JPH09235424A - Ethylene copolymer composition for inflation film and inflation film made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene copolymer composition which has excellent moldability and can give inflation films excellent in transparency and mechanical strengths by mixing polymers having specified properties with each other. SOLUTION: This composition comprises 30-85wt.% ethylene/α-olefin copolymer (A) having a density (d) of 0.880-0.940 and an intrinsic viscosity of 2.2-8 (in decalin at 135 deg.C) and satisfying the relationship: Tm ( deg.C)<400×d-250 (wherein Tm is the temperature at which the maximum peak appears in an endothermic curve as determined by differential scanning calorimetry) and 15-70wt.% ethylene/3-20C α-olefin copolymer (B) having a density (d) of 0.900-0.970 and an intrinsic viscosity of 0.3-1.5 and satisfying the relationship: Tm <400×d-250 and satisfies the requirements: the ratio of the density of component A to that of component B is below 1, and the ratio of the intrinsic viscosity of component A to that of component B is 4 or above.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an ethylene copolymer composition for blown film and an blown film comprising the composition, and more specifically to a film excellent in moldability, transparency and mechanical strength. The present invention relates to an ethylene-based copolymer composition for an inflation film, and an inflation film comprising the composition.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The ethylene copolymer has different required properties depending on the molding method and the application. For example, when molding blown film at a high speed, there is no fluctuation or breakage of bubbles, and in order to perform high-speed molding stably, an ethylene copolymer with a large melt tension relative to its molecular weight should be selected. Must. Similar properties are required to prevent sagging or tearing in blow molding or to minimize width reduction in T die molding. In addition, in such extrusion molding, it is necessary that the stress of the ethylene-based copolymer under extrusion under high shear is small from the economical viewpoint such as quality improvement of the molded article and reduction of power consumption during molding.

By the way, a method of improving the moldability by improving the melt tension and expansion ratio (die swell ratio) of an ethylene polymer obtained by using a Ziegler type catalyst, particularly a titanium-based catalyst, is disclosed in Japanese Patent Laid-Open No. 56-90810. Japanese Patent Laid-Open No. 60-106806 and the like. However, in general, an ethylene-based polymer obtained by using a titanium-based catalyst, particularly a low-density ethylene-based copolymer, has a wide composition distribution and has a problem that a molded product such as a film is sticky.

Among the Ziegler-type catalyst systems, it is known that the ethylene-based polymer obtained by using the metallocene catalyst system has an advantage that the composition distribution is narrow and a molded article such as a film is less sticky. However, an ethylene polymer obtained by using a zirconocene compound composed of a cyclopentadienyl derivative as a catalyst has a narrow molecular weight distribution, and thus there is a concern that the fluidity during extrusion molding is poor.

Therefore, if an ethylene polymer having a small stress in the high shear region, an excellent mechanical strength and a narrow composition distribution appears, its industrial value is extremely high.
As a result of intensive studies in view of such a situation, the present inventors have found that two types of ethylene / α- having different densities and intrinsic viscosities are obtained.
The ethylene-based copolymer composition obtained by blending the olefin copolymer has excellent film formability,
Moreover, it was found that the obtained film was excellent in transparency and mechanical strength.

Further, when a crystal nucleating agent was added to such an ethylene-based copolymer composition, the obtained film was found to be further excellent in transparency and mechanical strength, and the present invention was completed. .

[0007]

An object of the present invention is to provide an ethylene-based copolymer composition for blown film, which is capable of producing a film excellent in moldability, transparency, and mechanical strength, and a blown film comprising the composition. The purpose is to do.

[0008]

SUMMARY OF THE INVENTION Ethylene Copolymer Composition According to the Invention
Is (A) ethylene and α-olefin having 3 to 20 carbon atoms.
It is a copolymer with vinyl, and has (A-i) density of 0.880 to 0.940 g / cm^ThreeRange of
The (A-ii) 135 ° C, intrinsic viscosity measured in decalin
It is in the range of 2.2 to 8 dl / g, and (A-iii) shows an endothermic curve measured by a differential scanning calorimeter.
Temperature (Tm (° C)) and density (d)
(G / cm^Three)) Satisfies the relationship represented by Tm <400 × d-250, and (A-iv) melt tension (MT (g)) at 190 ° C.
Routh flow rate (MFR (g / 10 minutes)) is MT ≤ 2.2 x MFR^-0.84 And the shear stress at 190 ° C. of the (Av) molten polymer is 2.
4 × 10⁶dyne / cm ^TwoDefined by the shear rate when reaching
Liquidity index (FI (1 / sec))
Toflow rate (MFR (g / 10 min)) and FI <150 × MFR, and (A-vi) decane-soluble matter (W (wt%)) at 23 ° C.
And density (d (g / cm ^Three)) And the ethylene / α-olefin copolymerization weight satisfying the relationship of W <80 × exp (−100 (d−0.88)) + 0.1
Combined: 30 to 85% by weight, (B) ethylene, and α-olefin having 3 to 20 carbon atoms
(B-i) having a density of 0.900 to 0.970 g / cm 2^ThreeRange of
The (B-ii) has an intrinsic viscosity measured in decalin at 135 ° C.
In the range of 0.3 to 1.5 dl / g, (B-iii) the endothermic curve measured by a differential scanning calorimeter
Temperature (Tm (° C)) and density (d)
(G / cm^Three)) Satisfies the relationship of Tm <400 × d-250, and (B-iv) decane-soluble matter (W (wt%)) at 23 ° C.
And density (d (g / cm ^Three)) And MFR ≦ 10g / 10
When minutes, W <80 × exp (−100 (d−0.88)) + 0.1 MFR> 10 g / 10 minutes, W <80 × (MFR-9)^0.26× exp (-100 (d-
0.88)) + 0.1 ethylene / α-olefin copolymer weight satisfying the relationship
Coalescence: 15-70 wt% ethylene copolymer
A composition comprising: (i) the above ethylene / α-olefin
Density of copolymer (A) (d_A) And the above ethylene / α-
Density of olefin copolymer (B) (d_B) And (d_A
/ D_B) Is less than 1, and (ii) the above ethylene / α-o
Intrinsic viscosity of reffin copolymer (A) ([η_A]) And above
Intrinsic viscosity of ethylene / α-olefin copolymer (B)
([Η_B]) Ratio ([η_A] / [Η_B]) Is 4 or more
And (iii) the composition has a density of 0.890 to 0.95.
5g / cm^Three, (Iv) 190 ° C, 2.16
The melt flow rate of the composition under a kg load is 0.
In the range of 1-2 g / 10 min, (v) of the molten composition
Shear stress at 190 ℃ is 2.4 × 10⁶dyne / cm
^TwoThe fluidity index defined by the shear rate when reaching
Cus (FI (1 / sec)) and melt flow rate (MF
R (g / 10 min)) and FI> 150 × MFR, and (vi) decane at 23 ° C.
Soluble content (W (% by weight)) and density (d (g / cm^Three))When
Satisfies the relationship of W <80 × exp (−100 (d−0.88)) + 0.1, and (vii) melts at 190 ° C.
The melt tension is characterized by being 1.5 g or more.

The ethylene copolymer composition for blown film according to the present invention contains 0.001 to 5 parts by weight of a crystal nucleating agent based on 100 parts by weight of the ethylene copolymer composition.
You may mix | blend in the quantity of a weight part.

