JPH10195263A - Packaging film made of ethylenic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging film having an excellent mechanical strength such as dart impact strength while keeping various characteristics such as transparency and surface smoothness of the film. SOLUTION: This packaging film made of an ethylenic resin is composed of an ethylene-α-olefin copolymer having a density of 0.918-0.935g/cm and a melt-flow rate(MFR) of 0.05-1.0g/10min under a load of 2.16kg at 190 deg.C and satisfying the relationships of W<80×exp(-1.00(d-0.88))+0.1 (W is fraction of component soluble in decane at room temperature; (d) is density), FI >75×MFR (FI is fluidity index defined by the shear rate of the molten polymer under a shear stress of 2.4×10<6> dyne/cm<2> at 190 deg.C and MT>2.2×MFR<-0.84> (MT is melt tension at 190 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a packaging film made of polyethylene.

[0002]

BACKGROUND ART Many films have been manufactured so far, and films having characteristics suitable for each application have been selected and used. Above all, films produced from linear low-density polyethylene are widely used, but the physical properties of the resulting films vary depending on the type of monomer units constituting polyethylene or the method for producing polyethylene.

For example, a film formed from a linear low-density ethylene / 1-butene copolymer has excellent transparency and surface smoothness. However, since this film has low mechanical strength represented by dart impact strength and Elmendorf tear strength, it tends to break the film during molding, and there is a limit in increasing the molding speed.

On the other hand, a linear low-density polyethylene produced using a metallocene catalyst which has recently been in the limelight has a narrow composition distribution, so that the film is known as a film which is unlikely to cause blocking. In particular, when a linear low-density ethylene / 1-hexene copolymer produced using a metallocene catalyst is formed into a film, the resulting film has excellent physical properties such as mechanical strength, transparency, and heat sealability.

However, when the linear low-density ethylene / 1-hexene copolymer has a low melting index (MFR), for example, 1 g / 10 min or less, it tends to cause melt fracture and impair the smoothness of the film surface. May be

Accordingly, it is desired to develop a high-strength packaging film which can be formed at a high speed while maintaining the inherent properties of a linear low-density polyethylene film such as transparency and film surface smoothness. ing.

[0007]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide the transparency inherent in the film of linear low-density polyethylene,
It is an object of the present invention to provide a packaging film having excellent mechanical strength characteristics such as dirt impact strength while maintaining characteristics such as smoothness of a film surface.

Another object of the present invention is to provide a film having excellent low-temperature characteristics such as low-temperature drop strength, which can be sufficiently used for heavy packaging bags even in a cold region below the freezing point.

[0009]

SUMMARY OF THE INVENTION The first ethylene-based resin packaging film according to the present invention comprises: (a) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton; In the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound, ethylene and α having 6 to 20 carbon atoms are used.
-A copolymer obtained by copolymerizing an olefin with (i) a density in the range of 0.918 to 0.935 g / cm ³ and (ii) a melt at 190 ° C. and a load of 2.16 kg. Flow rate (MFR (g / 10 min)) is 0.05 to 5
(Iii) the decane-soluble component content rate (W (% by weight)) and the density (d (g / cm ³ )) at room temperature are W <80 × exp (− 100 (d-0.88)) + 0.1, and (iv) is defined as the shear rate at which the shear stress of the molten polymer at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ^2. Liquidity index (FI (1 / second))
And the melt flow rate (MFR (g / 10 min)) satisfy the relationship of FI> 75 × MFR, and (v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10
MT)> 2.2 × MFR− ^0.84, preferably 5.5 × MFR− ^0.65 >MT> 2.2 × MF
It is characterized by being composed of an ethylene / α-olefin copolymer [A] ^represented by R ^-0.84 .

When the average value of the number of branches on the high molecular weight side by GPC-IR of the ethylene / α-olefin copolymer [A] is B1 and the average value of the number of branches on the low molecular weight side is B2, B1 ≧ B2 It is preferable to be represented by

Further, a second ethylene resin packaging film according to the present invention comprises: [I] (a) a transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton; (b) In the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound, ethylene and α having 6 to 20 carbon atoms
A copolymer obtained by copolymerizing an olefin and (i) having a density in the range of 0.900 to 0.935 g / cm ³ , and (ii) a melt at 190 ° C. and a load of 2.16 kg. Flow rate (MFR (g / 10 minutes)) of 0.01 to 1.
0 g / 10 min, and (iii) the decane-soluble component content ratio (W (% by weight)) and the density (d (g / cm ³ )) at room temperature are W <80 × exp (-100 ( (iv) fluidity defined by the shear rate at which the shear stress at 190 ° C. of the molten polymer reaches 2.4 × 10 ⁶ dyne / cm ² . Index (FI (1 / second))
And the melt flow rate (MFR (g / 10 min)) satisfy the relationship of FI> 75 × MFR, and (v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10
MT)> 2.2 × MFR− ^0.84, preferably 5.5 × MFR− ^0.65 >MT> 2.2 × MF
R- ^0.84 is satisfied, and (vi) the temperature (Tm (° C.)) of the maximum peak position and the density (d) in the endothermic curve measured by the differential scanning calorimeter (DSC) are Tm <400d− Ethylene / α-olefin copolymer [a-1] satisfying the relationship shown by 250: 50 to 99 parts by weight, and [II] (i) having a density of 0.935 to 0.975 g / cm ³ . (Ii) a high-density polyethylene [b-1] having a melt flow rate (MFR (g / 10 min)) in the range of 0.1 to 100 g / 10 min at 190 ° C. and a load of 2.16 kg: 1 to 50 weight And an ethylene / α-olefin copolymer composition [B].

[0012] Such an ethylene resin packaging film
(A) Young's modulus is 4000 kg / cm ^Two(B)
It is preferable that the impact strength is 55 kg / cm or more.
New

Further, the third ethylene-based resin packaging film according to the present invention comprises: [I] (a) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton; (B) in the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound, ethylene and α having 4 to 12 carbon atoms.
A copolymer obtained by copolymerizing an olefin with an olefin having (i) a density in the range of 0.880 to 0.925 g / cm ³ , and (ii) a melt at 190 ° C. and a load of 2.16 kg. Flow rate (MFR (g / 10 min)) of 0.01 to 5.
0 g / 10 min, and (iii) the decane-soluble component content ratio (W (% by weight)) and the density (d (g / cm ³ )) at room temperature are W <80 × exp (-100 ( (iv) fluidity defined by the shear rate at which the shear stress at 190 ° C. of the molten polymer reaches 2.4 × 10 ⁶ dyne / cm ² . Index (FI (1 / second))
And the melt flow rate (MFR (g / 10 min)) satisfy the relationship of FI> 75 × MFR, and (v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10
MT)> 2.2 × MFR− ^0.84, preferably 5.5 × MFR− ^0.65 >MT> 2.2 × MF
An ethylene / α-olefin copolymer [a-2] satisfying the relationship ^represented by R ^-0.84 : 1 to 50 parts by weight, and [II] a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms. And (i) the density is 0.920 to 0.945 g / c
in the range of ^{m 3, (ii) 190 ℃} , melt flow rate at 2.16kg load (MFR) is 0.1 to 10 g / 10
And (iii) the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3 to 6 in terms of Mw / Mn. To 99 parts by weight of the ethylene / α-olefin copolymer composition [C].

[0014] Such an ethylene resin packaging film has (B) a dirt impact strength of 250 kg / cm or more,
(C) The Elmendorf tear strength in the longitudinal direction is preferably 60 kg / cm or more.

