and X is independently a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms. It is a group selected from a hydrogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. M is titanium, zirconium or hafnium.

As the preferred metallocene compound (a-1), a metallocene compound crosslinked with a dimethylsilylene group is selected, and among them, particularly preferred compounds are dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2- -Methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-n- Butylcyclopentadienyl) zirconium dichloride is chosen. In addition, the compound (a-1) used in the production examples and examples described later is a compound represented by the following formula (A-1) or the following formula (A-2). -1) is not limited to these two compounds.

  The metallocene compound (a-2) is a transition metal compound of Group 4 of the periodic table represented by the following general formula (II).

In general formula (II), M represents a group 4 transition metal atom in the periodic table, m represents an integer of 1 to 4, and R ⁹ represents the following general formula (II-1) or (II-2) R ^{10 to} R ¹⁴ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, sulfur A containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring. When m is 2, two groups out of the groups represented by R ^{10 to} R ¹⁴ may be linked (however, R ⁹ are not bonded to each other). n is a number that satisfies the valence of M, and X is
Indicates a group selected from a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a C1-C20 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. , When n is 2 or more, the plurality of groups represented by X may be the same or different from each other,
A plurality of groups represented by X may be bonded to each other to form a ring.

(In the formula, Ra represents a hydrogen atom, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, Rb and Rc represent a hydrogen atom or a methyl group, and may be the same or different from each other)

(In the formula, the broken line indicates that two C _βs are directly bonded to each other, or two C _β
Indicates that it is combined with
Among the transition metal compounds (a-2), in the general formula (II), R ⁹ is methyl, ethyl, n-propyl, n-hexyl, n-octadecyl, cyclohexyl, cycloheptyl, cyclooctyl, 4- Compounds which are tert-butylcyclohexyl, methylenecyclohexyl, isopropyl, 1-methylhexyl, 1,5-dimethylhexyl are preferably used. The compound (a-2) used in the Examples of the present application described later is a compound represented by the following formula (A-3), but is not limited to this compound in the present invention.

  Component (B) is a metallocene compound belonging to Group 4 of the periodic table represented by the following general formula (III).

In general formula (III), R ^{9 to} R ²⁰ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group. A group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring. Q ² is a divalent group that binds two ligands and contains a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, germanium, or tin. X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , A group selected from a nitrogen-containing group and a phosphorus-containing group, and M is a transition metal selected from titanium, zirconium and hafnium.

Among these, preferred components (B) include isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene. (Ridene (cyclopentadienyl)) 3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene ( Cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, cyclohexyl Den (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (2,7-di- tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (octamethyloctahydridodibenz Fluorenyl) zirconium dichloride, isopropylidene (indenyl) (fluorenyl) zirconium dichloride, isopropylidene (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (indenyl) (3,6- Di-tert-butylfluorenyl) zirconium Loride, isopropylidene (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (fluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (2,7-di-tert-butylfur Oleenyl) zirconium dichloride, cyclohexylidene (indenyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethyl Silyl (indenyl) (fluorenyl) zirconium dichloride, dimethylsilyl (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyindenyl) (3,6-di-tert-butylfluorenyl) ) Zirconium dichloride, dimethyl chloride Le (indenyl) (octamethyl octa hydride blunder benz fluorenyl) zirconium dichloride. The component (B) used in the examples of the present application described later is a metallocene compound represented by the following formula (B-1) or the following formula (B-2). In the present invention, the component (B) is The compound is not limited to this compound.

Component (C) is (c-1) an organometallic compound, (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: As these compounds, compounds disclosed in Japanese Patent Application Laid-Open No. 11-315109 and EP0874005A1 by the present applicant can be used without limitation, but preferred embodiments are described below.

(c-1) The organometallic compound is preferably an organoaluminum compound, and is used alone or in combination of two or more.
(c-2) The organoaluminum oxy compound is preferably an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum, and particularly preferably an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum. Such organoaluminum oxy compounds are used singly or in combination of two or more.

(c-3) As compounds that react with component (A) and component (B) to form ion pairs, JP-A-1-501950, JP-A-1-502036, JP-A-3-17905 JP-A-3-179006,
The Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207703, JP-A-3-207704, US5321106 and the like, as well as heteropoly compounds and isopoly compounds are used without limitation. be able to.

  Component (D) used as an optional component in the polymerization method according to the present invention is the same organoaluminum compound as component (c-1). In the production examples and examples, triisobutylaluminum is used, but in the present invention, the component (D) is not limited to this compound.

In addition, the component (C) used in the production examples and examples described later is an organoaluminum oxy compound (= methylaluminoxane) prepared from trimethylaluminum as the above (c-2).

  The solid catalyst component used in producing the ethylene polymer [R1] according to the present invention is the above component (A), component (B), and component (C) supported on a solid carrier (S). It is characterized by having.

The solid carrier (S) used in the present invention is an inorganic or organic compound and is a granular or fine particle solid.
Among these, as the inorganic compound, porous oxides, inorganic halides, clays, clay minerals or ion-exchangeable layered compounds are preferable, and porous oxides are more preferable.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 1 to 300 μm, preferably 3 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 800 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 80 to 1000 ° C., preferably 100 to 800 ° C., if necessary.

The supports used in the production examples and examples are of two types: silica having an average particle diameter of 12 μm and silica having an average particle system of 50 μm.
Next, a method for preparing a solid catalyst component according to the present invention from the component (S), component (A), component (B) and component (C) will be described.

The solid catalyst component (K) according to the present invention can be prepared by mixing and contacting the component (A), the component (B), the component (C), and the solid support (S) in an inert hydrocarbon. it can.
The mixing order of the components at this time is arbitrary, but as a preferred contact order, for example,
i) Component (S) and component (C) are mixed and contacted, and then component (A) is mixed and contacted to prepare particulate catalyst component (K-1). Separately, component (S) and component (C) Then, the solid catalyst component (K-2) is prepared by mixing and contacting the component (B), and the solid catalyst component (K-1) and the solid catalyst component (K-2) are blended. A method for preparing the solid catalyst component (K).
ii) Component (A) and component (C) are mixed and contacted, and then component (S) is contacted to prepare particulate catalyst component (K-1). Separately, component (B) and component (C) Are mixed and contacted, and then the component (S) is contacted to prepare a solid catalyst component (K-2), and the solid catalyst component (K-1) and the solid catalyst component (K2) are blended to obtain a solid catalyst A method of preparing component (K).
iii) A method in which the component (S) and the component (C) are mixed and contacted, then the component (A) is contacted, and then the component (B) is contacted to prepare the particulate catalyst component (K).
iv) A method in which the component (S) and the component (C) are mixed and contacted, then the component (B) is contacted, and then the component (A) is contacted to prepare the particulate catalyst component (K).
v) A method for preparing the particulate catalyst component (K) by mixing and contacting the component (S) and the component (C) and then contacting the mixed components of the component (A) and the component (B).
vi) A method of preparing the particulate catalyst component (K) by bringing the mixed component of the component (A) and the component (B) into contact with the component (C) and then contacting the component (S). Among these, a particularly preferable contact order is the contact method i) and v) described above. The solid catalyst component (K) obtained by the above contact method, the solid catalyst component (K-1) and the solid catalyst component (K-2) may be added to the polymerization system as they are at the time of polymerization,
You may use as a prepolymerization catalyst component which preliminarily polymerized the olefin. In the prepolymerization, ethylene or an olefin mainly composed of ethylene is used, and the prepolymerization amount is 0.01 to 1,000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, per 1 g of the solid catalyst component.

Examples of the solvent used for the preparation of the solid catalyst component of the present invention include inert hydrocarbon solvents, and specifically, aliphatic carbonization such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Examples include hydrogen, cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. be able to. The pre-contact time between the component (A) and the component (B) is usually 0 to 5 hours, preferably 0 to 1 hour, particularly preferably 0 to 30 minutes. Thereafter, the component (C) and the solid carrier (S The contact time with the contact product is usually 0 to 24 hours, preferably 0 to 5 hours, particularly preferably 0 to 2 hours. These loading operations are usually performed at -50 to 200 ° C, preferably -50 to 50 ° C, particularly preferably 0 to 40 ° C.

