WO2020050245A1

WO2020050245A1 - Film and packaging container

Info

Publication number: WO2020050245A1
Application number: PCT/JP2019/034556
Authority: WO
Inventors: 直子越智; 雄也岡積
Original assignee: 住友化学株式会社
Priority date: 2018-09-07
Filing date: 2019-09-03
Publication date: 2020-03-12
Also published as: JP7200998B2; CN112638997B; JPWO2020050245A1; CN112638997A

Abstract

Provided are a film which makes it possible to afford a packaging container having excellent bag-drop strength, and a packaging container having excellent bag-drop strength. The film is such that S1 determined from 0) to 7) is not less than 220 MPa and not more than 2000 MPa, wherein a nominal stress at 100% elongation in an MD direction during a tensile test under the condition of a tensile rate of 500 mm/min is not less than 11.0 MPa and not more than 30.0 MPa. 1) The tensile test is performed using a test piece at a velocity of 1 m/s on a high-velocity tensile testing machine. 7) S1 is determined by 7a) or 7b). 7a) During the tensile test 1), if the test piece is not broken at the point in time when a maximum principal strain is 2.0, S1 is determined according to expression (11). Expression (11): S1=(p-q)/0.3 (in expression (11), p is the true stress (MPa) when the maximum principal strain is 2.0, and q is the true stress (MPa) when the maximum principal strain is 1.7).

Description

Film and packaging containers

The present invention relates to a film and a packaging container containing the film.

Plastic film is used as a material for packaging containers. As a film included in a packaging container, for example, Patent Document 1 describes a film made of a resin composition containing an ethylene-α-olefin copolymer and a low-density polyethylene obtained by a high-pressure radical polymerization method. .

JP-A-11-181173

包装 When the packaging container containing the contents falls, the packaging container may be damaged, and in recent years, improvement in the dropping strength of the packaging container has been demanded.

Under such circumstances, the problem to be solved by the present invention is to provide a film capable of providing a packaging container having excellent dropping strength and a packaging container having excellent dropping strength.

The present invention provides the following.
[1] S1 determined by the following 0) to 7) is 220 MPa or more and 2000 MPa or less;
A film having a nominal stress of 11.0 MPa or more and 30.0 MPa or less at an elongation of 100% in the MD direction when subjected to a tensile test at a tensile speed of 500 mm / min.

0) A test piece is punched out of the film with a dumbbell cutter conforming to the ASTM D1822 Type S standard so that the longer side is in the MD direction.
1) A tensile test is performed on the test piece at a speed of 1 m / s using a high-speed tensile tester.
2) The test piece during the tensile test of 1) is photographed by a high-speed camera.
3) The captured image is analyzed by 3D inspection / analysis software to determine the maximum principal strain (ε ₁ ) and the minimum principal strain (ε ₃ ) at the constricted portion of the test piece.
4) The cross-sectional area of the constricted part of the test piece is determined by the following equation.
(Cross-sectional area of constriction of test piece)
= (Width of constricted part before test execution) × (thickness of constricted part before test execution) × {exp (ε ₃ )} ²
5) The load at each time obtained by the tensile test is divided by the cross-sectional area of the constricted portion of the test piece at each time to obtain the true stress at each time.
6) The true stress at each time obtained in 5) is plotted against the maximum principal strain (ε ₁ ) at each time to obtain a true stress-maximum principal strain curve.
7) S1 is determined by 7a) or 7b).
7a) In the tensile test of 1), when the test piece is not broken at the time when the maximum principal strain is 2.0, S1 is obtained by the following equation (11).
S1 = (p−q) /0.3 (11)
(In Equation (11), p is the true stress (MPa) at the maximum principal strain of 2.0, and q is the true stress (MPa) at the maximum principal strain of 1.7.)
7b) In the tensile test of 1), when the test piece breaks within a range where the maximum principal strain is larger than 1.7 and smaller than 2.0, S1 is calculated by the following equation (12).
S1 = (p'-q) / (r-1.7) (12)
(In the equation (12), p ′ is the true stress (MPa) at the breaking point, q is the true stress (MPa) at the maximum principal strain of 1.7, and r is the maximum principal strain at the breaking point. Is.)
[2] A multilayer film including a layer α composed of the film according to [1],
A multilayer film in which at least one of the two surface layers of the multilayer film is the layer α.
[3] A packaging container containing the film according to [1].

According to the present invention, it is possible to provide a packaging container having excellent bag drop strength.

[Definition]
As used herein, the following terms are defined or described as follows.
The “ethylene-based polymer” is a polymer having a monomer unit based on ethylene, and the content of the monomer unit based on ethylene is 50% based on 100% by weight of the total weight of the polymer. It is a polymer which is not less than weight%.
“Ethylene-α-olefin copolymer” is a copolymer having a monomer unit based on ethylene and a monomer unit based on α-olefin, and the total weight of the copolymer is 100%. A copolymer in which the total amount of monomer units based on ethylene and monomer units based on α-olefin is 95% by weight or more with respect to% by weight.
The “α-olefin” is a linear or branched olefin having a carbon-carbon unsaturated double bond at the α-position.
“Ethylene-based resin composition” refers to a composition containing an ethylene-based polymer.
The "high-pressure low-density polyethylene", ethylene, or ethylene and a small amount of density is produced by polymerizing a copolymerizable component refers to 930 kg / m ³ or less of the polymer by radical polymerization under a pressure of 100 ~ 400 MPa .
"Lubricant" refers to an agent that acts to lower the coefficient of friction of the material to which it is added.
"Anti-blocking agent" refers to an agent having a function of preventing the films from sticking, sticking or fusing together during storage or use of the film to prevent the films from peeling off.

The density in the present specification is a value measured according to the method A defined in JIS K7112-1980 after performing the annealing described in JIS K6760-1995.
The melt flow rate (hereinafter sometimes referred to as MFR; unit is g / 10 min) in the present specification is a condition at a temperature of 190 ° C. and a load of 21.18 N according to the method specified in JIS K7210-1995. Is the value measured in
The melt flow rate ratio (hereinafter sometimes referred to as MFRR) in the present specification is a condition at a temperature of 190 ° C. and a load of 211.82 N with respect to a melt flow rate measured at a temperature of 190 ° C. and a load of 21.18 N. Is the ratio of the melt flow rates measured in.
In the present specification, the number average molecular weight (hereinafter, sometimes referred to as Mn), weight average molecular weight (hereinafter, sometimes referred to as Mw), and z average molecular weight (hereinafter, sometimes referred to as Mz) are as follows. , By gel permeation chromatography (GPC). The GPC measurement is performed under the following conditions (1) to (8).
(1) Equipment: Waters 150C manufactured by Waters
(2) Separation column: TOSOH TSKgel GMH ₆ -HT
(3) Measurement temperature: 140 ° C
(4) Carrier: orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: differential refraction
(8) Molecular weight standard substance: standard polystyrene

The “MD direction” is the direction in which the film advances during film formation.
The “TD direction” is a direction orthogonal to the MD direction.
When the film is a roll, the longitudinal direction is the MD direction. Usually, one side in a film or a packaging container distributed on the market is parallel to the MD direction.
"True strain" is the length after deformation l, a length before deformation upon the l _0, a ε represented by the following formula.

The “principal strain” is a vertical strain component in a tensor (principal strain tensor) based on a coordinate system in which a shear strain becomes zero when a strain acting in an object is represented by a tensor. The principal distortion is defined as “maximum principal distortion (ε ₁ )”, “intermediate principal distortion (ε ₂ )”, and “minimum principal distortion (ε ₃ )” in descending order of value.

<Film>
The film according to the present invention contains a polymer. The film is preferably a film containing an ethylene-based polymer. The content of the ethylene polymer in the film is preferably from 70.0% by weight to 99.9% by weight, more preferably from 80.0% by weight to 99.8% by weight, and further preferably 90% by weight or less. The content is not less than 0.0% by weight and not more than 99.7% by weight, particularly preferably not less than 95.0% by weight and not more than 99.6% by weight. The ethylene-based polymer contained in the film is preferably a polymer having monomer units based on ethylene, and the total weight of the polymer is 100% by weight, and the monomer units based on ethylene are preferably used. It is a polymer having a content of 90% by weight or more.

[S1]
In the film according to the present invention, S1 determined by the following 0) to 7) is 220 MPa or more and 2000 MPa or less.
0) A test piece is punched out of the film with a dumbbell cutter conforming to the ASTM D1822 Type S standard so that the longer side is in the MD direction.
1) A tensile test is performed on the test piece at a speed of 1 m / s using a high-speed tensile tester.
2) The test piece during the tensile test of 1) is photographed by a high-speed camera.
3) The captured image is analyzed by 3D inspection / analysis software to determine the maximum principal strain (ε ₁ ) and the minimum principal strain (ε ₃ ) at the constricted portion of the test piece.
4) The cross-sectional area of the constricted part of the test piece is determined by the following equation.
(Cross-sectional area of constriction of test piece)
= (Width of constricted part before test execution) × (thickness of constricted part before test execution) × {exp (ε ₃ )} ²
5) The load at each time obtained by the tensile test is divided by the cross-sectional area of the constricted portion of the test piece at each time to obtain the true stress at each time.
6) The true stress at each time obtained in 5) is plotted against the maximum principal strain (ε ₁ ) at each time to obtain a true stress-maximum principal strain curve.
7) S1 is determined by 7a) or 7b).
7a) In the tensile test of 1), when the test piece is not broken at the time when the maximum principal strain is 2.0, S1 is obtained by the following equation (11).
S1 = (p−q) /0.3 (11)
(In Equation (11), p is the true stress (MPa) at the maximum principal strain of 2.0, and q is the true stress (MPa) at the maximum principal strain of 1.7.)
7b) In the tensile test of 1), when the test piece breaks within a range where the maximum principal strain is larger than 1.7 and smaller than 2.0, S1 is calculated by the following equation (12).
S1 = (p'-q) / (r-1.7) (12)
(In the equation (12), p ′ is the true stress (MPa) at the breaking point, q is the true stress (MPa) at the maximum principal strain of 1.7, and r is the maximum principal strain at the breaking point. Is.)

において In this specification, the “constriction of the test piece” means the center of the test piece in the long side direction. p, p ', and q use values subjected to smoothing processing.

The method of obtaining ε ₁ and ε ₃ in 1) to 3) is called a digital image correlation method. epsilon ₁ is the distortion caused in the pulling direction, and expressed as true strain. S1 is the slope of the true stress-maximum principal strain curve when the maximum principal strain is in the range of 1.7 to 2.0 or the maximum principal strain is in the range from 1.7 to the breaking point.

The high-speed camera of # 2) generally has a frame rate of 30 fps or more, preferably 10,000 fps. Further, the shutter speed of the high-speed camera is preferably 20.1 μs or less.

In the tensile test specified in (1) and (7), the test piece composed of the film of the present invention usually does not break when the maximum principal strain is less than 1.7.

The breaking point of # 7) is a point at which the film breaks and the tensile load becomes zero or less.

In one embodiment, S1 may be 250 or more and 1000 or less, 280 or more and 800 or less, 290 or more and 650 or less, or 290 or more and 500 or less, or 300 or more and 500 or less. It may be.

[Nominal stress at 100% elongation]
The film according to the present invention has a nominal stress of 11.0 MPa to 30.0 MPa at 100% elongation in the MD direction when subjected to a tensile test at a tensile speed of 500 mm / min. Hereinafter, the nominal stress at an elongation of 100% in the MD direction is referred to as “S2”.
S2 is preferably 11.0 or more and 18.0 or less, more preferably 11.0 or more and 14.0 or less, and further preferably 12.0 or more and 14.0 or less.

