JPWO2020050245A1 - Film and packaging - Google Patents

Abstract

Provided are a film capable of providing a packaging container having excellent bag-dropping strength and a packaging container having excellent bag-dropping strength. S1 determined by 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 a tensile test is performed under the condition of a tensile speed of 500 mm / min is 11.0 MPa or more and 30.0 MPa or less. the film. 1) Perform a tensile test on the test piece with a high-speed tensile tester at a speed of 1 m / s. 7) S1 is determined by 7a) or 7b). 7a) In the tensile test of 1), if the test piece is not broken at the time when the maximum principal strain is 2.0, S1 is obtained by the following formula (11). S1 = (p−q) /0.3 ・ ・ ・ (11) (In equation (11), p is the true stress (MPa) when the maximum principal strain is 2.0, and q is the maximum principal strain. True stress (MPa) at 1.7.)

Description

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 contained in a packaging container, for example, Patent Document 1 describes a film composed of a resin composition containing an ethylene-α-olefin copolymer and low-density polyethylene obtained by a high-pressure radical polymerization method. ..

Japanese Unexamined Patent Publication No. 11-181173

When the packaging container containing the contents is dropped, the packaging container may be damaged, and in recent years, improvement in the bag-dropping strength of the packaging container has been required.

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

The present invention provides:
[1] S1 obtained 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 100% elongation in the MD direction when a tensile test is performed under a tensile speed of 500 mm / min.

0) Punch a test piece from the film with a dumbbell cutter conforming to the ASTM D1822 Type S standard so that the MD direction is the long side.
1) Perform a tensile test on the test piece with a high-speed tensile tester at a speed of 1 m / s.
2) Take a picture of the test piece under the tensile test of 1) with a high-speed camera.
3) The captured image is analyzed by 3D inspection / analysis software to obtain the _{maximum principal strain (ε 1} ) and the minimum principal strain (ε _{3) at the constricted part of the test piece.}
4) The cross-sectional area of the constricted part of the test piece is calculated by the following formula.
(Cross-sectional area of test piece constriction)
= (Width of constriction before test) × (Thickness of constriction before test) × {exp (ε ₃ )} ²
5) Divide the load obtained by the tensile test at each time by the cross-sectional area of the constricted part 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, and the true stress-maximum principal strain curve is obtained.
7) S1 is determined by 7a) or 7b).
7a) In the tensile test of 1), if the test piece is not broken at the time when the maximum principal strain is 2.0, S1 is obtained by the following formula (11).
S1 = (p−q) /0.3 ・ ・ ・ (11)
(In equation (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.)
7b) In the tensile test of 1), if the test piece breaks within the range where the maximum principal strain is larger than 1.7 and less than 2.0, S1 is calculated by the following formula (12).
S1 = (p'-q) / (r-1.7) ... (12)
(In 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 containing the 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 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-dropping strength.

[Definition]
In the present specification, the following terms are defined or explained 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 with respect to 100% by weight of the total weight of the polymer. It is a polymer having a weight of% by weight or more.
The "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. It is a copolymer in which the total amount of ethylene-based monomer units and α-olefin-based monomer units 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.
The "ethylene-based resin composition" refers to a composition containing an ethylene-based polymer.
"High-pressure low-density polyethylene" refers to a polymer produced by polymerizing ethylene or ethylene with a small amount of copolymerization component by radical polymerization under a pressure of 100 to 400 MPa and having a density of 930 kg / m ³ or less. ..
"Glidant" refers to an agent that has the effect of reducing the coefficient of friction of the material to which it is applied.
The "anti-blocking agent" refers to an agent having a function of preventing the films from adhering to each other, adhering to each other, or fusing together and not peeling off during storage or use of the films.

The density in the present specification is a value measured according to the method A specified in JIS K7112-1980 after performing the annealing described in JIS K6760-1980.
The melt flow rate (hereinafter sometimes referred to as MFR; the unit is g / 10 minutes) in the present specification is a condition of a temperature of 190 ° C. and a load of 21.18 N according to the method specified in JIS K7210-1995. It is a value measured by.
The melt flow rate ratio (hereinafter, may be referred to as MFRR) in the present specification is a condition of a temperature of 190 ° C. and a load of 211.82 N with respect to a melt flow rate measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N. It is the ratio of the melt flow rate measured in.
In the present specification, the number average molecular weight (hereinafter, may be referred to as Mn), the weight average molecular weight (hereinafter, may be referred to as Mw), and the z average molecular weight (hereinafter, may be referred to as Mz) are defined. , Determined by gel permeation chromatography (GPC) method. The GPC measurement is performed under the following conditions (1) to (8).
(1) Equipment: Waters 150C manufactured by Waters
(2) Separation column: TOSOH TSKgelGMH _6- HT
(3) Measurement temperature: 140 ° C
(4) Carrier: Ortodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection amount: 500 μL
(7) Detector: Differential refractometer
(8) Molecular weight standard substance: Standard polystyrene

「主歪み」は、物体内にはたらく歪みをテンソルで表した際、せん断ひずみがゼロになる座標系を基準としたテンソル(主歪みテンソル)における垂直ひずみ成分である。主歪みは、値の大きい方から順に「最大主歪み(ε_１)」、「中間主歪み(ε_２)」、「最小主歪み(ε_３)」と定義される。The "MD direction" is the traveling direction of the film at the time of film molding.
The "TD direction" is a direction orthogonal to the MD direction.
When the film is a scroll, the longitudinal direction is the MD direction. Normally, one side of a film or packaging container 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 "main strain" is a vertical strain component in a tensor (main strain tensor) based on a coordinate system in which the shear strain becomes zero when the strain acting in the object is expressed by a tensor. The principal strain is defined as "maximum principal strain (ε ₁ )", "intermediate principal strain (ε ₂ )", and "minimum principal strain (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 polymer. The content of the ethylene-based polymer in the film is preferably 70.0% by weight or more and 99.9% by weight or less, more preferably 80.0% by weight or more and 99.8% by weight or less, and further preferably 90% by weight. It is 0.0% by weight or more and 99.7% by weight or less, and particularly preferably 95.0% by weight or more and 99.6% by weight or less. The ethylene-based polymer contained in the film is preferably a polymer having a monomer unit based on ethylene, and the monomer unit based on ethylene is preferably 100% by weight based on the total weight of the polymer. 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) Punch a test piece from the film with a dumbbell cutter conforming to the ASTM D1822 Type S standard so that the MD direction is the long side.
1) Perform a tensile test on the test piece with a high-speed tensile tester at a speed of 1 m / s.
2) Take a picture of the test piece under the tensile test of 1) with a high-speed camera.
3) The captured image is analyzed by 3D inspection / analysis software to obtain the _{maximum principal strain (ε 1} ) and the minimum principal strain (ε _{3) at the constricted part of the test piece.}
4) The cross-sectional area of the constricted part of the test piece is calculated by the following formula.
(Cross-sectional area of test piece constriction)
= (Width of constriction before test) × (Thickness of constriction before test) × {exp (ε ₃ )} ²
5) Divide the load obtained by the tensile test at each time by the cross-sectional area of the constricted part 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, and the true stress-maximum principal strain curve is obtained.
7) S1 is determined by 7a) or 7b).
7a) In the tensile test of 1), if the test piece is not broken at the time when the maximum principal strain is 2.0, S1 is obtained by the following formula (11).
S1 = (p−q) /0.3 ・ ・ ・ (11)
(In equation (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.)
7b) In the tensile test of 1), if the test piece breaks within the range where the maximum principal strain is larger than 1.7 and less than 2.0, S1 is calculated by the following formula (12).
S1 = (p'-q) / (r-1.7) ... (12)
(In 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.)