[0015]

DETAILED DESCRIPTION OF THE INVENTION First ethylene-based resin packaging film The first ethylene-based resin packaging film according to the present invention is formed from an ethylene / α-olefin copolymer [A]. First, the ethylene / α-olefin copolymer [A] will be described.

Ethylene / α-olefin copolymer [A] The ethylene / α-olefin copolymer [A] used in the present invention comprises ethylene and an α-olefin having 6 to 20 carbon atoms.

As the α-olefin having 6 to 20 carbon atoms, specifically, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene And the like.

The ethylene / α-olefin copolymer [A] used in the present invention has an ethylene content of usually 94 to 99.
Mol%, preferably 96 to 98 mol%, and the content of the comonomer α-olefin is usually 1 to 6 mol%, preferably 2 to 4 mol%.

The ethylene / α-olefin copolymer [A] used in the present invention has a density of 0.918 to 0.935 g / d.
cm ³ , preferably in the range of 0.905 to 0.930 g / cm ³ .

The ethylene / α-olefin copolymer [A] used in the present invention has a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg of 0.05 to 2.0 g / 10.
Min, preferably in the range of 0.1 to 2.0 g / 10 min.

The ethylene / α-olefin copolymer [A] used in the present invention has a decane-soluble component content ratio (W (weight%)) and a density (d (g / cm ³ )) at room temperature. W <80 × exp (-100 (d−0.88)) + 0.1 Preferably, the relationship represented by W <60 × exp (-100 (d−0.88)) + 0.1 is satisfied.

The ethylene / α-olefin copolymer [A] used in the present invention is defined as the shear rate at which the shear stress of the molten polymer at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ^2. The fluidity index (FI (1 / sec)) and the melt flow rate (MFR (g / 10 minutes)) satisfy FI> 75 × MFR, preferably, FI> 80 × MFR. I have.

The straight-chain ethylene α- used in the present invention
The olefin copolymer [A] has a melt tension (MT) at 190 ° C. and a melt flow rate (MFR (g / 10 minutes)) of MT> 2.2 × MFR- ^0.84, preferably 5.5 × MFR ^-0.65 >MT> 2.2 × MF
R− ^0.84, more preferably 5.5 × MFR− ^0.65 > MT
> 2.5 × MFR ^-0.84 .

In the ethylene / α-olefin copolymer [A] used in the present invention, the average value of the number of branches on the high molecular weight side by GPC-IR is B1, and the average value of the number of branches on the low molecular weight side is B2. Then, B1 ≧ B2.

Here, the average value (B1) of the number of branches on the high molecular weight side by GPC-IR means that the cumulative weight fraction of the amount of polymer eluted by GPC is 15 to 85%.
(I.e., the high-molecular-weight-equivalent value of the components measured in the range of (i.e., high-molecular-weight elution components excluding the low-molecular-weight region 15% and the high-molecular-weight region 15%)). On the other hand, the average value (B2) of the number of branches on the low molecular weight side is the average value on the low molecular weight side of the two-divided one.

The measurement conditions for B1 and B2 are as follows. Measuring device: PERKIN ELMER 1760X Column: TOSOH TSKgel GMMH-HT (7.5mmI.D. × 600mm)
× 1 eluent: o-dichlorobenzene (ODCB) containing 0.05% of MP-J [extra pure grad manufactured by Wako Pure Chemical Industries, Ltd.
e] Column temperature: 140 ° C Sample concentration: 0.1% (weight / volume) Injection volume inj.volume): 100 microliter detector: MCT resolution: 8 cm ^-1 This ethylene is used for the B1 and B2 in the above relationship. α
-Since the olefin copolymer [A] has a narrow composition distribution and a small amount of low molecular weight polymer, it has little tackiness.
Such an ethylene / α-olefin copolymer [A]
Can be suitably used for packaging films.

Such an ethylene / α-olefin copolymer [A] includes (a) a transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (b) an organoaluminum oxy group. Compound, (c) carrier, if necessary
(d) In the presence of an olefin polymerization catalyst formed from an organoaluminum compound, ethylene and α-C 3-20
The olefin and the resulting polymer having a density of 0.918 to
It can be produced by copolymerizing to 0.935 g / cm ³ .

The olefin polymerization catalyst and each catalyst component are described below. (a) Transition metal compound (a) A transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton (hereinafter sometimes referred to as “component (a)”) is specifically mentioned. Are transition metal compounds represented by the following formula [I].

ML ¹ _X ... [I] (wherein, M represents a transition metal selected from Group IV of the periodic table, L ² represents a ligand coordinated to a transition metal atom, and at least The two ligands L ² are a substituted cyclopentadienyl group having 2 to 5 substituents selected from a methyl group and an ethyl group, and the ligand L ² other than the substituted cyclopentadienyl group is hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, X is represents an atomic valence of the transition metal atom M.) L ¹ is the transition metal atom M indicates coordinating ligand, at least two ligands L ¹ are each a substituted cyclopentadienyl group having 2 to 5 substituents selected from methyl and ethyl, each distribution The ligands may be the same or different. The substituted cyclopentadienyl group is a substituted cyclopentadienyl group having two or more substituents, preferably a cyclopentadienyl group having two or three substituents, and a disubstituted cyclopentadienyl group. More preferably a 1,3-substituted cyclopentadienyl group. In addition, each substituent may be the same or different.

In the above general formula [I], M represents a transition metal atom selected from Group IV of the periodic table.
Zirconium, titanium or hafnium, preferably zirconium.

In the above formula [I], the ligand L ¹ other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
An aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

Examples of the transition metal compound represented by the general formula [I] include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, and bis (ethylcyclopentadienyl) zirconium. Dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopenta Dienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxy chloride, bis (N-butylcyclopentadienyl) zirconium ethoxycyclolide, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium ethoxide, bis (n-butylcyclopentadiene) Nil) zirconium methyl chloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n -Butylcyclopentadienyl) zirconium phenyl chloride, bis (n-butylcyclopentadienyl) zirconium hydride chloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (diethylcyclopentadienyl) zirconium dichloride, bis (methyl) Ethylcyclopentadienyl) zirconium dichloride, bis (dimethylethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dibromide, bis ( Dimethylcyclopentadienyl) zirconium methoxychloride, bis (dimethylcyclopentadienyl) zirconium ethoxychloride, bis (dimethylcyclopentadienyl) zirconium butoxycyclolide, bis (dimethylcyclopentadienyl) zirconium diethoxide, bis (dimethyl) Cyclopentadienyl) zirconium methyl chloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium benzyl chloride, bis (dimethylcyclopentadienyl) zirconium dibenzyl, bis (dimethylcyclopentadi (Enyl) zirconium phenyl chloride, bis (dimethylcyclopentadienyl) zirconium hydride chloride and the like. In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted includes 1,2,3- and 1,2,4-substituted. Including. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the zirconium compound as described above can be used.

Among these transition metal compounds represented by the general formula [I], bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1 -Methyl-3-n-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bis (1,
3-Dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride are particularly preferred.

The transition metal compound used in the present invention may be a mixture of two or more transition metal compounds represented by the above general formula [I]. Specifically, a combination of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-n-propyl Combination of methyl (cyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadiyl (Enyl) zirconium dichloride.

The transition metal compound used in the present invention may be a mixture of the transition metal compound represented by the above general formula [I] and the transition metal compound represented by the following general formula [II].

