JP4797486B2 - Polyethylene resin composition, film and bag - Google Patents

Description

  The present invention relates to a polyethylene resin composition, a film using the composition, and a bag made of the film.

  As a film used for packaging bags for foods, pharmaceuticals, cosmetics, etc., a film made of polyethylene resin is often used. For example, a two-layer to three-layer film made of a commercially available linear low density polyethylene resin (see, for example, Patent Document 1), or a film made of a linear low density polyethylene resin polymerized by a single active point catalyst ( For example, see Patent Document 2).

Japanese Examined Patent Publication No. 6-102375 JP-A-9-137132

However, when a conventional film made of linear low-density polyethylene is formed into a bag, it is not satisfactory in terms of the sealing strength of the bag, for example, the sealing strength of the gusset portion, and is sufficiently satisfactory in the gloss of the bag. I didn't want to go.
Under such circumstances, the problem to be solved by the present invention is a polyethylene-based resin composition used for the production of a film from which a bag excellent in sealing strength and gloss can be obtained, a film using the resin composition, and It is to provide a bag made of the film.

  According to the present invention, it is possible to provide a polyethylene resin composition used for production of a film from which a bag excellent in sealing strength and gloss can be obtained, a film using the resin composition, and a bag made of the film.

The first of the present invention contains the following component (A) and component (B), the total amount of component (A) and component (B) is 100% by weight, and the content of component (A) is 5 to 5%. The polyethylene resin composition is 50% by weight and the content of the component (B) is 95 to 50% by weight.
(A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density of 890 to 950 kg / m ³ , and a flow activation energy ( An ethylene-α-olefin copolymer having an Ea) of 35 kJ / mol or more, a melt flow rate ratio (MFRR) of 30 or more, and a molecular weight distribution (Mw / Mn) of 4.5 to 25.
(B): Ethylene polymer other than component (A)

  The second of the present invention relates to a film formed using the above resin composition.

  A third aspect of the present invention relates to a bag made of the above film.

  The ethylene-α-olefin copolymer of component (A) is an ethylene-α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 -Methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned, and 1-hexene and 1-octene are preferable. Moreover, said C3-C20 alpha olefin may be used independently and may use 2 or more types together.

  Examples of the ethylene-α-olefin copolymer of component (A) include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer. Examples thereof include ethylene-1-butene copolymer and ethylene-1-hexene copolymer. An ethylene-1-butene-1-hexene copolymer and an ethylene-1-butene-1-octene copolymer are also preferably used.

  The content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer of the component (A) is usually from 50 to 50% based on the total weight (100% by weight) of the ethylene-α-olefin copolymer. 99% by weight. The content of the monomer unit based on the α-olefin is usually 1 to 50% by weight with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer.

  The melt flow rate (MFR) of the ethylene-α-olefin copolymer of the component (A) measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N specified in JIS K7210-1995 is usually 0.01 to 100 g / 10 min. From the viewpoint of enhancing gloss, transparency and extrusion moldability, it is preferably 0.05 g / 10 min or more, more preferably 0.07 g / 10 min or more. Moreover, from a viewpoint of improving seal strength and impact resistance, it is preferably 10 g / 10 min or less, more preferably 4 g / 10 min or less, and further preferably 2 g / 10 min or less.

The density of the component (A) ethylene-α-olefin copolymer is 890 to 950 kg / m ³ . Said value is the gloss, transparency, from the viewpoint of enhancing impact resistance, preferably at 940 kg / m ³ or less, more preferably 930 kg / m ³ or less, more preferably 925 kg / m ³ or less. Moreover, said value, from the viewpoint of enhancing the rigidity, is preferably 900 kg / m ³ or more, more preferably 905 kg / m ³ or more. In addition, this density is measured according to the underwater substitution method prescribed | regulated to JISK7112-1980 using the sample which annealed as described in JISK6760-1995.

  The ethylene-α-olefin copolymer of component (A) is an ethylene-α-olefin copolymer excellent in melt tension having a long chain branch, and such an ethylene-α-olefin copolymer is The flow activation energy (Ea) is high and the melt flow rate ratio (MFRR) is high as compared with conventionally known ordinary ethylene-α-olefin copolymers. Conventionally known Ea of a normal ethylene-α-olefin copolymer is usually lower than 35 kJ / mol, and MFRR is usually smaller than 30, which contributes to gloss, transparency, seal strength, and extrudability. May be inferior. In addition, the melt flow rate ratio (MFRR) is the temperature 190 specified in JIS K7210-1995, the melt flow rate measured under the conditions of a temperature 190 ° C. and a load 211.8 N specified in JIS K7210-1995. It is the value divided by the melt flow rate measured under the conditions of ° C and a load of 21.18N.

  Ea of the ethylene-α-olefin copolymer of component (A) is preferably 40 kJ / mol or more, more preferably 50 kJ / mol or more, and further preferably from the viewpoint of further improving the sealing strength and transparency. 60 kJ / mol or more. Further, from the viewpoint of further improving gloss and impact resistance, Ea is preferably 100 kJ / mol or less, more preferably 90 kJ / mol or less.

The flow activation energy (Ea) is a master curve showing the dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. on the angular frequency (unit: rad / sec) based on the temperature-time superposition principle. Is a numerical value calculated by the Arrhenius equation from the shift factor (a _T ) at the time of creating the value, and is a value obtained by the following method. That is, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (the unit of melt complex viscosity is Pa · sec. The unit of the angular frequency is rad / sec.), Based on the temperature-time superposition principle, for each melt complex viscosity-angular frequency curve at each temperature (T), The shift factor (a _T ) at each temperature (T) obtained when superposed on the melt complex viscosity-angular frequency curve of the coalescence is obtained, and each temperature (T) and the shift factor at each temperature ( _T ) are obtained. From (a _T ), a first-order approximate expression (formula (I) below) of [ln (a _T )] and [1 / (T + 273.16)] is calculated by the method of least squares. Next, Ea is obtained from the slope m of the linear expression and the following expression (II).
ln (a _T ) = m (1 / (T + 273.16)) + n (I)
Ea = | 0.008314 × m | (II)
a _T : Shift factor Ea: Activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics is used. 4.4.4.
The shift factor (a _T ) is obtained by moving the logarithmic curve of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) = − log (X) axis direction (however, the Y axis Is the complex viscosity of the melt, and the X axis is the angular frequency.), And the amount of movement when superposed on the melt complex viscosity-angular frequency curve at 190 ° C., in the superposition, melting at each temperature (T) The logarithmic curve of complex viscosity-angular frequency shifts the angular frequency by a _T times and the melt complex viscosity by 1 / a _T times for each curve. Moreover, the correlation coefficient when calculating | requiring (I) Formula by the least squares method from the value of four points | pieces, 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is usually 0.99 or more.

