JPH05331324A - Ethylene/alpha-olefin copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the composition having a good balance among transparency, heat sealing temperature and tearing strength by mixing two ethylene/alpha-olefin copolymers of different properties with each other. CONSTITUTION:The composition comprises 60-95wt.% ethylene/alpha-olefin copolymer having a melt index(MI) of 0.1-25g/10min, a density of 0.900-0.940g/ml, a degree of branching of 10-40/1000C atoms and a maximum melting point (Tmmax) of 110-130 deg.C as measured with a differential scanning calorimeter(DSC) and 40-5wt.% ethylene/alpha-olefin copolymer of a melt index(MI) of 0.3-15g/10min, a density of 0.890-0.910g/ml, a molecular weight distribution of 2-5 (in terms of a weight-average molecular weight(Mw) to number-average molecular weight (Mn) ratio) a width of the molecular weight dependency of a branching degree of 0-5/100C atoms, a content of o-dichlorobenzene solubles of 10wt.% or below and a maximum melting point of 115 deg.C or below (DSC).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene / α-olefin copolymer composition, and more specifically, it has an excellent balance of transparency, heat seal temperature and tear strength.
-Olefin copolymer compositions.

[0002]

BACKGROUND OF THE INVENTION Generally, linear low density polyethylene (LLDPE) has higher tensile strength than high pressure low density polyethylene (HPLDPE).
Mechanical strength such as impact resistance and rigidity, environmental stress crack resistance (E
SCR), heat resistance, etc.
Demand is increasing in the packaging field such as sheets, blow molding and cable coatings. However, the balance of transparency, heat seal temperature, and tear strength of the film is not sufficient, and improvement is desired. In the conventional packaging field, a polypropylene film, a film obtained by blending LLDPE and HPLDPE (JP-A-59-1)
No. 49941), a film obtained by blending LLDPE and ethylene vinyl acetate (EVA), L
A film obtained by blending LDPE and a special polyolefin (Japanese Patent Publication No. 3-66341, JP-A-52-3974).
No. 1, JP-A-57-34145). However, has a high heat-sealing temperature, a narrow molecular weight distribution range and is inferior in productivity, is inferior in heat-sealing strength, hot tack property and film rigidity, is inferior in heat resistant film strength, oil resistance and film rigidity,
Has poor tear strength, and the vertical and horizontal tear strengths are not well balanced.

[0003]

Therefore, the present inventors have
As a result of intensive studies to solve the above problems, it was found that an ethylene / α-olefin copolymer composition comprising a specific ethylene / α-olefin copolymer solves the above problems. The present invention has been completed based on such findings.

That is, according to the present invention, (A) the melt index (MI) is 0.1 to 25 g / 10 minutes and the density is 0.90.
Ethylene / α-olefin copolymer having 0 to 0.940 g / ml, branch number of 10 to 40/1000 carbon, and maximum melting point (Tm (max)) of 110 to 130 ° C. measured by a differential scanning calorimeter (DSC). 60 to 95% by weight and (B) melt index (MI) of 0.3 to 15
g / 10 minutes, density 0.890 to 0.910 g / ml, molecular weight distribution defined by weight average molecular weight (Mw) / number average molecular weight (Mn) is 2-5, and molecular weight dependence width of branch number is 0 ~ 5 pieces / 1000 carbon, ortho-dichlorobenzene (ODCB) soluble content of 10 wt% or less, and maximum melting point (Tm (max)) by differential scanning calorimeter (DSC)
To provide an ethylene / α-olefin copolymer composition consisting of 40 to 5% by weight of an ethylene / α-olefin copolymer having a temperature of 115 ° C. or lower.

The ethylene / α-olefin copolymer as the component (A) used in the present invention has the following physical properties a to d. a. Melt index (MI) The measurement conditions were based on JIS K-7210. MI of the ethylene / α-olefin copolymer of the component (A)
Is 0.1 to 25 g / 10 minutes, preferably 0.5 to 1
It is 5 g / 10 minutes. If the amount is less than 0.1 g / 10 minutes, the extrusion characteristics will be deteriorated and the product appearance will be poor.
If it exceeds 10 minutes, the viscosity is low and the molding is not stable.