The use ratio of component (A) to component (B) varies depending on the molecular weight and molecular weight distribution of the desired ethylene polymer, but usually the product polymer weight (W _A ) due to component ( _A ) and component (B ) Ratio (= W _A / W _B ) of the resulting polymer weight (W _B ) due to 40/60 to 95/5, preferably 50/50 to 95/5, particularly preferably 60/40 to The usage ratio of component (A) and component (B) is determined so as to be 95/5. Regarding the component (A) and the component (B) used in the examples of the present application, the molar ratio of the component (A) and the component (B) [= molar amount of the component (A) / molar amount of the component (B)] is 0.1. It is about ~ 50.

The total transition metal atoms (M) in the component (A) and the component (B) supported on the carrier (S) can be obtained by inductively coupled plasma emission analysis (ICP analysis).
Component (c-1) usually has a molar ratio [(c-1) / M] of component (c-1) to all transition metal atoms (M) in component (A) and component (B). It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. Component (c-2) is a molar ratio [(c-2) / M] of aluminum atoms in component (c-2) to all transition metal atoms (M) in component (A) and component (B). Is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. Component (c-3) includes component (c-3) and all transition metal atoms (M) in component (A) and component (B).
The molar ratio [(c-3) / M] is usually 1 to 10, preferably 1 to 5.

In the polymerization method of the present invention, in the presence of the above-described solid catalyst component, ethylene and a carbon number of 4
Ethylene polymer [R1] is obtained by polymerizing or copolymerizing ˜10 α-olefins.
In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method, but a suspension polymerization method or a gas phase polymerization method is preferred.

  Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and the like aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof. The olefin itself is used as a solvent. You can also

In carrying out the polymerization using the polymerization catalyst as described above, the component (A) and the component (B) are usually 10 ⁻¹² to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² per liter of reaction volume. It is used in such an amount that it becomes a mole.

The polymerization temperature using such a polymerization catalyst is usually in the range of -50 to + 200 ° C, preferably 0 to 170 ° C, particularly preferably 60 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / 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 [R1] can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature.
Further, for the purpose of allowing the polymerization to proceed smoothly, an antistatic agent, an anti-fouling agent, or the like may be used in combination or supported on a carrier.

The olefin species that can be used in the polymerization method of the present invention are as described above, but the following olefins are used in combination as long as the ethylene resin [R] satisfies the requirements [1] to [5]. The present invention is not limited in any way. 3-30 carbon atoms
, Preferably cyclic olefins having 5 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, etc .; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, anhydrous Maleic acid, etc .; α, β-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid; vinyl esters such as vinyl acetate and vinyl propionate; glycidyl acrylate, Unsaturated glycidyls such as glycidyl methacrylate; halogenated olefins such as vinyl fluoride and vinyl chloride; vinylcyclohexane, diene or polyene; aromatic vinyl compounds such as styrene; functional group-containing styrene derivatives such as divinylbenzene.

In the present invention, the ethylene polymer [R2] as an optional component constituting the ethylene resin [R] has any one of the above requirements [1] to [5], or two or more plural requirements. Defined as an unsatisfied ethylene polymer. Examples of such an ethylene polymer [R2] include low-density polyethylene, Evolue SP1540, Evolue SP2040 (Prime Co., Ltd.) produced by Ziegler-Natta catalysts such as Ultzex 15150J and Ultozex 20100J (Prime Polymer Co., Ltd.). High pressure method low density polyethylene such as metallocene catalyst low density polyethylene such as (made by Polymer Co., Ltd.), Mirason 11P, and Mirason 14P (made by Prime Polymer Co., Ltd.) can be exemplified. In Reference Production Example 32 of the present invention, an example is shown in which ethylene / 4-methyl-1-pentene (trade name: ULTZEX UZ15150J) manufactured by Prime Polymer Co., Ltd. is used as the ethylene polymer [R2]. Usually, the composition ratio of the ethylene polymer [R1] in the ethylene resin [R] is 99% by weight or less, preferably 70% by weight or less, and more preferably 30% by weight or less.

Ethylene resin [R] blends with thermoplastic resin [R3] other than ethylene polymer [R1] and ethylene polymer [R2] to provide excellent heat resistance and excellent mechanical strength. A plastic resin composition may be obtained. Ethylene resin [R] of the present invention and thermoplastic resin [R3]
The blend ratio ([R] / [R3] (weight ratio)) is usually 99.1 / 0.1 to 0.1 / 99.9, preferably 70/30 to 0.1 / 99.9.

Examples of the thermoplastic resin [R3] include polyolefin which is a crystalline thermoplastic resin.
Specific examples of the polyolefin include a propylene polymer, a butene polymer, a 4-methyl-1-pentene polymer, a 3-methyl-1-butene polymer, and a hexene polymer. Of these, propylene polymers and 4-methyl-1-pentene polymers are preferred.

The thermoplastic resins [R3] as described above may be used alone or in combination of two or more.
The ethylene-based resin [R] is within a range that does not impair the object of the present invention, and is a weather resistance stabilizer, heat resistance stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, dye, nucleus. Additives such as an agent, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, and an antioxidant may be blended. The blending ratio of the ethylene-based resin [R] of the present invention and these additives ([R] / additive (weight ratio)) is usually 99.9 / 0.1 to 50/50, preferably 99.9 / 0.1 to 70/30. It is.

Resin composition containing ethylene resin [R] and, if necessary, thermoplastic resin [R3] and additives (
By processing the “resin composition [R]”), an easy tear film excellent in moldability and mechanical strength can be obtained.

In the present invention, only the ethylene resin [R] is used, that is, the thermoplastic resin [R3].
An embodiment that does not contain any additives is also referred to as a “composition”.
The resin composition [R] is processed by general film molding. Examples of film molding include extrusion lamination molding, T-die film molding, inflation molding (air cooling, water cooling, multistage cooling, high speed processing) and the like. In particular, the inflation molding method is a film molding method in which a molten film extruded from a die is drawn in a vertical direction, and air is blown into the inside thereof to be expanded, cooled, folded, and wound on a roll. When the film is wound, if bubbles do not rise or the film is swayed, these can cause wrinkles in the molded body. The resin composition [R] is excellent in the stability of bubbles in the molten film and is less likely to wrinkle in the film, so that the resulting molded body is also less likely to wrinkle and is suitable for inflation molding.

Furthermore, the resin composition [R] can be extruded with a low resin pressure and a low motor load even at low temperatures.
When a film is produced by inflation molding, the film take-up direction is usually referred to as MD direction, and the direction perpendicular to the take-up direction is called TD direction. The easily tearable film of the present invention produced using the resin composition [R] is excellent in easily tearable, and is a value obtained by dividing the Elmendorf tear strength in the MD direction by the Elmendorf tear strength in the TD direction (MD / TD) is preferably 0.3 or more and 1.0 or less, and more preferably 0.4 or more and 1.0 or less. When the MD / TD value is in the above range, the difference between the tear strength in the MD direction and the tear strength in the TD direction becomes small, and the balance of the tear strength in both directions is excellent, in the MD direction, TD direction, diagonal direction, etc. Not limited, the film can be easily torn in a random direction.

  If the easily tearable film of the present invention is used as a packaging material requiring tearability, the packaging material can be easily opened and cut in a random direction, and the contents can be easily taken out. Moreover, as for the packaging material of this invention, it is desirable to equip an edge part with the cut | notch of about 1-10 mm in arbitrary directions. Since the easily tearable film of the present invention has good tearability in the random direction, the notch shows the function of inducing any one direction when tearing, and when tearing by hand, Opening and incision are easy.