MKL ² _X-2 ... [II] (wherein, M represents a transition metal atom selected from Group IV of the periodic table, and K and L ² represent ligands coordinated to the transition metal atom. The ligand K is the same or different indenyl group,
A bidentate ligand in which a substituted indenyl group or a partial water additive thereof is bonded via a lower alkylene group, and a ligand L ²
Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom, and X represents the valence of the transition metal atom M. Examples of the transition metal compound represented by the general formula [II] include ethylenebis (indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, and ethylenebis (4,5,6). , 7-tetrahydro-
1-indenyl) zirconium dichloride and the like.

In the present invention, (a) the transition compound is selected from at least one selected from the transition metal compounds represented by the above general formula [I] and the transition metal compounds represented by the above general formula [II]. It is preferable to use at least one kind in combination.

At least one transition metal compound selected from the transition metal compounds (a-1) represented by the general formula [I] and the transition metal compound (a-2) represented by the general formula [II] )
And at least one transition metal compound selected from the group consisting of 99/1 to 50/50, preferably 9 / molar ratio (a-1 / a-2).
7/3 to 70/30, more preferably 95/5 to 75 /
Preferably, it is used in an amount such that it is in the range of 25, most preferably 90/10 to 80/20.

(B) Organic Aluminum Oxy Compound Next, the organic aluminum oxy compound (b) will be described. The organoaluminum oxy compound (b) (hereinafter sometimes referred to as “component (b)”) used in the present invention includes:
A conventionally known benzene-soluble aluminoxane may be used, or a benzene-insoluble organic aluminum oxy compound as disclosed in JP-A-2-276807 may be used.

The aluminoxane as described above can be prepared, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution.

(2) A method in which an organic aluminum compound such as trialkylaluminum is directly reacted with water, ice or water vapor in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover as a hydrocarbon solution.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trialkyl aluminum such as tri-sec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum Chloride, diethylaluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride;
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum and trialkylaluminum are particularly preferred. Further, as the organoaluminum compound represented by the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z (x, y, z are each a positive number, the z ≧ 2x) represented by Isoprenyl aluminum can also be used.

The organoaluminum compound as described above is
Used alone or in combination. Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrogen, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; and halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Hydrocarbon solvents such as chlorides, bromides and the like. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used.
Among these solvents, aromatic hydrocarbons are particularly preferred.

In the benzene-insoluble organic aluminum oxy compound, the Al component soluble in benzene at 60 ° C. is 10% or less, preferably 5% or less in terms of Al atom.
It is particularly preferably at most 2%, and is insoluble or hardly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is such that the organoaluminum oxy compound corresponding to 100 milligram atoms of Al is 10
After suspending in 0 ml of benzene and mixing at 60 ° C. for 6 hours with stirring, the mixture was filtered while hot at 60 ° C. using a G-5 glass filter equipped with a jacket, and the solid part separated on the filter was removed by 60 ° C. After washing four times with 50 ml of benzene at 50 ° C., the amount of Al atoms present in the total filtrate (x
Mmol) (x%).

(C) Carrier The carrier (c) used in the present invention is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 2 to 300 μm.
Granular or particulate solids of 0-200 μm are used. Of these, a porous oxide is preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , b-2O ₃ , CaO, ZnO, BaO, Th
O ₂ or the like or a mixture thereof, for example, SiO ₂ —MgO,
SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V
Examples thereof include ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. Of these, SiO ₂ and A
Those containing at least one component selected from the group consisting of l ₂ O ₃ as a main component are preferred.

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
Carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O,
Sulfate, nitrate and oxide components may be contained.

The nature of the carrier (c) varies depending on the kind and the production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. Having a pore volume of 0.3 to 2.
Desirably, it is 5 cm ² / g. The carrier is optionally at 100 to 1000 ° C, preferably 150 to 700 ° C.
It is used by firing at ℃.

Further, examples of the carrier that can be used in the present invention include a granular or fine solid of an organic compound having a particle size of 10 to 300 μm. As these organic compounds, ethylene, propylene, 1-butene, α-C2-C14 such as 4-methyl-1-pentene, etc.
Examples thereof include (co) polymers containing olefin as a main component, and polymers or copolymers containing vinylcyclohexane and styrene as a main component.

(D) Organoaluminum Compound The olefin polymerization catalyst used in the production of the ethylene / α-olefin copolymer used in the present invention comprises the above component (a),
Components (b) and (c) are formed from the carrier, but if necessary
(d) An organic aluminum compound may be used.

Examples of the (d) organoaluminum compound (hereinafter sometimes referred to as “component (d)”) used as necessary include, for example, an organoaluminum compound represented by the following general formula [III]: can do.

R ¹ _n AlX _3-n ... [III] (wherein, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms;
Represents a halogen atom or a hydrogen atom, and n is 1 to 3. In the above general formula [III], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group. -A propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (d),
A compound represented by the following general formula [IV] can also be used. During ^{_{R 1 n AlY 3-n ...}} [IV] ( wherein, R ¹ represents the same hydrocarbon and R ¹ in the general formula [III], Y is -OR ² group, -OSiR ³ ₃ group, - OAl
R ⁴ ₂ group, -NR ⁵ ₂ group, -SiR ⁶ ₃ group or -N (R ⁷⁾ Al
Indicates R ⁸ ₂ group, n is ^{1~2, R 2, R 3,} R 4 and R ⁸ are like a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl radical, R
⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group,
A phenyl group, a trimethylsilyl group or the like; and R ⁶ and R ⁷ are a methyl group, an ethyl group, or the like. The following compounds are specifically used as such organoaluminum compounds.

(1) A compound represented by R ¹ _n Al (OR ² ) _3-n , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (2) R ¹ _n Al (OSiR ³ ₃ ) Compounds represented by _3-n , for example, Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OSiM
_{e 3), (iso-Bu} ) 2 Al (OSiEt 3) , _{^{etc.; (3) R 1 n Al}} (OAlR 4 2) a compound represented by _3-n, e.g., _{Et 2 AlOAlEt 2, (iso-} Bu) 2 AlOAl (iso-B
u) _{2, ^{etc.; (4) R 1 n Al}} (NR 5 2) a compound represented by _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHEt,
_{Et 2 AlN (SiMe 3) 2} , (iso-Bu) 2 AlN (SiMe 3) 2 , _{^{etc.; (5) R 1 n Al}} (SiR 6 3) a compound represented by _3-n, e.g., (iso-Bu) such as _{2 AlSi Me 3; (6)} R 1 n Al (n (R 7) AlR 8 2) a compound represented by _3-n,
For example, Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN (E
t) Al (iso-Bu) ₂ etc.

[0059] Among the above general formula [III] and an organoaluminum compound represented by the [IV], formula R ¹ ₃ Al,
_{^{R 1 n Al (OR 2)}} 3-n, R 1 n Al (OAlR 4 2) compounds represented by _3-n are preferred, in particular R is isoalkyl group,
Compounds where n = 2 are preferred.

Catalyst Preparation Method In producing the ethylene / α-olefin copolymer [A] used in the present invention, the components (a), (b) and the carrier (c) as described above, if necessary, A catalyst prepared by contacting (d) is used. The order of contact of each component at this time is arbitrarily selected, but preferably the carrier
(c) and the component (b) are mixed and contacted, then the component (a) is mixed and contacted, and if necessary, the component (d) is mixed and contacted.