As used herein, the "necked portion of the test piece" means the center of the test piece in the long side direction. For p, p'and q, the smoothed values are used.

_{The method of obtaining ε 1} and ε ₃ in 1) to 3) is called a digital image correlation method. ε ₁ is the strain generated in the tensile direction and is 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 of 1.7 to the breaking point.

The high-speed camera of 2) usually has a frame rate of 30 fps or more, preferably 10000 fps. 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 made 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 where the film is broken and the tensile load becomes zero or less.

In one aspect, S1 may be 250 or more and 1000 or less, 280 or more and 800 or less, 290 or more and 650 or less, 290 or more and 500 or less, and 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 or more and 30.0 MPa or less at 100% elongation in the MD direction when a tensile test is performed under a tensile speed of 500 mm / min. Hereinafter, the nominal stress at 100% elongation 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 having the MD direction in the longitudinal direction is prepared according to the method described in "6.4 Tension cutting load and elongation" of JIS K6781-1994. The test piece is subjected to a tensile test under the conditions of a chuck distance of 80 mm, a marked line distance of 40 mm, and a tensile speed of 500 mm / min to obtain a nominal stress at 100% elongation. In the present specification, the "nominal stress" is a value obtained by dividing the tensile load at a predetermined elongation by the cross-sectional area of the test piece before the tensile test. The cross-sectional area of the test piece before the tensile test is the product of the width of the center of the test piece in the long side direction before the tensile test and the thickness of the center of the test piece in the long side direction before the tensile test.

As for the combination of S1 and S2, S1 is preferably 290 or more and 650 or less, S2 is preferably 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.

[Film resin density]
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 Is.
As used herein, the term "resin density" refers to the density of resin components contained in the film.
The film may contain 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 composed of a resin component and an inorganic component, the resin density of the film is the density of the resin component excluding the inorganic substance from the film.
The resin component refers to a component other than the inorganic component in the film.

[Ingredients contained in film]
The film preferably contains, for example, the following component (A) and the following component (B).
Component (A): It has a monomer unit based on ethylene and a monomer unit based on α-olefin having 3 to 20 carbon atoms, has a density of 920 kg / m ³ or more and 950 kg / m ³ or less, and has an MFR. Is 0.0001 g / 10 minutes or more and less than 0.1 g / 10 minutes, MFRR is 150 or more and 1000 or less, and zero shear viscosity at a temperature of 190 ° C. is 1 × 10 ⁵ Pa · sec or more and 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 and 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 minutes or more and 5 g / 10 minutes or less, and an ethylene-α-olefin copolymer having an MFRR of 10 or more and 30 or less.
The content of the component (A) in the film is preferably 31% by weight or more and 59% by weight or less, more preferably 35% by weight or more and 59% by weight or less, based on 100% by weight of the resin component of the film. More preferably, it is 40% by weight or more and 59% by weight or less, and particularly preferably 45% by weight or more and 59% by weight or less.
The content of the component (B) in the film is preferably 41% by weight or more and 69% by weight or less, more preferably 41% by weight or more and 65% by weight or less, based on 100% by weight of the resin component of the film. It is more preferably 41% by weight or more and 60% by weight or less, and particularly preferably 41% by weight or more and 55% by weight or less.
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 bag-dropping strength of the packaging container, and the total amount of the component (A) and the component (B) is 100% by weight, of the component (A). 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 component (A) and the component (B) is 90% by weight or more with respect to 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 40% by weight or more and 60% by weight or less, based on 100% by weight of the total amount of the component (A) and the component (B). More preferably, it is more preferably 45% by weight or more and 60% by weight or less.

S1 can be controlled by adjusting the composition distribution of the ethylene-based polymer in the film, the molecular weight distribution of the ethylene-based polymer, the MFR of the ethylene-based polymer, and [η] of the ethylene-based polymer. S1 can be increased by narrowing the composition distribution of the ethylene 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 polymer. S1 can be increased by increasing [η] of the ethylene polymer.
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]. Further, as an example of the ethylene-based polymer having a narrow composition distribution and a large [η], the component (B) can be mentioned. Therefore, the film contains the component (A) and the component (B), and the content of the component (A) is 35% by weight with respect to the total amount of the component (A) and the 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 amount of long chain branching 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 polymer. By widening the molecular weight distribution of the ethylene polymer, S2 can be increased.
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 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.
S2 can be increased by increasing the content of the component (A) in the resin component of the film.
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 11.0 MPa or more and 30.0 MPa or less.

From the viewpoint of bag-dropping strength, the tensile breaking strength of the film in the MD direction and the TD direction is preferably 43 MPa or more and 50 MPa or less.
From the viewpoint of bag-fall strength, the tensile elongation at break of the film according to the present invention in the MD direction and the TD direction is preferably 660 MPa or more and 730 MPa or less.

The film may contain a lubricant and / or an anti-blocking agent.
Further, as the additive, for example, an antioxidant, a neutralizing agent, a weather resistant agent, an antistatic agent, an anti-fog agent, a drip-free agent, a pigment or a filler may be contained.
The content of the antioxidant in the film is preferably 200% by weight or more and 1000% by weight or less. The content of the lubricant in the film is more preferably 100% by weight or more and 500% by weight or less. The content of the anti-blocking agent in the film is preferably 1000% by weight or more and 5000% by weight or less.

<Ingredient (A)>
Examples of the α-olefin having 3 to 20 carbon atoms forming a monomer unit based on the α-olefin having 3 to 20 carbon atoms in the component (A) include propylene, 1-butene, 1-pentene, and 1-. Examples include hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene. The component (A) may have only one type of monomer unit based on these α-olefins having 3 to 20 carbon atoms, or may have two or more types. The α-olefin having 3 to 20 carbon atoms is preferably 1-butene, 1-hexene, 4-methyl-1-pentene, or 1-octene, and is preferably 1-butene or 1-hexene. More preferred.

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

The component (A) may have a monomer unit based on a monomer other than ethylene and α-olefin having 3 to 20 carbon atoms. Examples of monomers other than ethylene and α-olefin having 3 to 20 carbon atoms include conjugated diene such as butadiene or isoprene; non-conjugated diene such as 1,4-pentadiene; acrylic acid; methyl acrylate or acrylic acid. Acrylic acid esters such as ethyl; methacrylic acid; methacrylic acid esters such as methyl methacrylate or ethyl methacrylate; and vinyl acetate.

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

Examples of the component (A) include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, and ethylene. Examples include -1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, and ethylene-1-butene-1-octene copolymer. The 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, and the like. Ethethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene-1-octene copolymer, or ethylene-1-butene-1-octene It is preferably a polymer, and is a combination of ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, or ethylene-1-butene-1-octene. It is more preferably a polymer, and even more preferably an ethylene-1-hexene copolymer or an ethylene-1-butene-1-hexene copolymer.

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 even 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 The following is more preferable.
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 There, in yet another embodiment, the density of component (a), is 923 kg / m ³ or more 930 kg / m ³ or less.

The MFR of the component (A) is preferably 0.0005 g / 10 minutes or more, and more preferably 0.001 g / 10 minutes 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 bagging strength of the film. It is more preferably less than / 10 minutes.
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. It is 0.06 g / 10 minutes or less, and in still another embodiment, the MFR of the component (A) is 0.005 g / 10 minutes or more and 0.05 g / 10 minutes or less. In the measurement of the MFR of the component (A), a sample containing about 1000 ppm of an antioxidant in the component (A) is usually used.