B. The density measurement conditions were based on JIS K-6760, and were measured by a density gradient tube method without annealing. The density of the ethylene / α-olefin copolymer as the component (A) is 0.900 to 0.9.
40 g / ml, preferably 0.910-0.
It is 935 g / milliliter. Where 0.900g /
If the volume is less than milliliters, the film becomes less stiff.
If it exceeds 940 g / ml, the film piercing strength and impact strength will decrease.

C. Number of branches The number of α-olefins having 3 to 10 carbon atoms as a branching species
^It was measured by ¹³ C-NMR.

D. A DSC 7 series TAS (manufactured by Perkin Elmer) was used as a maximum melting point (Tm (max)) measuring device by a differential scanning calorimeter (DSC). The measurement condition is 10 samples
Using mg / ml, first hold at 190 ° C. for 3 minutes, then lower the temperature at −10 ° C./minute to 25 ° C., hold at 25 ° C. for 3 minutes, then raise the temperature to 140 ° C. at 10 ° C./minute and raise the maximum melting peak temperature. Was defined as Tm (max). This Tm (max) is an index showing the amount of low branching components, and a large value thereof means that there are many low branching components. The Tm (max) of the ethylene / α-olefin copolymer of the component (A) is 11
It is 0 to 130 ° C, preferably 115 to 128 ° C. Here, when the temperature is lower than 110 ° C., stickiness occurs and the anti-blocking performance is deteriorated. On the other hand, when the temperature exceeds 130 ° C, the amount of low-branching components increases, and it is difficult to obtain a sufficient improvement effect.

The ethylene / α-olefin copolymer as the component (B) used in the present invention has the following a, b and d to g:
It has the following physical properties. a. Melt index (MI) The measurement conditions were based on JIS K-7210. MI of the ethylene / α-olefin copolymer as the component (B)
Is 0.3 to 15 g / 10 minutes, preferably 0.5 to 1
It is 3 g / 10 minutes. Here, when the MI is less than 0.3 g / 10 minutes or more than 15 g / 10 minutes, the compatibility with other resins is poor.

B. The density measurement condition was based on JIS K-6760, and was measured by a density gradient tube method without annealing. The density of the ethylene / α-olefin copolymer as the component (B) is 0.890 to 0.9.
It is 10 g / milliliter. Here, if it is less than 0.890 g / ml, the rigidity of the product is lowered, and
If it exceeds 910 g / ml, it is difficult to obtain the improvement effect.

D. A DSC 7 series TAS (manufactured by Perkin Elmer) was used as a maximum melting point (Tm (max)) measuring device by a differential scanning calorimeter (DSC). The measurement condition is 10 samples
Using mg / ml, first hold at 190 ° C. for 3 minutes, then lower the temperature at −10 ° C./minute to 25 ° C., hold at 25 ° C. for 3 minutes, then raise the temperature to 140 ° C. at 10 ° C./minute and raise the maximum melting peak temperature. Was defined as Tm (max). This Tm (max) is an index showing the amount of low branching components, and a large value thereof means that there are many low branching components. The Tm (max) of the ethylene / α-olefin copolymer of the component (B) is 11
The temperature is 5 ° C or lower, preferably 113 ° C or lower. Here, if the temperature exceeds 115 ° C., the effect of improving the transparency and the heat sealability decreases.