The contact of each of the above components can be carried out in an inert hydrocarbon solvent. Specific examples of the inert hydrocarbon medium used for preparing the catalyst include propane, butane, pentane, hexane, heptane and octane. , Decane, dodecane, kerosene, etc .; aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclopentane, etc., alicyclic hydrocarbons; benzene, toluene, xylene, etc., aromatic hydrocarbons; ethylene chloride, chlorobenzene, dichloromethane, etc. Examples thereof include halogenated hydrocarbons and mixtures thereof.

Upon mixing and contacting the component (a), the component (b), the carrier (c) and, if necessary, the component (d), the component (a)
(c) used in an amount of usually 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol per 1 g,
The concentration of (a) is about 10 ^-4 to 2 × 10 ^-2 mol / l,
Preferably it is in the range of 2 × 10 ⁻⁴ to 10 ⁻² mol / l. The atomic ratio (Al / transition metal) of aluminum of the component (b) to the transition metal in the component (a) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-b) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-b) of the component (b) used as required is
Usually, it is in the range of 0.02 to 3, preferably 0.05 to 1.5. The mixing temperature when mixing and contacting the component (a), the component (b), the carrier (c) and, if necessary, the component (d) is usually -50 to
The temperature is 150C, preferably -20 to 120C, and the contact time is 1 minute to 50 hours, preferably 10 minutes to 25 hours.

The olefin polymerization catalyst obtained as described above contains 5 × 10 ^{-6 to} 5 × 10 ^-4 gram atoms of transition metal atoms derived from the component (a) per gram of the carrier (c), preferably 1 gram atom.
0 ^{-5 to} 2 × 10 ^-4 gram-atoms, and the carrier
(c) aluminum atoms derived from the components (b) and (d) in an amount of 10 ^{-3 to} 5 × 10 ^-2 gram atoms, preferably 2 × 10 ^-3 to 2 × 10 ^-2 gram atoms per g; It is desirable to be carried.

The catalyst used in the production of the ethylene / α-olefin copolymer [A] includes the above-mentioned component (a), component (b), carrier (c) and, if necessary, component ( It may be a prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of d). The pre-polymerization is performed using the components as described above.
It can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of (a), component (b), carrier (c) and, if necessary, component (d).

The olefin used in the prepolymerization includes ethylene and an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1
-Dodecene, 1-tetradecene and the like. Among them, ethylene used in the polymerization or a combination of ethylene and an α-olefin is particularly preferred.

In the prepolymerization, the above component (a) is usually used in an amount of 10 ^-6 to 2 × 10 ^-2 mol / liter, preferably 5 ×
Used in an amount of 10 ^-5 to 10 ^-2 mol / liter,
(a) is used in an amount of usually 5 × 10 ^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol, per 1 g of the carrier (c). The atomic ratio (Al / transition metal) of aluminum of the component (b) to the transition metal in the component (a) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-b) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-b) of the component (b) used as required is usually from 0.02 to 0.02. 3, preferably in the range of 0.05 to 1.5. The prepolymerization temperature is -20 to 80C, preferably 0 to 6C.
0 ° C., and the prepolymerization time is 0.5 to 100 hours,
Preferably, it is about 1 to 50 hours.

The prepolymerization catalyst is prepared, for example, as follows. That is, the carrier (c) is suspended with an inert hydrocarbon. Next, an organoaluminum oxy compound (component (b)) is added to the suspension and reacted for a predetermined time. Thereafter, the supernatant is removed and the solid component obtained is resuspended with an inert hydrocarbon. After adding a transition metal compound (component (a)) into the system and reacting for a predetermined time, the supernatant is removed to obtain a solid catalyst component. Subsequently, the solid catalyst component obtained above is added to an inert hydrocarbon containing an organoaluminum compound (component (d)), and an olefin is introduced therein, whereby a prepolymerization catalyst is obtained to obtain a prepolymerization catalyst. The olefin copolymer to be used is 0.1 to 5 per gram of the carrier (c).
It is desirable that the amount is 00 g, preferably 0.2 to 300 g, more preferably 0.5 to 200 g. In addition, in the prepolymerized catalyst, the component (a) is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ g atoms, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ g atoms as a transition metal atom per 1 g of the support (c). Aluminum atoms (A) carried in the amount of atoms and derived from component (b) and component (d)
l) is a molar ratio (Al / M) to the transition metal atom (M) derived from the component (a), and is 5 to 200, preferably 10
It is desirable to be carried in an amount in the range of ~ 150.

The prepolymerization can be carried out either batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Intrinsic viscosity [η] measured in decalin at least 135 ° C. in the coexistence of hydrogen in the range of 0.2 to 7 dl / g;
It is desirable to produce a prepolymer of preferably 0.5-5 dl / g.

The ethylene / α-olefin copolymer [A] used in the present invention is prepared by reacting ethylene with an α-olefin having 6 to 20 carbon atoms in the presence of the above-mentioned olefin polymerization catalyst or prepolymerization catalyst. Is obtained by copolymerizing

In the present invention, the copolymerization of ethylene and α-olefin is carried out in a gas phase or in a liquid phase in the form of a slurry. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane, methylcyclopentane , Cyclohexane,
Alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; gasoline;
Examples include petroleum fractions such as kerosene and light oil. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

When carrying out the slurry polymerization method or the gas phase polymerization method, the olefin polymerization catalyst or the prepolymerization catalyst as described above is usually used in a concentration of 10 ⁻⁸ to 10 ⁻ as a transition metal atom concentration in the polymerization reaction system. It is desirably used in an amount of ³ gram atoms / liter, preferably 10 ^-7 to 10 ^-4 gram atoms / liter.

At the time of the main polymerization, the same organic aluminum oxy compound and / or organic aluminum compound (d) as the component (b) may be added. At this time, an aluminum atom (Al) derived from the organic aluminum oxy compound and the organic aluminum compound and a transition metal compound
Atomic ratio to transition metal atom (M) derived from (a) (Al /
M) is in the range of 5-300, preferably 10-200, more preferably 15-150.

When performing the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C., preferably 0 to 90 ° C. When performing the gas phase polymerization method, the polymerization temperature is: Usually, it is in the range of 0 to 120 ° C, preferably 20 to 100 ° C.

The polymerization pressure is usually from normal pressure to 100 kg /
cm ² , preferably under a pressurized condition of ^{2 to} 50 kg / cm ² , and the polymerization can be carried out in any of a batch system, a semi-continuous system, and a continuous system. The polymerization may be performed in multiple stages such as two stages.

Further, in the polymerization, using one or a plurality of polymerization vessels, the copolymerization is divided into two or more stages having different reaction conditions.
It is also possible to do. Ethylene-α- used in the present invention
The olefin copolymer [A] includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, as long as the object of the present invention is not impaired.
Additives such as an anti-slip agent, an anti-blocking agent, an anti-fogging agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an antioxidant, a hydrochloric acid absorbent, and an antioxidant may be added as necessary. . In addition, a small amount of another polymer compound can be blended without departing from the spirit of the present invention.

Second Ethylene Resin Packaging Film The second ethylene resin packaging film according to the present invention is formed from the ethylene / α-olefin copolymer composition [B]. Next, the ethylene / α-olefin copolymer composition [B] will be described.

Ethylene / α-olefin copolymer composition
[B] The ethylene / α-olefin copolymer composition [B] used in the present invention is an ethylene / α-olefin copolymer [a-
1] and high density polyethylene [b-1].

The ethylene / α-olefin copolymer composition [B] is an ethylene / α-olefin copolymer
[a-1]: 50 to 99 parts by weight, preferably 50 to 90 parts by weight, more preferably 55 to 80 parts by weight, and high density polyethylene [b-1]: 1 to 50 parts by weight, preferably 10 to 5 parts by weight.
0 parts by weight, more preferably 20 to 45 parts by weight.