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

The component (A) is in the presence of a polymerization catalyst obtained by contacting a cocatalyst carrier (hereinafter referred to as a component (H)) described later, a metallocene-based complex, an organoaluminum compound, and an electron-donating compound. It is obtained by copolymerizing ethylene and α-olefin by a slurry polymerization method or a vapor phase polymerization method. In the copolymerization, the ratio of the electron donating compound to 100 mol% of the organoaluminum compound of the polymerization catalyst is 2 to 50 mol%, and the ratio of hydrogen to 100 mol% of ethylene is 0.01 to 1.1 mol. ^{By setting%, 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.

Η ⁰ at a temperature of 190 ° C. is a shear viscosity (η *; unit is Pa · sec) at a measurement temperature of 190 ° C. using the Carreau-Yasuda model represented by the following equation (1) by the nonlinear least squares method. It 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 is measured by using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer RMS800 manufactured by Leometrics), and usually, geometry: parallel plate, plate diameter: 25 mm, thickness of measurement sample: about 2.0 mm. , Angle frequency: 0.1 to 100 rad / sec, Measurement point: ω 5 points per digit. The amount of strain is appropriately selected in the range of 3 to 10% so that the torque in the measurement range can be detected and the torque is not exceeded. The measurement sample is prepared by pressing at a pressure of 2 MPa for 5 minutes with a hot press at 150 ° C., cooling with a cooling press at 30 ° C. for 5 minutes, and press-molding to a thickness of 2 mm.

The activation energy of the flow of the component (A) (hereinafter referred to as Ea; the unit is kJ / mol) is preferably 50 kJ / mol or more from the viewpoint of further improving the bag-falling strength of the film. , 60 kJ / mol or more, and even more preferably 70 kJ / mol or more. Further, from the viewpoint of reducing the extrusion load during film formation, the 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 preferable to have. In one embodiment, the Ea of the component (A) is 50 kJ / mol or more and 120 kJ / mol or less, and in the other embodiment, the Ea of the component (A) is 60 kJ / mol or more and 110 kJ / mol or less, and further. In the embodiment, the Ea of the component (A) is 70 kJ / mol or more and 100 kJ / mol or less.

The activation energy (Ea) of the flow is the angular frequency (unit is rad / sec) of the molten complex viscosity (unit is Pa · sec) at 190 ° C. based on the temperature-time superposition principle. It is a numerical value calculated by the Arenius type equation from _{the shift factor (a T} ) when creating the master curve showing the dependence on. Ea is a value obtained by the following method. The melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at each temperature of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (expressed as T; unit: ° C.) is based on the temperature-time superposition principle. Based on this, each temperature obtained when the molten complex viscosity-angular frequency curve at each temperature (T) is superimposed on the molten complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at 190 ° C. Find the shift factor (a _T ) at T). 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: Flow activation energy (unit: kJ / mol)
T: Temperature (Unit: ° C)
Commercially available calculation software may be used for the above calculation. As the calculation software, for example, Rhios V. manufactured by Rheometrics Co., Ltd. 4.4.4 and the like.
For the shift factor (a _T ), the common logarithm of the molten complex viscosity at each temperature (T) is plotted on the X-axis, and the common logarithm of the angular frequency is plotted on the Y-axis. Is created, and the both logarithmic curves of the molten complex viscosity-angular frequency at 130 ° C., 150 ° C. and 170 ° C. are moved in the X-axis direction, respectively, and superimposed on the both logarithmic curves of the molten complex viscosity-angular frequency at 190 ° C. It 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. Further, the correlation coefficient when the equation (I) is obtained by the least squares method from the values of four points of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. is usually 0.99 or more.

The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate spacing: 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 carried out in a nitrogen atmosphere, and it is preferable to add an appropriate amount (for example, 1000 ppm) of an antioxidant in advance to the measurement sample.

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

The ratio of the z-average molecular weight of the component (A) to the weight average molecular weight (hereinafter referred to as Mz / Mw) is preferably 2.0 or more from the viewpoint of further improving the bagging strength of the film. It is more preferably 2.1 or more, and further preferably 2.2 or more.
The Mz / Mw of the component (A) is preferably 5 or less, more preferably 4 or less, and further preferably 3 or less, from the viewpoint of reducing appearance defects such as fish eyes of the film. .. The 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 further 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 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 / It is more preferably m ^{2 or less.}
The tensile impact strength of the component (A) is measured 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 according to ASTM D1822-68.
By adjusting the ratio of ethylene and α-olefin during polymerization, the tensile impact strength of the component (A) can be adjusted. Increasing the ratio of α-olefin to ethylene increases the tensile impact strength of the component (A), and decreasing the ratio decreases the tensile impact strength of the 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 copolymerized with ethylene. When the number of carbon atoms of the α-olefin is increased, the tensile impact strength of the component (A) increases, and when the number of carbon atoms is decreased, the tensile impact strength of the component (A) decreases.

The ultimate viscosity of the component (A) (hereinafter referred to as [η]; the unit is dl / g) is 1.0 dl / g or more from the viewpoint of further improving the bagging strength of the film. It is more preferably 1.2 dl / g or more, and even more preferably 1.3 dl / g or more. The [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. It is more preferably 1.7 dl / g or less. The [η] of the component (A) is preferably 1.0 dl / g or more and 2.0 dl / g or less, more preferably 1.2 dl / g or more and 1.9 dl / g or less, and 1.3 dl or more. It is more preferably / g or more and 1.7 dl / g or less. [Η] of the component (A) is measured using a Ubbelohde viscometer at a temperature of 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, more preferably 15 seconds or more, from the viewpoint of further improving the bagging strength of the film. , 18 seconds or more is more preferable. Further, from the viewpoint of reducing the extrusion load during film formation and the appearance of the film, the characteristic relaxation time of the component (A) is preferably 50 seconds or less, more preferably 45 seconds or less. It is more preferably 40 seconds or less. The characteristic relaxation time of the component (A) is preferably 10 seconds or more and 50 seconds or less, more preferably 15 seconds or more and 45 seconds or less, and further preferably 18 seconds or more and 40 seconds or less.

The property 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. If the long chain branch is short, the amount of long chain branch is small, or the high molecular weight component is small, the characteristic relaxation time becomes a small value. If the long chain branch is long, the amount of long chain branch is large, or the amount of high molecular weight component is large, the characteristic relaxation time becomes a large value.
After the ethylene-α-olefin copolymer having a long property relaxation time is extruded from the die of the inflation film forming machine, molecular chain entanglement causes oriented crystals to be formed in the take-up direction, so that the rigidity of the film in the MD direction is increased. 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 nominal stress at 100% elongation in the MD direction is high, and the film is more excellent in bagging strength.

The characteristic relaxation time is calculated from the master curve showing the angular frequency (unit: rad / sec) dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C., which is created based on the temperature-time superposition principle. It is a numerical value to be done. The characteristic relaxation time is determined by the method shown below. Molten 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 molten complex viscosity is Pa · sec, angle The unit of frequency is rad / sec) is superposed on the melt complex viscosity-angular frequency curve at 190 ° C. based on the temperature-time superposition principle to create a master curve, and the obtained master curve is shown below. It is a value calculated by approximating with the equation (5).
η = η0 / [1+ (τ × ω) n] (5)
η: Molten complex viscosity (unit: Pa · sec)
ω: Angular frequency (unit: rad / sec)
τ: Characteristic relaxation time (unit: sec)
η0: Constant (unit: Pa · sec) obtained for each ethylene-α-olefin copolymer
n: Constant obtained for each ethylene-α-olefin copolymer
Commercially available calculation software may be used for the above calculation. As the calculation software, for example, Rhios V. manufactured by Rheometrics Co., Ltd. 4.4.4 can be mentioned.