The nominal stress at 100% elongation in the MD direction is determined by the following method.
From the film, a test piece whose longitudinal direction is the MD direction is prepared according to the method described in JIS K6781-1994, “6.4 Tensile cutting load and elongation”. The test piece is subjected to a tensile test under the conditions of 80 mm between the chucks, 40 mm between the marked lines, and a tensile speed of 500 mm / min, and the nominal stress at 100% elongation is determined. In the present specification, the “nominal stress” is a value obtained by dividing a tensile load at a predetermined elongation by a cross-sectional area of a test piece before a tensile test. The cross-sectional area of the test piece before the tensile test is the product of the center width in the long side direction of the test piece before the tensile test and the thickness of the center in the long side direction before the tensile test.

The combination of S1 and S2 is preferably a combination in which S1 is 290 or more and 650 or less, S2 is 11.0 or more and 18.0 or less, S2 is 290 or more and 500 or less, and S2 is 11.0 or more and 14.0 or less. Is more preferable, and a combination in which S1 is 300 or more and 500 or less and S2 is 12.0 or more and 14.0 or less is further preferable.

[Resin density of film]
Resin density of the film is preferably not more than 890 kg / ^{m 3} or more 930 kg / ^{m 3,} more preferably not more than 900 kg / ^{m 3} or more 925 kg / ^{m 3,} more preferably 910 kg / ^{m 3} or more 920 kg / ^{m 3} or less It is.
In this specification, "resin density" refers to the density of the resin component contained in the film.
The film may include an inorganic component. When the film does not contain an inorganic component, the density of the film is defined as the resin density of the film. In the case of a film comprising a resin component and an inorganic component, the resin density of the film is the density of the resin component obtained by removing inorganic substances from the film.
The resin component refers to a component other than the inorganic component in the film.

[Components contained in the film]
The film preferably contains, for example, the following component (A) and the following component (B).
Component (A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density of 920 kg / m ³ or more and 950 kg / m ³ or less, and MFR Is from 0.0001 g / 10 min to less than 0.1 g / 10 min, the MFRR is from 150 to 1,000, and the zero shear viscosity at a temperature of 190 ° C. is from 1 × 10 ⁵ Pa · sec to 1 × 10 ⁷ Pa · sec. The following is an ethylene-α-olefin copolymer.
Component (B): and a monomer unit based on α- olefin monomer units having 3 to 20 carbon atoms based on ethylene, the density is at 890 kg / ^{m 3} or more 930 kg / ^{m 3} or less, MFR Is 0.5 g / 10 min or more and 5 g / 10 min or less, and the MFRR is 10 or more and 30 or less.
The content of the component (A) in the film is preferably from 31% by weight to 59% by weight, more preferably from 35% by weight to 59% by weight, based on 100% by weight of the resin component of the film. The content is more preferably from 40% by weight to 59% by weight, and particularly preferably from 45% by weight to 59% by weight.
The content of the component (B) in the film is preferably from 41% by weight to 69% by weight, more preferably from 41% by weight to 65% by weight, based on 100% by weight of the resin component of the film, The content is more preferably from 41% by weight to 60% by weight, and particularly preferably from 41% by weight to 55% by weight.
Details of the component (A) and the component (B) will be described later.

The film contains the component (A) and the component (B) from the viewpoint of the dropping strength of the packaging container. The total amount of the component (A) and the component (B) is 100% by weight, and A film having a content of 35% by weight or more and 65% by weight or less is preferable.
It is preferable that the total amount of the components (A) and (B) is 90% by weight or more based on 100% by weight of the total weight of the film.

The content of the component (A) is preferably 35% by weight or more and 65% by weight or less, and more preferably 40% by weight or more and 60% by weight or less based on 100% by weight of the total amount of the components (A) and (B). More preferably, the content is 45% by weight or more and 60% by weight or less.

S1 can be controlled by adjusting the composition distribution of the ethylene polymer in the film, the molecular weight distribution of the ethylene polymer, the MFR of the ethylene polymer, and the [η] of the ethylene polymer. S1 can be increased by narrowing the composition distribution of the ethylene-based polymer. By widening the molecular weight distribution of the ethylene polymer, S1 can be increased. S1 can be increased by lowering the MFR of the ethylene-based polymer. By increasing [η] of the ethylene polymer, S1 can be increased.
Component (A) is an example of an ethylene polymer having a narrow composition distribution, a wide molecular weight distribution, a small MFR, and a large [η]. Component (B) is an example of an ethylene polymer having a narrow composition distribution and a large [η]. Therefore, the film contains component (A) and component (B), and the content of component (A) is 35% by weight based on the total amount of component (A) and component (B) in the film of 100% by weight. By setting the content to 65% by weight or less, S1 can be set to 220 MPa or more and 2000 MPa or less.

S2 can be controlled by adjusting the long-chain branching amount of the ethylene-based polymer in the film, the length of the long chain of the ethylene-based polymer, the molecular weight distribution, and the resin density of the film.
S2 can be increased by increasing the amount of long chain branching of the ethylene polymer. S2 can be increased by increasing the length of the long chain of the ethylene-based polymer. S2 can be increased by widening the molecular weight distribution of the ethylene polymer.
S2 can be increased by increasing the resin density of the film.
Component (A) is an example of an ethylene polymer having a large amount of long chain branching, a long chain length, and a wide molecular weight distribution. Therefore, S2 can be controlled by adjusting the content of the component (A) in the film and / or the resin density of the film.
By increasing the content of the component (A) in the resin component of the film, S2 can be increased.
Relative to 100% by weight resin component of the film, and less 59% by weight of 31 wt% or more the content of the component (A), and the resin density of the film 915 kg / ^{m 3} or more 930 kg / ^{m 3} is set to be lower than or equal , S2 can be set to 11.0 MPa or more and 30.0 MPa or less.

From the viewpoint of bag drop strength, the tensile breaking strength in the MD and TD directions of the film is preferably 43 MPa or more and 50 MPa or less.
Further, from the viewpoint of bag drop strength, the tensile elongation at break in the MD and TD directions of the film according to the present invention is preferably both 660 MPa or more and 730 MPa or less.

The film may include a lubricant and / or an anti-blocking agent.
Further, as an additive, for example, an antioxidant, a neutralizing agent, a weathering agent, an antistatic agent, an antifogging agent, a dripless agent, a pigment or a filler may be included.
The content of the antioxidant in the film is preferably 200 ppm by weight or more and 1000 ppm by weight or less. The content of the lubricant in the film is more preferably 100 ppm by weight or more and 500 ppm by weight or less. The content of the anti-blocking agent in the film is preferably from 1,000 ppm by weight to 5,000 ppm by weight.

<Component (A)>
The α-olefin having 3 to 20 carbon atoms forming the monomer unit based on the α-olefin having 3 to 20 carbon atoms in the component (A) includes propylene, 1-butene, 1-pentene, 1-pentene, Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene. Component (A) may have only one kind of these monomer units based on α-olefins having 3 to 20 carbon atoms, or may have two or more kinds thereof. The α-olefin having 3 to 20 carbon atoms is preferably 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene, and more preferably 1-butene or 1-hexene. More preferred.

The content of the monomer unit based on ethylene in the component (A) is preferably from 80 to 97% by weight based on 100% by weight of the total weight of the component (A). The content of the monomer unit based on α-olefin is preferably 3 to 20% by weight based on 100% by weight of the total weight of component (A).

Component (A) may have a monomer unit based on a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms. Monomers other than ethylene and α-olefins having 3 to 20 carbon atoms include, for example, conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as 1,4-pentadiene; acrylic acid; methyl acrylate or acrylic acid Acrylates such as ethyl; methacrylic acid; methacrylates such as methyl methacrylate or ethyl methacrylate; and vinyl acetate.

Component (A) is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 4 to 20 carbon atoms. More preferably, it is a copolymer having a monomer unit based on an α-olefin having 4 to 10 carbon atoms, and a copolymer based on a monomer unit based on ethylene and an α-olefin having 4 to 8 carbon atoms. It is more preferable that the copolymer has a monomer unit.

Component (A) includes, for example, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, ethylene -1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, and ethylene-1-butene-1-octene copolymer. Component (A) is an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-butene-1-hexene copolymer, Ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene-1-octene copolymer, or ethylene-1-butene-1-octene copolymer It is preferably a polymer, and ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, or ethylene-1-butene-1-octene copolymer A polymer is more preferable, and an ethylene-1-hexene copolymer or an ethylene-1-butene-1-hexene copolymer is further preferable.

The density of the component (A), from the viewpoint of further improving the落袋strength of the film, is preferably 921kg / m ³ or more, more preferably 922 kg / m ³ or more, is 923 kg / m ³ or more Is more preferable. The density of the component (A), from the viewpoint of reducing the appearance defect such as fish eyes of the film, is preferably 945 kg / m ³ or less, more preferably 940 kg / m ³ or less, 930 kg / m ³ It is more preferred that:
In one embodiment, the density of component (A), or less 921kg / m ³ or more 945 kg / m ^3, in another embodiment, the density of component (A), 922kg / m ³ or more 940 kg / m ³ or less In yet another embodiment, the density of component (A) is no less than 923 kg / m ^{3 and no} more than 930 kg / m ³ .

The MFR of the component (A) is preferably 0.0005 g / 10 min or more, more preferably 0.001 g / 10 min or more, from the viewpoint of reducing the extrusion load during film formation. The MFR of the component (A) is preferably 0.08 g / 10 minutes or less, more preferably 0.06 g / 10 minutes or less, and 0.05 g from the viewpoint of further improving the bag drop strength of the film. / 10 minutes or less is more preferable.
In one embodiment, the MFR of component (A) is 0.0005 g / 10 min or more and 0.08 g / 10 min or less, and in another embodiment, the MFR of component (A) is 0.001 g / 10 min or more. In another embodiment, the MFR of the component (A) is 0.005 g / 10 min or more and 0.05 g / 10 min or less. In the measurement of the MFR of the component (A), a sample obtained by blending about 1000 ppm of an antioxidant with the component (A) is usually used.

The component (A) has a zero shear viscosity at a temperature of 190 ° C. (hereinafter referred to as η ⁰ ; the unit is Pa · sec), from the viewpoint of further improving the bag drop strength of the film, 2 × 10 ⁵ Pa ·. sec or more, more preferably 3 × 10 ⁵ Pa · sec or more, and even more preferably 5 × 10 ⁵ Pa · sec or more. Η ⁰ of the component (A) is preferably 5 × 10 ⁶ Pa · sec or less, more preferably 3 × 10 ⁶ Pa · sec or less, from the viewpoint of reducing the extrusion load during film formation. It is more preferably 1 × 10 ⁶ Pa · sec or less.
In one embodiment, η ⁰ of the component (A) is 2 × 10 ⁵ Pa · sec or more and 5 × 10 ⁶ Pa · sec or less, and in another embodiment, η ⁰ of the component (A) is 3 × 10 ⁵ Pa · sec. ⁵ Pa · sec or more and 3 × 10 ⁶ Pa · sec or less, and in still another embodiment, η ⁰ of the component (A) is 5 × 10 ⁵ Pa · sec or more and 1 × 10 ⁶ Pa · sec or less.

Component (A) is prepared in the presence of a polymerization catalyst obtained by contacting a co-catalyst carrier described below (hereinafter, referred to as component (H)), a metallocene complex, an organoaluminum compound, and an electron-donating compound. It is obtained by copolymerizing ethylene and an α-olefin by a slurry polymerization method or a gas phase polymerization method. In the copolymerization, the ratio of the electron donating compound is set to 2 to 50 mol% with respect to 100 mol% of the organic aluminum compound of the polymerization catalyst, and the ratio of hydrogen is set to 0.01 to 1.1 mol with respect to 100 mol% of ethylene. %, Η ⁰ of the obtained component (A) can be set to 1 × 10 ⁵ Pa · sec or more and 1 × 10 ⁷ Pa · sec or less.