Ethylene / α-olefin copolymer [a-1]
Are, as in the ethylene / α-olefin copolymer [A], (a) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (b) an organic aluminum oxy compound. And a copolymer obtained by copolymerizing ethylene and an α-olefin having 6 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing

Examples of such a catalyst component include those similar to the above-mentioned catalyst components. The ethylene / α-olefin copolymer [a-1] has (i) a density of 0.900 to 0.935.
g / cm ³ , and (ii) a melt flow rate (MFR (g / 10 min)) at 190 ° C. and a load of 2.16 kg of 0.0
(Iii) the amount of decane-soluble components at room temperature (W (% by weight)) and the density (d (g / c
m ³ )) and W <80 × exp (-100 (d−0.88)) + 0.1, and (iv) the shear stress of the molten polymer at 190 ° C. is 2.4 × 10 ⁶ dyne / Liquidity index (FI (1 / sec)) defined by the shear rate when reaching cm ²
And the melt flow rate (MFR (g / 10 min)) satisfy the relationship of FI> 75 × MFR, and (v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10
MT)> 2.2 × MFR− ^0.84, preferably 5.5 × MFR− ^0.65 >MT> 2.2 × MF
R ^−0.84 is satisfied, and the temperature (Tm (° C.)) at the maximum peak position and the density (d) in the endothermic curve measured by the differential scanning calorimeter (DSC) are Tm <400d-250. It is desirable that the relationship shown is satisfied.

Next, the high-density polyethylene [b-1] will be described. The high-density polyethylene [b-1] is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

The density of the high-density polyethylene [b-1] is 0.93.
5 to 0.975 g / cm ³ , preferably 0.935 to 0.96
It is desirable to be in the range of 5 g / cm ³ . The high-density polyethylene [b-1] has a melt flow rate (MFR (g / 10 minutes)) of 0.1 to 100 g / 10 at 190 ° C. and a load of 2.16 kg.
Min, preferably in the range of 0.5 to 80 g / 10 min.

Such a high-density polyethylene [b-1]
If it has the above properties, it can be manufactured using a known polymerization method, and such a high-density polyethylene
As [b-1], those produced using a titanium-based catalyst component or a metallocene-based catalyst component are preferable.

The ethylene / α-olefin copolymer composition [B] used in the present invention can be produced by using a known method. For example, it can be produced by the following method.

(1) Ethylene / α-olefin copolymer [a-
1], a method of mechanically blending the copolymer [b-1], and other components to be added as necessary with an extruder, a kneader or the like.

(2) Ethylene / α-olefin copolymer [a-
1], the copolymer [b-1], and other components that are added as needed, in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, and xylene). ) And then removing the solvent.

(3) Ethylene / α-olefin copolymer [a-
1], a copolymer [b-1] and other components to be added as necessary are prepared by separately dissolving them in a suitable good solvent, and then mixed, and then the solvent is removed. .

(4) A method in which the above methods (1) to (3) are combined. In addition to the above method, ethylene
The α-olefin copolymer composition [B] can also be produced. For example, it is produced by polymerizing an ethylene / α-olefin copolymer [a-1] and a copolymer [b-1] by dividing the polymerization into two or more stages having different reaction conditions using one polymerization vessel. can do. Specifically, in the two-stage polymerization process, the ethylene / α-olefin copolymer [a-1] is polymerized in the first stage, and the copolymer [b-1] is polymerized in the second stage. It can be produced by polymerizing the copolymer [b-1] and polymerizing the ethylene / α-olefin copolymer [a-1] in the subsequent stage. Further, using a plurality of polymerization reactors, one of the polymerization reactors was used to polymerize the ethylene / α-olefin copolymer [a-1], and the other was used to polymerize the ethylene / α-olefin copolymer
In the presence of the α-olefin copolymer [a-1], the copolymer [b-
1] or the copolymer [b-
1], and then the copolymer [b-1] in the other polymerization vessel
Can be also produced by polymerizing the ethylene / α-olefin copolymer [a-1] in the presence of Such an ethylene / α-olefin copolymer composition [B] can be suitably used for packaging films. The ethylene / α-olefin copolymer composition [B] used in the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, and an anti-blocking agent as long as the object of the invention is not impaired. If necessary, additives such as an anti-fogging agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an antioxidant, a hydrochloric acid absorbent, and an antioxidant may be blended. In addition, a small amount of another polymer compound can be blended without departing from the spirit of the present invention.

Third Ethylene Resin Packaging Film The third ethylene-based resin packaging film according to the present invention is formed from the ethylene / α-olefin copolymer composition [C]. Next, the ethylene / α-olefin copolymer composition [C] will be described.

Ethylene / α-olefin copolymer composition
[C] The ethylene / α-olefin copolymer composition [C] used in the present invention is an ethylene / α-olefin copolymer [a-
2] and an ethylene-based copolymer [b-2].

The ethylene / α-olefin copolymer composition [C] is an ethylene / α-olefin copolymer
[a-2]: 1 to 50 parts by weight, preferably 3 to 40 parts by weight,
More preferably, it contains 5 to 35 parts by weight, and ethylene-based copolymer [b-2]: 50 to 99 parts by weight, preferably 60 to 97 parts by weight, more preferably 65 to 95 parts by weight.

Ethylene / α-olefin copolymer [a-2]
In the presence of (a) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton and (b) an organoaluminum oxy compound, ethylene and carbon are present in the presence of an olefin polymerization catalyst. Copolymers obtained by copolymerizing α-olefins of formulas 4 to 12 are preferred. Examples of such a catalyst component include those similar to the above-described catalyst component.

Ethylene / α-olefin copolymer [a-2]
Has a (i) density in the range of 0.880 to 0.925 g / cm ³ , (ii) a melt flow rate (MFR (g / 10 min)) at 190 ° C. and a load of 2.16 kg of 0.01 to 5.0g / 10
(Iii) The ratio of the amount of decane-soluble components at room temperature (W (% by weight)) and the density (d (g / cm ³ )) at room temperature are W <80 × exp (-100 (d-0.88 )) + 0.1, and (iv) a fluidity index (FI) defined by the shear rate at which the shear stress of the molten polymer at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ^2. (1 second))
And the melt flow rate (MFR (g / 10 min)) satisfy the relationship of FI> 75 × MFR, and (v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10
MT)> 2.2 × MFR− ^0.84, preferably 5.5 × MFR− ^0.65 >MT> 2.2 × MF
It is desirable that the relationship ^represented by R ^-0.84 be satisfied.

Next, the ethylene copolymer [b-2] will be described. The ethylene copolymer [b-2] is a copolymer obtained by copolymerizing ethylene and an α-olefin having 4 to 10 carbon atoms.

The density of the ethylene copolymer [b-2] is 0.9.
20 to 0.945 g / cm ³ , preferably 0.920 to 0.9
It is desirable to be in the range of 35 g / cm ³ . The ethylene copolymer [b-2] has a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg in the range of 0.1 to 10 g / 10 min, preferably 0.1 to 8 g / 10 min. It is desirable.

The ethylene copolymer [b-2] has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of Mw / Mn.
Is preferably in the range of 3 to 6. Such a high-density polyethylene [b-2] can be produced by using a known polymerization method as long as it has the above properties, and such an ethylene-based copolymer [b-2] Is preferably produced using a titanium catalyst component.