In the present invention, the crystal nucleating agent is preferably a metal salt of rosin acid, more preferably at least one rosin acid selected from the group consisting of natural rosin, modified rosin and purified products thereof. More preferably, it is at least one rosin acid selected from dehydroabietic acid, dihydroabietic acid or dihydropimaric acid, or a derivative thereof, and a rosin acid represented by the following formula (ia) and the following formula (i-a) Particularly preferred is at least one rosin acid selected from rosin acids represented by i-b).

[0011]

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(In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different). Also,
In the present invention, the metal salt of rosin acid is preferably at least one metal salt of rosin acid selected from the group consisting of sodium salt, potassium salt and magnesium salt of rosin acid.

The ethylene-based copolymer composition for an inflation film of the present invention can provide an inflation film which is excellent in moldability at the time of film formation and is excellent in transparency and mechanical strength.

The blown film according to the present invention is characterized by comprising the above ethylene copolymer composition. The blown film of the present invention is excellent in transparency and mechanical strength.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The ethylene-based copolymer composition for blown film and the blown film comprising the composition according to the present invention will be specifically described below.

The ethylene copolymer composition according to the present invention comprises an ethylene / α-olefin copolymer (A) as described below and an ethylene / α-olefin copolymer (B) as described below. ing. The ethylene copolymer composition according to the present invention is an ethylene / α-olefin copolymer (A) and an ethylene / α-olefin copolymer (B).
In addition to and, a crystal nucleating agent (D) may be contained.

Ethylene / α-olefin copolymer (A) The ethylene / α-olefin copolymer (A) used in the present invention is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. It is united.

In this ethylene / α-olefin copolymer, the constitutional unit derived from ethylene is 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 70% by weight.
The constitutional unit which is present in an amount of ˜96 wt% and is derived from an α-olefin having 3 to 20 carbon atoms is 1 to 45 wt%, preferably 2-35 wt%, more preferably 4-3.
It is present in a proportion of 0% by weight.

Here, as the α-olefin having 3 to 20 carbon atoms, propylene, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
Examples include octadecene and 1-eicosene.

The ethylene / α-olefin copolymer (A) has a density of 0.880 to 0.940 g / c.
m ³ , preferably 0.890 to 0.935 g / cm ³ ,
It is more preferably in the range of 0.900 to 0.930 g / cm ³ .

The intrinsic viscosity [η _A ] measured in decalin at 135 ° C. is 2.2 to 8 dl / g, preferably 2.
3 to 7 dl / g, more preferably 2.4 to 6.5 dl / g
g.

The ethylene / α-olefin copolymer (A) used in the present invention has a temperature (Tm at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
(° C.)) and density (d (g / cm ³ )) are: Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, particularly preferably Tm <550. The relationship represented by xd-391 is satisfied.

The ethylene / α-olefin copolymer (A) used in the present invention has a melt tension (MT (g)) and a melt flow rate (MFR (g / 10 min)) of MT ≦ 2.2. × MFR- ^0.84 is satisfied.

The ethylene / α-olefin copolymer (A) used in the present invention is defined by the shear rate at which the stress of the molten polymer at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ^2. Liquidity index (FI (1 /
Sec)) and the melt flow rate (MFR (g / 10 min)) satisfy the relationship of FI <150 × MFR, preferably FI <100 × MFR, more preferably FI <75 × MFR.

The ethylene / α-olefin copolymer (A) used in the present invention has a n-decane-soluble component (W (% by weight)) and a density (d (g / cm ³ )) at 23 ° C. , W <80 × exp (−100 (d−0.88)) + 0.1, preferably W <60 × exp (−100 (d−0.88)) + 0.1, more preferably W <40 × exp ( The relationship shown by −100 (d−0.88)) + 0.1 is satisfied.

The relationship between the temperature (Tm) at the maximum peak position and the density (d) in the endothermic curve thus measured by the differential scanning calorimeter (DSC), and the n-decane-soluble content (W) and the density ( It can be said that the ethylene / α-olefin copolymer (A) having the above relationship with d) has a narrow composition distribution.

The ethylene / α-olefin copolymer (A) as described above is a transition metal compound (a) described later,
In the presence of (b) an organoaluminum oxy compound and (c) a carrier, and optionally (d) an organoaluminum compound-forming catalyst for olefin polymerization, ethylene and an α-olefin having 3 to 20 carbon atoms are added. Can be produced by copolymerizing the obtained copolymer so that the density of the obtained copolymer is 0.880 to 0.940 g / cm ³ .

Ethylene / α-olefin copolymer (B) The ethylene / α-olefin copolymer (B) used in the present invention is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. It is united.

Ethylene / α-olefin copolymer (B)
Then, the structural unit derived from ethylene is 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 7
It exists in a proportion of 0 to 96% by weight and has 3 to 20 carbon atoms.
The structural unit derived from the α-olefin of 1 to 45% by weight, preferably 2 to 35% by weight, more preferably 4 to 3% by weight.
It is present in a proportion of 0% by weight.

As the α-olefin having 3 to 20 carbon atoms, the same α-olefin as described above can be mentioned. Such an ethylene / α-olefin copolymer (B) is
The density is in the range of 0.900 to 0.970 g / cm ³ , preferably 0.915 to 0.955 g / cm ³ , and more preferably 0.920 to 0.950 g / cm ³ .

The intrinsic viscosity [η _B ] measured in decalin at 135 ° C. is 0.3 to 1.5 dl / g, preferably 0.3 to 1.3, more preferably 0.4 to 1. 2 dl
/ G.

The ethylene / α-olefin copolymer (B) used in the present invention has a temperature (Tm at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
(° C.)) and density (d (g / cm ³ )) are: Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, particularly preferably Tm <550. The relationship represented by xd-391 is satisfied.

The ethylene / α-olefin copolymer (B) used in the present invention has a n-decane-soluble component (W (% by weight)) and a density (d (g / cm ³ )) at 23 ° C. , M
When FR ≦ 10 g / 10 minutes, W <80 × exp (−100 (d−0.88)) + 0.1 Preferably, W <60 × exp (−100 (d−0.88)) + 0.1 Preferably, when W <40 × exp (−100 (d−0.88)) + 0.1 MFR> 10 g / 10 minutes, W <80 × (MFR-9) ^0.26 × exp (−100 (d-0. 88)) + 0.1.

The relationship between the temperature (Tm) at the maximum peak position and the density (d) in the endothermic curve thus measured by the differential scanning calorimeter (DSC), and the n-decane-soluble component (W) and the density ( It can be said that the ethylene / α-olefin copolymer (B) having the above relationship with d) has a narrow composition distribution.

The ethylene / α-olefin copolymer (B) as described above is a (a ') transition metal compound, (b) an organoaluminum oxy compound and (c) as described below.
In the presence of a carrier, and optionally (d) an olefin polymerization catalyst formed from an organoaluminum compound, ethylene and an α-olefin having 3 to 20 carbon atoms are added, and the resulting copolymer has a density of 0. 900-0.970 g / cm ³
It can be manufactured by copolymerizing so that

Next, the (a) transition metal compound, (b) organoaluminum oxy compound, (c) carrier and (d) organoaluminum used in the copolymerization of the ethylene / α-olefin copolymer (A). Compound, and (a ') transition metal compound, (b) organoaluminum oxy compound, (c) carrier and (d) organoaluminum compound used in copolymerization of ethylene / α-olefin copolymer (B) This will be specifically described.

Ethylene / α-olefin copolymer (A)
The (a) transition metal compound (hereinafter sometimes referred to as “component (a)”) used in the copolymerization of (1) is a transition metal compound represented by the following formula (I).