The η ⁰ at a temperature of 190 ° C. is the shear viscosity (η *; unit is Pa · sec) at a measurement temperature of 190 ° C. by a nonlinear least squares method of a Carreau-Yasuda model represented by the following equation (1). This is a value calculated by fitting to a frequency (ω, unit is rad / sec) curve.
η * = η ⁰ (1+ (λω) ^a ) ^{(n-1) / a} (1)
λ: Time constant
a: Breadth parameter
n: Power-Law index
The shear viscosity measurement is performed using a viscoelasticity measurement device (for example, Rheometrics Mechanical Spectrometer RMS800 manufactured by Rheometrics Co., Ltd.), and is usually a geometry: a parallel plate, a plate diameter: 25 mm, and a measurement sample thickness: about 2.0 mm. Angular frequency: 0.1 to 100 rad / sec, Measurement point: ω Five points per digit. The amount of distortion is appropriately selected within a range of 3 to 10% so that the torque in the measurement range can be detected and the torque does not exceed. The measurement sample is prepared by pressing for 5 minutes at a pressure of 2 MPa using a hot press machine at 150 ° C., then cooling for 5 minutes with a cooling press machine at 30 ° C., and press-molding to a thickness of 2 mm.

The flow activation energy (hereinafter referred to as Ea; unit is kJ / mol) of the component (A) is preferably 50 kJ / mol or more from the viewpoint of further improving the bag drop strength of the film. , 60 kJ / mol or more, and even more preferably 70 kJ / mol or more. In addition, from the viewpoint of reducing the extrusion load during film formation, Ea of the component (A) is preferably 120 kJ / mol or less, more preferably 110 kJ / mol or less, and 100 kJ / mol or less. It is more preferred that there be. In one embodiment, the Ea of component (A) is from 50 kJ / mol to 120 kJ / mol, and in another embodiment, the Ea of component (A) is from 60 kJ / mol to 110 kJ / mol, and In the embodiment, the Ea of the component (A) is from 70 kJ / mol to 100 kJ / mol.

The activation energy (Ea) of the flow is based on the temperature-time superposition principle, and the angular frequency (unit is rad / sec) of the melt complex viscosity at 190 ° C. (unit is Pa · sec). Is a numerical value calculated by an Arrhenius type equation from a shift factor (a _T ) at the time of creating a master curve showing the dependence on. Ea is a value obtained by the following method. The melting complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at each of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (denoted as T; unit: ° C.) is based on the temperature-time superposition principle. Each temperature (T) obtained by superimposing the melt complex viscosity-angular frequency curve at each temperature (T) on the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at 190 ° C. The shift factor (a _T ) at _T ) is obtained. And each temperature (T), from a shift factor (a _T) at each temperature (T), by the least squares method [ln (a _T)] and [1 / (T + 273.16) ] and the primary approximate expression ( The following equation (I) is calculated, and Ea is obtained from the slope m of the linear equation and the following equation (II).
ln (a _T ) = m (1 / (T + 273.16)) + n (I)
Ea = | 0.008314 × m | (II)
a _T : Shift factor
Ea: activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the above calculation, commercially available calculation software may be used. As calculation software, for example, Rios V.R. 4.4.4 and the like.
The shift factor (a _T ) is obtained by plotting the common logarithm of the melt complex viscosity at each temperature (T) on the X axis, and plotting the common logarithm of the angular frequency on the Y axis. The melt complex viscosity at 130 ° C., 150 ° C., and 170 ° C. are respectively moved in the X-axis direction at the melting complex viscosity-angular frequency logarithmic curve, and the melt complex viscosity at 190 ° C.-angular frequency logarithmic curve is superimposed. This is the amount of movement when combined. In the superposition, the melt complex viscosity at each temperature (T) - the angular log-log curve of the frequency, the angular frequency to a _T times, moving the melt complex viscosity 1 / a _T times. The correlation coefficient when the formula (I) is obtained by the least squares method from the values at four points of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. is usually 0.99 or more.

The measurement of the melt complex viscosity-angular frequency curve is carried out using a viscoelasticity measuring device (for example, Rheometrics @ Mechanical @ Spectrometer @ RMS-800, manufactured by Rheometrics), and the geometry is usually a parallel plate, a plate diameter: 25 mm, and a plate interval: 1. It is performed under the conditions of 5 to 2 mm, strain: 5%, and angular frequency: 0.1 to 100 rad / sec. The measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is previously added to the measurement sample.

The ratio of the weight average molecular weight to the number average molecular weight of the component (A) (hereinafter, referred to as Mw / Mn) is preferably 6.0 or more from the viewpoint of further improving the bag drop strength of the film. More preferably, it is 6.5 or more. The Mw / Mn of the component (A) is preferably 12 or less, more preferably 10 or less, further preferably 10 or less, from the viewpoint of reducing the extrusion load during film formation. Mw / Mn of the component (A) is preferably from 6.0 to 12, more preferably from 6.5 to 10.

The ratio of the z-average molecular weight to the weight-average molecular weight of the component (A) (hereinafter, referred to as Mz / Mw) is preferably 2.0 or more from the viewpoint of further improving the bag drop strength of the film. It is more preferably 2.1 or more, and further preferably 2.2 or more.
Mz / Mw of the component (A) is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, from the viewpoint of reducing appearance defects such as fish eyes of the film. . Mz / Mw of the component (A) is preferably 2.0 or more and 5 or less, more preferably 2.1 or more and 4 or less, and still more preferably 2.2 or more and 3 or less.

Tensile impact strength of the component (A) (unit is kJ / ^{m 2.),} From the viewpoint of enhancing the mechanical strength of the film, it is preferably 400 kJ / ^{m 2} or more, that is 500 kJ / ^{m 2} or more More preferably, it is still more preferably 600 kJ / m ² or more. Further, in view of enhancing the opening of a packaging container comprising the film, it is preferably 2000 kJ / ^{m 2} or less, more preferably 1800kJ / ^{m 2} or less, and more preferably 1500kJ / ^{m 2} or less. Tensile impact strength of the components (A), preferably in a 2000 kJ / ^{m 2} or less at 400 kJ / ^{m 2} or more, 500 kJ / ^{m 2} or more 1800kJ more preferably / ^{m 2} or less, 600 kJ / ^{m 2} or more 1500KJ / m ² or less is more preferable.
The tensile impact strength of the component (A) is measured according to ASTM D1822-68 on a sheet having a thickness of 2 mm, which is compression molded under the conditions of a molding temperature of 190 ° C., a preheating time of 10 minutes, a compression time of 5 minutes, and a compression pressure of 5 MPa.
By adjusting the ratio of ethylene and α-olefin at the time of polymerization, the tensile impact strength of component (A) can be adjusted. Increasing the ratio of α-olefin to ethylene increases the tensile impact strength of component (A), and decreasing the ratio decreases the tensile impact strength of component (A).
The tensile impact strength of the component (A) can also be adjusted by adjusting the number of carbon atoms of the α-olefin to be copolymerized with ethylene. Increasing the number of carbon atoms in the α-olefin increases the tensile impact strength of component (A), and decreasing the number of carbon atoms decreases the tensile impact strength of component (A).

The intrinsic viscosity of the component (A) (hereinafter referred to as [η]; the unit is dl / g) is preferably 1.0 dl / g or more from the viewpoint of further improving the bag drop strength of the film. Preferably, it is 1.2 dl / g or more, more preferably 1.3 dl / g or more. [Η] of the component (A) is preferably 2.0 dl / g or less, more preferably 1.9 dl / g or less, from the viewpoint of reducing appearance defects such as fish eyes of the film. More preferably, it is 1.7 dl / g or less. [Η] of the component (A) is preferably from 1.0 dl / g to 2.0 dl / g, more preferably from 1.2 dl / g to 1.9 dl / g, more preferably 1.3 dl / g. / G or more and 1.7 dl / g or less. [Η] of the component (A) is measured using an Ubbelohde viscometer at 135 ° C. using tetralin as a solvent.

The characteristic relaxation time (τ; unit is seconds) of the component (A) is preferably 10 seconds or more, and more preferably 15 seconds or more, from the viewpoint of further improving the bag drop strength of the film. , 18 seconds or more. In addition, from the viewpoint of reducing the extrusion load during film formation and from the viewpoint of the film appearance, the characteristic relaxation time of the component (A) is preferably 50 seconds or less, more preferably 45 seconds or less, More preferably, the time is 40 seconds or less. The characteristic relaxation time of the component (A) is preferably from 10 seconds to 50 seconds, more preferably from 15 seconds to 45 seconds, even more preferably from 18 seconds to 40 seconds.

The characteristic relaxation time (τ) is a numerical value related to the length of the long-chain branch, the amount of the long-chain branch, and the molecular weight distribution of the ethylene-α-olefin copolymer. When the long-chain branching is short, the amount of long-chain branching is small, or the amount of the high molecular weight component is small, the characteristic relaxation time has a small value. If the long-chain branching is long, the long-chain branching amount is large, or the high-molecular weight component is large, the characteristic relaxation time becomes a large value.
An ethylene-α-olefin copolymer having a long characteristic relaxation time is extruded from a die of an inflation film forming machine, and then forms an oriented crystal in a take-off direction due to entanglement of a molecular chain, thereby increasing the rigidity of the film in the MD direction. Since the film containing the component (A) having a characteristic relaxation time of 10 seconds or more has high rigidity in the MD direction, the film has a high nominal stress at 100% elongation in the MD direction, and is superior in bag drop strength.

The characteristic relaxation time is calculated from a master curve showing the angular frequency (unit: rad / sec) dependence of the complex viscosity at 190 ° C. (unit: Pa · sec), which is created based on the principle of temperature-time superposition. Is the number to be The characteristic relaxation time is obtained by the following method. Melt complex viscosity-angular frequency curve of ethylene-α-olefin copolymer at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (unit of melt complex viscosity is Pa · sec, angle The unit of the frequency is rad / sec.), And based on the principle of temperature-time superposition, a master curve is created by superimposing a melt complex viscosity at 190 ° C.-angular frequency curve. This is a value calculated by approximation using equation (5).
η = η0 / [1+ (τ × ω) n] (5)
η: melt complex viscosity (unit: Pa · sec)
ω: angular frequency (unit: rad / sec)
τ: characteristic relaxation time (unit: sec)
η0: constant determined for each ethylene-α-olefin copolymer (unit: Pa · sec)
n: constant determined for each ethylene-α-olefin copolymer
The calculation may use commercially available calculation software. As the calculation software, for example, Rios V.R. 4.4.4.

Measurement of the melt complex viscosity-angular frequency curve is performed in the same manner as the melt complex viscosity-angular frequency curve measured to calculate the activation energy of the flow described above.

The melt complex viscosity of component (A) at a temperature of 170 ° C. and an angular frequency of 0.1 rad / sec (η * 0.1; unit is Pa · sec), and the melt complex viscosity at a temperature of 170 ° C. and an angular frequency of 100 rad / sec The ratio (η * 100; unit is Pa · sec), η * 0.1 / η * 100, is preferably 70 or more, more preferably 80 or more, from the viewpoint of reducing the extrusion load during film formation. It is more preferably, more preferably 90 or more, and particularly preferably 100 or more. In addition, from the viewpoint of reducing appearance defects such as fish eyes of the film, η * 0.1 / η * 100 of the component (A) is preferably 150 or less, more preferably 140 or less, and 130 or less. Is more preferable, and particularly preferably 120 or less. Η * 0.1 / η * 100 of the component (A) is preferably 70 or more and 150 or less, more preferably 80 or more and 140 or less, further preferably 90 or more and 130 or less, and 100 or more and 120 or less. Is particularly preferred.