E. The molecular weight dependence width of the number of branches was measured using two columns of Shodex UT-806L, a sample amount of 5 mg / ml, a temperature of 135 ° C., a flow rate of 1 ml / min, and a solvent of trichlorobenzene (TCB). The measuring equipment is GPC measuring machine M150C (Wat
ers) and FTIR (Perkin Elmer, 1760) for measuring the degree of branching. Using the above measuring instrument, the molecular weight distribution was determined under the above measuring conditions, the molecular weight distribution was divided into 10 and the average number of branches of each fraction obtained by FTIR, that is, the difference between the maximum and minimum values of the number of branches for each molecular weight. Was defined as the width of the molecular weight dependence of the number of branches (however, the fraction having a division area of 4% or less was cut). The molecular weight dependence width of the number of branches of the ethylene / α-olefin copolymer as the component (B) is 0 to 5 carbons / 1000 carbons, preferably 0 to 4 carbons / 1000 carbons. That is, no matter what molecular weight fraction (whether high molecular weight fraction or low molecular weight fraction) is taken, there is no great difference in the number of branches of the copolymers. Copolymer carbon atoms in all molecular weight fractions 1
It means that the difference between the maximum branch number and the minimum branch number is 0 to 5 for 000. If the molecular weight dependence width exceeds 5, the modifying effect cannot be obtained.

F. Ortho-dichlorobenzene (ODCB)
Soluble content 100 mg of sample in 20 ml of ODCB
Dissolve at 35 ° C and apply 3 to the column packed with Chromosolve P.
It was gradually cooled to 5 ° C. for adsorption. The column temperature is raised at a constant rate, the concentration of the solution flowing out from the column is detected by an IR detector, and the concentration ratio (weight fraction) of the components not adsorbed at 35 ° C. and the total concentration is determined and used as the ODCB soluble component. This ODC
The B-soluble content is an index showing the amount of highly branched components, and a large value thereof means that there are many highly branched components. The (B)
The ODCB-soluble component of the component ethylene / α-olefin copolymer is 10% by weight or less, preferably 7% by weight or less. Here, if it exceeds 10% by weight, the heat sealability is deteriorated.

G. Molecular weight distribution (Mw / Mn) The measurement conditions were two columns Shodex UT-806L, sample amount 2 mg / ml, temperature 135 ° C., flow rate 1 ml / min, solvent trichlorobenzene (TCB) inflow amount 200 μg. Measuring equipment is GPC measuring machine M
Differential to 150C (manufactured by Waters)
A viscometer MODEL 110 (manufactured by Viscotek) was connected. The absolute molecular weight (Mw and Mn) and the molecular weight distribution were determined under the above measurement conditions using the above measuring instrument. The ethylene / α-olefin copolymer as the component (B) has a molecular weight distribution of 2 to 5, preferably 2.5 to 4.5. Here, when the molecular weight distribution is less than 2, the resin pressure is high and the extrusion characteristics are poor, and the melt elasticity is low, and the molten resin is not stable and moldability deteriorates. Further, if the molecular weight distribution exceeds 5, high molecular weight components and low molecular weight components increase, and good physical properties cannot be obtained.

Ethylene / α as the component (A) in the present invention
The olefin copolymer can be obtained by various known methods. As a raw material, for example, ethylene, or ethylene and at least one α-olefin and / or non-conjugated diene is used. That is, ethylene may be used alone, or ethylene and 1 of other α-olefins may be used.
One or more types may be used in combination, or ethylene and one or more non-conjugated dienes may be used in combination. Furthermore, it is also possible to use, for example, ethylene, at least one α-olefin and at least one non-conjugated diene. Here, as the α-olefin, for example, propylene, 1-
Butene; 1-hexene; 1-octene; 1-nonene; 1
-Decene; 1-undecene; linear monoolefins such as 1-dodecene; 3-methylbutene-1; 3-methylpentene-1; 4-methylpentene-1; 2-ethylhexene-1; 2,2,4 Examples thereof include branched-chain monoolefins such as trimethylpentene-1 and monoolefins substituted with an aromatic nucleus such as styrene. Moreover, as the non-conjugated diene, a non-conjugated diolefin having a linear or branched chain having 6 to 20 carbon atoms is preferable. For example,
1,5-hexadiene; 1,6-heptadiene; 1,7
-Octadiene; 1,8-nonadiene; 1,9-decadiene; 2,5-dimethyl-1,5-hexadiene; 1,
4-dimethyl-4-t-butyl-2,6-heptadiene and the like can be mentioned. Furthermore, polyenes such as 1,5,9-decatriene and endmethylene-based cyclic dienes such as 5-vinyl-2-norbornene can be used.
Also, there is no limitation on the catalyst used, and various catalysts can be used. For example, those prepared by preparing a magnesium compound, an aluminum compound and a transition metal compound can be mentioned. The magnesium compound has the general formula