ML ¹ _x (I) In the formula, M is a transition metal atom selected from Group IVB of the Periodic Table, specifically zirconium, titanium or hafnium, preferably zirconium.

X is the valence of the transition metal atom M. L
¹ is a ligand coordinated to a transition metal atom M, and at least two of these ligands L ¹ are a cyclopentadienyl group, a methylcyclopentadienyl group, and an ethylcyclopentadienyl group. Or has 3 to 10 carbon atoms
Is a substituted cyclopentadienyl group having at least one kind of substituent selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a carbon atom having 1 to 12 carbon atoms. It is a hydrogen group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. The substituted cyclopentadienyl group has at least 1 when it has two or more substituents.
Each of the substituents may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituent is a methyl group, an ethyl group or a hydrocarbon group having 3 to 10 carbon atoms. Further, the substituted cyclopentadienyl groups coordinated to M may be the same or different.

Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, as the alkyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group, pentyl group, hexyl group, octyl group, 2-
Examples thereof include alkyl groups such as ethylhexyl group and decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group.

Of these, an alkyl group is preferable, and an n-propyl group and an n-butyl group are particularly preferable. In the present invention, the (substituted) cyclopentadienyl group coordinated to the transition metal atom is preferably a substituted cyclopentadienyl group, and more preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms. The disubstituted cyclopentadienyl group is more preferable, and the 1,3-substituted cyclopentadienyl group is particularly preferable.

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 or an alkoxy group. , An aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group,
Examples thereof include alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group and octoxy group. Are exemplified, and examples of the aryloxy group include a phenoxy group and the like.

As halogen, fluorine, chlorine, bromine,
Examples include iodine. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.

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-propylcyclo) Pentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium Dibromide, bis (n-butylcyclopentadienyl) zirconium methoxy chloride, bis (n-butylcyclopentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclo) Pentadienyl) zirconium ethoxide, bis (n-butylcyclopentadienyl) 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, and the like.
In the above example, the cyclopentadienyl ring di-substituted product includes 1,2- and 1,3-substituted products, and the tri-substituted product is 1,2,3-
And 1,2,4-substituted. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among the 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 and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are particularly preferred.

Ethylene / α-olefin copolymer (B)
The (a ′) transition metal compound (hereinafter sometimes referred to as “component (a ′)”) used in the copolymerization of is a periodic table compound containing a ligand having a cyclopentadienyl skeleton.
It is not particularly limited as long as it is a group IV transition metal compound, but a transition metal compound represented by the following general formula (II) is preferable. The transition metal compound represented by the following general formula (II) includes the transition metal compound represented by the above general formula (I).

ML ² _x (II) In the formula, M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

X is the valence of the transition metal atom M and represents the number of L coordinated to the transition metal atom. L ² is a ligand that coordinates with a transition metal, and at least one L ² is a ligand having a cyclopentadienyl skeleton.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Of these ligands coordinated to the transition metal atom, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula (II) contains two or more groups having a cyclopentadienyl skeleton,
Groups having two cyclopentadienyl skeletons are alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene groups, diphenylsilylene groups, and methylphenylsilylene groups. May be bound via a linking group such as the substituted silylene group of.

The ligand L ² other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, halogen, SO ₃
It is an R group, a halogen atom or a hydrogen atom, and specifically includes the following.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, the alkyl group is a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, etc., a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc., an aryl group, a phenyl group, a tolyl group, etc., and an aralkyl group, Examples thereof include a benzyl group and a neophyll group.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. The transition metal compound containing such a ligand having a cyclopentadienyl skeleton is more specifically represented by the following general formula (II ′) when the transition metal atom has a valence of 4, for example.

R ^a R ^b R ^c R ^d M (II ′) (wherein M is the above transition metal, R ^a is a group (ligand) having a cyclopentadienyl skeleton, and R ^b , R ^c
And R ^d is a group having a cyclopentadienyl skeleton, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a SO ₃ R group, a halogen atom or a hydrogen atom. In the present invention, in the above general formula, at least two of R ^a , R ^b , R ^c and R ^d , for example, R ^a and R ^b.
A metallocene compound in which is a group (ligand) having a cyclopentadienyl skeleton is preferably used. The groups having these cyclopentadienyl skeletons may be bonded via the same bonding group as described above. In this case, R ^c and R ^d are a group having a cyclopentadienyl skeleton, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R, a halogen atom or hydrogen. Is an atom.

Specific examples of transition metal compounds in which M is zirconium will be shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5, 6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) Zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride , Dimethyl silylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), dimethyl silane Renbis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

It is also possible to use a compound in which zirconium is replaced with titanium or hafnium in the zirconium compound as described above. These general formulas (I
Among the transition metal compounds represented by I), the transition metal compounds exemplified as the transition metal compound (a) are preferably used, and among them, those described as the compounds particularly preferably used as the transition metal compound (a) are It is desirable to use.

Further, the transition metal compound (a) used for producing the ethylene / α-olefin copolymer (A) and the transition metal compound (a) used for producing the ethylene / α-olefin copolymer (B). It is desirable to use a compound which is the same as the transition metal compound with ').

The organoaluminum oxy compound (b) (hereinafter sometimes referred to as "component (b)") used for producing the ethylene / α-olefin copolymers (A) and (B) is conventionally known. Benzene-soluble aluminoxane may be used, or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807 may be used.

Conventionally known aluminoxane is obtained by bringing an organoaluminum compound as described below into contact with water such as adsorbed water, crystallization water, ice, or steam, or an organoaluminum compound as described below. It can be produced by reacting tin oxide.

Ethylene / α-olefin copolymer
Particulate carrier (c) used for producing (A) and (B)
Is an inorganic or organic compound having a particle size of 10 to 10.
300 μm, preferably 20-200 μm granular
A finely divided solid is used. Of these, an inorganic carrier
Is preferably a porous oxide, specifically, SiO 2_Two,
Al _TwoO_Three, MgO, ZrO_Two, TiO_Two, B_TwoO_Three, C
aO, ZnO, BaO, ThO_TwoEtc. or a mixture of these
Object, eg SiO_Two-MgO, SiO_Two-Al_TwoO_Three, Si
O_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr_TwoO_Three,
SiO_Two-TiO_Two-MgO etc. can be illustrated. This
SiO in these_TwoAnd Al_TwoO_ThreeSelected from the group consisting of
Preference is given to those containing at least one spilled ingredient as the main ingredient.
New

The 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 , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li
_It may contain carbonate, sulfate, nitrate and oxide components such as ₂ O.

The type of the particulate carrier (c) is
And the properties differ depending on the production method, but are preferably used in the present invention.
The particulate carrier to be used has a specific surface area of 50 to 1000 m.
^Two/ G, preferably 100 to 700 m^Two/ G, which is fine
Pore volume 0.3-2.5 cm ^ThreeDesired to be / g
Yes. The fine particle carrier may be 100 to 1000 as needed.
℃, preferably 150-700 ℃
You.

Further, the fine particle carrier has a particle size of 1
Granular or particulate solids of organic compounds having a size of 0 to 300 μm can be mentioned. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include (co) polymers containing α-olefins having 2 to 14 carbon atoms such as pentene as a main component, or polymers or copolymers containing vinylcyclohexane or styrene as a main component.

Ethylene / α-olefin copolymer (A)
The olefin polymerization catalyst used in the production of (a) is formed from the above-mentioned component (a), component (b) and (c) particulate carrier, but (d) an organoaluminum compound may be used if necessary.