Vicat softening point (unit: ° C.) is a numerical value related to the molecular weight, density, and composition distribution of an ethylene-α-olefin copolymer. When the molecular weight is high, the density is high, or the composition distribution is narrow, the Vicat softening point has a small value. If the molecular weight is low, the density is low, or the composition distribution is wide, the Vicat softening point becomes a large value. From the viewpoint of increasing the bag-falling strength, the Vicat softening point of the component (A) is preferably 108 ° C or lower, more preferably 106 ° C or lower, even more preferably 104 ° C or lower. From the viewpoint of increasing the heat resistance of the packaging container, the temperature is preferably 98 ° C. or higher, more preferably 100 ° C. or higher, even more preferably 102 ° C. or higher.

The melting point (unit: ° C.) is a numerical value related to the density and composition distribution of the ethylene-α-olefin copolymer. If the density is low or the composition distribution is narrow, the melting point will be a small value.
If the density is high or the composition distribution is wide, the melting point becomes a large value. From the viewpoint of increasing the bag drop strength, the melting point of the component (A) is preferably 120 ° C or lower, more preferably 115 ° C or lower, and further preferably 112 ° C or lower. From the viewpoint of increasing the rigidity of the film, it is preferably at least 95 ° C, more preferably at least 98 ° C, even more preferably at least 100 ° C.

結晶 The crystallization temperature (unit: ° C.) of the component (A) is a numerical value related to the density, molecular weight distribution, and composition distribution of the ethylene-α-olefin copolymer. When the density is low, the molecular weight distribution is narrow, or the composition distribution is narrow, the crystallization temperature becomes a small value. When the density is high, the molecular weight distribution is wide, or the composition distribution is wide, the crystallization temperature becomes a large value. From the viewpoint of increasing the low-temperature impact strength, the melting point of the component (A) is preferably at most 112 ° C, more preferably at most 110 ° C, even more preferably at most 108 ° C. From the viewpoint of increasing the rigidity of the film, it is preferably at least 95 ° C, more preferably at least 98 ° C, even more preferably at least 100 ° C.

The component (A) has a value obtained by subtracting the Vicat softening point from the melting point, which is preferably 14 ° C or lower, more preferably 12 ° C or lower, and further preferably 10 ° C or lower.

As a method for producing the component (A), a component (H) in which an activating co-catalyst component (hereinafter, referred to as component (I)) is supported on a particulate carrier, a metallocene complex, and an electron donating compound And a method of copolymerizing ethylene and an α-olefin in the presence of an olefin polymerization catalyst obtained by contacting

The component (I) includes a zinc compound. Examples of the zinc compound include a compound obtained by contacting diethyl zinc, a fluorinated phenol, and water.

The particulate carrier is a porous substance having a 50% volume average particle diameter of 10 to 500 μm. The 50% volume average particle diameter is measured by, for example, a light scattering laser diffraction method.
Examples of the particulate carrier include an inorganic substance and an organic polymer. Examples of the inorganic substance include inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ ; smectite, montmorillonite, hectorite, laponite , Saponite, and other clays and clay minerals. Examples of the organic polymer include polyethylene, polypropylene, and styrene-divinylbenzene copolymer. The fine-particle carrier is preferably a fine-particle carrier made of an inorganic substance (hereinafter, referred to as an inorganic fine-particle carrier).
The fine particle carrier usually has a pore volume of 0.3 to 10 ml / g. The specific surface area of the particulate carrier is usually from 10 to 1000 m ² / g. The pore volume and the specific surface area are measured by a gas adsorption method, and the pore volume is determined by analyzing the gas desorption amount by the BJH method, and the specific surface area is determined by analyzing the gas adsorption amount by the BET method.

[Component (H)]
The component (H) is a carrier in which the component (I) is supported on a particulate carrier.
Component (H) includes diethyl zinc (hereinafter, referred to as component (a)), fluorinated phenol (hereinafter, referred to as component (b)), water (hereinafter, referred to as component (c)), inorganic fine particle carrier ( Hereinafter, it can be obtained by bringing component (d) into contact with trimethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH) (hereinafter, referred to as component (e)).

As the component (b), for example, 3,4,5-trifluorophenol, 3,4,5-tris (trifluoromethyl) phenol, 3,4,5-tris (pentafluorophenyl) phenol, 3,5 -Difluoro-4-pentafluorophenylphenol or 4,5,6,7,8-pentafluoro-2-naphthol; and 3,4,5-trifluorophenol is preferred. By using the above-mentioned component (b), the amount of long-chain branching of the obtained component (A) can be increased.

Component (d) is preferably silica gel.

In the method for producing the component (I), the amounts of the components (a), (b), and (c) used are determined by the molar ratios of the amounts of the components (a): (b): When component (c) = 1: y: z, y and z can be used so as to satisfy the following formula.
| 2-y-2z | ≦ 1 (2)
z ≧ −2.5y + 2.48 (3)
y <1 (4)
(In the above formulas (2) to (4), y and z represent numbers larger than 0.)
The molar ratio y of the amount of the component (b) used to the amount of the component (a) used and the molar ratio z of the used amount of the component (c) to the used amount of the component (a) are represented by the above formulas (2) and (3). ) And (4) are not particularly limited. y is generally 0.55 to 0.99, preferably 0.55 to 0.95, more preferably 0.6 to 0.9, and 0.7 to 0.8. It is more preferred that there be. In order to obtain an ethylene-α-olefin copolymer having η * 0.1 / η * 100 of 50 or more, y is preferably 0.55 or more. When y is 1 or more, the resulting film containing the ethylene-α-olefin copolymer has poor appearance such as fish eyes.

The number of moles of zinc atoms derived from the component (a) contained in 1 g of particles obtained by contacting the component (a) with the component (d) is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol. The amounts of the components (a) and (d) used are adjusted so as to be as follows. The amount of the component (e) to be used is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol, per 1 g of the component (d). .

The metallocene complex is a transition metal compound having a ligand having a cyclopentadiene-type anion skeleton.
As the metallocene complex, a transition metal compound represented by the following general formula [1] or a dimer of a μ-oxo type transition metal compound is preferable.
L ² _a M ² X ¹ _b [1]
(Wherein, M ² is a transition metal atom belonging to Groups 3 to 11 of the periodic table or a lanthanoid series).
L ² is a group having a cyclopentadiene-type anion skeleton, and a plurality of L ² are directly connected to each other or a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. May be connected via a. X ¹ is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton), or a hydrocarbon oxy group. a represents 2 and b represents 2. )

In the general formula [1], M ² is a transition metal atom belonging to Groups 3 to 11 of the periodic table (IUPAC 1989) or a lanthanoid series, such as a scandium atom, an yttrium atom, a titanium atom, a zirconium atom, a hafnium atom, and a vanadium atom. Atoms, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, samarium atom, and ytterbium atom. M ² in the general formula [1] is preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a chromium atom, an iron atom, a cobalt atom or a nickel atom, and more preferably a titanium atom, a zirconium atom or a hafnium atom. Is more preferable, and more preferably a zirconium atom.

In the general formula [1], L ² is an η ^5- (substituted) indenyl group, and two L ² may be the same or different. The two L ² are linked to each other via a bridging group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
An η ^5- (substituted) indenyl group refers to an η ⁵ -indenyl group which may have a substituent.

The (substituted) indenyl group, at least, 5, eta ⁵ 6-position is a hydrogen atom - - eta ⁵ in L ² (substituted) indenyl group, specifically, eta ⁵ - indenyl group, eta ⁵ -2-methylindenyl group, eta ^{5-3-methylindenyl} group, eta ^{5-4-methylindenyl} group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, eta ⁵ -3-tert-butyl indenyl group, η ⁵ -4-tert- butylindenyl group, η ⁵ -7-tert- butyl indenyl group, eta ^{5-2,3-dimethyl-indenyl} group, eta ⁵ 4,7-dimethyl-indenyl group, eta ^{5-2,4,7-trimethyl} indenyl group, eta ^{5-2-methyl-4-isopropylindenyl} group, eta ^5-4-phenyl indenyl group, eta ⁵ -2-methyl-4-phenyl indenyl group, eta ⁵ -2 Methyl-4-naphthyl indenyl group, and substituted products thereof.
In the present specification, “η ⁵ −” may be omitted for the name of the transition metal compound. L ² is preferably an indenyl group.

Two (substituted) indenyl groups are linked via a bridging group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of the crosslinking group include an alkylene group such as an ethylene group and a propylene group; a substituted alkylene group such as a dimethylmethylene group and a diphenylmethylene group; or a substituted alkylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, and a tetramethyldisilylene group. A silylene group; a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. (4) The crosslinking group is preferably an ethylene group, a dimethylmethylene group, or a dimethylsilylene group, and more preferably an ethylene group.

X ¹ in the general formula [1] is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton), or a hydrocarbon oxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group here include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Examples of the hydrocarbon oxy group include an alkoxy group, an aralkyloxy group and an aryloxy group.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, neopentyl, amyl, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group and n-eicosyl group. The alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group substituted with a halogen atom include, for example, fluoromethyl group, trifluoromethyl group, chloromethyl group, trichloromethyl group, fluoroethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, and perfluorobutyl group. Examples include a fluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group. All of these alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; or an aralkyloxy group such as a benzyloxy group, in which some of the hydrogen atoms are substituted. Good.

Examples of the aralkyl group include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (4-methylphenyl) methyl group, a (2,3-dimethylphenyl) methyl group, a (2 , 4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) Methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethyl Phenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethyl Phenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl Group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexyl) Phenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, and anthracenylmethyl group. Examples of the aralkyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; and an aralkyloxy group such as a benzyloxy group. You may have it as a substituent.

Examples of the aryl group include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6- Xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, -trimethylphenyl Group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group Pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphen Group, neopentyl phenyl group, n- hexylphenyl group, n- octylphenyl group, n- decyl phenyl group, n- dodecyl phenyl group, n- tetradecyl phenyl group, a naphthyl group and an anthracenyl group. The aryl group is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group. It may have as a group.

Examples of the 基 alkenyl group include an allyl group, a methallyl group, a crotyl group, and a 1,3-diphenyl-2-propenyl group.

Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, Examples thereof include an n-octoxy group, an n-dodesoxy group, an n-pentadeoxy group, and an n-icosoxy group. The alkoxy group is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group. It may have as a group.

Examples of the aralkyloxy group include a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group, a (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethyl Phenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5 -Trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) metho Si, (2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy , (Pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (Tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group and anthracenylmethoxy group. Examples of the aralkyloxy group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. You may have it as a substituent.

Examples of the aryloxy group include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, and a 2,5-dimethyl Phenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group , 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6 -Trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 2 tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl- 3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3 4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6- Trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert- Tyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n -Butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, and anthracenoxy group. . The aryloxy group includes, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. You may have it as a substituent. X ¹ is preferably a chlorine atom, a methoxy group, or a phenoxy group, more preferably a chlorine atom or a phenoxy group, and even more preferably a phenoxy group.

Ａa in the general formula [1] represents 2, and b represents 2.

Specific examples of the metallocene complex include dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis ( 2,3-dimethylindenyl) titanium dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylenebis (2 -Phenylindenyl) titanium dichloride, dimethylsilylenebis (4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) titanium dichloride Dimethylsilylenebis (2-methyl-4-naphthylindenyl) titanium dichloride, a compound in which titanium of these compounds is changed to zirconium or hafnium, dimethylsilylene in methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethyl Compounds obtained by changing silylene, diphenylsilylene, or dimethoxysilylene, difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide) , Diphenoxide, or di (pentafluorophenoxide).