  Packaging materials include, for example, water packaging bags, liquid soup bags, liquid paper containers, laminating fabrics, food laminate bags, special-shaped liquid packaging bags (standing pouches, etc.), standard bags, laminate printing standard bags, heavy bags Wrap film, sugar bag, oil packaging bag, noodle packaging bag, freezing bag, refrigeration bag, confectionery packaging bag, bread packaging bag, retort bag, pickle bag, sandwich bag, drinking water bag, part coat Examples include packaging films or packaging bags for foods, confectionery, medicines, etc. in bags, microwave oven-compatible bags, flower packaging films, chemical bags, etc., and cut tapes, standing pouches, tubes, tear caps, and the like. In order to use the easily tearable film as a packaging material such as a bag, a known processing method such as cutting or heat sealing can be used. Since the easily tearable film of the present invention has easy tearability in a random direction, there is no need to consider the orientation of the film during these processes, which is convenient.

  Although the obtained film can be used as a single layer, various functions can be imparted by forming a multilayer. In that case, the coextrusion method in each said shaping | molding method is mentioned. On the other hand, lamination with paper and barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to co-extrusion by laminating molding methods such as extrusion laminating and dry laminating are listed. It is done. Production of high-functional products by multilayering by co-extrusion methods in blow molding, injection molding, and extrusion molding is possible in the same manner as film molding.

As a film obtained by processing the resin composition [R], in addition to the easily tearable film, it is also suitable for a protective film, an infusion bag, an agricultural material, and the like. It can also be used as a multilayer film by being bonded to a base material such as nylon or polyester.

Furthermore, as a molded product obtained by processing the resin composition [R], in addition to the packaging material, a blow infusion bag, a blow bottle, a tube by extrusion molding, a pipe, an injection molded product such as daily miscellaneous goods, fiber And large molded products by rotational molding.

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not restrict | limited at all by this Example. Of the methods for analyzing and evaluating ethylene-based resins used in the present invention, methods not described in the above description are as follows. [m1] Number average molecular weight (Mn), Z average molecular weight (Mz), ratio of weight average molecular weight to number average molecular weight
(Mw / Mn), ratio of Z average molecular weight to weight average molecular weight (Mz / Mw)
Number average molecular weight (Mn), Z average molecular weight (Mz), ratio of weight average molecular weight to number average molecular weight (Mw / Mn), ratio of Z average molecular weight to weight average molecular weight (Mz / Mw) is GPC manufactured by Waters Using / V2000, measurement was performed as follows. The guard column uses Shodex AT-G, the analytical column uses two AT-806, the column temperature is 145 ° C, the mobile phase uses o-dichlorobenzene and 0.3% by weight BHT as an antioxidant, 1.0 ml / The sample concentration was 0.1 wt%, and a differential refractometer and 3-capillary viscometer were used as detectors. Standard polystyrene used was manufactured by Tosoh Corporation. The molecular weight was calculated by measuring the measured viscosity from a viscometer and a refractometer, and calculating from the measured universal calibration.

[m2] Neck-in The obtained ethylene-based polymer was placed on 50 g / m ² kraft paper as a base material using a 65 mmφ extruder and a Sumitomo Heavy Industries Laminator having a T die with a die width of 500 mm. Extrusion lamination was performed under the following conditions.

・ Air gap: 130 mm
・ Resin temperature under die: 295 ℃
・ Take-off speed: 80m / min, 120m / min, 200m / min ・ Film thickness: 20μm at take-up speed of 80m / min, 13μm at take-up speed of 120m / min, take-up speed 200m / min
8μm for minutes
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, the neck-in is calculated by L ₀ -L.

[m3] Film breakage rate, take-off surging generation rate The obtained ethylene-based polymer was used as a base material by using a 65 mmφ extruder and a Sumitomo Heavy Industries Laminator having a T die having a die width of 500 mm. Extrusion lamination was carried out on m ² kraft paper under conditions of an air gap of 130 mm and a resin temperature under the die 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 was defined as the film cut-off speed.
Also, increase the take-off speed, measure the neck-in at each take-up speed 5 times, take-off speed when the value that is more than ± 1.5mm against the average value of the neck-in is measured twice or more Was taken as the rate of occurrence of surging.

[m4] Heat-seal strength The obtained ethylene-based polymer was used with a 65 mmφ extruder and a Sumitomo Heavy Industries Laminator having a T-die with a die width of 500 mm. Extrusion lamination was carried out to a film thickness of 25 μm under the conditions of ℃ and take-up speed of 80 m / min. The base material has a thickness of 15
A urethane anchor coat agent is applied to one side of a μm biaxially stretched nylon film (trade name Emblem ONM, manufactured by Unitika Co., Ltd.). A laminate obtained by extrusion-laminating an ethylene-based mixed resin blended with 50 parts by weight of density polyethylene in a thickness of 25 μm was used. The ethylene polymer is extrusion-laminated on the ethylene mixed resin layer side of the laminate. The heat seal strength between the ethylene polymer layers of this extruded laminate film was measured or evaluated according to the following method.

・ Uses single-side heated bar sealer ・ Heat seal pressure: 2kg / cm ²
・ Heat seal time: 0.5 seconds ・ Width of seal bar: 10mm
・ Specimen width: 15mm
・ Peeling angle: 180 degrees ・ Peeling speed: 300 mm / min
[m5] Density (d)
Using a hydraulic heat press manufactured by Shindo Metal Industry Co., Ltd. set at 190 ° C, a 0.5mm thick sheet was formed at a pressure of 100kgf / cm ² (spacer shape; 45 × 45 × on a 240 × 240 × 0.5mm thick plate) A sample for measurement was prepared by compressing at a pressure of 100 kgf / cm ² using another hydraulic heat press machine manufactured by Shinfuji Metal Industry Co., Ltd., set to 20 ° C., which was set to 20 ° C., and cooled. The hot plate was a 5 mm thick SUS plate. The press sheet was heat-treated at 120 ° C. for 1 hour, slowly cooled over 1 hour, and then measured with a density gradient tube.

[m6] Melt flow rate (MFR)
According to ASTM D1238-89, the melt flow rate (MFR) was measured at 190 ° C. and a 2.16 kg load.

[m7] Melt tension (MT)
Melt tension (MT) was measured with a melt tension tester manufactured by Toyo Seiki Seisakusho. The measurement conditions are as follows.

<Measurement conditions> Nozzle used: L = 8.0000 mm, D = 2.095 mm
Measurement temperature: 190 ° C. Resin extrusion speed: 15 mm / min
Resin take-up speed: 24m / min
[m8] Motor load / resin pressure <Production example and comparative production example>
The obtained ethylene-based polymer was placed on a 50 g / m ² kraft paper as a base material using a 65 mmφ extruder and a T die with a die width of 500 mm. Extrusion lamination was carried out so that the film thickness was 20 μm under the conditions of a resin temperature of 295 ° C. and a take-off speed of 80 m / min. The resin pressure of the crosshead part at that time was measured.

<Examples and Comparative Examples>
The motor load and the resin pressure in the extruder of each molding machine described in the examples and comparative examples were measured. A smaller value indicates better moldability and is preferable.

[m9] Bubble stability [1] When film forming is performed by inflation molding (single layer), the bubbles are visually checked, and a) the bubbles are very stable B) If the bubble is stable and less swaying c) If the bubble stability is slightly worse, swaying △ d) If the bubble is not stable and does not rise or shake The film was difficult to produce such as a lot of wrinkles. The closer to ◎, the better the moldability and the better.

[m10] Elmendorf tear strength ( unit: N / cm)
Based on ASTM D1922, the measurement was performed under the following conditions.
Using a light load tear tester (Toyo Seiki Seisakusho: capacity weight B: 79 g attached to the left end of the pendulum), the length of 63.5 in the tear direction (MD direction and TD direction) from the multilayer film
Cut out a rectangular test piece with a width of 50 mm (short side) in mm (long side) and a direction perpendicular to the tear direction (TD direction and MD direction), and insert a 12.7 mm cut from the end in the center of the short side. Prepare a test piece. A preliminary test is performed by stacking a plurality of test pieces so that the indicator (placement needle) of the testing machine is within a range of 20 to 80, and after adjusting the number of test pieces used for measurement, a tear test is performed, and the following test is performed. The tear strength (N / cm) in each direction of MD direction and TD direction was calculated | required by the type | formula. The obtained MD direction tear strength was divided by the TD direction tear strength to obtain an MD / TD value. The measurement range (R) of the testing machine was 200.