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

  The MFRR of the ethylene-α-olefin copolymer of component (A) is preferably 35 or more from the viewpoint of further improving the sealing strength and transparency. Further, from the viewpoint of further improving impact resistance, the MFRR is preferably 500 or less, more preferably 400 or less.

The ethylene / α-olefin copolymer of component (A) has a melt complex viscosity of η * (unit: Pa · sec) at a temperature of 190 ° C. and an angular frequency of 100 rad / sec, from the viewpoint of further improving transparency and extrusion moldability. ) And satisfying the following formula (1) with the melt flow rate measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N specified in JIS K7210-1995 as MFR (unit: g / 10 min). Is preferred,
η * <1550 × MFR ^-0.25 -420 (1)
More preferably, the following formula (1-2) is satisfied,
η * <1500 × MFR ^-0.25 -420 (1-2)
More preferably, the following formula (1-3) is satisfied,
η * <1450 × MFR ^-0.25 -420 (1-3)
It is particularly preferable that the following formula (1-4) is satisfied.
η * <1350 × MFR ^-0.25 -420 (1-4)
Note that η * is measured under the same conditions as in the viscoelasticity measurement for obtaining Ea.

  The molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer of component (A) is preferably 4.5 to 25, more preferably from the viewpoint of enhancing transparency, seal strength, and extrusion moldability. 4.7-20. The molecular weight distribution (Mw / Mn) is a value obtained by calculating a polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) by gel permeation chromatography, and dividing Mw by Mn (Mw / Mn). Mn).

The component (A) ethylene-α-olefin copolymer has a temperature of 190 ° C. and a load of 21 as defined in JIS K7210-1995 from the viewpoint of improving gloss, transparency, seal strength, impact resistance, and extrusion moldability. It is preferable that the melt flow rate measured under the condition of .18N is MFR (unit: g / 10 min), the melt tension at 190 ° C. is MT (unit: cN), and the following formula (2) is satisfied.
2 x MFR ^-0.59 <MT <40 x MFR ^-0.59 (2)
More preferably, the ethylene-α-olefin copolymer of component (A) satisfies the following formula (2-2) from the viewpoint of further improving transparency, seal strength, and extrusion moldability.
2.2 x MFR ^-0.59 <MT (2-2)
It is more preferable to satisfy the following formula (2-3).
2.5 × MFR ^-0.59 <MT (2-3)
The component (A) ethylene-α-olefin copolymer preferably satisfies the following formula (2-4) from the viewpoint of further improving gloss and impact resistance,
MT <25 × MFR ^-0.59 (2-4)
It is more preferable to satisfy the following formula (2-5).
MT <15 × MFR ^-0.59 (2-5)
In addition, the conventional normal ethylene-alpha-olefin copolymer does not normally satisfy the left side of Formula (2).

The component (A) ethylene-α-olefin copolymer has a temperature of 190 ° C. and a load of 21 as defined in JIS K7210-1995 from the viewpoint of improving gloss, transparency, seal strength, impact resistance, and extrusion moldability. It is preferable that the melt flow rate measured under the condition of .18N is MFR (unit: g / 10 minutes) and the intrinsic viscosity is [η] (unit: dl / g) to satisfy the following formula (3).
1.02 × MFR ^−0.094 <[η] <1.50 × MFR ^−0.156 (3)
More preferably, the ethylene-α-olefin copolymer of component (A) satisfies the following formula (3-2) from the viewpoint of further improving gloss and impact resistance.
1.05 × MFR ^−0.094 <[η] (3-2)
It is more preferable to satisfy the following formula (3-3).
1.08 × MFR ^−0.094 <[η] (3-3)
More preferably, the ethylene-α-olefin copolymer of component (A) satisfies the following formula (3-4) from the viewpoint of further improving transparency, seal strength, and extrusion moldability.
[Η] <1.47 × MFR ^−0.156 (3-4)
It is more preferable to satisfy the following formula (3-5).
[Η] <1.42 × MFR ^−0.156 (3-5)
In addition, the conventional ethylene-α-olefin copolymer having the same melt flow rate measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N as defined in JIS K7210 and ethylene-α- of component (A) When compared with the olefin copolymer, the intrinsic viscosity of the conventional ethylene-α-olefin copolymer is usually higher than the intrinsic viscosity of the ethylene-α-olefin copolymer of component (A).

  The component (A) ethylene-α-olefin copolymer can be obtained by bringing the following promoter support (A), crosslinked bisindenylzirconium complex (B) and organoaluminum compound (C) into contact with each other. Examples thereof include a method of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst.

The promoter support (A) comprises (a) diethylzinc, (b) fluorinated phenol, (c) water, (d) silica and (e) trimethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH). It is a carrier obtained by contact.

The amount of each component (a), (b), (c) used is not particularly limited, but the molar ratio of the amount of each component used is the component (a): component (b): component (c) = 1: When y: z, y and z preferably satisfy the following formula.
| 2-y-2z | ≦ 1
Y in the above formula is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably a number of 0.20 to 1.50. Most preferably, the number is 0.30 to 1.00.

  The amount of component (d) used relative to component (a) is such that the number of moles of zinc atoms contained in the particles obtained by contacting component (a) and component (d) is 1 g of the particles. The amount is preferably 0.1 mmol or more, and more preferably 0.5 to 20 mmol. The amount of the component (e) to be used with respect to the component (d) is preferably an amount that makes the component (e) 0.1 mmol or more per 1 g of the component (d), and an amount that becomes 0.5 to 20 mmol. More preferably.