Metallocene complexes include ethylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylmethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium diphenoxide, dimethylsilylenebis (indenyl) zirconium diphenoxide, It is preferably dimethylmethylenebis (indenyl) zirconium diphenoxide, more preferably ethylenebis (indenyl) zirconium diphenoxide.

オレフィン The olefin polymerization catalyst obtained by contacting the component (H) with the metallocene complex is preferably an olefin polymerization catalyst obtained by bringing the component (H) into contact with the metallocene complex and an organoaluminum compound.

Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tributylaluminum triisobutylaluminum, and trinormal octylaluminum.Triisobutylaluminum is preferably trinormal octylaluminum, and more preferably triisobutylaluminum. preferable.

Examples of the electron donating compound include triethylamine, triisobutylamine, and trinormal octylamine. Triethylamine is preferable.

The use amount of the metallocene complex is preferably 5 × 10 ⁻⁵ to 5 × 10 ⁻⁴ mol per 1 g of the component (H). The amount of the organoaluminum compound used is preferably 50 to 500, expressed as the ratio of the number of moles of aluminum atoms of the organoaluminum compound to the number of moles of metal atoms of the metallocene complex (Al / M).

In the polymerization catalyst obtained by contacting the component (H), the metallocene complex, the organoaluminum compound, and the electron-donating compound, a polymerization catalyst obtained by contacting oxygen may be used, if necessary.

使用 The amount of the electron donating compound used is preferably 25 to 40 mol%, more preferably 28 to 35 mol%, based on the number of moles of aluminum atoms in the organic aluminum compound. By increasing the amount of the electron-donating compound used relative to the number of moles of aluminum atoms in the organoaluminum compound, it is possible to increase the amount of long-chain branches of the component (A) obtained.

The amount of oxygen used is preferably from 1 to 100 mol%, more preferably from 10 to 20 mol%, even more preferably from 10 to 15 mol%, based on the number of moles of aluminum atoms in the organoaluminum compound. . By increasing the amount of oxygen used relative to the number of moles of aluminum atoms in the organoaluminum compound, the molecular weight distribution of component (A) obtained can be broadened.

The olefin polymerization catalyst is obtained by polymerizing a small amount of olefin (hereinafter, referred to as prepolymerization) in the presence of a catalyst component obtained by bringing the component (H), a metallocene complex, and an organoaluminum compound into contact. Preferred prepolymerized catalyst components are preferred.

Examples of the method for producing the prepolymerized catalyst component include a method for producing a prepolymerized catalyst component having the following steps (1), (2), (3) and (4).
Step (1): a step of heat-treating a saturated aliphatic hydrocarbon compound solution containing a metallocene complex at 40 ° C. or higher to obtain a heat-treated product.
Step (2): a step of bringing the heat-treated product obtained in step (1) into contact with the component (H) to obtain a contact-treated product.
Step (3): a step of bringing the contact-treated product obtained in step (2) into contact with an organoaluminum compound to obtain a catalyst component.
Step (4): a step of prepolymerizing the olefin in the presence of the catalyst component obtained in step (3) to obtain a prepolymerized catalyst component.

飽和 The saturated aliphatic hydrocarbon compound solution containing the metallocene complex in the step (1) is prepared, for example, by a method of adding the metallocene complex to a saturated aliphatic hydrocarbon compound solvent. The metallocene complex is usually added as a powder or a slurry of a saturated aliphatic hydrocarbon compound liquid.

Examples of the saturated aliphatic hydrocarbon compound used for preparing the saturated aliphatic hydrocarbon compound solution containing the metallocene complex include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, and heptane. . The saturated aliphatic hydrocarbon compound solution may contain only one kind of these saturated aliphatic hydrocarbon compounds, or may contain two or more kinds thereof. The saturated aliphatic hydrocarbon compound preferably has a boiling point at normal pressure of 100 ° C. or lower, more preferably 90 ° C. or lower at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal More preferably, they are hexane and cyclohexane.

熱処理 The heat treatment of the saturated aliphatic hydrocarbon compound solution containing the metallocene complex may be performed by adjusting the temperature of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex to a temperature of 40 ° C. or higher. During the heat treatment, the solvent may be allowed to stand, or the solvent may be stirred. The temperature is preferably 45 ° C. or higher, and more preferably 50 ° C. or higher, from the viewpoint of enhancing the processability of the film. Further, from the viewpoint of enhancing the catalytic activity, the temperature is preferably 100 ° C or lower, more preferably 80 ° C or lower. The heat treatment time is usually 0.5 to 12 hours. The time is preferably 1 hour or more, and more preferably 2 hours or more, from the viewpoint of enhancing the processability of the film. From the viewpoint of stability of the catalyst performance, it is preferably 6 hours or less, more preferably 4 hours or less.

In the step (2), the heat-treated product and the component (H) may be in contact with each other. Examples of the contacting method include a method of adding the component (H) to the heat-treated product, and a method of adding the component (H) to the saturated aliphatic hydrocarbon compound. The component (H) is usually added as a powder or a slurry of a saturated aliphatic hydrocarbon compound solvent.

温度 The temperature of the contact treatment in step (2) is preferably 70 ° C or lower, more preferably 60 ° C or lower, preferably 10 ° C or higher, and more preferably 20 ° C or higher. The time for the contact treatment is usually 0.1 hour to 2 hours.

In step (3), the contact-treated product obtained in step (2) may be brought into contact with the organoaluminum compound. As a method of contacting, for example, a method of adding an organoaluminum compound to the contact-treated product obtained in the step (2), or a method of contacting the contact-treated product obtained in the step (2) in a saturated aliphatic hydrocarbon compound And an organoaluminum compound are added.

温度 The temperature of the contact treatment in the step (3) is preferably 70 ° C or lower, more preferably 60 ° C or lower. From the viewpoint of efficiently exhibiting the activity of the prepolymerization, the temperature is preferably 10 ° C. or higher, more preferably 20 ° C. or higher. The time for the contact treatment is usually from 0.01 hour to 0.5 hour.

接触 The contact treatment in step (3) is preferably performed in the presence of an olefin. Examples of the olefin include olefins that are usually used as raw materials in preliminary polymerization. The amount of the olefin is preferably 0.05 to 1 g per 1 g of the component (H).

The above steps (1) to (3) are carried out by separately adding the saturated aliphatic hydrocarbon compound, the component (H), the metallocene complex and the organoaluminum compound to a prepolymerization reactor. ) To (3) may be performed in a prepolymerization reactor, steps (2) and (3) may be performed in a prepolymerization reactor, or step (3) may be performed in a prepolymerization reactor. It may be performed in a reactor.

Step (4) is a step of obtaining a prepolymerized catalyst component by prepolymerizing olefin (polymerizing a small amount of olefin) in the presence of the catalyst component obtained in step (3). The preliminary polymerization is usually performed by a slurry polymerization method, and the preliminary polymerization may be any of a batch system, a semi-batch system, and a continuous system. Further, the prepolymerization may be performed by adding a chain transfer agent such as hydrogen.

行う When the prepolymerization is performed by a slurry polymerization method, a saturated aliphatic hydrocarbon compound is usually used as a solvent. Examples of the saturated aliphatic hydrocarbon compound include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, and heptane. These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point at normal pressure of 100 ° C. or lower, more preferably 90 ° C. or lower at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, and the like. More preferably, they are normal hexane and cyclohexane.

When the preliminary polymerization is carried out by a slurry polymerization method, the slurry concentration is such that the amount of the component (H) per liter of the solvent is usually 0.1 to 600 g, preferably 0.5 to 300 g. The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the pre-polymerization, the polymerization temperature may be appropriately changed, but the temperature at which the pre-polymerization is started is preferably 45 ° C. or lower, more preferably 40 ° C. or lower. Further, the partial pressure of the olefin in the gas phase during the prepolymerization is usually from 0.001 to 2 MPa, preferably from 0.01 to 1 MPa. The pre-polymerization time is usually from 2 minutes to 15 hours.

オレフィン Examples of the olefin used for the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene, and cyclohexene. These can be used alone or in combination of two or more. It is preferable to use only ethylene or a combination of ethylene and an α-olefin, and to select only ethylene or 1-butene, 1-hexene and 1-octene. More preferably, at least one kind of α-olefin is used in combination with ethylene.

含有 The content of the prepolymerized polymer in the prepolymerized catalyst component is usually 1 to 1000 g, preferably 10 to 100 g, more preferably 20 to 50 g per 1 g of the component (H).

スラリー As a method for producing the component (A), slurry polymerization or gas phase polymerization is preferable, and continuous gas phase polymerization is more preferable. Examples of the solvent used in the slurry polymerization method include inert hydrocarbon solvents such as propane, butane, isobutane, pentane, hexane, heptane, and octane. The gas phase polymerization reactor used for the continuous gas phase polymerization method is usually a device having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be provided in the reaction tank.

When the olefin polymerization catalyst is an olefin polymerization catalyst containing a pre-polymerization catalyst component, a method of supplying the pre-polymerization catalyst component to a continuous polymerization reaction tank for forming particles of the component (A) is usually a method such as argon. A method using an active gas, nitrogen, hydrogen, or ethylene to supply in a water-free state, or a method in which each component is dissolved or diluted in a solvent and supplied in a solution or slurry state is used.

The polymerization temperature of the gas phase polymerization of the component (A) is usually lower than the temperature at which the component (A) melts, preferably from 0 to 150 ° C, more preferably from 30 to 100 ° C, and more preferably from 70 to 100 ° C. It is more preferred that the temperature be between 0 ° C and 87 ° C. Hydrogen may be added to adjust the melt fluidity of component (A). Hydrogen is preferably controlled to be 0.3 to 0.6 mol% with respect to 100 mol% of ethylene. The ratio of hydrogen to ethylene during gas phase polymerization can be controlled by the amount of hydrogen generated during polymerization and the amount of hydrogen added during polymerization. An inert gas may coexist in the mixed gas of the polymerization reaction tank. When the olefin polymerization catalyst is an olefin polymerization catalyst containing a prepolymerization catalyst component, the olefin polymerization catalyst may contain a cocatalyst component such as an organoaluminum compound. By reducing the ratio of hydrogen to ethylene during gas phase polymerization, the molecular weight of the component (A) obtained can be increased.

<Component (B)>
The α-olefin having 3 to 20 carbon atoms forming the monomer unit based on the α-olefin having 3 to 20 carbon atoms in the component (B) includes propylene, 1-butene, 1-pentene, 1-pentene, Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene. Component (B) may have only one type of these monomer units based on α-olefins having 3 to 20 carbon atoms, or may have two or more types of monomer units. The α-olefin having 3 to 20 carbon atoms is preferably 1-hexene, 4-methyl-1-pentene or 1-octene, and more preferably 1-hexene or 1-octene.

The content of the monomer unit based on ethylene in the component (B) is preferably 50 to 99.5% by weight based on 100% by weight of the total weight of the component (B). Further, the content of the monomer unit based on the α-olefin is preferably 0.5 to 50% by weight based on 100% by weight of the total weight of the component (B).

Component (B) may have a monomer unit based on a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms. Monomers other than ethylene and α-olefins having 3 to 20 carbon atoms include, for example, conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as 1,4-pentadiene: acrylic acid; methyl acrylate and acrylic acid Acrylates such as ethyl; methacrylic acid; methacrylates such as methyl methacrylate or ethyl methacrylate; and vinyl acetate.

The component (B) is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 4 to 20 carbon atoms. More preferably, it is a copolymer having a monomer unit based on an α-olefin having 5 to 20 carbon atoms, and a copolymer based on a monomer unit based on ethylene and an α-olefin having 6 to 20 carbon atoms. It is more preferable that the copolymer has a monomer unit.