T = (A × 0.001 × 9.81 × R / 100) / (t)
T: Tear strength (N / cm)
A: Value indicated by the pointer (g)
t: Total thickness of stacked specimens (cm)
[m11] Hand tearability The following [1] Film produced on the blow molding (single layer) molding machine and conditions is TD
An incision of 5 mm was made in the direction, and sensory evaluation was performed when the hand was torn about 10 cm.
a) Especially easy to tear ◎ b) Easy to tear ○ c) Somewhat difficult to tear △ d)
The thing which is hard to tear was made into x.

(Production Example 1)
[Preparation of solid component (S-1)]
In a reactor equipped with a stirrer with an internal volume of 260 liters, 10 kg of silica (SiO ₂ : average particle size 12 μm) dried at 250 ° C. for 10 hours in a nitrogen atmosphere was suspended in 90.5 liters of toluene, and then cooled to 0 to 5 ° C. did. To this suspension, 45.5 liters of a toluene solution of methylalumoxane (3.0 mmol / ml in terms of Al atoms) was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 to 5 ° C. Subsequently, the mixture was reacted at 0 to 5 ° C for 30 minutes, then heated to 95 to 100 ° C over about 1.5 hours, and then reacted at 95 to 100 ° C for 4 hours. Thereafter, the temperature was lowered to room temperature, and the supernatant was removed by decantation. The solid component thus obtained was washed twice with toluene, and then toluene was added to make a total amount of 129 liters to prepare a toluene slurry of the solid component (S-1). A part of the obtained solid component was collected and examined for concentration. As a result, the slurry concentration was 137.5 g / L and the Al concentration was 1.1 mol / L.

[Preparation of solid catalyst component (X-1)]
Under a nitrogen atmosphere, 21.0 liters of toluene and 15.8 liters of the toluene slurry of the solid component (S-1) prepared above (2400 g as the solid component) were added to a reactor equipped with a stirrer having an internal volume of 114 liters. On the other hand, 31.0 liters of toluene was placed in a reactor with an internal volume of 100 liters under a nitrogen atmosphere, and 10.0 liters of a toluene solution of metallocene compound (A-1) (8.25 mmol / L in terms of Zr atoms) was added with stirring. Subsequently, 2.0 liters of a toluene solution of metallocene compound (B-1) (2.17 mmol / L in terms of Zr atoms) was added and mixed for several minutes [(A-1) / (B-1) molar ratio = 95 / Five〕. Subsequently, the prepared mixed solution was pumped to the reactor in which the toluene slurry of the solid component (S-1) was previously applied. After pumping, the reaction was carried out at an internal temperature of 20 to 25 ° C. for 1 hour. Thereafter, the supernatant was removed by decantation. The solid catalyst component thus obtained was washed three times with hexane, and then hexane was added to make a total volume of 56 liters to prepare a hexane slurry of the solid catalyst component (X-1).

[Preparation of prepolymerization catalyst (XP-1)]
Subsequently, after the hexane slurry of the solid catalyst component (X-1) obtained above was cooled to 10 ° C., ethylene was continuously supplied into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 2.8 mol of triisobutylaluminum (TIBAL) and 157 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was supplied again at 1.8 kg / hr to start prepolymerization.
After 40 minutes from the start of the prepolymerization, the system temperature rose to 24 ° C, and the subsequent system temperature was maintained at 24-26 ° C. 70 minutes after the start of the prepolymerization, 79.0 ml of 1-hexene was added, and 79.0 ml of 1-hexene was added 140 minutes later.

220 minutes after the start of prepolymerization, the ethylene supply was stopped, the inside of the system was replaced with nitrogen, and the prepolymerization was stopped. Thereafter, the supernatant was removed by decantation. The prepolymerized catalyst thus obtained was washed 6 times with hexane to obtain a prepolymerized catalyst (XP-1) in which 2.87 g of polymer was polymerized per 1 g of the solid catalyst component. A portion of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.72 mg of Zr atoms were contained per 1 g of the solid catalyst component.

[polymerization]
An ethylene polymer was produced using the pre-polymerization catalyst (XP-1) in a completely stirred and mixed polymerization tank having an internal volume of 290 liters.

In the polymerization tank, the solvent hexane is 45 L / h, the prepolymerization catalyst (XP-1) is converted to Zr atoms, 0.44 mmol / h, triisobutylaluminum is 20.0 mmol / hr, ethylene is 6.6 kg / hr, 1- Hexene was continuously supplied at a rate of 500 g / hr. In addition, the polymer slurry is continuously withdrawn from the polymerization tank so that the amount of solvent in the polymerization tank is constant, and the total pressure is 0.8 MPa-G, the polymerization temperature is 80 ° C., and the residence time is 2.6 hours.
Polymerization was performed under the conditions. From the polymer slurry continuously extracted from the polymerization tank, unreacted ethylene is substantially removed by a flash drum. Thereafter, hexane in the polymer slurry was removed with a solvent separator and dried to obtain an ethylene polymer at 4.4 kg / hr (see Table 1).
.

To the obtained ethylene polymer, Irganox 1076 (manufactured by Ciba Specialty Chemicals) was added as a heat-resistant stabilizer to 0.1% by weight, and Irgafos168 (manufactured by Ciba Specialty Chemicals) was added to 0.1% by weight. Using a single-shaft 65 mmφ extruder, melt kneading was carried out under the conditions of a preset temperature of 180 ° C. and a screw rotation speed of 50 rpm, and then extruded into a strand and pelletized with a cutter was used as a measurement sample. Tables 5 and 10 show the results of physical property measurement and extrusion laminate molding using the sample.

(Production Example 2) to (Production Example 4)
[polymerization]
In Production Example 1, an ethylene-based polymer was obtained in the same manner as in Production Example 1 except that the ethylene / 1-hexene copolymerization was changed to the conditions shown in Table 1 (see Table 1). Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Production Example 1. Tables 5 and 10 show the results of physical property measurement and extrusion lamination molding using the sample.

(Production Example 5)
[Preparation of solid catalyst component (X-2)]
Under a nitrogen atmosphere, 18.6 liters of toluene and 7.9 liters of the toluene slurry of the solid component (S-1) prepared above (1200 g of the solid component) were added to a reactor equipped with a stirrer having an internal volume of 114 liters. On the other hand, 14.5 liters of toluene was placed in a reactor with a stirrer with an internal volume of 100 liters under a nitrogen atmosphere, and 5.0 liters of a toluene solution of metallocene compound (A-1) (7.81 mmol / L in terms of Zr atoms) was added with stirring. Subsequently, 2.0 liters of a toluene solution of metallocene compound (B-1) (2.17 mmol / L in terms of Zr atom) was added and mixed for several minutes [(A-1) / (B-1) molar ratio = 85 / 15].
Subsequently, the prepared mixed solution was pumped to the reactor in which the toluene slurry of the solid component (S-1) was previously applied. After pumping, the reaction was carried out at an internal temperature of 20 to 25 ° C. for 1 hour. Thereafter, the supernatant was removed by decantation. The solid catalyst component thus obtained was washed three times with hexane, and then hexane was added to make a total volume of 30 liters to prepare a hexane slurry of the solid catalyst component (X-2).

[Preparation of prepolymerization catalyst (XP-2)]
Subsequently, after the hexane slurry of the solid catalyst component (X-2) obtained above was cooled to 10 ° C., ethylene was continuously supplied into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 1.6 mol of triisobutylaluminum and 80 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was supplied again at 1.8 kg / hr to start prepolymerization. After 25 minutes from the start of the prepolymerization, the system temperature rose to 24 ° C, and the subsequent system temperature was maintained at 24-26 ° C. 35 minutes after the start of prepolymerization, 39.0 ml of 1-hexene was added, and 39.0 ml of 1-hexene was also added 60 minutes later.