  The cross-linked bisindenyl zirconium complex (B) is preferably racemic-ethylenebis (1-indenyl) zirconium dichloride or racemic-ethylenebis (1-indenyl) zirconium diphenoxide.

  The organoaluminum compound (C) is preferably triisobutylaluminum or trinormaloctylaluminum.

The amount of the bridged bisindenyl zirconium complex (B) used is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol per 1 g of the promoter support (A). The amount of the organoaluminum compound (C) used is preferably such that the aluminum atom of the organoaluminum compound (C) is 1 to 2000 moles per mole of zirconium atoms in the cross-linked bisindenyl zirconium complex (B). is there.

  The polymerization method is preferably a continuous polymerization method involving the formation of ethylene-α-olefin copolymer particles, for example, continuous gas phase polymerization, continuous slurry polymerization, continuous bulk polymerization, preferably continuous gas phase Polymerization. The gas phase polymerization reaction apparatus is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

As a method of supplying each component of the metallocene-based olefin polymerization catalyst used for the production of the ethylene-α-olefin copolymer of component (A) to the reaction vessel, usually an inert gas such as nitrogen or argon, hydrogen, A method in which ethylene or the like is used to supply in a state free from moisture, or a method in which each component is dissolved or diluted in a solvent and supplied in a solution or slurry state is used. Each component of the catalyst may be supplied individually, or arbitrary components may be supplied in contact in advance in an arbitrary order.
Moreover, it is preferable to carry out prepolymerization before carrying out the main polymerization and to use the prepolymerized prepolymerized catalyst component as a catalyst component or catalyst for the main polymerization.

The polymerization temperature is usually lower than the temperature at which the ethylene-α-olefin copolymer melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C.
Further, hydrogen may be added as a molecular weight regulator for the purpose of regulating the melt fluidity of the copolymer. An inert gas may coexist in the mixed gas.

  Component (B) is a polymer other than component (A) containing a monomer derived from ethylene, for example, an ethylene homopolymer, a copolymer of a monomer other than α-olefin and ethylene, or At least one of the density, flow activation energy, MFRR or molecular weight distribution of the component (A) is an ethylene-α-olefin copolymer other than the above-mentioned range. For example, ethylene-α-olefin copolymer, ethylene homopolymer, copolymer of ethylene and vinyl ester, copolymer of ethylene and unsaturated carboxylic acid having a flow activation energy (Ea) of less than 35 kJ / mol. And a copolymer of ethylene and an unsaturated carboxylic acid ester. Specifically, an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-4-methyl-1-pentene. Copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, high-pressure low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer Examples thereof include a polymer, an ethylene-methacrylic acid copolymer, and an ethylene-methyl methacrylate copolymer. These may be used alone or in combination of two or more.

  The ethylene-based polymer of component (B) is preferably an ethylene-α-olefin copolymer having a flow activation energy (Ea) of less than 35 kJ / mol, and the ethylene-α-olefin copolymer , Preferably an α-olefin having 3 to 20 carbon atoms, more preferably an ethylene-1-butene copolymer, an ethylene-4-methyl-1-pentene copolymer, and an ethylene-1-hexene copolymer. , An ethylene-1-octene copolymer.

  The content of monomer units based on ethylene in the ethylene-based polymer of component (B) is usually 50% by weight or more with respect to the total weight (100% by weight) of the polymer. The content of the monomer unit based on the α-olefin is usually 50% by weight or less with respect to the total weight (100% by weight) of the polymer.

  The melt flow rate measured under conditions of a temperature of 190 ° C. and a load of 21.18 N as defined in JIS K7210-1995 of the component (B) is preferably 0.1 g / from the viewpoint of enhancing seal strength and impact resistance. It is 10 minutes or more, More preferably, it is 0.3 g / 10 minutes or more, More preferably, it is 0.5 g / 10 minutes or more. The value is preferably 50 g / 10 min or less, more preferably 8 g / 10 min or less, and even more preferably 5 g / 10 min or less from the viewpoint of improving gloss, transparency, and extrusion moldability.

  The MFRR of the component (B) is preferably 15 or more, more preferably 17 or more, from the viewpoint of improving the extrusion moldability. Moreover, from a viewpoint of improving impact resistance, the value is preferably 30 or less, more preferably 27 or less, and further preferably 25 or less.

The density of the component (B) is preferably 898 kg / m ³ or more, more preferably 905 kg / m ³ or more, from the viewpoint of increasing rigidity. From the viewpoint of improving impact resistance, preferably at 950 kg / m ³ or less, more preferably 940 kg / m ³ or less, more preferably 930 kg / m ³ or less.

From the viewpoint of enhancing the low temperature heat sealability of the film or bag of the present invention, the density of the component (A) is preferably 915 kg / m ³ or less, and the density of the component (B) is preferably 920 kg / m ³ or less. The ratio of the density DB (kg / m ³ ) of (B) to the density DA (kg / m ³ ) of the component (A), DB / DA is more preferably 1 or more.

From the viewpoint of improving the handleability of the film or bag of the present invention, the density of the component (A) is preferably 920 kg / m ³ or more, and the density of the component (B) is preferably 915 kg / m ³ or more. ) Density DB (kg / m ³ ) and component (A) density DA (kg / m ³ ), DB / DA is more preferably 1 or less.

  The resin composition of the present invention contains the component (A) and the component (B), and the content thereof is 100% by weight as the total amount of the component (A) and the component (B). Is 5 to 50% by weight, and the content of component (B) is 95 to 50% by weight. If the amount of component (A) is too small (too much component (B)), the sealing strength and gloss may be reduced, and if too much component (A) is contained (too little component (B)), the gloss and impact resistance will be reduced. May decrease. Preferably, the content of component (A) is 5 to 35% by weight, and the content of component (B) is 95 to 65% by weight.

  The resin composition of the present invention may be blended with additives such as antioxidants, anti-blocking agents, lubricants, antistatic agents, processability improving agents; other resins, and the like. May be used alone or in combination of two or more.