The olefin polymerization catalyst used in the production of the ethylene / α-olefin copolymer (B) is formed of the above-mentioned components (a '), (b) and (c) as a fine particle carrier. Depending on the above, (d) an organoaluminum compound may be used.

Examples of the (d) organoaluminum compound (hereinafter sometimes referred to as “component (d)”) which is used as necessary include, for example, the organoaluminum compounds 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, X 1
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, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n -Propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl 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), compounds 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, -
OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -SiR ⁶ ₃ group or -
Shows the N (R ⁷⁾ AlR ⁸ ₂ group, n is 1-2,
R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group. , Trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) Among such organoaluminum compounds, R ¹ _n A
a compound represented by l (OAlR ⁴ ₂ ) _3-n , for example Et ₂
AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) _{2 and the} like are preferable.

[0075] Among the organic aluminum compounds represented by the general formula (III) and (IV), the general formula R ¹ ₃ Al
The compound represented by is preferable, and the compound in which R ¹ is an isoalkyl group is particularly preferable.

Ethylene / α-olefin copolymer (A)
The catalyst prepared by contacting the above-mentioned component (a), component (b) and component (c) and, if necessary, component (d) is used for the production of the above.

The contact of each of the above components can be carried out in an inert hydrocarbon solvent, and specific examples of the inert hydrocarbon medium used for preparing the catalyst include propane, butane, pentane, hexane, heptane and octane. Aliphatic hydrocarbons such as decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride, chlorobenzene, dichloromethane, etc. Examples thereof include halogenated hydrocarbons and mixtures thereof.

Ethylene / α-olefin copolymer (A)
The catalyst used for the production of the component (a) as described above,
Component (b), component (c) and optionally component (d)
It may be a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of. The prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above component (a), component (b), component (c) and, if necessary, component (d). You can

As the olefin used in the prepolymerization, ethylene and the same number of carbon atoms as described above having 3 to 2 carbon atoms are used.
Examples thereof include 0-α-olefin and the like. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

The prepolymerization can be carried out 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 of at least 135 ° C. in the presence of hydrogen in the range of 0.2 to 7 dl / g,
It is desirable to produce a prepolymer such that it is preferably 0.5-5 dl / g.

The ethylene / α-olefin copolymer (A) used in the present invention can be prepared in the presence of the catalyst as described above.
Ethylene and α- with 3 to 20 carbon atoms similar to the above
It is obtained by copolymerizing with an olefin.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the slurry liquid phase. 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 butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons; 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 above catalyst usually has a concentration of transition metal atoms in the polymerization reaction system of usually 10 ^-8 to 10 ^-3 gram atom /
It is desirable to use it in an amount of liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

In the main polymerization, an organoaluminumoxy compound and / or an organoaluminum compound (d) similar to the component (b) may be added. At this time, the atomic ratio (Al / M) between the aluminum atom (Al) derived from the organic aluminum oxy compound and the organic aluminum compound and the transition metal atom (M) derived from the transition metal compound (a) is 5 to 300. , Preferably 10 to 20
The range is 0, more preferably 15 to 150.

Ethylene / α-olefin copolymer (A)
Is usually -50 to 90 ° C., preferably 0 to 80 ° C., when it is produced by the slurry polymerization method.
When producing by a gas phase polymerization method, the polymerization temperature is usually 0 to
It can be obtained by copolymerization under the conditions of 90 ° C., preferably 20 to 80 ° C.

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

Ethylene / α-olefin copolymer (B)
The catalyst prepared by contacting the above-mentioned component (a ′), component (b) and component (c) and, if necessary, component (d) is used for the production of the above.

The contact of the above components can be carried out in the same inert hydrocarbon solvent as described above. The catalyst used for producing the ethylene / α-olefin copolymer (B) is present in the presence of the above-mentioned component (a ′), component (b), component (c) and, if necessary, component (d). It may be a prepolymerization catalyst obtained by preliminarily polymerizing an olefin. The prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above-mentioned component (a ′), component (b), component (c) and optionally component (d). be able to.

As the olefin used in the prepolymerization, ethylene and the same number of carbon atoms as described above having 3 to 2 carbon atoms are used.
Examples thereof include 0-α-olefin and the like. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

The prepolymerization can be carried out 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 of at least 135 ° C. in the presence of hydrogen in the range of 0.2 to 7 dl / g,
It is desirable to produce a prepolymer such that it is preferably 0.5-5 dl / g.

The ethylene / α-olefin copolymer (B) used in the present invention can be prepared in the presence of the catalyst as described above.
Ethylene and α- with 3 to 20 carbon atoms similar to the above
It is obtained by copolymerizing with an olefin.

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

As the inert hydrocarbon solvent used in the slurry polymerization, the same ones as mentioned above can be mentioned. 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 above-mentioned catalyst usually has a concentration of the transition metal atom in the polymerization reaction system of usually 10 ^-8 to 10 ^-3 g atom / min.
It is desirable to use it in an amount of liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

In the main polymerization, the same organoaluminumoxy compound and / or organoaluminum compound (d) as the component (b) may be added. At this time, the atomic ratio (Al / M) between the aluminum atom (Al) derived from the organoaluminum oxy compound and the organoaluminum compound and the transition metal atom (M) derived from the transition metal compound (a ′) is 5 to 300, preferably 10-20
The range is 0, more preferably 15 to 150.

When the ethylene / α-olefin copolymer (B) used in the present invention is produced by the slurry polymerization method, the polymerization temperature is usually -30 to 100 ° C, preferably 20 to 90 ° C. When producing by a gas phase polymerization method, the polymerization temperature is usually 20 to 120 ° C., preferably 40 to 120 ° C.
It can be obtained by copolymerization under the conditions of 100 ° C.

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

[Ethylene Copolymer Composition] The ethylene copolymer composition of the present invention comprises the ethylene / α-olefin copolymer (A) and the ethylene / α-olefin copolymer (B). And the ethylene / α-olefin copolymer (A) is 30 to 95% by weight, preferably 45 to 90%.
The ethylene / α-olefin copolymer (B) is contained in an amount of 5 to 70% by weight, preferably 10 to 55% by weight.

The ethylene / α-olefin copolymers (A) and (B) are the density (d _A ) of the ethylene / α-olefin copolymer ( _A ) and the ethylene / α-olefin copolymer (B). the ratio between the density (d _B) of (d _a / d _B) is 1
Less than, preferably 0.930 to 0.999 are used in combination. Further, the intrinsic viscosity [η _A ] of the ethylene / α-olefin copolymer (A) and the intrinsic viscosity [η _B ] of the ethylene / α-olefin copolymer (B).
And the ratio ([η _A ] / [η _B ]) is 4 or more, preferably 4
˜15, more preferably 4.5 to 10 are used in combination.

Such an ethylene copolymer composition is
Density 0.890~0.955g / cm ^3, preferably in the range of 0.900~0.950g / cm ^3, 19
MFR at 0 ° C and 2.16 kg load is 0.01 to 2
g / 10 minutes, preferably 0.05 to 1.0 g / 10 minutes.

The ethylene copolymer composition according to the present invention has a stress of 2.4 × 10 at 190 ° C. of the molten polymer.
^The fluidity index (FI (1 / sec)) and the melt flow rate (MFR (g / 10 min)) defined by the shear rate when reaching ⁶ dyne / cm ² are FI> 150 × MFR, preferably FI> 180 × MFR More preferably, the relationship represented by FI> 200 × MFR is satisfied.