The ethylene / α-olefin copolymer composition [C] used in the present invention can be produced by using a known method, for example, by the above method. Such an ethylene / α-olefin copolymer composition [C] can be suitably used for packaging films.

Ethylene-based Resin Packaging Film The first ethylene-based resin packaging film according to the present invention comprises the above-mentioned ethylene / α-olefin copolymer [A], which is prepared by using an inflation film molding machine or T
The film can be produced by supplying the film to an extruder equipped with a die or the like.

The second ethylene-based resin packaging film according to the present invention is obtained by extrusion-molding the above-mentioned ethylene / α-olefin copolymer composition [B] with a blown film molding machine or a T-die. The film can be manufactured by supplying the film to a machine or the like. The ethylene / α-olefin copolymer composition [B] may be supplied to an extruder directly after mixing each component in a pellet state, or a commonly used mixer such as a Henschel mixer, a tumbler, The mixture may be mixed in advance using a single-screw extruder or a twin-screw extruder and then supplied to an extruder for forming a film.

The first or second ethylene-based resin packaging film has a Young's modulus of 4000 kg / cm ² or more, preferably 4,000 to 4,000 kg / cm ² , measured according to JIS K 6781.
10,000 kg / cm ² , a dirt impact strength measured according to ASTM D 1709 A method of 55 kg / cm, preferably 55 to 150 kg / cm or more, and a film thickness of usually 30
２００200 μm.

Such a first or second ethylene-based resin packaging film can be sufficiently used for a heavy packaging bag even in a cold region below the freezing point. Further, since the ethylene-based resin packaging film according to the present invention is excellent in low-temperature characteristics, the film thickness can be reduced and high-speed molding of the film is possible.

The third ethylene resin packaging film according to the present invention is a film formed from the above-mentioned ethylene / α-olefin copolymer composition [C] by an air-cooled inflation method.

[0104] The third ethylene-based resin-made packaging film has a Young's modulus was measured according to JIS K 6781 is 250 kg / cm ² or more, preferably 250~1000kg / cm ²
And a longitudinal Elmendorf tear strength of 55 when subjected to a tear test in accordance with ASTM D-1922.
kg / cm, preferably 55 to 150 kg / cm, and the film thickness is usually about 10 to 100 μm.

Such a third ethylene-based resin packaging film can maintain the inherent properties of a linear low-density polyethylene film, such as transparency and film surface smoothness, while maintaining its properties. It has excellent mechanical strength characteristics such as dirt impact strength and Elmendorf tear strength, and enables high-speed film formation.

[0106]

As described above, the packaging film of the present invention retains the inherent properties of a linear low-density polyethylene film such as transparency and film surface smoothness.

Furthermore, the film of the present invention maintains mechanical properties such as dart impact strength while maintaining the inherent properties of a linear low density polyethylene film such as transparency and film surface smoothness. Since a film having excellent characteristics can be formed at a high speed, a thin film having such characteristics can be manufactured with high productivity.

The resin composition for a film according to the present invention having the above-mentioned effects can be used as a single-layer film, or can be laminated with another film such as a polyester or polyamide film to form a multilayer film. You can also. These films are suitable for packaging foods, office supplies, furniture, toys, electrical appliances, mechanical parts and the like.

The ethylene-based resin packaging film according to the present invention can be sufficiently used for a heavy packaging bag even in a cold region below the freezing point.

[0110]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The measurements of the physical properties of the films and bags in the examples and comparative examples were performed by the following methods. (1) Young's modulus A tensile test was performed in the MD and TD directions of the film using a constant crosshead moving speed type tensile tester (manufactured by Instron).

[Test conditions] Sample: JIS K6781 Atmospheric temperature: 23 ° C Pulling speed: 500 mm / min Chart speed: 200 mm / min From the chart obtained in the above test, the film Young in the MD and TD directions was obtained by the following formula. The modulus was calculated, and the average of the calculated values was defined as Young's modulus (E).

E ₀ = R ₀ (L ₀ / A) [where E ₀ is the Young's modulus in each direction, R ₀ is the initial gradient, L ₀ is the distance between the chucks, and A is the value at the time of sample preparation. The minimum area is shown. This R ₀ was calculated by the following equation.

R ₀ = F ₁ / L ₁ [wherein F ₁ represents a load at an arbitrary point on the initial tangent, and L ₁ represents an elongation corresponding to F ₁ on the tangent. (2) Dart Impact Strength The value obtained by dividing the value measured according to the ASTM D 1709 A method by the thickness of the film was defined as the dart impact strength. (3) Haze Haze was measured according to JIS K6714. (4) Low-temperature characteristics (a) Low-temperature vertical bag strength test With a content of 25 kg, the heater gap is 150% and the cooler gap is 200% with a neuron HS-33D top sealer (trade name, manufactured by Tester Sangyo Co., Ltd.). Prepare 10 bags with the top and bottom sealed under the conditions of
The number of torn bags dropped from a height of 2 m from the bottom of the bag under an atmosphere of ° C was examined. The drop height is 1.75m, 1.
The test was similarly performed for 10 bags each at 5 m and 1 m.

(B) Low-Temperature Falling Bag Strength Test Using a Neurong HS-33D top sealer (trade name, manufactured by Tester Sangyo Co., Ltd.) with a content weight of 25 kg, with a heater gap of 150% and a cooler gap of 200%. Prepare 10 bags with the top and bottom sealed, -20
The number of torn bags dropped from the side of the bag from a height of 2 m in a temperature of 2 ° C. was examined. The drop height is 1.75m,
The test was similarly performed for 10 bags each at 1.5 m and 1 m. (5) Elmendorf tear strength A tear test was performed in accordance with ASTM D-1922, and the tear strength in the longitudinal and transverse directions was measured.

[0116]

[Production Example 1] Production of ethylene / α-olefin copolymer (A-1) [Preparation of catalyst] Silica 10 dried at 250 ° C for 10 hours
After suspending the suspension in 154 liters of toluene,
Cooled to ° C. Thereafter, a toluene solution of methylaminooxane (Al = 1.33 mol / liter) 57.5.
One liter was added dropwise over one hour. At this time, the temperature in the system is set to 0
C. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 20 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. After the solid component thus obtained was washed twice with toluene, toluene 100
Resuspended in liters. 16.8 of a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr = 27.0 mmol / l) was introduced into the system.
Liters at 80 ° C for 30 minutes and then at 80 ° C
For 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.5 mg of zirconium per gram.

[Preparation of Preliminary Polymerization Catalyst] To 87 liters of hexane containing 2.5 mol of triisobutylaluminum, 870 g of the solid catalyst obtained above and 260 g of 1-hexene were added, and the ethylene preliminarily was added at 35 ° C. for 5 hours. By performing the polymerization, a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[Polymerization] Using a continuous type fluidized-bed gas-phase polymerization apparatus, ethylene was reacted with ethylene at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C.
Copolymerization with hexene was performed. The above-prepared prepolymerized catalyst was continuously supplied at a rate of 0.33 mmol / h in terms of zirconium atoms and triisobutylaluminum at a rate of 10 mmol / h, and ethylene and 1- to maintain a constant gas composition during the polymerization. Hexene, hydrogen and nitrogen were continuously supplied (gas composition; 1-hexene / ethylene = 0.02, hydrogen / ethylene = 10.5 × 10 ⁻⁴ , ethylene concentration = 70%).