The melt complex viscosity-angular frequency curve is measured in the same manner as the melt complex viscosity-angular frequency curve measured for calculating the activation energy of the flow described above.

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

The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate spacing: 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 carried out in a nitrogen atmosphere, and it is preferable to add an appropriate amount (for example, 1000 ppm) of an antioxidant in advance to the measurement sample.

The Vicat softening point (unit: ° C.) is a numerical value related to the molecular weight, density, and composition distribution of the ethylene-α-olefin copolymer. When the molecular weight is high, the density is high, or the composition distribution is narrow, the Vicat softening point becomes a small value. When 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-dropping strength, the Vicat softening point of the component (A) is preferably 108 ° C. or lower, more preferably 106 ° C. or lower, and 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, and 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-dropping 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, the temperature is preferably 95 ° C. or higher, more preferably 98 ° C. or higher, and even more preferably 100 ° C. or higher.

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. If the density is low, the molecular weight distribution is narrow, or the composition distribution is narrow, the crystallization temperature will be 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 112 ° C. or lower, more preferably 110 ° C. or lower, and further preferably 108 ° C. or lower. From the viewpoint of increasing the rigidity of the film, the temperature is preferably 95 ° C. or higher, more preferably 98 ° C. or higher, and even more preferably 100 ° C. or higher.

The value of the component (A) obtained by subtracting the Vicat softening point from the melting point 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 activation cocatalyst component (hereinafter referred to as a component (I)) is supported on a fine particle carrier, a metallocene-based complex, and an electron-donating compound. In the presence of an olefin polymerization catalyst formed by contacting with and, a method of copolymerizing ethylene and α-olefin can be mentioned.

Examples of the component (I) include zinc compounds. Examples of the zinc compound include compounds obtained by contacting diethylzinc, fluorinated phenol, and water.

The fine particle carrier is a porous substance having a 50% volume average particle diameter of 10 to 500 μm. The 50% volume average particle size is measured by, for example, a light scattering laser diffraction method.
Examples of the fine particle carrier include inorganic substances and organic polymers. 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, ThO ₂ ; smectite, montmorillonite, hectorite, and laponite. , Clays such as saponite and clay minerals. Examples of the organic polymer include polyethylene, polypropylene, and a styrene-divinylbenzene copolymer. As the fine particle carrier, a fine particle carrier made of an inorganic substance (hereinafter, referred to as an inorganic fine particle carrier) is preferable.
The pore volume of the fine particle carrier is usually 0.3 to 10 ml / g. The specific surface area of the fine particle carrier is usually 10 to 1000 m ² / g. The pore volume and the specific surface area are measured by the gas adsorption method, and the pore volume is determined by analyzing the amount of gas desorption by the BJH method and the specific surface area by analyzing the amount of gas adsorption by the BET method.

[Component (H)]
The component (H) is a carrier in which the component (I) is supported on a fine particle carrier.
The component (H) includes diethylzinc (hereinafter referred to as component (a)), fluorinated phenol (hereinafter referred to as component (b)), water (hereinafter referred to as component (c)), and an inorganic fine particle carrier (hereinafter referred to as component (c)). It can be obtained by contacting component (d)) and trimethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH) (hereinafter referred to as component (e)).

The component (b) includes, 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, preferably 3,4,5-trifluorophenol. By using the above component (b), the amount of long chain branching of the obtained component (A) can be increased.

The component (d) is preferably silica gel.

In the method for producing the component (I), the amount of each component of the component (a), the component (b), and the component (c) determines the molar ratio of the amount of each component used. When the 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 equations (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 amount of the component (c) used to the amount of the component (a) used are the above formulas (2) and (3). ) And (4) are not particularly limited. y is usually 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 preferable to have. 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 obtained film containing the ethylene-α-olefin copolymer has a poor appearance such as fish eye.

The number of moles of zinc atoms derived from the component (a) contained in 1 g of the particles obtained by the contact between the component (a) and the component (d) is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol. The amount of the component (a) and the component (d) used is adjusted so as to be. The amount of the component (e) used with respect to the component (d) is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol, based on 1 g of the component (d). ..

The metallocene complex is a transition metal compound having a ligand containing a cyclopentadiene-type anionic skeleton.
As the metallocene complex, a transition metal compound represented by the following general formula [1] or a μ-oxo type transition metal compound dimer thereof is preferable.
L ² _a M ² X ¹ _b [1]
(In the equation, M ² is a transition metal atom of the Group 3-11 of the Periodic Table or the lanthanoid series.
L ² is a group having a cyclopentadiene type anion skeleton, or a plurality of L ² are connected directly to each other or residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or phosphorus atom It may be connected via. X ¹ is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene 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 of the Group 3-11 or Lantanoid series of the Periodic Table (IUPAC 1989), for example, a scandium atom, an yttrium atom, a titanium atom, a zirconium atom, a hafnium atom, and a vanadium. Examples include atoms, niobium atoms, tantalum atoms, chromium atoms, iron atoms, ruthenium atoms, cobalt atoms, rhodium atoms, nickel atoms, palladium atoms, samarium atoms, and itterbium atoms. ^{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 is a titanium atom, a zirconium atom or a hafnium atom. More preferably, it is further preferably a zirconium atom.

In the general formula [1], L ² is eta ⁵ - a (substituted) indenyl group, the two L ² may be different even in the same. Two L ² each other, a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, are linked via a bridging group containing a sulfur atom or a phosphorus atom.
The η ^5- (substituted) indenyl group ^{represents a 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 from the name of the transition metal compound. L ² is preferably an indenyl group.

The two (substituted) indenyl groups are linked via a cross-linking group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of the cross-linking 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 substitution such as a silylene group, a dimethylsilylene group, a diphenylsilylene group and a tetramethyldisylylene group. Syrylene group; heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom can be mentioned. The cross-linking 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 referred to 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, a neopentyl group and an amyl group. Examples thereof include an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-pentadecyl group and an n-eicosyl group. The alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group substituted with the halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a per. Examples thereof include a fluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group and a perbromopropyl group. All of these alkyl groups are alkoxy groups such as methoxy group and ethoxy group; aryloxy group such as phenoxy group; or aralkyloxy group such as benzyloxy group, even if some 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, and (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-tetramethylphenyl) 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-hexylphenyl) methyl group, Examples thereof include a (n-octylphenyl) methyl group, a (n-decylphenyl) methyl group, a (n-dodecylphenyl) methyl group, a naphthylmethyl group, and an anthrasenyl methyl group. The aralkyl group may be, 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 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-kisilyl group, a 2,4-kisilyl group, a 2,5-kisilyl group, and 2,6-. Kisilyl group, 3,4-kisilyl group, 3,5-kisilyl 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, 2,3,4,5-trimethylphenyl 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-pentylphenyl group, neopentylphenyl group, n Examples thereof include −hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group and 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 alkenyl group include an allyl group, a metharyl group, a crotyl group, and a 1,3-diphenyl-2-propenyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, a neopentoxy group and an n-hexoxy group. Examples thereof include an n-octoxy group, an n-dodesoxy group, an n-pentadesoxy 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, and 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) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, ( 2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propyl) (Phenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n) Examples thereof include a (octylphenyl) methoxy group, a (n-decylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group. The aralkyloxy group includes, 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 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 group. 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 group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethyl Phenoxy 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-butyl-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, anthracenoxy group and the like. The aryloxy 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 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.

In the general formula [1], a represents 2 and b represents 2.