As the component (B), for example, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer Polymers, ethylene-1-butene-4-methyl-1-pentene copolymer, and ethylene-1-butene-1-octene copolymer. Component (B) is preferably an ethylene-1-hexene copolymer, an ethylene-4-methyl-1-pentene copolymer or an ethylene-1-octene copolymer, and is preferably an ethylene-1-hexene copolymer. More preferably, they are united.

The density of the component (B) is 890 kg / m ³ or more 930 kg / m ³ or less. From the viewpoint of improving the slipperiness of the film, it is preferably 895kg / m ³ or more, more preferably 900 kg / m ³ or more, still more preferably 905 kg / m ³ or more, 910 kg / m ³ It is particularly preferable that the above is satisfied. The density of the component (B), from the viewpoint strength of the film, is preferably 925 kg / m ³ or less, more preferably 920 kg / m ³ or less, still be at 915 kg / m ³ or less preferable. Component density of (B) is preferably not more than 895kg / m ³ or more 925 kg / m ^3, more preferably at most 900 kg / m ³ or more ^{920kg / m 3, 905kg / m} 3 or more 915 kg / m ³ more preferably less, and particularly preferably not more than 910 kg / m ³ or more 915 kg / m ^3.

Ｍ The MFR of the component (B) is 0.5 g / 10 min, 5 g / 10 min or less. The MFR of the component (B) is preferably 0.8 g / 10 min or more, and more preferably 1.0 g / 10 min, from the viewpoint of film formability, particularly from the viewpoint of reducing the extrusion load during film formation. More preferably, it is the above. From the viewpoint of the strength of the film, the MFR of the component (B) is preferably 4.0 g / 10 min or less, more preferably 3.0 g / 10 min or less, and 2.5 g / 10 min or less. It is more preferred that there be. The MFR of the component (B) is preferably from 0.8 g / 10 min to 4.0 g / 10 min, more preferably from 1.0 g / 10 min to 3 g / 10 min, and more preferably from 1 g / 10 min. It is more preferable that the amount is not less than 2.5 g / 10 minutes. In the measurement of MFR, a sample in which an antioxidant is added to the component (B) at about 1000 ppm is usually used.

The MFRR of the component (B) is 10 or more and 30 or less. The MFRR of the component (B) is preferably 15 or more, more preferably 17 or more, and more preferably 20 or more, from the viewpoint of processability of the film, particularly from the viewpoint of reducing the extrusion load during film formation. Is more preferable. The MFRR of the component (B) is preferably 28 or less, more preferably 26 or less, from the viewpoint of the strength of the film. The MFRR of the component (B) is preferably 15 or more and 28 or less, more preferably 17 or more and 26 or less, and even more preferably 20 or more and 26 or less.
In the measurement of the MFRR of the component (B), a sample in which the component (B) is mixed with an antioxidant at 1000 ppm is usually used.

The ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight of the component (B) is preferably 2 or more from the viewpoint of bubble stability when the film is formed by the inflation film forming method. , 2.1 or more, more preferably 2.2 or more, and particularly preferably 2.3 or more. Mw / Mn of the component (B) is preferably 7 or less, more preferably 6 or less, still more preferably 5 or less, and particularly preferably 4 or less, from the viewpoint of the strength of the film. preferable. Mw / Mn of the component (B) is preferably 2 or more and 7 or less, more preferably 2.1 or more and 6 or less, further preferably 2.2 or more and 5 or less, and 2.3 or more. It is particularly preferred that it is 4 or less. The Mw / Mn of the component (B) is measured by the same method as the Mw / Mn of the component (A).

Ea of the component (B) is preferably at least 15 kJ / mol, more preferably at least 20 kJ / mol, from the viewpoint of bubble stability when the film is formed by the inflation film forming method. More preferably, it is at least 25 kJ / mol. In light of the strength of the film, Ea of the component (B) is preferably equal to or less than 50 kJ / mol, more preferably equal to or less than 45 kJ / mol, and still more preferably equal to or less than 40 kJ / mol. Ea of the component (B) is preferably from 15 kJ / mol to 50 kJ / mol, more preferably from 20 kJ / mol to 45 kJ / mol, further preferably from 25 kJ / mol to 40 kJ / mol. preferable. The Ea is measured by the same method as the Ea of the component (A).

Component (B) can be produced by copolymerizing ethylene and an α-olefin in the presence of a metallocene polymerization catalyst or a Ziegler-Natta polymerization catalyst.

Examples of the metallocene-based polymerization catalyst include the following catalysts (1) to (4).
(1) A catalyst comprising a component containing a transition metal compound having a group having a cyclopentadiene-type skeleton and a component containing an alumoxane compound. (2) A component containing the transition metal compound and ions such as trityl borate and anilinium borate. (3) a catalyst comprising a component containing an ionic compound; a catalyst comprising a component containing the transition metal compound; a component containing the ionic compound; and a component containing an organoaluminum compound. A catalyst obtained by supporting or impregnating each component according to any one of the above on an inorganic particulate carrier such as SiO ₂ or Al ₂ O ₃ or a particulate polymer carrier such as an olefin polymer such as ethylene or styrene.

As the Ziegler-Natta polymerization catalyst, a so-called Mg-Ti Ziegler catalyst obtained by combining a solid catalyst component in which a titanium compound is supported on a magnesium compound and organoaluminum (for example, “Catalyst Enlargement Dictionary; See “Application System Diagram—Transition of Olefin Polymerization Catalyst—; Published by the Invention Association of 1995” and the like).

触媒 The catalyst used for the production of the component (B) is preferably a metallocene-based polymerization catalyst from the viewpoint of film drop strength.

重合 As a polymerization method of the component (B), for example, bulk polymerization, solution polymerization, slurry polymerization, gas phase polymerization, or high pressure ionic polymerization method can be mentioned. Here, bulk polymerization refers to a method of performing polymerization using a liquid olefin at a polymerization temperature as a medium, and solution polymerization or slurry polymerization refers to inert hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane. It refers to a method of performing polymerization in a solvent. Gas phase polymerization refers to a method in which a gaseous monomer is used as a medium and the gaseous monomer is polymerized in the medium. These polymerization methods may be any of a batch type and a continuous type, and may be any of a single-stage type performed in a single polymerization tank and a multi-stage type performed in a polymerization apparatus in which a plurality of polymerization reaction tanks are connected in series. May be. Various conditions (polymerization temperature, polymerization pressure, monomer concentration, catalyst addition amount, polymerization time, and the like) in the polymerization step may be appropriately determined.

The film may further contain the following component (C). The content of the component (C) in the film is preferably 1% by weight or more and 10% by weight or less based on 100% by weight of the total amount of the components (A), (B) and (C). % To 5% by weight, more preferably 1% to 2% by weight.

<Component (C)>
Component (C) has a density is at 890 kg / ^{m 3} or more 930 kg / ^{m 3} or less, MFR is not more than 5 g / 10 min 0.5 g / 10 min or more, the high-pressure low-density MFRR is 31 to 150 Polyethylene (hereinafter sometimes referred to as component (D)), and a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and having a density of 890 kg / M ³ or more and 930 kg / m ³ or less, an MFR of 0.3 g / 10 min or more and 5 g / 10 min or less, and an MFRR of 31 or more and 150 or less (hereinafter, component ( E) may be one or more ethylene-based polymers selected from the group consisting of:

<Component (D)>
Component (D) is a low-density polyethylene produced by a high-pressure radical polymerization method.
As a general method for producing high-density low-density polyethylene, ethylene is polymerized in a tank reactor or a tubular reactor under the conditions of a polymerization pressure of 140 to 300 MPa and a polymerization temperature of 200 to 300 ° C. in the presence of a radical generator. (Koji Saeki, “Polymer Manufacturing Process”, Industrial Research Council (1971), etc.).

ＭMw / Mn of the component (D) is preferably 3 or more and 10 or less. The molecular weight distribution (Mw / Mn) of the component (D) is measured by the same method as that for the Mw / Mn of the component (A).

Ea of the component (D) is preferably 30 kJ / mol or more and 80 kJ / mol or less.
Ea of component (D) is measured by the same method as Ea of component (A).

<Component (E)>
Component (E) has a monomer unit based on α- olefin monomer units having 3 to 20 carbon atoms based on ethylene, the density is at 890 kg / ^{m 3} or more 930 kg / ^{m 3} or less, MFR Is 0.3 g / 10 min or more and 5 g / 10 min or less, and the MFRR is 31 or more and 150 or less.
As the α-olefin having 3 to 20 carbon atoms forming the monomer unit based on the α-olefin having 3 to 20 carbon atoms in the component (E), propylene, 1-butene, 1-pentene, 1-pentene, Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 4-methyl-1-hexene. Component (E) may have only one type of these monomer units based on α-olefins having 3 to 20 carbon atoms, or may have two or more types of monomer units. The α-olefin having 3 to 20 carbon atoms is preferably 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene, and more preferably 1-butene or 1-hexene. More preferred.

含有 The content of the monomer unit based on ethylene in the component (E) is preferably 50 to 99.5% by weight based on 100% by weight of the total weight of the component (E). The content of the monomer unit based on α-olefin is preferably 0.5 to 50% by weight based on 100% by weight of the total weight of the component (E).

Component (E) may have a monomer unit based on a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of monomers other than ethylene and α-olefins having 3 to 20 carbon atoms include conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as 1,4-pentadiene; acrylic acid; methyl acrylate and acrylic acid Acrylates such as ethyl; methacrylic acid; methacrylates such as methyl methacrylate or ethyl methacrylate; and vinyl acetate.

Component (E) is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 4 to 20 carbon atoms. More preferably, it is a copolymer having a monomer unit based on an α-olefin having 5 to 20 carbon atoms, and a copolymer based on a monomer unit based on ethylene and an α-olefin having 6 to 20 carbon atoms. It is more preferable that the copolymer has a monomer unit.

As the component (E), for example, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, ethylene -1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, and ethylene-1-butene-1-octene copolymer. Component (E) is preferably an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, or an ethylene-1-butene-1-hexene copolymer.

ＭMw / Mn of the component (E) is preferably 3 or more and 15 or less. The molecular weight distribution (Mw / Mn) of the component (E) is measured by the same method as that of the Mw / Mn of the component (A).

Ea of the component (E) is preferably 30 kJ / mol or more and 80 kJ / mol or less.
Ea of component (E) is measured by the same method as Ea of component (A).

Component (E) can be produced by copolymerizing ethylene and an α-olefin in the presence of a metallocene polymerization catalyst or a Ziegler-Natta polymerization catalyst. From the viewpoint of bubble stability when the film is formed by the inflation film forming method, a metallocene-based polymerization catalyst is preferable as the catalyst used for the production of the component (E).

メタ The metallocene-based olefin polymerization catalyst used for producing the component (E) is not particularly limited, and examples thereof include the same olefin polymerization catalyst as the olefin polymerization catalyst used for producing the component (A).

The method for producing the component (E) is not particularly limited. For example, a slurry is prepared in the presence of a polymerization catalyst obtained by contacting the aforementioned component (H), a metallocene-based complex, an organoaluminum compound, and an electron-donating compound. It can be obtained by copolymerizing ethylene and an α-olefin by a polymerization method or a gas phase polymerization method. The component (E) is obtained by allowing more than 1.1 mol% of hydrogen to be present with respect to 100 mol% of ethylene during copolymerization. The polymerization method of the component (E) is preferably a gas phase polymerization method. In the gas phase polymerization, triethylamine, triisobutylamine, or trinormal octylamine may be added as an electron donating compound.