The yield of the obtained polyethylene (A-1) was 60 kg / hr, the density was 0.925 g / cm ³ , and the MFR was 0.3 g / 10 min. Table 1 shows the properties of the obtained ethylene / α-olefin copolymer (A-1).

[0120]

[Example 1] [Production of film] Ethylene / α- obtained in Production Example 1
The olefin copolymer (A-1) was pelletized by an extruder and molded by an air-cooled inflation method under the following molding conditions to produce a film having a thickness of 150 μm and a width of 450 mm.

[Molding conditions] Molding machine: 90 mmφ inflation molding machine manufactured by Modern Machinery Co., Ltd. (high-pressure low-density polyethylene resin specification) Screw: L / D = 28, CR = 2.8, with intermediate mixing Is: 200 mmφ (diameter), 2.5 mm (lip width) Air ring: 2 gap type Molding temperature: 190 ° C. Take-off speed: 20 m / min The Young's modulus, dart impact strength and The low temperature characteristics of the bag were measured by the measurement method described above.

Table 2 shows the results.

[0123]

Production Example 2 Preparation of Ethylene / α-Olefin Copolymer Composition (A-4)
An ethylene / α-olefin copolymer (A) was prepared in the same manner as in Production Example 1 except that the production density and MFR were adjusted as shown in Table 1.
-2) and (A-3) were obtained. [Preparation of Composition] The ethylene / α-olefin copolymers (A-2) and (A-3) obtained in Production Example 2 were mixed in a weight ratio (A
-2) / (A-3) = 60/40 and melt-kneaded to obtain an ethylene / α-olefin copolymer composition (A-4).
Ethylene / α-olefin copolymer (A-2), (A-
Table 1 shows the characteristics of 3) and (A-4).

[0124]

Example 2 The ethylene / α-olefin copolymer composition (A-4) obtained in Production Example 2 was molded by the air-cooled inflation method under the same molding conditions as in Example 1, and the thickness was 150 μm. And a film having a width of 450 mm. The resulting film was measured for Young's modulus, dart impact strength, and low-temperature characteristics of the bag.

Table 2 shows the results.

[0126]

Production Example 3 Production of Ethylene / α-Olefin Copolymer (A-5) In the preparation of the catalyst component in Production Example 1, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was replaced with a toluene solution. Of toluene, bis (1,3-n-butylmethylmethylcyclopentadienyl) zirconium dichloride (Zr = 34.0 mmol / l) and toluene of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride Solution (Zr = 28.4)
(mmol / liter) 2 liters, density, MFR
Was prepared in the same manner as in Production Example 1 except that it was prepared as shown in Table 1 to obtain an ethylene / α-olefin copolymer (A-5).

[0127]

Example 3 The ethylene / α-olefin copolymer (A-5) obtained in Production Example 3 was molded by the air-cooled inflation method under the same molding conditions as in Example 1 to obtain a wall thickness of 150.
A film having a thickness of 450 μm and a width of 450 mm was produced. The resulting film was measured for Young's modulus, dart impact strength, and low-temperature characteristics of the bag.

Table 2 shows the results.

[0129]

Production Example 4 Preparation of ethylene / α-olefin copolymer composition (A-6)
Production Example 1 was repeated except that bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was used instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride.
An ethylene / α-olefin copolymer (a-6) produced in the same manner as in Production Example 1 except that the titanium-based catalyst component described in JP-A-54289 is used and triethylaluminum is used instead of methylaluminoxane. (Density; 0.915
g / cm ³ ) and the ethylene / α-olefin copolymer (b-
6) (Density: 0.933 g / cm ³ ) was obtained. The obtained ethylene / α-olefin copolymer (a-6) and (b-6) are melt-kneaded so that the weight ratio (a-6) / (b-6) becomes 60/40. Ethylene / α-olefin copolymer composition (A
-6) was prepared.

Table 1 shows the properties of the obtained ethylene / α-olefin copolymer composition (A-6).

[0131]

Comparative Example 1 The ethylene / α-olefin copolymer composition obtained in Production Example 4 was molded by the air-cooled inflation method under the same molding conditions as in Example 1, and the thickness was 150 μm.
m, a film having a width of 450 mm was produced. The resulting film was measured for Young's modulus, dart impact strength, and low-temperature characteristics of the bag.

Table 2 shows the results.

[0133]

[Table 1]

[0134]

[Table 2]

[0135]

Production Example 5 An ethylene α-olefin copolymer (A) was prepared in the same manner as in Production Example 1 except that the production density and MFR of the ethylene / α-olefin copolymer (A-7) were adjusted as shown in Table 3. −
7) was obtained.

Table 3 shows the properties of the obtained ethylene / α-olefin copolymer (A-7).

[0137]

Example 4 As the component [b-2] constituting the ethylene / α-olefin copolymer composition, the 1-butene content was 3.3.
Mol% of ethylene / 1-butene random copolymer (B-
1) was prepared. Table 3 shows the properties of the ethylene / 1-butene random copolymer (B-1).

The ethylene / α-olefin copolymer (A-7) obtained in Production Example 5 was pelletized by an extruder,
After melt-kneading the ethylene / α-olefin copolymer (A-7) and the component [b-2] at the mixing ratios shown in Table 5, molding was performed by the air-cooled inflation method under the following molding conditions.
A film having a thickness of 30 μm was produced.

[Molding conditions] Screw: L / D = 2.8, C / R = 2.8, Dice with intermediate mixing section: 200 mmφ (diameter), 2.5 mm (lip width) Air ring: 2 gaps Type Molding temperature: 190 ° C. Take-off speed: 20 m / min For the film obtained as above,
The dirt impact strength and Elmendorf tear strength were measured by the methods described above, and the smoothness of the film surface was visually observed and evaluated.

Table 4 shows the results.

[0141]

[Production Example 6] An ethylene / α-olefin copolymer (A) was produced in the same manner as in Production Example 1 except that the production density and MFR of the ethylene α-olefin copolymer (A-8) were adjusted as shown in Table 3.
-8) was obtained. Table 3 shows the properties of the obtained ethylene / α-olefin copolymer (A-8).

[0142]

Example 5 The ethylene / α-olefin copolymer (A-8) obtained in Production Example 6 was pelletized with an extruder as the component [a-2]. After melt-kneading at a mixing ratio shown in Example 4, molding was performed by air-cooled inflation under the same molding conditions as in Example 4 to produce a film having a thickness of 30 µm. The resulting film was measured for haze, dart impact strength and Elmendorf tear strength by the above-described methods, and evaluated by visually observing the smoothness of the film surface.

Table 4 shows the results.

[0144]

Example 6 The mixture of the ethylene / α-olefin copolymer (A-8) obtained in Production Example 6 and the component [b-2] was melt-kneaded at the mixing ratio shown in Table 4, and then mixed. Molding was performed by the air-cooled inflation method under the same molding conditions as in Example 4 to produce a film having a thickness of 30 μm. The resulting film was measured for haze, dart impact strength and Elmendorf tear strength by the above-described methods, and evaluated by visually observing the smoothness of the film surface.

Table 4 shows the results.

[0146]

Production Example 7 Production of Ethylene α-Olefin Copolymer (A-9) In the preparation of the catalyst component of Production Example 1, instead of the toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride toluene solution
(Zr; 28.1 mmol / L) 3.2 L and bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride toluene solution (Zr; 34.0 mmol / L) 10.7 L Except for using, a polymerization catalyst was obtained in the same manner as in Production Example 1.