The ethylene copolymer composition according to the present invention has a decane-soluble content (W (wt%)) and a density (d (g / cm ³ )) at 23 ° C. of W <80 × exp ( −100 (d−0.88)) + 0.1 Preferably W <60 × exp (−100 (d−0.88)) + 0.1 More preferably W <40 × exp (−100 (d-0. 88)) + 0.1.

The ethylene copolymer composition according to the present invention has a melt tension at 190 ° C. of 1.5 g or more, preferably 2 to 20 g, more preferably 2.5 to 15 g. The ethylene-based copolymer composition of the present invention, within the range that does not impair the object of the present invention, a weather resistance stabilizer, a heat resistance stabilizer,
Antistatic agent, anti-slip agent, anti-blocking agent,
If necessary, additives such as an antifogging agent, a lubricant, a pigment, a dye, a crystal nucleating agent, a plasticizer, an antiaging agent, a hydrochloric acid absorbent, and an antioxidant may be added.

The ethylene-based copolymer composition of the present invention comprises
A crystal nucleating agent is preferably blended, and conventionally known various nucleating agents for olefins are used without limitation. Of these, crystal nucleating agents such as aromatic phosphate salts, benzylidene sorbitol, and metal salts of rosin acid listed below are preferable.

[0106]

Embedded image

(In the formula, R ⁴ represents an oxygen atom, a sulfur atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ⁵ and R ⁶ may be the same or different and may be R ^{5 s} , R ^{6 s,} or R ⁵ and R ⁶ may be bonded to form a ring, and M is 1 ~ Represents a trivalent metal atom, and n is an integer of 1 to 3.) Specifically, sodium-2,2'-methylene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2 ' -Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-
6-t-butylphenyl) phosphate, lithium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-
t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6 -t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4, 6-di-t-butylphenyl) phosphate],
Magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2, 2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2 , 2'-t-octylmethylene-bis (4,6-
Di-t-butylphenyl) phosphate, calcium
Bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) ) Phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-
Butylphenyl) phosphate], sodium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-
6-t-butylphenyl) phosphate, sodium (4,
4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-
Di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 ' -
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6
-Di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfell) phosphate] and aluminum-tris [2,
2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof. Particularly preferred is sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate.

[0108]

Embedded image

(In the formula, R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, M represents a metal atom having a valence of 1 to 3, and n is an integer of 1 to 3.) Specifically, sodium-bis (4-t-butylphenyl)
Phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-
Octylphenyl) phosphate, potassium-bis (4
-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium
-Bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and mixtures of two or more thereof can do. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferable.

[0110]

Embedded image

(In the formula, R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) Specifically, 1,3,2,4-dibenzylidene sorbitol, 1,
3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3- p-ethylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4
-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol,
1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,
3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,
2,4-di (pn-propylbenzylidene) sorbitol, 1,
3,2,4-di (pi-propylbenzylidene) sorbitol,
1,3,2,4-di (pn-butylbenzylidene) sorbitol,
1,3,2,4-di (ps-butylbenzylidene) sorbitol,
1,3,2,4-di (pt-butylbenzylidene) sorbitol,
1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p- Ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4- p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-
Methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and these And a mixture of two or more of 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di ( p-Ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof Is preferred.

The metal salt of rosin acid used as a crystal nucleating agent in the present invention means a reaction product of rosin acid and a metal compound. As rosin acid, natural rosin such as gum rosin, tall oil rosin and wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α,
Various modified rosins such as β-ethylenically unsaturated carboxylic acid modified rosin; purified products of the above-mentioned natural rosin, purified rosins, and the like. The unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin includes, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid. , Methacrylic acid and the like. Among these, at least one rosin acid selected from the group consisting of natural rosin, modified rosin, purified product of natural rosin, and purified product of modified rosin is preferable. Here, rosin acid is a plurality of resin acids selected from pimaric acid, sandaracopimaric acid, parastophosphoric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid, and the like. Contains.

Examples of the metal compound which reacts with the rosin acid to form a metal salt include compounds having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin acid. Specific examples thereof include chlorides, nitrates, acetates, sulfates, carbonates, oxides and hydroxides of the above metals.

The crystal nucleating agent used in the present invention is a metal salt of at least one rosin acid selected from dehydroabietic acid, dehydroabietic acid derivatives, dihydroabietic acid, dihydroabietic acid derivatives, dihydropimaric acid and dihydropimaric acid derivatives. Preferably there is.

In the present invention, the rosin acid is represented by the following formula (i
at least one rosin acid selected from rosin acid represented by formula (a) and a rosin acid represented by the following formula (i-b): [compound (i-a)] It is preferable.

[0116]

[Chemical 6]

In formula (i-a) and formula (i-b), R ¹ and R
² and R ³ may be the same or different from each other;
It is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
Examples include alkyl groups having 1 to 8 carbon atoms such as tert-butyl, pentyl, heptyl, and octyl, and these groups may have a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group, and a halogen. .

Specific examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl. These groups include hydroxyl group, carboxyl group, alkoxy group, halogen and the like. It may have a substituent.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. These groups are substituents such as a hydroxyl group, a carboxyl group, an alkoxy group, and a halogen. May have.

Such compounds (ia) and compounds
In (i-b), R¹, R^TwoAnd R^ThreeEach
Preferred are rosin acids that are the same or different alkyl groups.
R ¹Is an i-propyl group, R^TwoAnd R^ThreeBut
More preferred is a rosin acid that is a chill group. Such a logic
The metal salt of acid is especially effective in improving the crystallization rate of crystalline resins.
The fruit is excellent.

Specific examples of the compound (i-a) include dehydroabietic acid and the like, and specific examples of the compound (i-b) include dihydroabietic acid and the like.
Of such compounds (i-a) and compounds (i-b), for example, the rosin acid represented by the formula (i-a) disproportionates natural rosins such as gum rosin, tall oil rosin, and wood rosin. Alternatively, it is obtained by dehydrogenation and then purification. In addition, natural rosin is usually a plurality of resin acids such as pimaric acid, sandaracopimaric acid, parastophosphoric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, and tetrahydroabietic acid. Seed included.

Examples of the metal salt of compound (i-a) include compounds represented by the following formula (ii-a) [compound (ii-a)], and examples of the metal salt of compound (i-b) include , The following formula (ii-b)
A compound [compound (ii-b)] represented by

[0124]

Embedded image

In the formulas (ii-a) and (ii-b), R ¹ and R ²
And R ³ are the same as the above formula (i-a) and formula (i-b). M is a monovalent metal ion such as lithium, sodium, potassium, rubidium and cesium; and divalent metal such as beryllium, magnesium, calcium, strontium, barium and zinc. Metal ions; trivalent metal ions such as aluminum. Of these, monovalent or divalent metal ions are preferable, and sodium ions, potassium ions, and magnesium ions are more preferable.

N is the same integer as the valence of the metal ion M and is an integer of 1 to 3. Among the compounds (ii-a) and (ii-b), R ¹ , R ² and R ³ are the same or different alkyl groups, respectively, a rosin acid metal salt, or M is a monovalent or divalent group. A rosin acid metal salt which is a metal ion is preferred, and R ¹ is an i-propyl group, and R ² and R ³ are methyl groups, a rosin acid metal salt, or M is a sodium ion, potassium ion or magnesium ion. A metal salt of rosin acid is more preferable, R ¹ is an i-propyl group, and R ² and R ^{3 are}
Is a methyl group, and M is a sodium ion, potassium ion or magnesium ion, and a rosin acid metal salt is particularly preferred. Such a rosin acid metal salt is
Especially, the effect of improving the crystallization rate is excellent.