Specific examples of the metallocene-based complex include dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, and 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-naphthylinde) Nyl) Titanium dichloride, compounds in which titanium of these compounds is changed to zirconium or hafnium, compounds in which dimethylsilylene is changed to methylene, ethylene, dimethylmethylene (isopropyridene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxycilylene. , Dichloride to difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxydo, diethoxydo, di (n-propoxide), di (isopropoxide), diphenoxide, or di (pentafluorophenoxide) Examples include modified compounds.

Metallocene-based 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.

The olefin polymerization catalyst formed by contacting the component (H) with the metallocene complex is preferably an olefin polymerization catalyst formed by contacting the component (H), the metallocene complex, and the organoaluminum compound.

Examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, tributylaluminum triisobutylaluminum, and trinormaloctylaluminum, preferably triisobutylaluminum and trinormaloctylaluminum, and more preferably triisobutylaluminum. preferable.

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

The amount of the metallocene complex used is preferably ^{5 × 10 -5 to} 5 × 10 ^-4 mol with respect to 1 g of the component (H). The amount of the organoaluminum compound used is preferably 50 to 500 in terms of the ratio (Al / M) of the number of moles of aluminum atoms of the organoaluminum compound to the number of moles of metal atoms of the metallocene complex.

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

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 of the organoaluminum compound. By increasing the amount of the electron-donating compound used with respect to the number of moles of aluminum atoms of the organoaluminum compound, the amount of long-chain branching of the obtained component (A) can be increased.

The amount of oxygen used is preferably 1 to 100 mol%, more preferably 10 to 20 mol%, and even more preferably 10 to 15 mol% with respect to the number of moles of aluminum atoms of the organoaluminum compound. .. By increasing the amount of oxygen used with respect to the number of moles of aluminum atoms of the organoaluminum compound, the molecular weight distribution of the obtained component (A) can be widened.

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 formed by contacting the component (H), a metallocene complex, and an organoaluminum compound. Prepolymerization catalyst components are preferred.

Examples of the method for producing the prepolymerized catalyst component include a method for producing the 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 the step (1) into contact with the component (H) to obtain a contact-treated product.
Step (3): A step of contacting the contact-treated product obtained in step (2) with an organoaluminum compound to obtain a catalyst component.
Step (4): A step of prepolymerizing an olefin in the presence of the catalyst component obtained in step (3) to obtain a prepolymerization catalyst component.

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

Examples of the saturated aliphatic hydrocarbon compound used for preparing a saturated aliphatic hydrocarbon compound solution containing a metallocene-based 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. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or lower at normal pressure, more preferably 90 ° C. or lower at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal. Hexane and cyclohexane are more preferable.

In the heat treatment of the saturated aliphatic hydrocarbon compound solution containing the metallocene complex, the temperature of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex may be adjusted to a temperature of 40 ° C. or higher. During the heat treatment, the solvent may be allowed to stand or the solvent may be agitated. The temperature is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of improving the moldability of the film. Further, from the viewpoint of increasing 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 improving the moldability of the film. From the viewpoint of stability of catalyst performance, it is preferably 6 hours or less, and more preferably 4 hours or less.

In the step (2), the heat-treated product and the component (H) may come into contact with each other. Examples of the method of contacting include a method of adding the component (H) to the heat-treated product, and a method of adding the heat-treated product and 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.

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

In the step (3), the contact-treated product obtained in the 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 contact-treated product obtained in the step (2) in a saturated aliphatic hydrocarbon compound. And an organoaluminum compound are added.

The temperature of the contact treatment in the step (3) is preferably 70 ° C. or lower, more preferably 60 ° C. or lower. Further, from the viewpoint of efficiently expressing the activity of the prepolymerization, the temperature is preferably 10 ° C. or higher, and more preferably 20 ° C. or higher. The contact treatment time is usually 0.01 to 0.5 hours.

The contact treatment in step (3) is preferably carried out in the presence of an olefin. Examples of the olefin usually include an olefin as a raw material for prepolymerization. The amount of olefin is preferably 0.05 to 1 g per 1 g of the component (H).

In the above steps (1) to (3), the saturated aliphatic hydrocarbon compound, the component (H), the metallocene complex, and the organoaluminum compound are separately added to the prepolymerization reactor, thereby performing the step (1). )-(3) may be performed in a prepolymerization reactor, steps (2) and (3) may be performed in a prepolymerization reactor, or step (3) may be prepolymerized. It may be carried out in a reactor.

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

When the prepolymerization is carried out by the slurry polymerization method, a saturated aliphatic hydrocarbon compound is usually used as the solvent. Examples of the saturated aliphatic hydrocarbon compound include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane and heptane. These are used alone or in combination of two or more. As the saturated aliphatic hydrocarbon compound, the boiling point at normal pressure is preferably 100 ° C. or lower, more preferably the boiling point at normal pressure is 90 ° C. or lower, and propane, normal butane, isobutane, normal pentane, isopentane, It is more preferably normal hexane or cyclohexane.

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

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, preferably ethylene alone, or ethylene and an α-olefin in combination, selected from ethylene alone, or 1-butene, 1-hexene and 1-octene. It is more preferable to use ethylene in combination with at least one α-olefin.

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

As a method for producing the component (A), a slurry polymerization method or a gas phase polymerization method is preferable, and a continuous gas phase polymerization method 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 reaction apparatus used in the continuous vapor phase polymerization method is usually an apparatus having a fluidized bed type reaction vessel, and an apparatus having a fluidized bed type reaction vessel having an enlarged portion is preferable. A stirring blade may be installed in the reaction vessel.

When the olefin polymerization catalyst is an olefin polymerization catalyst containing a prepolymerization catalyst component, as a method of supplying the prepolymerization catalyst component to the continuous polymerization reaction tank for forming the particles of the component (A), usually, argon or the like is not used. A method of supplying in a water-free state using an active gas, nitrogen, hydrogen or ethylene, or a method of dissolving or diluting each component in a solvent and supplying in a solution or slurry state is used.

The polymerization temperature of the vapor phase polymerization of the component (A) is usually lower than the temperature at which the component (A) melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C, and 70. It is more preferably ° C. to 87 ° C. Hydrogen may be added to regulate 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 the vapor phase polymerization can be controlled by the amount of hydrogen generated during the polymerization and the amount of hydrogen added during the 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 co-catalyst component such as an organoaluminum compound. By lowering the ratio of hydrogen to ethylene during gas phase polymerization, the molecular weight of the obtained component (A) can be increased.

<Ingredient (B)>
Examples of the α-olefin having 3 to 20 carbon atoms forming a monomer unit based on the α-olefin having 3 to 20 carbon atoms in the component (B) include propylene, 1-butene, 1-pentene, and 1-. Examples include hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene. The component (B) may have only one type of monomer unit based on these α-olefins having 3 to 20 carbon atoms, or may have two or more types. 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 ethylene-based monomer unit 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). The content of the monomer unit based on the α-olefin is preferably 0.5 to 50% by weight with respect to 100% by weight of the total weight of the component (B).

The component (B) may have a monomer unit based on a monomer other than ethylene and α-olefin having 3 to 20 carbon atoms. Examples of monomers other than ethylene and α-olefin having 3 to 20 carbon atoms include conjugated diene such as butadiene or isoprene; non-conjugated diene such as 1,4-pentadiene: acrylic acid; methyl acrylate and acrylic acid. Acrylic acid esters such as ethyl; methacrylic acid; methacrylic acid esters 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 α-olefin having 4 to 20 carbon atoms, and is preferably a monomer unit based on ethylene. It is more preferable that the polymer has a monomer unit based on α-olefin having 5 to 20 carbon atoms, and a simple polymer having a monomer unit based on ethylene and an α-olefin based on α-olefin having 6 to 20 carbon atoms. It is more preferable that it is a copolymer having a monomer unit.