In the film according to the present invention, S1 is 220 MPa or more and 2000 MPa or less, and the nominal stress at 100% elongation in the MD direction when subjected to a tensile test at a tensile speed of 500 mm / min is 11.0 MPa or more and 30.0 MPa or less. It may be a certain single-layer film.

<Multilayer film>
In the multilayer film according to the present invention, S1 is 220 MPa or more and 2000 MPa or less, and the nominal stress at 100% elongation in the MD direction when subjected to a tensile test at a tensile speed of 500 mm / min is 11.0 MPa or more and 30.0 MPa or less. A multilayer film comprising a layer consisting of a film (hereinafter, sometimes referred to as a layer α), wherein at least one of the two surface layers of the multilayer film is the layer α. It may be.
One embodiment of the present invention is a multilayer film including a layer α and a layer β containing an ethylene-based polymer (provided that the layer β is different from the layer α).
Of the two surface layers of the multilayer film, at least one of the surface layers may be a multilayer film of layer α.

One embodiment of the present invention is a multilayer film including a layer α and a layer γ containing no ethylene polymer (provided that the layer γ is different from the layer α).
Of the two surface layers of the multilayer film, at least one of the surface layers may be a multilayer film of layer α.

において In the multilayer film, examples of the ethylene polymer contained in the layer β include a high-pressure low-density polyethylene and an ethylene-α-olefin copolymer containing no component (A).

In the multilayer film, examples of the material constituting the layer γ include cellophane, paper, paperboard, woven fabric, aluminum foil, polyamide resins such as nylon 6 and nylon 66, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and polypropylene resins. Is mentioned.

A multilayer film having a layer α and a layer γ, wherein at least one surface layer of the two surface layers of the multilayer film is the layer α, for example, a layer α and a layer γ And a two-layer film in which one surface layer is a layer α and the other surface layer is a layer γ.
A multilayer film having a layer α and a layer γ, wherein at least one of the two surface layers of the multilayer film has a layer α, such as a layer α, a layer β And a layer γ, wherein one surface layer is a layer α and the other surface layer is a layer γ.

製造 Examples of the method for producing a single-layer film and a multilayer film include an extrusion molding method such as an inflation film molding method and a T-die film molding method, an injection molding method, and a compression molding method. As a method for producing a single-layer film and a multilayer film, an inflation film molding method is preferable. It is preferable to produce a resin composition by dry-blending or melt-blending each polymer as a raw material of the single-layer film, and to produce a single-layer film using the resin composition. Examples of the dry blending method include a method using various blenders such as a Henschel mixer and a tumbler mixer. Examples of the melt blending method include a method using various mixers such as a single screw extruder, a twin screw extruder, a Banbury mixer, and a hot roll.

When the multilayer film is a multilayer film having a layer α and a layer γ, a method for producing the multilayer film includes, for example, a single-layer film consisting of only the layer α, or a multilayer film having the layer α and the layer β. A lamination method in which a film is laminated on the layer γ can be used. Examples of the lamination method include a dry lamination method, a wet lamination method, and a sand lamination method. The lamination method is preferably a dry lamination method.

The multilayer film of the present invention can be used as a material for a packaging container, and is used for packaging various contents. The contents include, for example, foods, beverages, seasonings, milk and the like, dairy products, pharmaceuticals, electronic components such as semiconductor products, pet food, pet care products, detergents and toiletry products.
The packaging container including the film according to the present invention is preferably manufactured by heat-sealing the layers α of the multilayer film. The packaging container containing the film according to the present invention preferably contains the layer β and / or the layer γ from the viewpoint of the strength of the packaging container. Since the packaging container is a packaging container in which the layers α are heat-sealed, the packaging container has excellent dropping strength.

測定 The measured values of each item in the examples and comparative examples were measured according to the following methods.

[Component (H)]
(1) Elemental analysis Zn: A sample was put in an aqueous solution of sulfuric acid (concentration: 1 M), and then irradiated with ultrasonic waves to extract metal components. The obtained solution was quantified by ICP emission spectrometry.
F: The sample was burned in a flask filled with oxygen, the generated combustion gas was absorbed in an aqueous sodium hydroxide solution (10%), and the obtained aqueous solution was quantified by an ion electrode method.

[Physical properties of component (A)]
(2) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method specified in JIS K7210-1995, the measurement was carried out by the method A at a temperature of 190 ° C. and a load of 21.18 N.

(3) Melt flow rate ratio (MFRR, unit:-)
The MFRR was obtained by dividing the melt flow rate measured under the conditions of a temperature of 190 ° C. and a load of 211.82 N (21.60 kg) by the MFR measured in the above (2) in accordance with the method defined in JIS K7210-1995. Value.

(3) Density (unit: kg / m ³ )
After the annealing described in JIS K6760-1995, the measurement was performed by the method A according to the method specified in JIS K7112-1980.

(4) Mw, Mn, Mz, Mw / Mn, Mz / Mw
The weight average molecular weight (Mw), number average molecular weight (Mn) and Z average molecular weight (Mz) in terms of polystyrene were determined by gel permeation chromatography (GPC) measurement.
The molecular weight distribution (Mw / Mn) was determined by dividing Mw by Mn. Mz was divided by Mw to obtain Mz / Mw.
Equipment: Waters 150C made by Waters
Separation column: TOSOH TSKgel GMH ₆ -HT
Measurement temperature: 140 ° C
Carrier: ortho-dichlorobenzene Flow rate: 1.0 mL / min Injection volume: 500 μL
Detector: Differential refraction
Molecular weight standard substance: standard polystyrene

(5) η * 0.1 / η * 100
The dynamic complex viscosity at an angular frequency of 0.1 rad / sec to 100 rad / sec was measured under the following conditions using a strain control type rotary viscometer (rheometer). Next, the dynamic complex viscosity at an angular frequency of 0.1 rad / sec (η * 0.1) is divided by the dynamic complex viscosity at an angular frequency of 100 rad / sec (η * 100) to obtain η * 0.1 / η * 100. Was.
Temperature: 170 ° C
Geometry: Parallel plate Plate diameter: 25mm
Plate interval: 1.5 to 2 mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(6) Activation energy of flow (Ea, unit: kJ / mol)
The activation energy Ea of the flow was measured by a strain control type rotary viscometer (rheometer) under the following conditions (a) to (d) under the conditions of ethylene-α-olefin copolymer at each temperature T (unit: ° C). A melt complex viscosity-angular frequency curve (unit of melt complex viscosity is Pa · sec and unit of angular frequency is rad / sec) of the coalesced was measured. Next, based on the principle of temperature-time superposition, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at 190 ° C. was obtained for each melt complex viscosity-angular frequency curve at each temperature (T). The shift factor (a _T ) at each temperature (T) obtained when superimposing was obtained. Next, the primary and the temperature (T), because the shift factor (a _T) at each temperature (T), by the least squares method [ln (a _T)] and [1 / (T + 273.16) ] An approximate expression (formula (I) below) was calculated. Next, Ea was determined from the gradient m of the linear equation and the following equation (II).
ln (a _T ) = m (1 / (T + 273.16)) + n (I)
Ea = | 0.008314 × m | (II)
a _T : Shift factor
Ea: activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
The calculation software includes Reometrics Rios V.R. 4.4.4 was used. The Ea value when the correlation coefficient r2 when the equation (I) was calculated from the value of each temperature (T) by the least square method was 0.99 or more was adopted. The measurement of the melt viscosity versus angular frequency curve was performed under a nitrogen atmosphere.
(A) Geometry: parallel plate, plate diameter 25 mm, plate interval: 1.5 to 2 mm
(B) Strain: 5%
(C) Shear rate: 0.1 to 100 rad / sec (d) Temperature: 130 ° C, 150 ° C, 170 ° C, 190 ° C

(7) Tensile impact strength (unit: kJ / m ² )
The tensile impact strength of a sheet having a thickness of 2 mm, which was compression molded under the conditions of a molding temperature of 190 ° C., a preheating time of 10 minutes, a compression time of 5 minutes, and a compression pressure of 5 MPa, was measured according to ASTM D1822-68.

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

(9) Melting point (Tm, unit: ° C), crystallization temperature (Tc, unit: ° C)
Thermal analyzer The measurement was carried out using a differential scanning calorimeter (Diamond DSC Perkin Elmer) according to the following method. The melting point was determined as the endothermic peak of the heat flow curve observed during step 3), and the crystallization temperature was determined as the exothermic peak of the heat flow curve observed during step 2). Hold at 150 ° C for 5 minutes
2) Cooling 150 ° C to 20 ° C (5 ° C / min) for 2 minutes
3) Temperature rise 20 ° C to 150 ° C (5 ° C / min)

(10) Intrinsic viscosity ([η], unit: dl / g)
The polymer was dissolved in a tetralin solvent and measured at 135 ° C. using an Ubbelohde viscometer.

(11) Vicat softening point (° C)
The Vicat softening point was measured according to the method specified in JIS K7206-1979.

[Film physical properties]

(12) S1
0) Preparation of Test Specimen The formed film was punched out with a dumbbell cutter conforming to the test specimen shape ASTM D1822 Type S standard so that the take-off direction (MD direction) was the longitudinal direction, and a test specimen was prepared. Small dots were randomly written on the test piece with an oil-based magic having an extremely fine pen tip to create a random pattern. Further, in order to prevent reflection of illumination at the time of photographing, ECO ANISPOT, a Darling spray manufactured by CONDOR FOTO, was sprayed on the surface of the test piece.
1) High-speed tensile test A test specimen was subjected to a tensile test at 1 m / s using a high-speed tensile tester Hydroshot HITS-T10 (manufactured by Shimadzu Corporation) equipped with a load cell having a maximum load of 2 kN, and a load-displacement curve was obtained. I got The origin of the load-displacement curve was determined so that the load-displacement curve could be extrapolated to a point where the load = 0 kN and the displacement = 0 mm. The sampling time interval of the load and the displacement was 20 μs.
2) Photographing with a high-speed camera The test piece at the time of the high-speed tensile test of 1) was used as a high-speed camera GX-8F (manufactured by NAC Image Technology Co., Ltd. (lens AI AF Micro-Nikkor 200 mm f / 4D IF-ED). The imaging conditions were a frame rate of 10000 fps, a frame size of 176 horizontal pixels × 1280 vertical pixels, a shutter speed of 20.1 μs, and a distance between the camera and the test piece of 1 m. Two LED lighting boxes LLBK-LA-W-0001 manufactured by ITEC System Co., Ltd. were used as illumination for photographing, and light was irradiated from the left and right of the high-speed camera toward the sample. At the start of the high-speed tensile test, a signal is issued from the high-speed tensile tester, and when the signal is input, shooting with the high-speed camera is started, so that the time of the high-speed tensile tester and the time of the high-speed camera can be synchronized. ing.
3) Analysis by Digital Image Correlation Method Using the images captured in 2), the maximum principal strain distribution and the minimum principal distortion on the test piece at the time of each image capturing are performed by GOM Correlation Professional 2017 manufactured by GOM GmbH, which is 3D inspection / analysis software. (True strain distribution) was calculated. The facet size was 19 pixels and the point distance was 16 pixels. The facet matching was performed on the immediately preceding image, and the analysis was performed on a region near the center of the test piece having an actual length of about 3.19 mm × 1.7 mm on the test piece. For the test piece, the maximum principal strain and the minimum principal strain at one point in the central constriction were determined.
4) Calculation of cross-sectional area of neck portion The cross-sectional area of the neck portion of the test piece was calculated by the following equation.
(Cross-sectional area of constriction of test piece)
= (Width of constricted part before test execution) × (thickness of constricted part before test execution) × {exp (minimum principal strain in constricted part)} ²
5) Calculation of true stress The load at each time obtained by the high-speed tensile test described above was divided by the cross-sectional area of the constricted portion of the test piece at each time to obtain the true stress at each time.
6) Creation of true stress-maximum principal strain curve The true stress at each time was plotted against the maximum principal strain at each time to create a true stress-maximum principal strain curve.
7) Calculation of S1 S1 was determined by 7a) or 7b).
7a) In the tensile test of 1), when the test piece was not broken at the time when the maximum principal strain was 2.0, S1 was determined by the following equation (11).
S1 = (p−q) /0.3 (11)
(In Equation (11), p is the true stress (MPa) at the maximum principal strain of 2.0, and q is the true stress (MPa) at the maximum principal strain of 1.7.)
7b) In the tensile test of 1), when the test piece broke within the range where the maximum principal strain was greater than 1.7 and less than 2.0, S1 was determined by the following equation (12).
S1 = (p'-q) / (r-1.7) (12)
(In the equation (12), p ′ is the true stress (MPa) at the breaking point, q is the true stress (MPa) at the maximum principal strain of 1.7, and r is the maximum principal strain at the breaking point. Is.)
p, p ', and q were obtained by averaging the true stress at 11 points in total, at 5 points before and after each data point, as a smoothing process.
(13) Nominal stress at 100% elongation in MD direction S2 (unit: MPa)
From the formed film, a test piece whose longitudinal direction was the take-off direction (MD) was prepared according to the method described in JIS K6781-1994 “6.4 Tensile cutting load and elongation”. The obtained test piece was subjected to a tensile test under the conditions of 80 mm between chucks, 40 mm between marked lines, and a tensile speed of 500 mm / min, and a nominal stress at an elongation of 100% was obtained. The nominal stress at 100% elongation was described as S2.