Specific examples of the compound (ii-a) include lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, and zinc dehydroabietic acid. , A metal salt of dehydroabietic acid such as aluminum dehydroabietic acid, and the like, and sodium dehydroabietic acid, potassium dehydroabietic acid, and magnesium dehydroabietic acid are preferable.

Specific examples of the compound (ii-b) include lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, and zinc dihydroabietic acid. , A metal salt of dihydroabietic acid such as aluminum dihydroabietic acid, and the like, and sodium dihydroabietic acid, potassium dihydroabietic acid, and magnesium dihydroabietic acid are preferable.

As a method for producing the above-mentioned metal salt of rosin acid, a conventionally known method can be adopted. Such metal salts of rosin acid may be used alone or in combination of two or more. As a combination of two or more kinds, a combination with a rosin acid metal salt having the same rosin acid and a different metal, a combination of rosin acid metal salts having a different rosin acid and the same metal, and a rosin acid different rosin acid and a different metal A combination of metal salts may be mentioned. Among these, at least 2 metal salts of rosin acid having the same rosin acid but different metals are used.
It is preferred to use seed-containing rosin acid metal salts.

The amount ratio of the rosin metal salt in the at least two rosin acid partial metal salts is arbitrary, but one kind of rosin metal salt in the at least two rosin acid partial metal salts can be used. Of rosin acid metal salt of 1 mol% or more, preferably 5 to 95 mol%, and other rosin acid metal salt of 99%
It is desirable to combine them so that the ratio is less than mol%, preferably 95 to 5 mol%.

The combination of at least two rosin acid partial metal salts is preferably a combination of rosin acid partial potassium salt and rosin acid partial sodium salt or rosin acid partial magnesium salt. Further, potassium rosinate is 20 mol% or more, preferably 40 to 99 mol%, more preferably 45 to 80 mol%, and rosin acid based on the total amount of the rosin acid metal salt in the two types of rosin acid partial metal salts. Sodium salt or magnesium rosin acid salt is less than 80 mol%, preferably 60 to 1 mol%, more preferably 55 to 55 mol%.
It is desirable to combine them in a proportion of 20 mol%.

Such a rosin acid partial metal salt containing at least two metals is superior in dispersibility in an ethylene copolymer as compared with a rosin acid partial metal salt containing only one metal. Among the crystal nucleating agents containing a metal salt of rosin acid as a main component, a partial metal salt of rosin acid is preferable. Here, the rosin acid partial metal salt means both a mixture of a rosin acid metal salt and an unreacted rosin acid, and a rosin acid metal salt containing no unreacted rosin acid. In this rosin acid partial metal salt, it is desirable that the rosin acid metal salt is contained in a proportion of 10 to 100 mol%, preferably 20 to 70 mol%, and particularly preferably 30 to 50 mol%.

Examples of other crystal nucleating agents include aromatic carboxylic acids, aliphatic carboxylic acids, and metal salts thereof. Specific examples include benzoic acid, cinnamic acid, aluminum benzoate, and pt-butyl. Aluminum benzoate, sodium adipate, sodium thiophenecarboxylate,
Examples thereof include sodium pyrrolecarboxylate.

Inorganic compounds such as talc can also be exemplified. Such a crystal nucleating agent is used in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the ethylene copolymer composition.

The ethylene-based copolymer composition of the present invention can be produced by a known method, for example, the following method. (1) The ethylene / α-olefin copolymer (A), the ethylene / α-olefin copolymer (B), and optionally a crystal nucleating agent are mechanically added using an extruder, a kneader or the like. How to blend into.

(2) an ethylene / α-olefin copolymer (A), an ethylene / α-olefin copolymer (B),
And a crystal nucleating agent or the like which is optionally added are dissolved in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then the solvent is removed.

(3) an ethylene / α-olefin copolymer (A), an ethylene / α-olefin copolymer (B),
And a method in which a crystal nucleating agent and the like, which is optionally added, are separately dissolved 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. Furthermore, the ethylene-based copolymer composition of the present invention uses one polymerization vessel and divides the copolymerization into two or more stages under different reaction conditions to obtain an ethylene / α-olefin copolymer (A) and an ethylene / α-olefin copolymer. -It can be produced by copolymerizing the olefin copolymer (B), and using a plurality of polymerization vessels, for example, one ethylene-α-olefin copolymer (A) is produced, Next, in another polymerization vessel, ethylene / α
-Ethylene / α-in the presence of olefin copolymer (A)
It can also be produced by copolymerizing the olefin copolymer (B). When the crystal nucleating agent is added to the ethylene copolymer composition produced in this manner, it is mechanically blended using, for example, an extruder or a kneader.

The ethylene-based copolymer composition of the present invention is processed into a film by ordinary air-cooling inflation molding, air-cooling two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooling inflation molding or the like. Obtainable.

The film obtained by processing the ethylene-based copolymer composition of the present invention is a standard bag, heavy bag, wrap film, raw lami film, sugar bag, oil packaging bag, aquatic packaging bag, food product. It is suitable for various packaging films for packaging, infusion bags, agricultural materials and the like. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester.

[0141]

The ethylene-based copolymer composition for blown film of the present invention comprises ethylene / α-olefin copolymers (A) and (B) having specific physical properties and different density and intrinsic viscosity. Since it is blended, a film having excellent moldability, mechanical strength, and transparency can be produced.

The blown film of the present invention has excellent mechanical strength and transparency.

[0143]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

Next, the definition, measurement method and molding method of the physical property values used in the present invention will be shown. (1) Granulation of ethylene-based copolymer Powdery ethylene-based copolymer 1 obtained by gas phase polymerization
To 100 parts by weight, tri (2,4-
0.05 parts by weight of di-t-butylphenyl) phosphate, and n-octadecyl-3- (4'hydroxy-3 ', 5'-di-t-butylphenyl) propionate as a heat-resistant stabilizer were added in an amount of 0.
1% by weight and 0.05 part by weight of calcium stearate as a hydrochloric acid absorbent are mixed. Thereafter, a conical taper type twin-screw extruder manufactured by Haake Co. is used and melt-extruded at a preset temperature of 180 ° C. to prepare granulated pellets. (2) Density The strand obtained at the time of measuring the melt flow rate under a load of 2.16 kg at 190 ° C. is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured with a density gradient tube. (3) Composition of copolymer Determined by ¹³ C-NMR. That is, ¹³ C of a sample prepared by uniformly dissolving about 200 mg of copolymer powder in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.
-It is determined by measuring the NMRR spectrum under the measuring conditions of a measuring temperature of 120 ° C, a measuring frequency of 25.05 MHz, a spectrum width of 1500 Hz, a pulse repetition time of 4.2 sec and a pulse width of 6 µsec. (4) Melt flow rate (MFR) ASTM D12 was prepared using granulated pellets of the copolymer.
It is measured under the conditions of 190 ° C. and a load of 2.16 kg according to 38-65T. (5) Maximum peak temperature (Tm) by DSC The measurement was performed using a DSC-7 type apparatus manufactured by Perkin Elmer. Temperature (Tm) at the maximum peak position on the endothermic curve
Packs about 5 mg of sample in an aluminum pan at 20 ° C / min.
After raising the temperature to 0 ° C and holding at 200 ° C for 5 minutes, 10
It is determined from the endothermic curve when the temperature is lowered to room temperature at ° C / min and then the temperature is raised at 10 ° C / min. (6) n-decane-soluble component (W) The n-decane-soluble component of the copolymer was measured by measuring about 3 g of the copolymer.
Add 450 ml of n-decane, melt at 145 ° C, cool to 23 ° C, remove the insoluble part of n-decane by filtration, and remove from the filtrate.
This is done by collecting the n-decane soluble part.