  As said antioxidant, a phenolic antioxidant, phosphorus antioxidant, etc. are mentioned. Each may be used alone or in combination of two.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol (BHT) and n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate (trade name Irganox 1076, manufactured by Ciba Specialty Chemicals), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name Irganox 1010, manufactured by Ciba Specialty Chemicals) ), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name Irganox 3114, manufactured by Ciba Specialty Chemicals), 1,3,5-trimethyl-2,4 , 6-Tris (3,5-di-tert-butyl-4-hydroxyben L) benzene, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane (trade name Sumilizer GA80, manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the phosphorus-based antioxidant include distearyl pentaerythritol diphosphite (trade name ADK STAB PEP8), tris (2,4-di-t-butylphenyl) phosphite (trade name Irgafos 168, manufactured by Ciba Specialty Chemicals) ), Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphonite (trade name Sandostab P- EPQ (manufactured by Clariant Shapin), bis (2-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl -4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d , F] [1, 3, 2] dioxaphosphine (trade name: Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Examples of the anti-blocking agent include inorganic anti-blocking agents and organic anti-blocking agents. Examples of the inorganic anti-blocking agent include silica, diatomaceous earth, talc, aluminosilicate, kaolin, calcium carbonate and the like. Examples of the organic anti-blocking agent include Eposta-MA (manufactured by Nippon Shokubai Co., Ltd.).

  Examples of the lubricant include higher fatty acid amides and higher fatty acid esters.

  Examples of the antistatic agent include glycerin esters and sorbitan acid esters of fatty acids having 8 to 22 carbon atoms, alkyl dialkanolamides of fatty acids having 8 to 22 carbon atoms, polyethylene glycol esters, and alkyldiethanolamines. .

  Examples of the other resins include polyolefin resins, and examples thereof include polypropylene resins and elastomers.

  The resin composition of the present invention is obtained by melt-kneading the component (A), the component (B), and a component blended as necessary (the above additives, other resins, etc.) by a known method, for example, After mixing with a tumbler blender, Henschel mixer or the like, the mixture is further melt-kneaded with a single-screw extruder or multi-screw extruder, or melt-kneaded with a kneader or Banbury mixer.

  The film of the present invention is a film having a layer made of the above resin composition, and may be a single layer film or a multilayer film. When using with a multilayer film, it is desirable to have the layer which consists of the said resin composition in single side | surface or both surfaces.

  In the case of a multilayer film, the layers other than the layer composed of the present resin composition include a layer composed of a polyolefin resin such as polyethylene resin and polypropylene resin, a layer composed of a polyester resin such as polyethylene terephthalate and polybutylene terephthalate, nylon 6 and nylon 66. And a layer made of polyamide resin such as cellophane, paper, aluminum foil, and the like.

  The thickness of the film of this invention is 20-100 micrometers normally, Preferably it is 30-90 micrometers, More preferably, it is 30-80 micrometers. In the case of a multilayer film, the thickness of the layer made of the present resin composition is usually 50% or more, and preferably 65% or more.

  As a method for producing the film, a known method is used. For example, an inflation film molding method, a T-die cast film molding method, or the like is used. When a multilayer film is used, for example, a coextrusion method, a dry lamination method, a wet lamination method, a sand lamination method, a hot melt lamination method, or the like may be used.

  Moreover, when performing extrusion molding, such as an inflation film molding method or a T-die cast film molding method, the extrusion molding temperature is usually 110 to 250 ° C. From the viewpoint of enhancing the appearance of the film, it is preferably 230 ° C. or lower, more preferably 210 ° C. or lower, still more preferably 190 ° C. or lower, and particularly preferably 170 ° C. or lower. Moreover, from a viewpoint of improving extrusion moldability, Preferably it is 120 degreeC or more, More preferably, it is 125 degreeC or more, More preferably, it is 130 degreeC or more.

  The film of the present invention is formed into a bag by a known method such as heat sealing. The bag is excellent in gloss and sealing strength (pressure resistance strength of the sealing portion when the bags are stacked), and is used for packaging of foods, pharmaceuticals, cosmetics, disposable diapers, toilet paper, and plastic bags. Moreover, since the film of this invention can be excellent in the sealing strength of a gusset part, it is used suitably as a gusset bag.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

[Physical properties of polymer]
(1) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method defined in JIS K7210-1995, the measurement was performed by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(2) Melt flow rate ratio (MFRR)
In accordance with the method defined in JIS K7210-1995, the melt flow rate value measured by the A method under the conditions of a load of 211.8 N and a temperature of 190 ° C. was measured by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C. The value divided by the flow rate value was defined as MFRR.

(3) Density (Unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(4) Molecular weight distribution (Mw / Mn)
Using a gel permeation chromatograph (GPC) method, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured under the following conditions (1) to (7), and the molecular weight distribution (Mw / Mn) was determined.
(1) Equipment: Waters 150C manufactured by Water
(2) Separation column: TOSOH TSKgelGMH-HT
(3) Measurement temperature: 145 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refraction

(5) Flow activation energy (Ea, unit: kJ / mol)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured under the following measurement conditions. From the obtained melt complex viscosity-angular frequency curve, calculation software Rhios V. The activation energy (Ea) was determined using 4.4.4.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(6) Melt complex viscosity (η *, unit: Pa · s)
From the melt viscoelasticity at 190 ° C. measured in the above (5), the melt viscosity at 190 ° C. at an angular frequency of 100 rad / sec was determined.

(7) Melt tension (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a 9.5 mmφ barrel at a temperature of 190 ° C., a piston descending speed of 5.5 mm / min, a diameter of 2.09 mmφ, and a length of 8 mm The melted resin extruded from the orifice was wound up at a winding speed of 40 rpm / min using a winding roll having a diameter of 150 mmφ, and the tension value immediately before the molten resin broke was measured. It shows that melt tension is so large that this value is large.

(8) Intrinsic viscosity ([η], unit: dl / g)
A tetralin solution (hereinafter referred to as a blank solution) in which 0.5% by weight of 2,6-di-t-butyl-p-cresol (BHT) is dissolved, and the concentration of the ethylene polymer resin with respect to the blank solution. And a tetralin solution at 135 ° C. (hereinafter referred to as a sample solution) having a concentration of 1 mg / ml, and the falling time of the blank solution and the sample solution at 135 ° C. is measured by an Ubbelohde viscometer, After obtaining the relative viscosity (ηrel) at 135 ° C. from the fall time, it was calculated from the following formula.
[Η] = 23.3 × log (ηrel)

[Physical properties of film]
(9) Gloss (unit:%)
It measured according to the measuring method of 45 degree specular glossiness prescribed | regulated to JISK7105-1981. The larger this value, the better the gloss.