[Polymerization] An ethylene / α-olefin copolymer (A-9) was prepared in the same manner as in Production Example 1 except that the density and MFR were adjusted as shown in Table 3, and the above-mentioned polymerization catalyst was used. Was. The obtained ethylene / α-olefin copolymer (A
Table 3 shows the characteristics of -9).

[0148]

Example 7 The ethylene / α-olefin copolymer (A-9) obtained in Production Example 7 was pelletized with an extruder.
After melt-kneading with the above-mentioned component [b-2] at a mixing ratio shown in Table 4, molding was performed by an air-cooled inflation method under the same molding conditions as in Example 4 to produce a film having a thickness of 30 µm. The resulting film was measured for haze, dart impact strength and Elmendorf tear strength by the above-described methods, and evaluated by visually observing the smoothness of the film surface.

Table 4 shows the results.

[0150]

Comparative Example 2 Ethylene / 1-butene random copolymer ([b
Using the (-2) component), molding was performed by an air-cooled inflation method under the same molding conditions as in Example 4 to produce a film having a thickness of 30 μm. The resulting film was measured for haze, dart impact strength and Elmendorf tear strength by the above-described methods, and evaluated by visually observing the smoothness of the film surface.

Table 4 shows the results.

[0152]

[Production Example 8] In Production Example 1, a titanium-based catalyst component described in JP-B-63-54289 was used in place of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, and methylaluminoxane was used. The same procedure as in Production Example 1 was repeated except that the comonomer content was adjusted as shown in Table 3 using triethylaluminum.
An olefin copolymer (A-10) was produced. Table 3 shows the properties of the obtained ethylene / α-olefin copolymer (A-10).

[0153]

Comparative Example 3 The ethylene / α-olefin copolymer (A-10) obtained in Production Example 8 was pelletized with an extruder.
After melt-kneading with the component [b-2] at a mixing ratio shown in Table 4, molding was performed by an air-cooled inflation method under the same molding conditions as in Example 4 to produce a film having a thickness of 30 µm. The resulting film was measured for haze, dart impact strength and Elmendorf tear strength by the above-described methods, and evaluated by visually observing the smoothness of the film surface.

Table 4 shows the results.

[0155]

[Table 3]

[0156]

[Table 4]

Claims (6)

[Claims] 1. An olefin polymerization catalyst comprising: (a) a transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton; and (b) an organoaluminum oxy compound. A copolymer obtained by copolymerizing ethylene and an α-olefin having 6 to 20 carbon atoms, wherein (i) the density is in the range of 0.918 to 0.935 g / cm ³ , and (ii) 19
The melt flow rate (MFR (g / 10 minutes)) at 0 ° C. and a load of 2.16 kg is in the range of 0.05 to 2.0 g / 10 minutes, and (iii) the decane-soluble component amount ratio (W ( Weight%)) and density (d (g / cm ³ )) satisfy the relationship expressed by W <80 × exp (-100 (d-0.88)) + 0.1, and (iv) 190 ° C. of the molten polymer. Index (FI (1 / sec)) defined by the shear rate at which the shear stress reaches 2.4 × 10 ⁶ dyne / cm ²
And the melt flow rate (MFR (g / 10 min)) satisfy the relationship of FI> 75 × MFR, and (v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10
A) an ethylene / α-olefin copolymer [A] ^represented by the ^formula: MT> 2.2 × MFR- ^0.84 . 2. The average value of the number of branches on the high molecular weight side of the ethylene / α-olefin copolymer [A] determined by GPC-IR is B1, and the average value of the number of branches on the low molecular weight side is B2. The ethylene-based resin packaging film according to claim 1, which satisfies a relationship represented by? B2. 3. An olefin polymerization catalyst comprising: (I) (a) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton; and (b) an organoaluminum oxy compound. A copolymer obtained by copolymerizing ethylene and an α-olefin having 6 to 20 carbon atoms, wherein (i) the density is in the range of 0.900 to 0.935 g / cm ³ , (ii) 19
The melt flow rate (MFR (g / 10 minutes)) at 0 ° C. and a load of 2.16 kg is in the range of 0.01 to 1.0 g / 10 minutes, and (iii) the decane-soluble component amount ratio (W ( Weight%)) and density (d (g / cm ³ )) satisfy the relationship expressed by W <80 × exp (-100 (d-0.88)) + 0.1, and (iv) 190 ° C. of the molten polymer. Index (FI (1 / sec)) defined by the shear rate when the shear stress reaches 2.4 × 10 ⁶ dyne / cm ²
And the melt flow rate (MFR (g / 10 min)) satisfy the relationship of FI> 75 × MFR, and (v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10
) ^Satisfies the relationship expressed by MT> 2.2 × MFR ^-0.84 , and (vi) a differential scanning calorimeter (DS)
The ethylene / α-olefin copolymer [a-1] in which the temperature (Tm (° C.)) at the maximum peak position in the endothermic curve measured by C) and the density (d) satisfy the relationship represented by Tm <400d-250. : 50 to 99 parts by weight, and [II] ethylene homopolymer or ethylene and carbon number 3
(I) a density in the range of 0.935 to 0.975 g / cm ³ , and (ii) a copolymer having an α-olefin of
Ethylene containing 1 to 50 parts by weight of a high-density polyethylene [b-1] having a melt flow rate (MFR (g / 10 min)) at 0 ° C. and a load of 2.16 kg within a range of 0.1 to 100 g / min. -An ethylene-based resin packaging film comprising the α-olefin copolymer composition [B]. 4. The ethylene system according to claim 1, wherein (A) the Young's modulus is 4000 kg / cm ² or more, and (B) the dirt impact strength is 55 kg / cm or more. Resin packaging film. 5. An olefin polymerization catalyst comprising (I) (a) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (b) an organoaluminum oxy compound. A copolymer obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms, wherein (i) the density is in the range of 0.880 to 0.925 g / cm ³ , (ii) 19
The melt flow rate (MFR (g / 10 minutes)) at 0 ° C. and a load of 2.16 kg is in the range of 0.01 to 5.0 g / 10 minutes, and (iii) the amount of decane-soluble components at room temperature (W ( Weight%)) and density (d (g / cm ³ )) satisfy the relationship expressed by W <80 × exp (-100 (d-0.88)) + 0.1, and (iv) 190 ° C. of the molten polymer. Index (FI (1 / sec)) defined by the shear rate when the shear stress reaches 2.4 × 10 ⁶ dyne / cm ²
And the melt flow rate (MFR (g / 10 minutes)) satisfy the relationship of FI> 75 × MFR, and (v) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10
) ^Satisfying the following relationship: MT> 2.2 × MFR ^-0.84 , ethylene-α-olefin copolymer [a-2]: 1 to 50 parts by weight, [II] ethylene and carbon number 4 A copolymer obtained by copolymerizing an α-olefin of from 10 to 10,
(i) the density is in the range of 0.920 to 0.945 g / cm ³ ,
i) The melt flow rate (MFR (g / 10 min)) at 190 ° C. under a load of 2.16 kg is in the range of 0.1 to 10 g / min, and (iii) the weight average molecular weight (Mw) and number average molecular weight (M
n), an ethylene / α-olefin copolymer composition [C] containing 50 to 99 parts by weight of an ethylene copolymer [b-2] having an Mw / Mn in the range of 3 to 6. A film for packaging made of an ethylene-based resin, comprising: 6. The ethylene resin according to claim 5, wherein (B) the dart impact strength is 250 kg / cm or more, and (C) the Elmendorf tear strength in the longitudinal direction is 60 kg / cm or more. Packaging film.