Examples of the component (B) include ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, and ethylene-1-butene-1-hexene. Polymers, ethylene-1-butene-4-methyl-1-pentene copolymers, and ethylene-1-butene-1-octene copolymers can be mentioned. The 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. It is more preferable that they are coalesced.

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 The above is particularly preferable. 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, further not more 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.

The MFR of component (B) is 0.5 g / 10 minutes 5 g / 10 minutes or less. The MFR of the component (B) is preferably 0.8 g / 10 minutes or more, preferably 1.0 g / 10 minutes or more, from the viewpoint of film forming processability, particularly from the viewpoint of reducing the extrusion load during film formation. The above is more preferable. The MFR of the component (B) is preferably 4.0 g / 10 minutes or less, more preferably 3.0 g / 10 minutes or less, and 2.5 g / 10 minutes or less from the viewpoint of film strength. It is more preferable to have. The MFR of the component (B) is preferably 0.8 g / 10 minutes or more and 4.0 g / 10 minutes or less, more preferably 1.0 g / 10 minutes or more and 3 g / 10 minutes or less, and 1 g / 10 minutes. It is more preferably minutes or more and 2.5 g / 10 minutes or less. In the measurement of MFR, a sample containing about 1000 ppm of an antioxidant in the component (B) is usually used.

The MFRR of 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 film forming processability, 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 film strength. 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 further preferably 20 or more and 26 or less.
For the measurement of the MFRR of the component (B), a sample containing 1000 ppm of an antioxidant in the component (B) is usually used.

The ratio (Mw / Mn) of the weight average molecular weight of the component (B) to the number average molecular weight 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. From the viewpoint of film strength, the Mw / Mn of the component (B) is preferably 7 or less, more preferably 6 or less, further preferably 5 or less, and particularly preferably 4 or less. preferable. The 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 preferably 4 or less. The Mw / Mn of the component (B) is measured by the same method as the Mw / Mn of the component (A).

The Ea of the component (B) is preferably 15 kJ / mol or more, more preferably 20 kJ / mol or more, from the viewpoint of bubble stability when the film is formed by the inflation film forming method. It is more preferably 25 kJ / mol or more. From the viewpoint of film strength, the Ea of the component (B) is preferably 50 kJ / mol or less, more preferably 45 kJ / mol or less, and even more preferably 40 kJ / mol or less. The Ea of the component (B) is preferably 15 kJ / mol or more and 50 kJ / mol or less, more preferably 20 kJ / mol or more and 45 kJ / mol or less, and further preferably 25 kJ / mol or more and 40 kJ / mol or less. preferable. The Ea is measured by the same method as that of the component (A) Ea.

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

Examples of the metallocene-based polymerization catalyst include the following catalysts (1) to (4).
(1) A catalyst composed of a component containing a transition metal compound having a group having a cyclopentadiene-type skeleton and a component containing an almoxane compound (2) A component containing the transition metal compound and ions such as tritylborate and aniliniumborate. A catalyst composed of a component containing a sex compound (3) A catalyst composed of a component containing the transition metal compound, a component containing the ionic compound, and a component containing an organic aluminum compound (4) (1) to (3) A catalyst obtained by supporting or impregnating each component described in any one of the above with _{an inorganic particulate carrier such as SiO 2} , Al ₂ O ₃ or a particulate polymer carrier such as an olefin polymer such as ethylene or styrene.

As the Ziegler-Natta-based polymerization catalyst, a so-called Mg-Ti-based Ziegler catalyst (for example, "Catalyst Utilization Dictionary; published by 2004 Industrial Research Council"), which is a combination of a solid catalyst component in which a titanium compound is supported on a magnesium compound and organoaluminum, is used. "Application system diagram-Transition of olefin polymerization catalyst-; published by Japan Institute of Invention and Innovation in 1995" and the like) is preferable.

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

Examples of the polymerization method of the component (B) include bulk polymerization, solution polymerization, slurry polymerization, vapor phase polymerization, and high-pressure ion polymerization. Here, bulk polymerization refers to a method of polymerizing using a liquid olefin as a medium at a polymerization temperature, and solution polymerization or slurry polymerization refers to inert hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane. A method of polymerizing in a solvent. Further, the gas phase polymerization refers to a method of polymerizing a gaseous monomer in the medium using a gaseous monomer as a medium. These polymerization methods may be either a batch type or a continuous type, and may be a single-stage type performed in a single polymerization tank or a multi-stage type performed in a polymerization apparatus in which a plurality of polymerization reaction tanks are connected in series. It may be. Various conditions (polymerization temperature, polymerization pressure, monomer concentration, catalyst addition amount, polymerization time, etc.) 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 component (A), the component (B) and the component (C). % Or more and 5% by weight or less is more preferable, and 1% by weight or more and 2% by weight or less is further preferable.

<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 It has polyethylene (hereinafter, may be referred to as component (D)), a monomer unit based on ethylene, and a monomer unit based on α-olefin having 3 to 20 carbon atoms, and has a density of 890 kg. Ethylene-α-olefin copolymer having / m ³ or more and 930 kg / m ³ or less, MFR of 0.3 g / 10 minutes or more and 5 g / 10 minutes or less, and MFRR of 31 or more and 150 or less (hereinafter, components (hereinafter, components (hereinafter, components) It is one or more ethylene-based polymers selected from the group consisting of (may be described as E)).

<Component (D)>
The component (D) is a low-density polyethylene produced by a high-pressure radical polymerization method.
High-pressure method As a general method for producing 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.).

The Mw / 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 of the component (A) Mw / Mn.

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

<Ingredient (E)>
Component (E) has a monomer unit based on α- olefin monomer units and 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 an ethylene-α-olefin copolymer having an MFRR of 0.3 g / 10 minutes or more and 5 g / 10 minutes or less and an MFRR of 31 or more and 150 minutes or less.
Examples of the α-olefin having 3 to 20 carbon atoms forming a monomer unit based on the α-olefin having 3 to 20 carbon atoms in the component (E) include propylene, 1-butene, 1-pentene, and 1-. Examples include hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 4-methyl-1-hexene. The component (E) may have only one type of monomer unit based on these α-olefins having 3 to 20 carbon atoms, or may have two or more types. The α-olefin having 3 to 20 carbon atoms is preferably 1-butene, 1-hexene, 4-methyl-1-pentene, or 1-octene, and is preferably 1-butene or 1-hexene. More preferred.

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

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

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

Examples of the component (E) include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, and ethylene. Examples include -1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, and ethylene-1-butene-1-octene copolymer. The component (E) is preferably an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, or an ethylene-1-butene-1-hexene copolymer.

The Mw / 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 component (A) Mw / Mn.

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

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

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, and for example, the slurry is in the presence of a polymerization catalyst formed by contacting the above-mentioned component (H), a metallocene-based complex, an organoaluminum compound, and an electron-donating compound. It is obtained by copolymerizing ethylene and α-olefin by a polymerization method or a vapor 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 at the time of copolymerization. The polymerization method of the component (E) is preferably a vapor phase polymerization method, and triethylamine, triisobutylamine, and trinormal octylamine may be added as electron-donating compounds to the vapor phase polymerization.

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

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

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

Examples of the ethylene-based polymer contained in the layer β in the multilayer film include 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 resin such as nylon 6 and nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, and polypropylene resin. Can be mentioned.

A multilayer film having a layer α and a layer γ, wherein at least one of the two surface layers of the multilayer film is the layer α, for example, the layer α and the layer γ. A bilayer film having the above, wherein one surface layer is the layer α and the other surface layer is the 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 is a layer α, for example, a layer α and a layer β. Examples of the multilayer film having the layer γ and the layer γ include a multilayer film in which one surface layer is the layer α and the other surface layer is the layer γ.