  85 minutes after the start of the prepolymerization, the ethylene supply was stopped, the inside of the system was replaced with nitrogen, and the prepolymerization was stopped. Thereafter, the supernatant was removed by decantation. The prepolymerized catalyst thus obtained was washed four times with hexane to obtain a prepolymerized catalyst (XP-2) in which 2.93 g of polymer was polymerized per 1 g of the solid catalyst component. A portion of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.72 mg of Zr atoms were contained per 1 g of the solid catalyst component.

[polymerization]
An ethylene-based polymer was obtained in the same manner as in Production Example 1, except that the prepolymerization catalyst (XP-2) was used and the ethylene / 1-hexene copolymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Production Example 1. Tables 5 and 10 show the results of physical property measurement and extrusion lamination molding using the sample.

(Production Example 6) to (Production Example 8)
[polymerization]
An ethylene-based polymer was obtained in the same manner as in Production Example 5, except that the ethylene / 1-hexene copolymerization conditions in Production Example 5 were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Production Example 1. The results of physical property measurement and extrusion lamination molding using the sample are shown in Tables 5 and 10 (Production Example 6 only performs physical property measurement).

(Production Example 9)
[polymerization]
An ethylene-based polymer was obtained in the same manner as in Production Example 5, except that the ethylene / 1-hexene copolymerization was changed to the conditions shown in Table 1 in Production Example 5. However, when the density of the polymer is lower than 935 kg / m ³ , the supernatant of the polymer slurry extracted from the polymerization tank becomes cloudy, and after 8 hours from the arrival of the polymer density of 920 kg / m ³ Since the coalescence and the solvent were not separated and the slurry properties deteriorated, the continuous operation was stopped. A measurement sample was prepared in the same manner as in Production Example 1 using the ethylene polymer obtained before the operation was stopped. Tables 5 and 10 show the results of physical property measurement and extrusion lamination molding using the sample.

(Production Example 10)
[Preparation of solid component (S-2)]
460 ml of 30 g of silica (SiO ₂ : average particle size 50 μm) dried at 250 ° C. for 10 hours under nitrogen flow
After being suspended in toluene, the mixture was cooled to 0 ° C. To this suspension, 140 ml of a toluene solution of methylalumoxane (1.52 mmol / ml in terms of Al atom) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 2 ° C. Subsequently, after reacting at 0 ° C. for 30 minutes, the temperature was raised to 95 ° C. over 1.5 hours and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed three times with toluene, and then toluene was added to prepare a toluene slurry of the solid component (S-2). A part of the obtained solid component (S-2) was collected and examined for concentration. As a result, the slurry concentration was 0.1665 g / ml, and the Al concentration was 0.697 mmol / ml.

[Preparation of solid catalyst component (X-3)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S-2) prepared above was charged with stirring. Next, a premixed toluene solution of metallocene compound (A-1) (0.0015 mmol / ml in terms of Zr atom) 11.2 ml and a toluene solution of metallocene compound (B-1) (0.0015 mmol / ml in terms of Zr atom) 2.8 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-3)]. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 80/20. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-3) was sampled to examine the concentration, the Zr concentration was 0.037 mg / ml and the Al concentration was 2.27 mg / ml.

[polymerization]
Purified heptane (500 ml) was placed in a 1-liter SUS autoclave thoroughly purged with nitrogen, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. Next, after replacing the system with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.45 vol%), 1 ml of 1-hexene, 0.375 mmol of triisobutylaluminum, 0.01 mmol of a solid catalyst component (X- 3) was charged in this order. The temperature was raised to 80 ° C., and polymerization was carried out at 0.78 MPa-G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 87.4 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 10 are shown in Table 2.

In order to prepare a measurement sample, Irgafos168 (manufactured by Ciba Specialty Chemicals) was adjusted to 0.1% by weight so that Irganox 1076 (manufactured by Ciba Specialty Chemicals) was 0.1% by weight as the heat stabilizer. In addition, as described above, the mixture was melt kneaded for 5 minutes at a resin temperature of 180 ° C. and a rotation speed of 50 rpm using a lab plast mill manufactured by Toyo Seiki Seisakusho. Further, this molten polymer was cooled using a press molding machine manufactured by Shindo Metal Industry Co., Ltd. under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm ² . Table 6 shows the results of physical properties measured using the sample.

(Production Example 11)
[Preparation of solid catalyst component (X-4)]
38.9 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry of solid component (S-1) prepared in Production Example 1 (2.0 g in terms of solid part) was charged with stirring. Next, 34.4 ml of a premixed metallocene compound (A-1) in toluene solution (0.002 mmol / ml in terms of Zr atoms) and a metallocene compound (B-1) in toluene solution (0.001 mmol / ml in terms of Zr atoms) 3.6 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-4)]. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 95/5. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-4) was collected and the concentration was examined, Zr
The concentration was 0.062 mg / ml, and the Al concentration was 3.64 mg / ml.

[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.2 vol%) and 0.0025 mmol of the solid catalyst component (X-4) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 71.1 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 11 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.

(Production Example 12)
[Preparation of solid catalyst component (X-5)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (2.0 g in terms of solid part) of the solid component (S-1) prepared above was charged with stirring. Next, a premixed toluene solution of metallocene compound (A-1) (0.0015 mmol / ml in terms of Zr atoms) and 44.0 ml of a toluene solution of metallocene compound (B-1) (0.0015 mmol / ml in terms of Zr atoms) 1.83 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-5)]. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 96/4. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-5) was collected and examined for concentration, Zr
The concentration was 0.061 mg / ml, and the Al concentration was 3.71 mg / ml.

[polymerization]
The polymerization in Production Example 10 was performed in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.1 vol%) and 0.0025 mmol of the solid catalyst component (X-5) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 46.2 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 12 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.

(Production Example 13)
The polymerization in Production Example 12 was performed in the same manner as in Production Example 12 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.2 vol%) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 52.2 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 13 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.

(Production Example 14)
The polymerization in Production Example 12 was carried out in the same manner as in Production Example 12 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.25 vol%) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 58.6 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 14 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.

(Production Example 15)
[Preparation of solid catalyst component (X-6)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, the amount of the toluene slurry charged with the solid component (S-1) was 1.9 g in terms of solid part, and the toluene of the metallocene compound (A-1) Solution (0.0015 mmol / ml in terms of Zr atoms) 40.3 ml, toluene solution of metallocene compound (B-1) (0.0015 mmol / ml in terms of Zr atoms) Except for using 5.50 ml, the same method as in Production Example 12 A solid catalyst component (X-6) was prepared. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 88/12. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-6) was sampled to examine the concentration, it was found that the Zr concentration was 0.059 mg / ml and the Al concentration was 3.43 mg / ml.

[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.75 vol%) and 0.0025 mmol of the solid catalyst component (X-6) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 71.3 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 15 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.

(Production Example 16)
The polymerization in Production Example 15 was performed in the same manner as in Production Example 15 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.83 vol%) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 65.9 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 16 are shown in Table 2. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 6 shows the results of physical properties measured using the sample.

(Production Example 17)
[Preparation of solid catalyst component (X-7)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, the amount of the toluene slurry of the solid component (S-1) was 1.0 g in terms of solid part, and the toluene of the metallocene compound (A-1) 16.6 ml of solution (0.002 mmol / ml in terms of Zr atoms), toluene solution of metallocene compound (B-1) (0.001 mmol / ml in terms of Zr atoms) A solid catalyst component (X-7) was prepared. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 92/8. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-7) was collected to examine the concentration, the Zr concentration was 0.058 mg / ml and the Al concentration was 3.52 mg / ml.

[polymerization]
In the polymerization of Production Example 10, a hydrogen-ethylene mixed gas (hydrogen concentration: 0.65 vol%) was used, the amount of 1-hexene was changed to 3 ml, and the solid catalyst component (X-7) of 0.0026 mmol in terms of zirconium was used. The procedure was the same as in Production Example 10 except that The obtained polymer was vacuum-dried for 10 hours to obtain 63.9 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 17 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.