(10) HAZE (unit:%)
The method specified in ASTM D1003 was followed. It shows that transparency is excellent, so that this value is small.

(11) Rigidity (1% SM) (Unit: MPa)
A strip-shaped test piece having a width of 20 mm and a length of 120 mm was sampled so that the longitudinal direction was a take-up direction (MD) and a direction (TD) perpendicular to the MD direction, and the test piece was used to make a chuck. A tensile test was performed under the conditions of a distance of 60 mm and a tensile speed of 5 mm / min, and a stress-strain curve was measured. From the stress-strain curve, the load at 1% elongation (unit: N) was determined, and 1% SM was determined from the following formula, which was used as the film rigidity.
1% SM = [F / (t × l)] / [s / L ₀ ] / 10 ⁶
F: Load at 1% elongation (unit: N)
t: Test piece thickness (unit: m)
l: Specimen width (Unit: m, 0.02)
L ₀ : Distance between chucks (Unit: m, 0.06)
s: 1% distortion (Unit: m, 0.0006)

(12) Impact strength (unit: kJ / m)
The dart impact strength was measured according to the method (Method A) defined in ASTM D1709. The higher this value, the better the impact resistance of the film. When the film was not broken by the prescribed method, it was determined as non-destructive (NB: 200 kJ / m or more).

(13) Heat sealability After two films are stacked, the two stacked films are sandwiched between two 15 μm nylon films, and a heat sealer (manufactured by Tester Sangyo Co., Ltd.) is used for each nylon film under the following sealing conditions. And heat sealed.
Sealing temperature: 90 to 170 ° C., 5 ° C. interval Sealing time: 1 second Sealing pressure: 0.98 MPa
Seal width: 10mm
After conditioning the obtained sample at 23 ° C. for 24 hours or more, a test piece having a width of 15 mm was cut out in a direction perpendicular to the seal width direction, and then the seal portion of the test piece was measured at 200 mm / min by a tensile tester. The seal peeled at a speed of 180 °, and the seal strength at each seal temperature was measured. The maximum strength (unit: N / 15 mm width) was the strength at which the seal strength was maximum, and the maximum sealing temperature was the maximum strength temperature (unit: ° C). The higher the maximum strength, the better the seal strength, and the lower the maximum strength temperature temperature, the better the low-temperature heat sealability.

Example 1
(1) Preparation of promoter support In the same manner as the preparation of component (A) in Example 10 (1) and (2) of JP-A No. 2003-171415, a solid product (hereinafter referred to as promoter support (a -1)).

(2) Preliminary polymerization In an autoclave with a stirrer having an internal volume of 210 liters, which was previously purged with nitrogen, 0.63 kg of the above-mentioned promoter support (a-1), 80 liters of butane, 0.03 kg of 1-butene, and normal temperature and normal pressure After charging 11 liters as hydrogen, the autoclave was raised to 40 ° C. Further, ethylene was charged at a gas phase partial pressure in the autoclave of 0.21 MPa, and after the system was stabilized, 208 mmol of triisobutylaluminum and 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. did. While raising the temperature to 49 ° C. and continuously supplying ethylene and hydrogen, preliminary polymerization was carried out at 49 ° C. for a total of 4 hours. After completion of the polymerization, purging ethylene, butane, hydrogen gas and the like, the remaining solid was vacuum dried at room temperature, and 14.1 g of ethylene-1-butene copolymer per 1 g of the above-mentioned promoter support (a-1) was obtained. A prepolymerized catalyst component (hereinafter referred to as prepolymerized catalyst component (a-1p)) was obtained.

(3) Continuous gas phase polymerization Using the above prepolymerization catalyst component (a-1p), copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 75.5 ° C., a total pressure of 2 MPa, a gas linear velocity of 0.31 m / s, a molar ratio of hydrogen to ethylene of 0.285%, and a molar ratio of 1-hexene to ethylene of 1.20%. During the polymerization, ethylene, 1-hexene, and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the pre-polymerization catalyst component (a-1p) and triisobutylaluminum are continuously supplied at a constant ratio so that the total powder weight of the fluidized bed is maintained at 80 kg and the average polymerization time is 3.8 hr. did. By polymerization, a powder of an ethylene-1-hexene copolymer (hereinafter referred to as PE-A1) was obtained with a production efficiency of 21.0 kg / hr.

(4) Granulation of ethylene-1-hexene copolymer powder A blend of 750 ppm of an antioxidant (Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.) and PE-A1 powder obtained above was used as an extruder ( By granulating under the conditions of a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.2 MPa, and a resin temperature of 200 to 230 ° C. using LCM50 manufactured by Kobe Steel, Ltd. PE-A1 pellets were obtained. The physical properties of PE-A1 are shown in Table 1.

(5) Film processing 20 parts by weight of PE-A1 pellets, commercially available ethylene-1-hexene copolymer (manufactured by Nippon Evolution Co., Ltd., Sumitomo Chemical Co., Ltd. Sumikasen E FV203; hereinafter referred to as PE-B1) The physical properties of PE-B1 are shown in Table 2.) 80 parts by weight, anti-blocking agent masterbatch (EMB-21 manufactured by Sumitomo Chemical Co., Ltd.) 2.0 parts by weight, and lubricant masterbatch (Sumitomo Chemical Industries) EMB-10 manufactured by Co., Ltd. A mixture of 1.5 parts by weight was formed into an inflation film having a screw diameter of 55 mmφ and a L / D32 single-screw extruder, and a lip gap of 125 mmφ and a circular die with a lip gap of 2.0 mm. Machine (made by SHI Modern Machinery Co., Ltd.), processing temperature (extruder and die setting temperature) 180 ° C, external cold air temperature 15 ° C, blow -Up ratio of about 2.0, subjected to blown film processing under the conditions of take-up speed 12m / min, to obtain a tubular film having a thickness of 50μm and folding width 393 mm. The extrusion rate during processing was 26.2 kg / hr, and the screw rotation speed was 22 rpm. Table 3 shows the physical property evaluation results of the obtained film.