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 that each polymer as a raw material of the single-layer film is dry-blended or melt-blended to obtain a resin composition, and the single-layer film is produced 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 thermal roll.

When the multilayer film is a multilayer film having a layer α and a layer γ, the method for producing the multilayer film is, for example, a single-layer film composed 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 a layer γ can be mentioned. Examples of the lamination method include a dry laminating method, a wet laminating method and a sand laminating method. The lamination method is preferably a dry laminating method.

The multilayer film of the present invention can be used as a material for packaging containers, and is used for packaging various contents. Examples of the contents include foods, beverages, seasonings, milk and the like, dairy products, pharmaceuticals, electronic parts such as semiconductor products, pet foods, pet care products, detergents and toiletry products.
The packaging container containing the film according to the present invention is preferably produced 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 with each other, the packaging container has excellent bag-dropping strength.

The measured values of each item in Examples and Comparative Examples were measured according to the following method.

[Component (H)]
(1) Elemental analysis Zn: A sulfuric acid aqueous solution (concentration 1M) was added to the sample, and then ultrasonic waves were irradiated to extract the metal component. 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 by a sodium hydroxide aqueous solution (10%), and the obtained aqueous solution was quantified by an ion electrode method.

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

(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 (2) above according to the method specified in JIS K7210-1995. The value.

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

(4) Mw, Mn, Mz, Mw / Mn, Mz / Mw
By gel permeation chromatography (GPC) measurement, polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and Z average molecular weight (Mz) were determined.
The molecular weight distribution (Mw / Mn) was determined by dividing Mw by Mn. Mz / Mw was obtained by dividing Mz by Mw.
Equipment: Waters 150C made by Waters
Separation column: TOSOH TSKgelGMH _6- HT
Measurement temperature: 140 ° C
Carrier: Ortodichlorobenzene Flow rate: 1.0 mL / min Injection volume: 500 μL
Detector: Differential refractometer
Molecular weight standard substance: Standard polystyrene

(5) η * 0.1 / η * 100
Using a strain-controlled rotary viscometer (rheometer), the dynamic complex viscosity from an angular frequency of 0.1 rad / sec to 100 rad / sec was measured under the following conditions. Next, the dynamic complex viscosity (η * 0.1) at an angular frequency of 0.1 rad / sec is divided by the dynamic complex viscosity (η * 100) at an angular frequency of 100 rad / sec to obtain η * 0.1 / η * 100. rice field.
Temperature: 170 ℃
Geometry: Parallel plate Plate diameter: 25 mm
Plate spacing: 1.5-2 mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(6) Flow activation energy (Ea, unit: kJ / mol)
The flow activation energy Ea is measured by a strain-controlled rotary viscometer (leometer) under the following conditions (a) to (d) under the common weight of ethylene-α-olefin at each temperature T (unit: ° C.). The molten complex viscosity-angular frequency curve of the coalescence (the unit of the molten complex viscosity is Pa · sec, and the unit of the angular frequency is rad / sec) was measured. Next, based on the temperature-time superposition principle, the molten complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at 190 ° C. for each molten complex viscosity-angular frequency curve at each temperature (T). _{The shift factor (a T} ) at each temperature (T) obtained when superposed on the above was determined. Next, the primary of each 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 formula (formula (I) below) was calculated. Next, Ea was 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: Flow activation energy (unit: kJ / mol)
T: Temperature (Unit: ° C)
For the calculation software, Ryos V. 4.4.4 was used. The Ea value when the correlation coefficient r2 when the equation (I) was calculated by the least squares method from the value of each temperature (T) was 0.99 or more was adopted. The melt complex viscosity-angular frequency curve was measured in a nitrogen atmosphere.
(A) Geometry: Parallel plate, plate diameter 25 mm, plate spacing: 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)
A melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics) under the following measurement conditions. Next, from the obtained molten complex viscosity-angular frequency curve, the calculation software Rhios V. Using 4.4.4, a master curve of the molten complex viscosity-angular frequency curve at 190 ° C. was created. The characteristic relaxation time (τ) was obtained by approximating the obtained master curve with the following equation (5).
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25 mm
Plate spacing: 1.5-2 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 Measured by the following method using a differential scanning calorimeter (manufactured by Diamond DSC Perkin Elmer). 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). Lower, 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) Extreme 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.

[Physical characteristics of film]

(12) S1
0) Preparation of test piece The film was punched out with a dumbbell cutter compliant with the test piece shape ASTM D1822 Type S standard so that the take-back direction (MD direction) was the longitudinal direction, and a test piece was prepared. Small dots were randomly drawn on the test piece with an oil-based magic pen with a fine nib to create a random pattern. Further, in order to prevent reflection of the illumination during shooting, ECO ANTISPOT, which is a darling spray manufactured by CONDOR FOTO, was sprayed on the surface of the test piece.
1) High-speed tensile test The test piece is 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 with a maximum load of 2 kN, and a load-displacement curve. Got The origin of the load-displacement curve is defined so that the load-displacement curve can be extrapolated to a point where the load = 0 kN and the displacement = 0 mm. The load and displacement sampling time intervals were 20 μs.
2) Shooting with a high-speed camera 1) The test piece during the high-speed tensile test is a high-speed camera GX-8F manufactured by Nack Image Technology Co., Ltd. 4D IF-ED was used). The shooting conditions were a frame rate of 10000 fps, a frame size of 176 horizontal × 1280 pixels high, a shutter speed of 20.1 μs, and a distance of 1 m between the camera and the test piece. Two LED lighting boxes LLBK-LA-W-0001 manufactured by Aitec System Co., Ltd. were used as lighting for photography, and light was emitted from the left and right sides of the high-speed camera toward the sample. A signal is emitted from the high-speed tensile tester at the start of the high-speed tensile test, and the high-speed camera starts shooting from the time when the signal is input, so that the times of the high-speed tensile tester and the high-speed camera can be synchronized. ing.
3) Analysis by digital image correlation method Using the images taken in 2), the maximum main strain distribution and the minimum main strain on the test piece at the time of each image capture by the GOM Correlate 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. Facet matching was performed on the immediately preceding image, and 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 main strain and the minimum main strain at one point in the central constriction were determined.
4) Calculation of the cross-sectional area of the constricted part The cross-sectional area of the constricted part of the test piece was calculated by the following formula.
(Cross-sectional area of test piece constriction)
= (Width of constriction before test) × (Thickness of constriction before test) × {exp (Minimum main distortion in constriction)} ²
5) Calculation of true stress The load at each time obtained by the above-mentioned high-speed tensile test was divided by the cross-sectional area of the constricted part 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, and the true stress-maximum principal strain curve was created.
7) Calculation of S1 S1 was obtained by 7a) or 7b).
7a) In the tensile test of 1), when the maximum principal strain was 2.0 and the test piece was not broken, S1 was calculated by the following formula (11).
S1 = (p−q) /0.3 ・ ・ ・ (11)
(In equation (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.)
7b) In the tensile test of 1), when the test piece broke within the range where the maximum principal strain was larger than 1.7 and less than 2.0, S1 was determined by the following formula (12).
S1 = (p'-q) / (r-1.7) ... (12)
(In 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.)
As smoothing treatment, p, p'and q were obtained by averaging the true stresses of 5 points before and after each data point, for a total of 11 points.
(13) Nominal stress S2 (unit: MPa) at 100% elongation in the MD direction
From the film-formed film, a test piece having a longitudinal direction in the take-up 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 a chuck distance of 80 mm, a marked line distance of 40 mm, and a tensile speed of 500 mm / min, and a nominal stress at 100% elongation was determined. The nominal stress at 100% elongation is described as S2.