(Production Example 18)
[Preparation of solid catalyst component (X-8)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, 32.5 ml of a toluene solution of metallocene compound (A-1) (0.002 mmol / ml in terms of Zr atom), a toluene solution of metallocene compound (B-1) ( The solid catalyst component (X-8) was prepared in the same manner as in Production Example 12, except that 7.23 ml was used (0.001 mmol / ml in terms of Zr atoms). The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 90/10. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-8) was collected to examine the concentration, the Zr concentration was 0.065 mg / ml and the Al concentration was 3.77 mg / ml.

[polymerization]
In the polymerization of Production Example 10, the polymerization temperature was set to 70 ° C., a hydrogen-ethylene mixed gas (hydrogen concentration: 0.064 vol%) was used, the amount of 1-hexene was changed to 30 ml, and the solid catalyst component of 0.0026 mmol in terms of zirconium The procedure was the same as in Production Example 10 except that (X-8) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 92.9 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 18 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.

(Production Example 19)
The polymerization in Production Example 18 was carried out in the same manner as in Production Example 18, except that 0.1 g of the solid catalyst component (X-7) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 44.5 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 19 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.

(Production Example 20)
[Preparation of prepolymerization catalyst (XP-4)]
52.7 ml of hexane was placed in a 200 ml glass flask purged with nitrogen, and the hexane slurry (4.0 g in terms of solid part) of the solid catalyst component (X-4) prepared above was charged. Next, after cooling to 10 ° C., 5.32 mmol of TIBAL and 0.535 ml of 1-hexene were added, and ethylene feeding was started at 30 L / hr under normal pressure. Polymerization was carried out at 25 ° C. until the cumulative amount of ethylene absorbed by the solid catalyst component reached 10.3 liters. After completion of the polymerization, the system was replaced with nitrogen to complete the prepolymerization. Thereafter, the supernatant was removed by decantation and washed with decane three times to prepare a decane slurry to prepare a prepolymerized catalyst (XP-4). A portion of the resulting decane slurry of the prepolymerized catalyst (XP-4) was collected and examined for concentration. As a result, the Zr concentration was 0.067 mg / ml, and the Al concentration was 4.77 mg / ml.

[polymerization]
In the polymerization of Production Example 10, the polymerization temperature was set to 70 ° C., ethylene gas was used, the amount of 1-hexene was changed to 30 ml, and a prepolymerization catalyst (XP-4) of 0.0026 mmol in terms of zirconium was used. In the same manner as in Example 10. The obtained polymer was vacuum-dried for 10 hours to obtain 60.8 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 20 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.

(Production Example 21)
[Preparation of prepolymerization catalyst (XP-9)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, 14.5 ml of a toluene solution of metallocene compound (A-1) (0.004 mmol / ml in terms of Zr atom), a toluene solution of metallocene compound (B-1) ( A solid catalyst component (X-9) was prepared in the same manner as in Production Example 12, except that 7.23 ml was used (0.002 mmol / ml in terms of Zr atoms). The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 80/20. Subsequently, a decane slurry of the prepolymerized catalyst (XP-9) was prepared in the same manner as the preparation of the prepolymerized catalyst (XP-4) of Production Example 20. A portion of the resulting decane slurry of the prepolymerized catalyst (XP-9) was collected and examined for concentration. As a result, the Zr concentration was 0.062 mg / ml and the Al concentration was 4.16 mg / ml.

[polymerization]
In the polymerization of Production Example 10, the polymerization temperature was 50 ° C., ethylene gas was used, the amount of 1-hexene was changed to 50 ml, and a prepolymerization catalyst (XP-9) of 0.0012 mmol in terms of zirconium was used. In the same manner as in Example 10. The obtained polymer was vacuum-dried for 10 hours to obtain 25.6 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 21 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.

(Production Example 22)
[Preparation of prepolymerization catalyst (XP-10)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, 12.7 ml of a toluene solution of metallocene compound (A-1) (0.004 mmol / ml in terms of Zr atom), a toluene solution of metallocene compound (B-1) ( A solid catalyst component (X-10) was prepared in the same manner as in Production Example 12, except that 10.8 ml (0.002 mmol / ml in terms of Zr atoms) was used. The mixing molar ratio of the metallocene compounds (A-1) and (B-1) during the preparation of the solid catalyst component is (A-1) / (B-1) = 70/30. Subsequently, a decane slurry of the prepolymerized catalyst (XP-10) was prepared in the same manner as the preparation of the prepolymerized catalyst (XP-4) of Production Example 20. A portion of the resulting decane slurry of the prepolymerized catalyst (XP-10) was sampled and examined for concentration. As a result, the Zr concentration was 0.060 mg / ml and the Al concentration was 4.12 mg / ml.

[polymerization]
In the polymerization of Production Example 10, the polymerization temperature was 50 ° C., ethylene gas was used, the amount of 1-hexene was changed to 50 ml, and a prepolymerization catalyst (XP-10) of 0.002 mmol in terms of zirconium was used. In the same manner as in Example 10. The obtained polymer was vacuum-dried for 10 hours to obtain 56.6 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 22 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.

(Production Example 23)
The polymerization in Production Example 22 was carried out in the same manner as in Production Example 22, except that the amount of 1-hexene was changed to 40 ml. The obtained polymer was vacuum-dried for 10 hours to obtain 50.3 g of an ethylene polymer.
The production conditions for the polymer obtained in Production Example 23 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.

(Production Example 24)
[Preparation of prepolymerization catalyst (XP-11)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, the same as Production Example 12 except that only 18.1 ml of a toluene solution of metallocene compound (A-1) (0.004 mmol / ml in terms of Zr atom) was used. The solid catalyst component (X-11) was prepared by the method described above. Subsequently, a decane slurry of the prepolymerized catalyst (XP-11) was prepared in the same manner as the preparation of the prepolymerized catalyst (XP-4) of Production Example 20. A portion of the resulting decane slurry of the prepolymerized catalyst (XP-11) was collected and examined for concentration. As a result, the Zr concentration was 0.065 mg / ml and the Al concentration was 5.46 mg / ml.

[Preparation of prepolymerization catalyst (XP-12)]
In the preparation of the solid catalyst component (X-5) of Production Example 12, the same as Production Example 12 except that only 18.1 ml of a toluene solution of metallocene compound (B-1) (0.004 mmol / ml in terms of Zr atoms) was used. The solid catalyst component (X-12) was prepared by the method described above. Further, a decane slurry of the prepolymerized catalyst (XP-12) was prepared in the same manner as in the preparation of the prepolymerized catalyst (XP-4) of Production Example 20. A portion of the resulting decane slurry of the prepolymerized catalyst (XP-12) was collected and examined for concentration. As a result, the Zr concentration was 0.063 mg / ml and the Al concentration was 3.72 mg / ml.

[polymerization]
Purified heptane (500 ml) was placed in a 1-liter SUS autoclave thoroughly purged with nitrogen, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. Next, after replacing the inside of the system with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.20 vol%), 1 ml of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and a prepolymerization catalyst (XP-11) 0.0025 mmol in terms of zirconium and 0.00028 mmol in the pre-polymerization catalyst (XP-12) were charged (in terms of the molar ratio of zirconium, pre-polymerization catalyst (XP-11) / pre-polymerization catalyst (XP-12) = 90 /Ten〕. The temperature was raised to 80 ° C., and polymerization was carried out at 0.78 MPa-G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 55.3 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 24 are shown in Table 3. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 7 shows the results of physical properties measured using the sample.

(Production Example 25)
The polymerization in Production Example 24 was carried out in the same manner as in Production Example 24 except that the polymerization temperature was 70 ° C., ethylene gas was used, and the amount of 1-hexene was changed to 30 ml. The obtained polymer was vacuum-dried for 10 hours to obtain 76.8 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 25 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.

(Production Example 26)
The polymerization in Production Example 25 was performed in the same manner as in Production Example 25 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.20 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 62.8 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 26 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.

(Production Example 27)
The polymerization in Production Example 25 was performed in the same manner as in Production Example 25 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.31 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 72.3 g of an ethylene-based polymer. The production conditions for the polymer obtained in Production Example 27 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.