Example 2
(1) Preparation of promoter support In the same manner as in Example 1 (1) Preparation of promoter support, a solid product (hereinafter referred to as promoter support (a-2)) was obtained.

(2) Prepolymerization In an autoclave with a stirrer having an internal volume of 210 liters, which was previously purged with nitrogen, 0.69 kg of the above promoter support (a-2), 80 liters of butane, 0.2 kg of 1-butene, and normal temperature and normal pressure After charging 4 liters as hydrogen, the autoclave was raised to 17 ° C. Further, ethylene was charged at 0.1 MPa in the gas phase partial pressure in the autoclave, and after the system was stabilized, 368 mmol of triisobutylaluminum and 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. did. While raising the temperature to 28 ° C. and continuously supplying ethylene and hydrogen, preliminary polymerization was carried out at 28 ° C. for a total of 2 hours. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature, so that 11.3 g of ethylene-1-butene copolymer per 1 g of the promoter support (a-2) is obtained. A prepolymerized catalyst component (hereinafter referred to as prepolymerized catalyst component (a-2p)) was obtained.

(3) Continuous gas phase polymerization Using the above prepolymerization catalyst component (a-2p), copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 75.2 ° C., a total pressure of 2 MPa, a gas linear velocity of 0.25 m / s, a molar ratio of hydrogen to ethylene of 0.703%, and a molar ratio of 1-hexene to ethylene of 1.85%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the pre-polymerization catalyst component (a-2p) and triisobutylaluminum are continuously supplied at a constant ratio so that the total powder weight of the fluidized bed is maintained at 80 kg and the average polymerization time is 3.2 hr. did. By polymerization, a powder of an ethylene-1-hexene copolymer (hereinafter referred to as PE-A2) was obtained with a production efficiency of 25.1 kg / hr.

(4) Granulation of ethylene-1-hexene copolymer powder Except that PE-A2 powder is used instead of PE-A1 powder, it is carried out according to the granulation of the powder of Example 1, and pellets of PE-A2 Got. Table 1 shows the physical properties of PE-A2.

(5) Film processing In film processing, it implemented according to Example 1 except using PE-A2 instead of PE-A1. Table 3 shows the physical property evaluation results of the obtained film.

Example 3
(1) Preparation of promoter support In the same manner as in Example 1 (1) Preparation of promoter support, a solid product (hereinafter referred to as promoter support (a-3)) was obtained.

(2) Prepolymerization Into an autoclave with a stirrer having an internal volume of 210 liters, which was previously purged with nitrogen, 0.70 kg of the above promoter support (a-3), 80 liters of butane, 0.02 kg of 1-butene, and normal temperature and normal pressure After charging 11 liters as hydrogen, the autoclave was raised to 41 ° C. Further, ethylene was charged at a gas phase partial pressure in the autoclave of 0.21 MPa, and after the system was stabilized, 312 mmol of triisobutylaluminum and 105 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to start polymerization. did. While raising the temperature to 50 ° C. and supplying ethylene and hydrogen continuously, prepolymerization was carried out at 50 ° C. for a total of 4 hours. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature to obtain 12.8 g of ethylene-1-butene copolymer per 1 g of the above-mentioned promoter support (a-3). A prepolymerized catalyst component (hereinafter referred to as prepolymerized catalyst component (a-3p)) was obtained.

(3) Continuous gas phase polymerization Using the above prepolymerization catalyst component (a-3p), copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 75.5 ° C., a total pressure of 2 MPa, a gas linear velocity of 0.34 m / s, a molar ratio of hydrogen to ethylene of 0.600%, and a molar ratio of 1-butene to ethylene of 7.5%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the pre-polymerization catalyst component (a-3) and triisobutylaluminum are continuously supplied at a constant ratio so that the total powder weight of the fluidized bed is maintained at 80 kg and the average polymerization time is 3.6 hr. did. By polymerization, a powder of ethylene-1-butene copolymer (hereinafter referred to as PE-A3) was obtained with a production efficiency of 22.3 kg / hr.

(4) Granulation of ethylene-1-butene copolymer powder Except that PE-A3 powder is used instead of PE-A1 powder, it is carried out according to the granulation of the powder of Example 1, and pellets of PE-A3 Got. Table 1 shows the physical properties of PE-A3.

(5) Film processing In film processing, it implemented according to Example 1 except using PE-A3 instead of PE-A1. Table 3 shows the physical property evaluation results of the obtained film.

Example 4
In film processing, instead of PE-B1, a commercially available ethylene-1-hexene copolymer (manufactured by Nippon Evolution Co., Ltd., sold by Sumitomo Chemical Co., Ltd. Sumikasen E FV104; hereinafter referred to as PE-B2). Were carried out according to Example 1, except that the physical properties of the Table 3 shows the physical property evaluation results of the obtained film.

Comparative Example 1
In film processing, it was carried out according to Example 1 except that PE-B1 was 100 parts by weight and PE-A1 was not blended. Table 4 shows the physical property evaluation results of the obtained film.

Comparative Example 2
The film processing was performed in accordance with Comparative Example 1 except that PE-B2 was changed to 100 parts by weight instead of PE-B1. Table 4 shows the physical property evaluation results of the obtained film.

Comparative Example 3
In film processing, 80 parts by weight of PE-B1 and a commercially available ethylene-1-hexene copolymer (manufactured and sold by Sumitomo Chemical Co., Ltd. Excelen FX CX1001; hereinafter referred to as PE-B3. Physical properties of PE-B3 This was carried out in accordance with Comparative Example 1 except that 20 parts by weight of (shown in Table 2) was used. Table 4 shows the physical property evaluation results of the obtained film.

Example 5
(1) Preparation of promoter support In the same manner as in Example 1 (1) Preparation of promoter support, a solid product (hereinafter referred to as promoter support (a-4)) was obtained.