(14) Tensile breaking strength (unit: MPa), tensile breaking elongation (unit:%)
From the formed film, test pieces having longitudinal directions corresponding to a take-off direction (MD direction) and a TD direction, respectively, were prepared according to the method described in JIS K6781-1994 “6.4 Tensile cutting load and elongation”. The obtained test piece was subjected to a tensile test under the conditions of 80 mm between the chucks, 40 mm between the marked lines, and a tensile speed of 500 mm / min, and the tensile strength at break and the tensile elongation at break were determined.

(15) Dropping strength 1) Preparation of dropping strength evaluation sample From the multilayer film described below, 20 rectangular films having a length in the MD direction of 60 mm and a length in the TD direction of 70 mm were cut out. The two multilayer films are stacked so that the MD directions of the multilayer films match and the inflation film surfaces face each other and installed on a heat sealer manufactured by Tester Sangyo Co., Ltd., with a seal width of 10 mm, a seal bar temperature of 180 ° C., and a seal pressure of 0.1 mm. Two long sides and one short side were heat-sealed at 03 MPa and a sealing temperature of 2 seconds, respectively, to obtain a bag. After filling the obtained bag with 10 ml of pure water, the short side of the opening was heat-sealed with an impulse sealer so that air did not enter, to obtain a sample for evaluation. The size inside the heat seal portion of the obtained evaluation sample was 40 mm (MD direction) and 50 mm (TD direction).
2) Measurement of bag drop strength The evaluation sample was kept at 5 ° C. for 24 hours. Next, the evaluation sample was set on a Dupont impact tester, and a 2 kg weight was dropped onto the evaluation sample 20 times repeatedly from a height of 175 mm. The survival probability was determined by the following equation.
Survival probability (%) = 100 ｛(number of times the weight falls when the evaluation sample breaks) −1｝ / 20
When the weight was not broken even after falling 20 times, the survival probability was set to 100%. In each example, a test was performed on 10 bags of evaluation samples, and the average value of the survival probabilities was defined as “bag drop strength”.

[Production Example of Component (A)]
[Example 1]
(1) Production of Component (H) Component (H) was produced in the same manner as in the preparation of component (A) of Examples 1 (1) and (2) described in JP-A-2009-79180. . As a result of elemental analysis, Zn = 11% by weight and F = 6.4% by weight.
(2) Production of Prepolymerization Catalyst Component 41 liters of butane was added to an autoclave with a stirrer having an internal volume of 210 liters which had been purged with nitrogen in advance, and then 60.9 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. The temperature of the autoclave was raised to 50 ° C., and the mixture was stirred for 2 hours. Next, 0.60 kg of the component (H) obtained in the above (1) was added to the autoclave.
Thereafter, the temperature of the autoclave was lowered to 31 ° C., and after the inside of the system was stabilized, 0.1 kg of ethylene and 0.1 liter of hydrogen (normal temperature and normal pressure) were added to the autoclave, and then 240 mmol of triisobutylaluminum was added to perform prepolymerization. Started. Ethylene and hydrogen (normal temperature and normal pressure) are supplied to the autoclave at 0.5 kg / hr and 1.1 liter / hr, respectively, for 30 minutes, and then the temperature is raised to 50 ° C. and ethylene and hydrogen (normal temperature and normal pressure) are supplied. The autoclave was supplied at 2.7 kg / hr and 8.2 liter / hr, respectively. A total of 10.0 hours of prepolymerization was performed. After the completion of the prepolymerization, ethylene, butane, hydrogen and the like were purged, and the remaining solid was vacuum-dried at room temperature to obtain a prepolymerization catalyst component containing 39.6 g of polyethylene per 1 g of the component (H). [Η] of the polyethylene was 1.17 dl / g.
(3) Production of Component (A) (LLDPE1-10) In the presence of the prepolymerization catalyst component obtained in (2), copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized-bed gas-phase polymerization apparatus. An ethylene-1-hexene copolymer (hereinafter, referred to as LLDPE1-10) powder was obtained. The polymerization conditions were a polymerization temperature of 96 ° C., a polymerization pressure of 2 MPa, an average amount of hydrogen of 0.56% with respect to 100 mol% of ethylene, and a molar ratio of 1-hexene to the total of ethylene and 1-hexene of 1.09. %. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the above prepolymerized catalyst component, triisobutylaluminum, triethylamine (a molar ratio to triisobutylaluminum of 30%) and oxygen (a molar ratio to triisobutylaluminum of 12%) were continuously supplied, and the total powder weight of the fluidized bed was reduced to 80 kg. It was kept constant. The average polymerization time was 3.4 hours. Using an extruder (LCM50 manufactured by Kobe Steel Ltd.), the obtained powder of LLDPE1-10 was fed at a feed speed of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200. Granulation was performed under the conditions of ～ 230 ° C. to obtain pellets of LLDPE1-10. The physical properties of the obtained pellets of LLDPE1-10 were evaluated, and the results are shown in Table 1.

[Blown film molding]
The following components (B), (D) and (E) were used in the examples.

Component (B)
Ethylene-1-hexene copolymer 2-1 (LLDPE2-1): Metallocene-catalyzed linear low-density polyethylene Sumikacene EFV203 (manufactured by Sumitomo Chemical Co., Ltd., ethylene-1-hexene copolymer). Table 1 shows the physical properties.

Component (D)
High pressure method low density polyethylene 1 (LDPE1): High pressure method low density polyethylene Sumikasen F200 (manufactured by Sumitomo Chemical Co., Ltd., high pressure method low density polyethylene). Table 1 shows the physical properties.

Component (E)
Ethylene-1-butene-1-hexene copolymer 2-2 (LLDPE2-2): metallocene-catalyzed linear low-density polyethylene Sumikacene EP CU5003 (manufactured by Sumitomo Chemical Co., Ltd., ethylene-1-butene-1-hexene copolymer) United). Table 1 shows the physical properties.

The following master batches were used in the examples.
Masterbatch 1 (MB1): Sumikasen E MB CMB-735 (Sumitomo Chemical Co., Ltd., antioxidant masterbatch)
Masterbatch 2 (MB2): Sumikasen E MB EMB-21 (manufactured by Sumitomo Chemical Co., Ltd., anti-blocking agent masterbatch)
Masterbatch 3 (MB3): Sumikasen MB A-26 (Sumitomo Chemical Co., Ltd., antiblocking agent / lubricant masterbatch)

[Example 1]
(1) Film processing Each resin was mixed by a tumble mixer according to the composition shown in Table 2. Next, the obtained mixture was subjected to an inflation film molding machine (a single screw extruder with a full flight type screw (diameter: 50 mm, L / D = 28), a die (die diameter: 125 mm, lip gap: 2.0 mm) manufactured by Placo). A blown film having a thickness of 100 μm was formed at a processing temperature of 190 ° C., an extrusion rate of 25 kg / hr, a frost line distance (FLD) of 200 mm, and a blow ratio of 2.0. Table 2 shows the physical properties of the obtained blown film.
(2) Production of multilayer film By dry lamination using a test coater (manufactured by Yasui Seiki Co., Ltd.), an inflation film and a biaxially stretched nylon film (thickness: 15 μm) are bonded to a two-component curable polyurethane adhesive (Takeda). After laminating via Takelac A310 / Takenate A-3) manufactured by Yakuhin Kogyo Co., Ltd., it was aged at 40 ° C. for 48 hours to obtain a multilayer film. The layer constitution of the multilayer film was blown film / adhesive layer / biaxially stretched nylon film. Table 2 shows the results of the dropping strength.

[Example 2, Example 3]
Except that the composition was changed as shown in Table 2, a blown film and a multilayer film were obtained in the same manner as in Example 1. Table 2 shows the results.

[Comparative Examples 1 to 4]
An inflation film and a multilayer film were obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 3. Table 3 shows the results.

Claims

S1 obtained by the following 0) to 7) is 220 MPa or more and 2000 MPa or less, and the nominal stress at 100% elongation in the MD direction when subjected to a tensile test at a tensile speed of 500 mm / min is 11.0 MPa or more and 30.0 MPa or less. Film.

0) A test piece is punched out of the film with a dumbbell cutter conforming to the ASTM D1822 Type S standard so that the longer side is in the MD direction.
1) A tensile test is performed on the test piece at a speed of 1 m / s using a high-speed tensile tester.
2) The test piece during the tensile test of 1) is photographed by a high-speed camera.
3) The captured image is analyzed by 3D inspection / analysis software to determine the maximum principal strain (ε 1 ) and the minimum principal strain (ε 3 ) at the constricted portion of the test piece.
4) The cross-sectional area of the constricted part of the test piece is determined by the following equation.
(Cross-sectional area of constriction of test piece)
= (Width of constricted part before test execution) × (thickness of constricted part before test execution) × {exp (ε 3 )} 2
5) The load at each time obtained by the tensile test is divided by the cross-sectional area of the constricted portion of the test piece at each time to obtain the true stress at each time.
6) The true stress at each time obtained in 5) is plotted against the maximum principal strain (ε 1 ) at each time to obtain a true stress-maximum principal strain curve.
7) S1 is determined by 7a) or 7b).
7a) In the tensile test of 1), when the test piece is not broken at the time when the maximum principal strain is 2.0, S1 is obtained by the following equation (11).
S1 = (p−q) /0.3 (11)
(In Equation (11), p is the true stress (MPa) at the maximum principal strain of 2.0, and q is the true stress (MPa) at the maximum principal strain of 1.7.)
7b) In the tensile test of 1), when the test piece breaks within a range where the maximum principal strain is larger than 1.7 and smaller than 2.0, S1 is calculated by the following equation (12).
S1 = (p'-q) / (r-1.7) (12)
(In the equation (12), p ′ is the true stress (MPa) at the breaking point, q is the true stress (MPa) at the maximum principal strain of 1.7, and r is the maximum principal strain at the breaking point. Is.)
A multilayer film comprising a layer α composed of the film according to claim 1,
A multilayer film in which at least one of the two surface layers of the multilayer film is the layer α.
包装 A packaging container comprising the film according to claim 1.