(Production Example 28)
Purified heptane (500 ml) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, and ethylene was passed through to replace the system. Next, 30 ml of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and 0.00238 mmol of the prepolymerized catalyst (XP-11) was added in terms of zirconium and 0.00013 mmol of the prepolymerized catalyst (XP-12) was charged in terms of zirconium. [Preliminary polymerization catalyst (XP-11) / Preliminary polymerization catalyst (XP-12) = 95/5 in terms of the molar ratio of zirconium]. The temperature was raised to 70 ° C., and polymerization was carried out at 0.78 MPa-G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 60.9 g of an ethylene-based polymer. The production conditions for the polymer obtained in Production Example 28 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.

( Reference Production Example 29)
[Preparation of solid catalyst component (X-13)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (2.0 g in terms of solid part) of the solid component (S-2) prepared above was charged with stirring. Next, 37.6 ml of a premixed metallocene compound (A-1) in toluene solution (0.001 mmol / ml in terms of Zr atoms) and a metallocene compound (B-2) in toluene solution (0.001 mmol / ml in terms of Zr atoms) 4.18 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-13)]. The mixing molar ratio of the metallocene compounds (A-1) and (B-2) during the preparation of the solid catalyst component is (A-1) / (B-2) = 90/10. Further, when a part of the resulting decane slurry of the solid catalyst component (X-13) was sampled to examine the concentration, it was found that the Zr concentration was 0.035 mg / ml and the Al concentration was 2.46 mg / ml.

[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.31 vol%) and 0.003 mmol of the solid catalyst component (X-13) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 38.4 g of an ethylene polymer. The production conditions for the polymer obtained in Reference Production Example 29 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.

(Production Example 30)
[Preparation of solid catalyst component (X-14)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S-2) prepared above was charged with stirring. Next, a premixed toluene solution of metallocene compound (A-2) (0.002 mmol / ml in terms of Zr atoms) 2.25 ml and a toluene solution of metallocene compound (B-1) (0.002 mmol / ml in terms of Zr atoms) 9.01 A mixed solution of ml was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-14)]. The mixing molar ratio of the metallocene compound (A-2) and (B-1) during the preparation of the solid catalyst component is (A-2) / (B-1) = 20/80. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-14) was collected and examined for concentration, it was found that the Zr concentration was 0.015 mg / ml and the Al concentration was 1.27 mg / ml.

[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that ethylene gas was used, the polymerization temperature was 70 ° C., and 0.0005 mmol of the solid catalyst component (X-14) in terms of zirconium was used. The obtained polymer was vacuum-dried for 10 hours to obtain 72.0 g of an ethylene polymer. Production Example 30
The production conditions of the polymer obtained in 1 were described in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.

(Production Example 31)
[Preparation of solid catalyst component (X-15)]
50 ml of toluene was placed in a 200 ml glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S-2) prepared above was charged with stirring. Next, 4.18 ml of a premixed transition metal compound (A-3) in toluene solution (0.001 mmol / ml in terms of Zr atoms) and a metallocene compound (B-1) in toluene solution (0.0015 mmol / ml in terms of Zr atoms) 11.15 ml of the mixed solution was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a decane slurry [solid catalyst component (X-15)]. The mixing molar ratio of the transition metal compound (A-3) and the metallocene compound (B-1) during the preparation of the solid catalyst component is (A-3) / (B-1) = 20/80. Further, when a portion of the resulting decane slurry of the solid catalyst component (X-15) was sampled to examine its concentration, it was found that the Zr concentration was 0.034 mg / ml and the Al concentration was 2.17 mg / ml.

[polymerization]
The polymerization in Production Example 10 was carried out in the same manner as in Production Example 10, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.02 vol%) and 0.001 mmol of the solid catalyst component (X-15) in terms of zirconium were used. It was. The obtained polymer was vacuum-dried for 10 hours to obtain 67.7 g of an ethylene polymer. The production conditions for the polymer obtained in Production Example 31 are shown in Table 4. A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 8 shows the results of physical properties measured using the sample.

[Comparative Production Example 1]
Ethylene 4-methyl-1-pentene copolymer (trade name: Ultozex 20100J) by the solution polymerization method marketed by Prime Polymer Co., Ltd. uses product pellets as measurement samples.
Physical property evaluation and extrusion lamination were performed. The results are shown in Tables 9 and 10.

Comparative Production Example 1 deviates from the requirement described in claim 1 with respect to MT / η *. For this reason, a neck-in is large compared with a manufacture example.
[Comparative Production Example 2]
Polyethylene (trade name: Mirason 11) by high pressure radical polymerization commercially available from Prime Polymer Co., Ltd. was subjected to physical property evaluation and extrusion lamination molding using a product pellet as a measurement sample. The results are shown in Tables 9 and 10.

Comparative Production Example 2 deviates from the requirement described in claim 1 regarding the sum of the number of methyl branches and the number of ethyl branches (A + B). For this reason, heat seal strength is inferior compared with a manufacture example.
[Comparative Production Example 3]
[Preparation of solid component (S-3)]
In a reactor equipped with a stirrer with an internal volume of 180 liters, 10 kg of silica (SiO ₂ ) dried at 250 ° C. for 10 hours in a nitrogen atmosphere was suspended in 77 liters of toluene, and then cooled to 0 to 5 ° C. To this suspension, 39.5 liters of methylalumoxane in toluene (1.79 mmol / ml in terms of Al atoms) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 5 ° C. Subsequently, the mixture was reacted at 0 to 5 ° C. for 30 minutes, then heated to 95 to 100 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 55-60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed four times with toluene, and then toluene was added to make a total volume of 166.3 liters to prepare a toluene slurry of the solid component (S-3). A part of the obtained solid component (S-3) was collected and examined for concentration. As a result, the slurry concentration was 84.6 g / L and the Al concentration was 0.422 mol / L.

[Preparation of solid catalyst component (X-16)]
Next, 11.8 liters of the toluene slurry of the solid component (S-3) prepared above (1000 g of the solid component) was added to a reactor equipped with a stirrer with an internal volume of 114 liters under a nitrogen atmosphere. 14.7 liters of a toluene solution of (indenyl) zirconium dichloride (0.0017 mmol / ml in terms of Zr atoms) was added dropwise at 78 to 80 ° C. over 30 minutes, and reacted at this temperature for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane, and then hexane was added to a total volume of 25 liters to prepare a hexane slurry of the solid catalyst component (X-16).

[Preparation of prepolymerization catalyst (XP-16)]
After cooling the hexane slurry of the solid catalyst component (X-16) obtained above to 5 ° C., ethylene was continuously supplied into the system under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 1.9 liters of a hexane solution of triisobutylaluminum (40.0 mmol / L in terms of Al atom) and 65.3 ml of 1-hexene were added to start prepolymerization. After 1 hour, the temperature in the system rose to 35 ° C, but thereafter, the temperature in the system was maintained at 34 to 35 ° C. 70 minutes after the start of prepolymerization, 65.3 ml of 1-hexene was added again.

Thereafter, 4 hours after the start of the prepolymerization, the system was replaced with nitrogen, and the prepolymerization was stopped. Next, the supernatant was removed and washed 4 times with hexane to obtain a prepolymerized catalyst (XP-16) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component (X-16). Thereafter, the temperature inside the system was raised to 34 to 35 ° C., and 10 liters of a hexane solution of Emulgen 108 (polyoxyethylene lauryl ether manufactured by Kao Corporation) (1.0 g / L in the concentration of Emulgen) was added. Stir at this temperature for 2 hours,
A prepolymerization catalyst (XPV-16) in which emulgen was supported on the prepolymerization catalyst (XP-16) was obtained.

[polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, ethylene and 1-hexene were copolymerized at a total pressure of 2.0 MPa-G, a polymerization temperature of 70 ° C., and a gas linear velocity of 0.8 m / sec. The pre-polymerized catalyst (XPV-16) prepared above is dried and continuously fed at a rate of 25-30 g / hr to maintain a constant gas composition during the polymerization, ethylene, 1-hexene, hydrogen and Nitrogen was continuously supplied (gas composition: 1-hexene / ethylene = 1.1 to 1.3 × 10 ⁻² , ethylene concentration = 71.4%). The yield of the obtained ethylene polymer was 5.3 kg / hr.

Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Production Example 1. Using this sample, physical properties were measured and extrusion lamination was performed. The results are shown in Tables 9 and 10.
Comparative Production Example 3 deviates from the requirement described in claim 1 with respect to MT / η *. For this reason, the neck in at the time of shaping | molding is large compared with the manufacture example. Furthermore, the relationship between the zero shear viscosity (η ₀ ) and the weight average molecular weight (Mw) deviates from the requirement described in claim 1. For this reason, unlike the manufacturing example, takeover surging occurs.

[Comparative Production Example 4]
[Preparation of solid catalyst component (X-17)]
100 ml of toluene was placed in a 200 ml glass flask purged with nitrogen and stirred, and the toluene slurry of the solid component (S-3) prepared above (2.0 g in terms of solid part) was charged. Next, 32.1 ml of a toluene solution of Me ₂ Si (Ind) ₂ ZrCl ₂ (component A) (0.0015 mmol / ml in terms of Zr atoms) was added dropwise,
The reaction was allowed to proceed for 1 hour at room temperature. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain 100 ml of decane slurry [solid catalyst component (X-17)]. A portion of the resulting decane slurry of the solid catalyst component (X-17) was collected and examined for concentration. As a result, the Zr concentration was 0.043 mg / ml, and the Al concentration was 2.49 mg / ml.

[polymerization]
Purified heptane (500 ml) was placed in a 1-liter SUS autoclave thoroughly purged with nitrogen, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. Next, after replacing the inside of the system with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.54 vol%), 1 ml of 1-hexene, 0.375 mmol of triisobutylaluminum, 0.5 g of the solid catalyst component (X-17) We inserted in order. 80 ℃
The temperature was raised to 0.78 MPa-G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 86.7 g of an ethylene polymer.

A measurement sample was prepared by the same method as in Production Example 10 using the obtained ethylene polymer. Table 9 shows the results of physical properties measured using the sample.
[Comparative Production Example 5]
The ethylene 1-octene copolymer (trade name: Affinity PF1140) by the solution polymerization method marketed by Dow Chemical Company was evaluated for physical properties using the product pellet as a measurement sample. The results are shown in Table 9.

Comparative production examples 4 and 5 deviate from the requirements described in claim 1 with respect to MT / η *. For this reason,
It is estimated that the neck-in is larger than the manufacturing example. Furthermore, the relationship between the zero shear viscosity (η ₀ ) and the weight average molecular weight (Mw) deviates from the requirement described in claim 1. For this reason, it is estimated that takeover surging occurs unlike the manufacturing example.

( Reference Production Example 32)
[Ethylene polymer [R1-1]]
Ethylene polymer [R1-1] was produced in the same manner as in Production Example 11. Using the obtained ethylene polymer [R1-1], a measurement sample was prepared in the same manner as in Production Example 10. Table 11 shows the results of physical properties measured using the sample.

[Ethylene polymer [R2-1]]
As the ethylene-based polymer [R2-1], an ethylene-4-methyl-1-pentene copolymer (trade name: Ultzex UZ15150J) commercially available from Prime Polymer Co., Ltd. was used. Table 11 shows the results of physical property evaluation using product pellets as measurement samples.

[Ethylene resin]
After dry blending ethylene polymer [R1-1] and ethylene polymer [R2-1] at a weight ratio ([R1-1] / [R2-1] = 30/70), manufactured by Toyo Seiki Seisakusho Using Laboplast Mill, resin temperature 180 ° C
The mixture was melt-kneaded for 5 minutes at a rotation speed of 50 rpm to obtain an ethylene-based resin. Further, this molten polymer was cooled using a press molding machine manufactured by Shinto Metal Industry, under conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm ² . Table 12 shows the results of physical properties measured using the sample.

[Preparation Example 1]
Irganox 1076 (manufactured by Ciba Specialty Chemicals) is 0.1% by weight, and Irgafos168 (manufactured by Ciba Specialty Chemicals) is 0.1% by weight as a heat stabilizer to the ethylene polymer obtained by the method described in Production Example 8. In addition, using a single-axis 65 mmφ extruder manufactured by Plako Co., Ltd., melt-kneaded under the conditions of a set temperature of 180 ° C. and a screw rotation speed of 50 rpm, then extruded into a strand shape and measured as pellets with a cutter. It was.

[Production of film]
Using the ethylene-based resin composition obtained in Preparation Example 1, air-cooled inflation molding (single layer) was performed under the following molding conditions to produce a film having a film thickness of 40 μm and a width of 320 mm.

<Film forming conditions>
Molding machine: Modern machinery 50mmφ inflation molding machine Screw: Barrier type screw Dies: 100mmφ (diameter), 2.0mm (lip width)
Air ring: 2-gap type Molding temperature: 190 ° C
Extrusion amount: 28.8 kg / h
Take-off speed: 20 m / min
Film thickness: 40μm
Table 13 shows the measurement of physical properties and molding evaluation of the obtained ethylene-based resin composition and film.
[Comparative Example 1]
Using a prime polymer UZ5010F product pellet as a measurement sample, a film was prepared in the same manner as in Example 1, and physical properties were measured and evaluated for molding. The results are shown in Table 13.

It is the figure which plotted the weight average molecular weight (Mw) and zero shear viscosity ((eta) ₀ ) of the ethylene-type resin disclosed by all the manufacture examples and all the comparative manufacture examples. The numbers in the figure are manufacturing example numbers or comparative manufacturing example numbers. The two straight lines in the figure are boundary lines indicating the upper and lower limits of the parameter formula.

Explanation of symbols

□ ・ ・ ・ Production example ■ ・ ・ ・ Comparative production example

Claims (3)

Ethylene, a copolymer with α- olefin having 4 to 10 carbon atoms, Ri Do from the following requirements [1] to the resin composition comprising an ethylene-based resin satisfying [6] at the same time, pull the time of film forming take direction Elmendorf tear strength the Elmendorf divided by tear strength der 0.3 to 1.0 Rukoto the direction perpendicular to the drawing direction (the compliant ASTM D1922) (TD direction) of (MD direction) A film characterized by
[1] Melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 50 g / 10 min.
[2] The density (d) is in the range of 875 to 970 kg / m ³ .
[3] 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. The range is from 1.50 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ .
[4] Sum [(A + B) (/ 1000C) of methyl branch number [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR )] Is 1.8 or less.
[5] Zero shear viscosity [η ₀ (P)] at 200 ° C. and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01 × 10 ^-13 × Mw ^3.4 ≦ η ₀ ≦ 4.5 × 10 ^-13 × Mw ^3.4 ----- (Eq-1)
[6] The intrinsic viscosity ([η] (dl / g)) measured in decalin at 135 ° C. and the weight average molecular weight Mw measured by GPC-viscosity detector method (GPC-VISCO) 7) Satisfies.
0.80 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.65 × 10 ^-4 × Mw ^0.776 ----- (Eq-7) Ethylene, a copolymer with α- olefin having 4 to 10 carbon atoms, and wherein the processing a resin composition comprising simultaneously satisfy ethylene-based resin of the following requirements [1] to [6], The manufacturing method of the film of Claim 1 .
[1] Melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 50 g / 10 min.
[2] The density (d) is in the range of 875 to 970 kg / m ³ .
[3] 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. The range is from 1.50 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ .
[4] Sum [(A + B) (/ 1000C) of methyl branch number [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR )] Is 1.8 or less.
[5] Zero shear viscosity [η ₀ (P)] at 200 ° C. and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01 × 10 ^-13 × Mw ^3.4 ≦ η ₀ ≦ 4.5 × 10 ^-13 × Mw ^3.4 ----- (Eq-1)
[6] The intrinsic viscosity ([η] (dl / g)) measured in decalin at 135 ° C. and the weight average molecular weight Mw measured by GPC-viscosity detector method (GPC-VISCO) 7) Satisfies.
0.80 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.65 × 10 ^-4 × Mw ^0.776 ----- (Eq-7) A packaging material comprising the film according to claim 1 .

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