(2) Preliminary polymerization In an autoclave with a stirrer having an internal volume of 210 liters previously substituted with nitrogen, 0.72 kg of the above promoter support (a-4), 80 liters of butane, 0.01 kg of 1-butene, and normal temperature and normal pressure After charging 4 liters as hydrogen, the autoclave was raised to 45 ° C. Further, 0.09 MPa of ethylene was charged at a gas phase partial pressure in the autoclave. After the system was stabilized, 224 mmol of triisobutylaluminum and 75 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to start polymerization. did. While raising the temperature to 50 ° C. and continuously supplying ethylene and hydrogen, preliminary polymerization was carried out at 50 ° C. for a total of 6 hours. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature to obtain 13.0 g of ethylene-1-butene copolymer per 1 g of the above-mentioned promoter support (a-4). A prepolymerized catalyst component (hereinafter referred to as prepolymerized catalyst component (a-4p)) was obtained.

(3) Continuous gas phase polymerization Using the above prepolymerization catalyst component (a-4p), copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 85.3 ° C., a total pressure of 2 MPa, a gas linear velocity of 0.25 m / s, a molar ratio of hydrogen to ethylene of 0.237%, and a molar ratio of 1-butene to ethylene of 0.61%, During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the pre-polymerization catalyst component (a-4p) and triisobutylaluminum are continuously supplied at a constant ratio so that the total powder weight of the fluidized bed is maintained at 80 kg and the average polymerization time is 3.8 hr. did. By polymerization, a powder of ethylene-1-butene copolymer (hereinafter referred to as PE-A4) was obtained at a production efficiency of 20.8 kg / hr.

(4) Granulation of ethylene-1-butene copolymer powder Except that PE-A4 powder is used instead of PE-A1 powder, it is carried out according to the granulation of the powder of Example 1, and pellets of PE-A4 Got. Table 5 shows the physical properties of PE-A4.

(5) Film processing In film processing, 20 parts by weight of PE-A4 was used instead of PE-A1, and a commercially available ethylene-1-hexene copolymer (manufactured by Nippon Evolution Co., Ltd., Sumitomo Chemical) was used instead of PE-B1. Industrial Co., Ltd. Sales Sumikasen E FV205; hereinafter referred to as PE-B4. Physical properties of PE-B4 are shown in Table 5) were carried out in accordance with Example 1, except that 80 parts by weight were used. Table 6 shows the physical property evaluation results of the obtained film.

Comparative Example 4
The film processing was performed according to Comparative Example 1 except that PE-B4 was changed to 100 parts by weight instead of PE-B1. Table 6 shows the physical property evaluation results of the obtained film.

Comparative Example 5
In film processing, in place of PE-B1, 80 parts by weight of PE-B4 and a commercially available ethylene-1-hexene copolymer (manufactured and sold by Sumitomo Chemical Co., Ltd. Sumikasen α FZ203-0; hereinafter referred to as PE-B5) The physical properties of PE-B5 are shown in Table 5.) It was carried out according to Comparative Example 1 except that 20 parts by weight were used. Table 6 shows the physical property evaluation results of the obtained film.

Example 6
(1) Preparation of cocatalyst carrier Silica (Sypolol 948 manufactured by Devison, average particle size = 55 μm; pore volume = 1.67 ml) heat-treated at 300 ° C. under nitrogen flow in a reactor equipped with a nitrogen-substituted stirrer / G; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Then, after cooling to 5 ° C, a mixed solution of 0.91, 1 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene was maintained while maintaining the temperature in the reactor at 5 ° C. Dropped in minutes. After completion of the dropping, the mixture was stirred at 5 ° C. for 1 hour and then at 95 ° C. for 3 hours and filtered. The obtained solid component was washed 6 times with 21 kg of toluene. Thereafter, 6.9 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 2.05 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 1.3 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.77 kg of pentafluorophenol and 1.17 kg of toluene was added dropwise over 61 minutes while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.11 kg of H ₂ O was added dropwise over 1.5 hours while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 55 ° C. for 2 hours. Thereafter, 1.4 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 0.8 kg of hexane were added at room temperature. After cooling to 5 ° C., a mixed solution of 3,4,5-trifluorophenol 0.42 kg and toluene 0.77 kg was added dropwise over 60 minutes while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.077 kg of H ₂ O was added dropwise over 1.5 hours while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. After stirring, the supernatant was extracted to a residual amount of 16 L, charged with 11.6 kg of toluene, heated to 95 ° C., and stirred for 4 hours. After stirring, the supernatant liquid was extracted to obtain a solid component. The obtained solid component was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, by drying, a solid product (hereinafter referred to as a promoter support (a-5)) was obtained.

(2) Prepolymerization Into an autoclave equipped with a stirrer with an internal volume of 210 liters, which was previously purged with nitrogen, 0.70 kg of the promoter support (a-5) was charged, 3 liters of hydrogen at room temperature and normal pressure, and 1-butene were added. After charging 10 g and 80 liters of butane, the autoclave was heated to 40 ° C. Further, 0.03 MPa of ethylene was charged at a gas phase partial pressure in the autoclave, and after the system was stabilized, 210 mmol of triisobutylaluminum and 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. . The temperature was raised to 43 ° C., and prepolymerization was performed for 30 minutes while continuously supplying ethylene and hydrogen, and the temperature was further raised to 50 ° C. to carry out prepolymerization for 3.5 hours. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature, and 14.3 g of ethylene-1-butene copolymer per 1 g of the above-mentioned promoter support (a-5) is obtained. A prepolymerized catalyst component (hereinafter referred to as prepolymerized catalyst component (a-5p)) was obtained.

(3) Continuous gas phase polymerization Using the prepolymerization catalyst component (a-5p) obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus. As polymerization conditions, the temperature was 75 ° C., the total pressure was 2 MPa, the gas linear velocity was 0.25 m / s, the molar ratio of hydrogen to ethylene was 0.9%, and the molar ratio of 1-hexene to ethylene was 1.4%. did. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the pre-polymerization catalyst component (a-5p) and triisobutylaluminum are continuously supplied at a constant rate so that the total powder weight of the fluidized bed is maintained at 80 kg and the average polymerization time is 3.8 hr. did. By polymerization, a powder of an ethylene-1-hexene copolymer (hereinafter referred to as PE-A5) was obtained with a production efficiency of 21.2 kg / hr.