W = n-decane soluble part weight / (n-decane insoluble part and soluble part weight) × 100% The smaller the soluble amount of decane, the narrower the composition distribution. (7) Melt tension (MT) It is determined by measuring the stress when the molten polymer is stretched at a constant rate. That is, using a granulated pellet of the copolymer as a measurement sample, and using an MT measuring machine manufactured by Toyo Seiki Seisaku-sho, resin temperature 190 ° C., extrusion speed 15 mm
/ Min, winding speed 10 to 20 m / min, nozzle diameter 2.09
mmφ and the nozzle length is 8 mm. (8) Fluidity Index (FI) The fluidity index was determined by extruding the resin from the capillary while changing the shear rate and measuring the stress at that time. That is, using a sample similar to MT measurement, using a capillary flow characteristic tester manufactured by Toyo Seiki Seisakusho,
Resin temperature 190 ° C, shear stress range 5 × 10 ^{4 to} 3 ×
It is measured at about 10 ⁶ dyne / cm ² .

The MFR of the resin to be measured (g / 10 minutes)
Depending on the diameter of the nozzle (capillary),
Change and measure. 0.5 mm when MFR> 20 1.0 mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0 mm when 0.8 ≧ MFR (9) Intrinsic viscosity ([η]) It is a value measured at 135 ° C. using a decalin solvent.
That is, about 20 mg of granulated pellets are added to 15 ml of decalin.
And the specific viscosity η in an oil bath at 135 ° C. _spMeasure
I do. Add 5 ml of decalin solvent to this decalin solution.
After dilution with_spIs measured. This dilution
The operation was repeated twice more, and the concentration (C) was extrapolated to 0.
Η of time_spThe value of / C is determined as the intrinsic viscosity.

[Η] = lim (η _sp / C) (C → 0) (10) Film processing method 20 mmφ · L /
D = 28 single screw extruder, 25 mmφ die, lip width 0.7 mm, single slit air ring, air flow rate =
90 liter / min. , Extrusion rate = 9 g / min. , Blow ratio = 1.8, take-up speed = 2.4 m / min. ,
A film having a thickness of 30 μm was extruded at a processing temperature of 200 ° C. (11) Film physical property evaluation method (a) Haze (cloudiness): measured according to ASTM-D-1003-61.

(B) Gloss (Gloss): Measured according to JIS Z8741. (C) Film impact strength: Pendulum type film impact tester (film impact tester) manufactured by Toyo Seiki Seisakusho Ltd.
Was measured by

(D) Elmendorf tear strength (Elmen): Measured by using an Elmendorf tear tester manufactured by Toyo Seiki Co., Ltd. according to JIS Z1702. MD is the case where the cut is inserted in the take-up direction of the film, and TD is the case where the cut is inserted at a right angle to the take-up direction.

(E) Elastic Modulus: From film to JIS K6
A dumbbell of a size according to 718 is used as a punched test piece. MD when punching parallel to the film take-up direction,
The case of punching at a right angle to the film take-up direction is TD.

Set on an air chuck of an Instron type universal material testing machine, chuck distance 86 mm, pulling speed 2
A tensile test is performed at 00 mm / min, and the slope of the initial stress with respect to the displacement is taken as the elastic modulus.

[0152]

[Production Example] Production of ethylene / α-olefin copolymer (A) [Preparation of solid catalyst] Silica (specific surface area: 3) dried at 250 ° C for 10 hours in a glass flask sufficiently purged with nitrogen.
57 m ² / g, average particle size; 47 μm), 6.9 g and 100 ml of toluene were charged, and the mixture was cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (Al;
64 ml of 0.830 mol / liter) was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 to 3 ° C. Subsequently, the reaction was carried out at 0 ° C. for 20 minutes, and then the reaction was continued for 9 hours over 9 hours.
The temperature was raised to 5 ° C, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended by adding toluene so that the total volume became 125 ml. 50 ml of this suspension
Was transferred to another glass flask, and 6.4 ml of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 23.8 mmol / liter) was added thereto at room temperature ( Al / Zr = in the reaction system
It was added so that the molar ratio was 130), and the mixture was further reacted at 80 ° C. for 2 hours. Then, the supernatant liquid was removed, and the residue was washed twice with hexane to give 3.5 mg per 1 g.
A solid catalyst (a-1) containing zirconium and 138 mg of aluminum was obtained.

[Preparation of prepolymerization catalyst] To 130 ml of hexane containing 7.7 mmol of triisobutylaluminum, 3.9 g of the solid catalyst (a-1) obtained above and 0.53 ml of 1-hexene were added. The ethylene was prepolymerized at 35 ° C. for 2 hours. The supernatant was removed, the residue was washed twice with hexane, the solid components were filtered off with a glass filter (G3), and then the solids were filtered at room temperature using a vacuum pump.
By drying for an hour, a prepolymerized catalyst (b-1) containing 3.3 mg of zirconium and 3 g of polymer per 1 g of the solid catalyst (a-1) was obtained.

At this time, no adhesion of the prepolymerized catalyst (b-1) to the reactor or the stirring blade was observed, and the obtained prepolymerized catalyst (b-1) had a good shape.

[Polymerization] 1 liter of hexane was charged into a stainless steel autoclave having an internal volume of 2 liter which had been sufficiently replaced with nitrogen, and the system was replaced with ethylene. Then, 80 ml of 1-hexene was charged and the temperature in the system was raised to 55 ° C. Subsequently, 0.75 mmol of triisobutylaluminum and 0.005 mmol of zirconium as the prepolymerized catalyst (a-2) prepared above were injected with ethylene to initiate polymerization.

Then, while continuously feeding ethylene, polymerization was carried out at 8 kg / cm ² -G and 60 ° C. for 1 hour.
The polymer was recovered by filtration and dried under reduced pressure at 80 ° C. overnight. The ethylene / α-olefin copolymer (A-1) thus obtained had a density of 0.915 g / cm ³ and MF
R is 0.20 g / 10 minutes, the temperature at the maximum peak position of the endothermic curve measured by DSC is 113.8 ° C.,
The decane-soluble part at room temperature was 0.10 parts by weight.

Ethylene / α-olefin copolymer (B)
Except that the gas composition was changed so that the production density and MFR of the ethylene / α-olefin copolymer (B-1) had the values shown in Table 1. A polymer (B-1) was obtained.

[0159]

Example 1 Ethylene / α-olefin copolymer (A-
1) and ethylene / α-olefin copolymer (B-1) were dry blended at a weight ratio of (A-1) / (B-1 = 60/40) and then melt-kneaded into pellets. A film having a thickness of 30 μm was subjected to inflation molding, and the physical properties of the copolymer composition and the film are shown in Tables 2 and 3.

[0160]

Examples 2 to 4 Ethylene / α-olefin copolymers (A-2) and (A-3) and ethylene / α-olefin copolymers (B-2 having the density and MFR values shown in Table 1) ), (B
-3) except that the gas composition was changed so that the ethylene / α-olefin copolymer (A-
2), (A-3) and ethylene / α-olefin copolymers (B-2), (B-3) were obtained.

The ethylene / α-olefin copolymers (A-2) and (A-3) and the ethylene / α-olefin copolymers (B-2) and (B-3) are shown in Table 2. After dry blending at various mixing ratios, the mixture was pelletized by melt-kneading, and a film having a thickness of 30 μm was inflation-molded using the pellets. Physical properties of the copolymer composition and the film are shown in Tables 2 and 3.