(14) Tensile breaking strength (unit: MPa), tensile breaking elongation (unit:%)
From the film-formed film, test pieces were prepared in which the longitudinal directions were the take-up direction (MD direction) and the TD direction, respectively, 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 a chuck distance of 80 mm, a marked line distance of 40 mm, and a tensile speed of 500 mm / min to determine tensile breaking strength and tensile breaking elongation.

(15) Bag drop strength 1) Preparation of sample for bag drop strength evaluation Twenty rectangular films having a length of 60 mm in the MD direction and a length of 70 mm in the TD direction were cut out from the multilayer film described later. Two multilayer films were stacked so that the MD directions of the multilayer films were the same and the inflation film surfaces were facing each other, and the films were installed in a heat sealer manufactured by Tester Sangyo Co., Ltd., and the seal width was 10 mm, the seal bar temperature was 180 ° C, and the seal pressure was 0. Two long sides and one short side were heat-sealed at 03 MPa and a sealing temperature of 2 seconds 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 as not to allow air to enter, and an evaluation sample was obtained. The sizes of the inside of the heat-sealed portion of the obtained evaluation sample were 40 mm (MD direction) and 50 mm (TD direction).
2) Measurement of bag drop strength The evaluation sample was held at 5 ° C. for 24 hours. Next, the evaluation sample was placed on a DuPont impact tester, and a weight of 2 kg was repeatedly dropped onto the evaluation sample from a height of 175 mm 20 times. The survival probability was calculated by the following formula.
Survival probability (%) = 100 {(number of times the weight falls when the evaluation sample is torn) -1} / 20
If the weight was not torn even after being dropped 20 times, the survival probability was set to 100%. In each example, a test was conducted with 10 bags of evaluation samples, and the average value of 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 After adding 41 liters of butane to an autoclave with an internal volume of 210 liters that had been replaced with nitrogen in advance, 60.9 mmol of racem-ethylenebis (1-indenyl) zirconium diphenoxide was added. The temperature of the autoclave was raised to 50 ° C., and stirring was performed for 2 hours. Next, 0.60 kg of the component (H) obtained in the above (1) was added to the autoclave.
Then, 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 pressure) were added to the autoclave, and then 240 mmol of triisobutylaluminum was added for prepolymerization. It started. Ethylene and hydrogen (normal temperature and normal pressure) were supplied to the autoclave at 0.5 kg / hr and 1.1 liter / hr, respectively, for 30 minutes, and then the temperature was raised to 50 ° C., and ethylene and hydrogen (normal temperature and normal pressure) were added. They were supplied to the autoclave at 2.7 kg / hr and 8.2 liters / hr, respectively. Prepolymerization was carried out for a total of 10.0 hours. After 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). The [η] of the polyethylene was 1.17 dl / g.
(3) Production of component (A) and (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 flow bed gas phase polymerization apparatus. A powder of an ethylene-1-hexene copolymer (hereinafter referred to as LLDPE1-10) was obtained. As the polymerization conditions, the polymerization temperature was 96 ° C., the polymerization pressure was 2 MPa, the average amount of hydrogen was 0.56% with respect to 100 mol% of ethylene, and the molar ratio of 1-hexene to the total of ethylene and 1-hexene was 1.09. %. Ethylene, 1-hexene, and hydrogen were continuously supplied to maintain the gas composition constant during the polymerization. Further, the prepolymerization catalyst component, triisobutylaluminum, triethylamine (molar ratio to triisobutylaluminum 30%), and oxygen (molar ratio to triisobutylaluminum 12%) were continuously supplied to reduce the total powder weight of the fluidized bed to 80 kg. It was kept constant. The average polymerization time was 3.4 hr. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the obtained LLDPE1-10 powder is fed at a feed rate 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 condition of ~ 230 ° C. to obtain pellets of LLDPE1-10. The physical characteristics of the obtained pellets of LLDPE1-10 were evaluated, and the results are shown in Table 1.

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

Ingredient (B)
Ethylene-1-hexene copolymer 2-1 (LLDPE2-1): Metallocene-catalyzed linear low-density polyethylene Sumikasen E FV203 (manufactured by Sumitomo Chemical Co., Ltd., ethylene-1-hexene copolymer). The physical characteristics are shown in Table 1.

Ingredient (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). The physical characteristics are shown in Table 1.

Ingredient (E)
Ethylene-1-butene-1-hexene copolymer 2-2 (LLDPE2-2): Metallocene-catalyzed linear low-density polyethylene Sumikasen EP CU5003 (manufactured by Sumitomo Chemical Co., Ltd., ethylene-1-butene-1-hexene copolymer weight) Combined). The physical characteristics are shown in Table 1.

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

[Example 1]
(1) Film processing Each resin was mixed with a tumble mixer according to the composition shown in Table 2. Next, the obtained mixture was used as an inflation film forming machine manufactured by PLACO Co., Ltd. (full-flight type screw single-screw extruder (diameter 50 mm, L / D = 28), die (die diameter 125 mm, lip gap 2.0 mm)). An inflation film having a thickness of 100 μm was formed under the processing conditions of 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 characteristics of the obtained inflation film.
(2) Manufacture of multilayer film By dry laminating using a test coater (manufactured by Yasui Seiki Co., Ltd.), an inflation film and a biaxially stretched nylon film (thickness 15 μm) are combined with 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 structure of the multilayer film was an inflation film / adhesive layer / biaxially stretched nylon film. Table 2 shows the results of bag drop strength.

[Example 2, Example 3]
An inflation film and a multilayer film were obtained in the same manner as in Example 1 except that the compounding composition was changed as shown in Table 2. The results are shown in Table 2.

[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 compounding composition was changed as shown in Table 3. The results are shown in Table 3.

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

Claims (3)

S1 determined by 0) to 7) below is 220 MPa or more and 2000 MPa or less, and the nominal stress at 100% elongation in the MD direction when a tensile test is performed under the condition of a tensile speed of 500 mm / min is 11.0 MPa or more and 30.0 MPa or less. The film that is.

0) Punch a test piece from the film with a dumbbell cutter conforming to the ASTM D1822 Type S standard so that the MD direction is the long side.
1) Perform a tensile test on the test piece with a high-speed tensile tester at a speed of 1 m / s.
2) Take a picture of the test piece under the tensile test of 1) with a high-speed camera.
3) The captured image is analyzed by 3D inspection / analysis software to obtain the _{maximum principal strain (ε 1} ) and the minimum principal strain (ε _{3) at the constricted part of the test piece.}
4) The cross-sectional area of the constricted part of the test piece is calculated by the following formula.
(Cross-sectional area of test piece constriction)
= (Width of constriction before test) × (Thickness of constriction before test) × {exp (ε ₃ )} ²
5) Divide the load obtained by the tensile test at each time by the cross-sectional area of the constricted part 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, and the true stress-maximum principal strain curve is obtained.
7) S1 is determined by 7a) or 7b).
7a) In the tensile test of 1), if the test piece is not broken at the time when the maximum principal strain is 2.0, S1 is obtained by the following formula (11).
S1 = (p−q) /0.3 ・ ・ ・ (11)
(In equation (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.)
7b) In the tensile test of 1), if the test piece breaks within the range where the maximum principal strain is larger than 1.7 and less than 2.0, S1 is calculated by the following formula (12).
S1 = (p'-q) / (r-1.7) ... (12)
(In 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 containing the 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 layer α. A packaging container containing the film according to claim 1.