(4) Granulation of ethylene-1-hexene copolymer powder A blend of PE-A5 powder obtained above and an antioxidant (Sumilyzer GP manufactured by Sumitomo Chemical Co., Ltd.) 750 ppm was used as an extruder ((stock ) By using the LCM50) manufactured by Kobe Steel Co., Ltd., granulation is performed under the conditions of 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 to 230 ° C. PE-A5 pellets were obtained. Table 7 shows the physical properties of PE-A5.

(5) Multilayer film processing 20 parts by weight of the above PE-A5 pellets, 80 parts by weight of a commercially available linear ethylene-1-hexene copolymer, PE-B1, an antiblocking agent master batch (Sumitomo Chemical Co., Ltd.) EMB-21) 2.0 parts by weight and 1.0 parts by weight of lubricant masterbatch (Sumitomo Chemical Co., Ltd. EMB-10) were mixed by pellet using a tumbler mixer, and the resulting mixture was screw diameter Introduced into an inner layer extruder of a three-layer coextrusion blown film processing machine (die system 150 mm, lip opening 2.0 mm) consisting of three 50 mmφ extruders, 20 parts by weight of the above PE-A5 pellets, commercially available 80 parts by weight of a linear ethylene-1-hexene copolymer, PE-B1, 1.0 part by weight of a lubricant masterbatch (EMB-10 manufactured by Sumitomo Chemical Co., Ltd.), and a tumbler mixer The resulting mixture was introduced into an intermediate layer extruder, and a commercially available ethylene-1-hexene copolymer (manufactured by Nippon Evolution Co., Ltd., Sumitomo Chemical Co., Ltd. Sumikasen E FV201; The physical properties of PE-B6 are shown in Table 8.) 100 parts by weight, anti-blocking agent masterbatch (EMB-21 manufactured by Sumitomo Chemical Co., Ltd.), and lubricant master 1.0 part by weight of batch (EMB-10 manufactured by Sumitomo Chemical Co., Ltd.) was mixed with pellets using a tumbler mixer, and the resulting mixture was introduced into an extruder for outer layers, and the processing temperature (extruder and die set temperature). ) At 180 ° C., coextrusion blown film formation with a thickness of 50 μm and a width of 518 mm under the conditions of the intermediate layer, the inner layer and the outer layer with an extrusion rate of 8.5 kg / hr and a take-up speed of 8.0 m / min. Was Tsu. The physical property evaluation results of the obtained multilayer film are shown in Table 9.

Example 7
(1) Preparation of promoter support In the same manner as in Example 6 (1) Preparation of promoter support, a solid product (hereinafter referred to as promoter support (a-6)) was obtained.

(2) Prepolymerization Into an autoclave equipped with a stirrer with an internal volume of 210 liters, which was previously purged with nitrogen, 0.70 kg of the promoter support (a-6) was charged, 3 liters of hydrogen at room temperature and normal pressure, and 1-butene were added. After charging 20 g and 80 liters of butane, the autoclave was heated to 30 ° C. Further, 0.03 MPa of ethylene was charged at a gas phase partial pressure in the autoclave, and after the system was stabilized, 210 mmol of triisobutylaluminum and 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. . While raising the temperature to 31 ° C., prepolymerization was continued for 30 minutes while continuously supplying ethylene and hydrogen, and the temperature was further raised to 50 ° C. to carry out prepolymerization for 3.5 hours. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature to obtain 9.1 g of ethylene-1-butene copolymer per 1 g of the above-mentioned promoter support (a-6). A prepolymerized catalyst component (hereinafter referred to as catalyst component (a-6p)) that was prepolymerized was obtained.

(3) Continuous gas phase polymerization Using the prepolymerized catalyst component (a-6p) obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus. As polymerization conditions, the temperature was 85 ° C., the total pressure was 2 MPa, the gas linear velocity was 0.25 m / s, the molar ratio of hydrogen to ethylene was 0.35%, and the molar ratio of 1-hexene to ethylene was 1.1%. did. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Further, the pre-polymerization catalyst component (a-6p) and triisobutylaluminum are continuously supplied at a constant rate so that the total powder weight of the fluidized bed is maintained at 80 kg and the average polymerization time is 4.0 hr. did. By polymerization, a powder of an ethylene-1-hexene copolymer (hereinafter referred to as PE-A6) was obtained with a production efficiency of 20.1 kg / hr.

(4) Granulation of ethylene-1-hexene copolymer powder Except that PE-A6 powder is used instead of PE-A5 powder, it is carried out according to the granulation of the powder of Example 6, and PE-A6 pellets Got. Table 7 shows the physical properties of PE-A6.

(5) Multilayer film processing PE-A6 in place of PE-A5, PE-B4 in place of PE-B1, PE-B4 in place of PE-B6, commercially available ethylene-1-hexene copolymer (Nippon Evolution Co., Ltd.) Manufactured and sold by Sumitomo Chemical Co., Ltd. Sumikasen E FV202; hereinafter referred to as PE-B7. Physical properties of PE-B7 are shown in Table 8.) Coextruded inflation film in the same manner as in Example 6 Molding was performed. The physical property evaluation results of the obtained multilayer film are shown in Table 9.

Claims (4)

The following component (A) and component (B) are contained, the total amount of component (A) and component (B) is 100% by weight, the content of component (A) is 5 to 50% by weight, The polyethylene-type resin composition whose content of (B) is 95 to 50 weight%.
(A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a density of 890 to 950 kg / m ³ , and a flow activation energy ( An ethylene-α-olefin copolymer having an Ea) of 50 kJ / mol or more, a melt flow rate ratio (MFRR) of 30 or more, and a molecular weight distribution (Mw / Mn) of 4.5 to 25.
(B): An ethylene-α-olefin copolymer having a flow activation energy (Ea) of less than 35 kJ / mol and a melt flow rate ratio (MFRR) of 15 to 27. Component (B), the polyethylene resin composition of claim 1 wherein the ethylene polymer to further satisfy the following requirements and (b1) a (b3).
(B1): The melt flow rate measured under conditions of a temperature of 190 ° C. and a load of 21.18 N specified in JIS K7210 is 0.1 to 50 g / 10 minutes.
(B3): The density is 898 to 950 kg / m ³ . The film which has a layer which consists of a polyethylene-type resin composition of Claim 1 or 2 . A gusset bag comprising the film according to claim 3 .