[0162]

Examples 5 and 6 Table 2 shows the ethylene / α-olefin copolymers (A-1) and (A-2) and the ethylene / α-olefin copolymers (B-1) and (B-2). After dry-blending at the mixing ratio as shown, 100 parts by weight of the obtained ethylene-based copolymer composition was used, and potassium-sodium salt of dehydroabietic acid (equivalent of potassium metal to equivalent of carboxyl machine was 15 %, And 0.5 parts by weight of a metal salt having an equivalent weight of sodium metal of 15%) were mixed and pelletized by melt-kneading. A film having a thickness of 30 μm was inflation-molded using the pellets. Physical properties of the copolymer composition and the film are shown in Tables 2 and 3.

[0163]

Example 7 Ethylene / α-olefin copolymer (A-
1) and the ethylene / α-olefin copolymer (B-1) were dry blended at a weight ratio (A-1) / (B-1 = 60/40), and then 100 parts by weight of the obtained composition Benzoic acid was added in an amount of 0.25 part by weight, and the mixture was pelletized by melt-kneading.

A film having a thickness of 30 μm was inflation-molded using the above pellets. Physical properties of the copolymer composition and the film are shown in Tables 2 and 3.

[0165]

Example 8 Ethylene / α-olefin copolymer (A-
1) and the ethylene / α-olefin copolymer (B-1) were dry blended at a weight ratio (A-1) / (B-1 = 60/40), and then 100 parts by weight of the obtained composition 0.3 parts by weight of adipic acid monosodium salt was blended and pelletized by melt-kneading.

A film having a thickness of 30 μm was inflation-molded using the above pellets. Physical properties of the copolymer composition and the film are shown in Tables 2 and 3.

[0167]

Example 9 Ethylene / α-olefin copolymer (A-
1) and the ethylene / α-olefin copolymer (B-1) were dry blended at a weight ratio (A-1) / (B-1 = 60/40), and then 100 parts by weight of the obtained composition 0.25 parts by weight of cinnamic acid were mixed and pelletized by melt-kneading.

A film having a thickness of 30 μm was inflation-molded using the above pellets. Physical properties of the copolymer composition and the film are shown in Tables 2 and 3.

[0169]

[Table 1]

[0170]

[Table 2]

[0171]

[Table 3]

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C08L 93:04) B29K 23:00 B29L 7:00

Claims (10)

[Claims] 1. (A) Ethylene and 3 to 20 carbon atoms.
A copolymer of α-olefin with (A-i) density of 0.880 to 0.940 g / cm^ThreeRange of
The (A-ii) 135 ° C, intrinsic viscosity measured in decalin
It is in the range of 2.2 to 8 dl / g, and (A-iii) shows an endothermic curve measured by a differential scanning calorimeter.
Temperature (Tm (° C)) and density (d)
(G / cm^Three)) Satisfies the relationship represented by Tm <400 × d-250, and (A-iv) melt tension (MT (g)) at 190 ° C.
Routh flow rate (MFR (g / 10 minutes)) is MT ≤ 2.2 x MFR^-0.84 And the shear stress at 190 ° C. of the (Av) molten polymer is 2.
4 × 10⁶dyne / cm ^TwoDefined by the shear rate when reaching
Liquidity index (FI (1 / sec))
Tflow rate (MFR (g / 10 min)) and FI <150 x MFR satisfy the relationship, and (A-vi) Deca at 23 ° C
Soluble content (W (% by weight)) and density (d (g / cm ^Three))
And are ethylene / α-olefin copolymers that satisfy the relationship represented by W <80 × exp (−100 (d−0.88)) + 0.1.
Combined: 30 to 85% by weight, (B) ethylene, and α-olefin having 3 to 20 carbon atoms
(B-i) having a density of 0.900 to 0.970 g / cm 2^ThreeRange of
The (B-ii) has an intrinsic viscosity measured in decalin at 135 ° C.
In the range of 0.3 to 1.5 dl / g, (B-iii) the endothermic curve measured by a differential scanning calorimeter
Temperature (Tm (° C)) and density (d)
(G / cm^Three)) Satisfies the relationship of Tm <400 × d-250, and (B-iv) decane-soluble matter (W (wt%)) at 23 ° C.
And density (d (g / cm ^Three)) And MFR ≦ 10g / 10
When minutes, W <80 × exp (−100 (d−0.88)) + 0.1 MFR> 10 g / 10 minutes, W <80 × (MFR-9)^0.26× exp (-100 (d-
0.88)) + 0.1 ethylene / α-olefin copolymer weight satisfying the relationship
Coalescence: 15-70 wt% ethylene copolymer
A composition comprising: (i) the above ethylene / α-olefin
Density of copolymer (A) (d_A) And the above ethylene / α-
Density of olefin copolymer (B) (d_B) And (d_A
/ D_B) Is less than 1, and (ii) the above ethylene / α-o
Intrinsic viscosity of reffin copolymer (A) ([η_A]) And above
Intrinsic viscosity of ethylene / α-olefin copolymer (B)
([Η_B]) Ratio ([η_A] / [Η_B]) Is 4 or more
And (iii) the composition has a density of 0.890 to 0.95.
5g / cm^Three, (Iv) 190 ° C, 2.16
The melt flow rate of the composition under a kg load is 0.
In the range of 1-2 g / 10 min, (v) of the molten composition
Shear stress at 190 ℃ is 2.4 × 10⁶dyne / cm
^TwoThe fluidity index defined by the shear rate when reaching
Cus (FI (1 / sec)) and melt flow rate (MF
R (g / 10 min)) and FI> 150 × MFR, and (vi) decane at 23 ° C.
Soluble content (W (% by weight)) and density (d (g / cm^Three))When
Satisfies the relationship of W <80 × exp (−100 (d−0.88)) + 0.1, and (vii) melts at 190 ° C.
Inflation characterized by a melt tension of 1.5 g or more
Ethylene-based copolymer composition for motion picture film. 2. An inflation film comprising the ethylene-based copolymer composition according to claim 1. 3. Inflation characterized by comprising (C) 100 parts by weight of the ethylene copolymer composition according to claim 1 and (D) a crystal nucleating agent: 0.001 to 5 parts by weight. Ethylene copolymer composition for film. 4. The ethylene copolymer composition for an inflation film according to claim 3, wherein the crystal nucleating agent is a metal salt of rosin acid. 5. The ethylene copolymer composition for an inflation film according to claim 3, wherein the rosin acid is at least one rosin acid selected from the group consisting of natural rosin, modified rosin and purified products thereof. 6. The rosin acid is dehydroabietic acid, dihydroabietic acid or dihydropimaric acid,
The ethylene copolymer composition for blown film according to claim 3, which is at least one kind of rosin acid selected from these derivatives. 7. The rosin acid is at least one rosin acid selected from rosin acids represented by the following formula (ia) and rosin acids represented by the following formula (ib). Three
An ethylene-based copolymer composition for blown film according to item 1; (Wherein, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, which may be the same or different). 8. The ethylene-based blown film-based ethylene film according to claim 7, wherein R ¹ is an isopropyl group and R ² and R ³ are methyl groups in the formulas (i-a) and (i-b). Copolymer composition. 9. The metal salt of rosin acid is at least one metal salt of rosin acid selected from the group consisting of sodium salt, potassium salt and magnesium salt of rosin acid. An ethylene-based copolymer composition for blown film as described. 10. An inflation film comprising the ethylene-based copolymer composition according to any one of claims 3 to 9.