[0016]

[Chemical 1]

(In the formula, Z ¹ represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, an alkylaryl group, an aryl group, an aryloxy group, an aralkyl group or an arylalkoxy group. A known compound represented by a halogen atom and f is a real number of 0 to 2 (JP-A-2-142807) can be mentioned. These compounds can be used alone or in combination of two or more. Further, as the aluminum compound,

[0018]

[Chemical 2]

(In the formula, Z ² and Z ³ each independently represent an alkyl group or an aryl group having 1 to 20 carbon atoms. Hal
Is the same as above, g represents 0, 1 or 2, and h represents 0 or 1. ), A known compound represented by the formula (JP-A-2-142807). These compounds can be used alone or in combination of two or more. Examples of transition metal compounds include titanium compounds, vanadium compounds, and zirconium compounds. A titanium compound is preferable. This titanium compound has the general formula

[0020]

[Chemical 3]

(In the formula, Z ⁴ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Hal has the same meaning as described above.
i represents a real number satisfying 0 ≦ i ≦ 4 as an average value of the mixture of titanium compounds. ), A known compound represented by the formula (JP-A-2-142807). These compounds can be used alone or in combination of two or more. The method for preparing the catalyst is not particularly limited, and for example, the polymerization monomer and the magnesium compound, aluminum compound and transition metal compound can be added arbitrarily. In the polymerization, a known activator (Japanese Patent Laid-Open No. 142807/1990) or the like may be allowed to coexist with the above catalyst for polymerization. Although the copolymerization method for producing the ethylene / α-olefin copolymer of the component (A) in the present invention is not limited, it is usually a slurry copolymerization method, a gas phase copolymerization method, a bulk copolymerization method, A solution copolymerization method and a suspension copolymerization method can be mentioned. Preferred are a slurry copolymerization method, a gas phase copolymerization method and a solution copolymerization method. The copolymerization temperature is usually −20 to 300 ° C., preferably 20 to 300 ° C.
It is 250 ° C, particularly preferably 60 to 200 ° C. The reaction pressure is 0 to 100 kg / cm ² G, preferably 1 to 70 kg / cm ² G.

Component (B) of the present invention, ethylene.α
The olefin copolymer can be obtained by various methods. As the raw material, those exemplified in the description of the ethylene / α-olefin copolymer as the component (A) can be used.

There is no limitation on the catalyst used,
Various things can be applied. For example, selected from (a) a transition metal compound, (b) a compound that reacts with a transition metal compound to form an ionic complex, (c) a catalyst containing an organoaluminum compound as a main component, and (d) a periodic table IVB. Transition metal compound containing a transition metal and the above (B)
Component as a main component, and the component (d) and / or (b)
In the case where the component (a) is carried on the carrier (e), the component (d) and the component (b) are the main components, and the component (d) and / or the component (b) is carried on the carrier (e), c)
Some include organic aluminum compounds. Here, as the transition metal compound which is the component (a), a transition metal compound containing a transition metal belonging to the IVB group, VB group, VIB group, VIIB group and VIII group of the periodic table can be used. The transition metal is preferably titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum or the like, and particularly preferably zirconium, hafnium, titanium, nickel or palladium.
Examples of such a transition metal compound include various compounds, particularly compounds containing a transition metal of IVB group or VIII group,
Among them, a compound containing a transition metal selected from Group IVB of the periodic table, that is, titanium, zirconium or hafnium (that is, the component (d)) can be preferably used.
In particular, compounds represented by the following general formulas (I) to (III) or derivatives thereof or compounds represented by the following general formula (IV) or derivatives thereof are preferable.

Used as the component (a) in the present invention
The compound represented by the general formula CpMR¹ _aR² _bR³ _c ... (I) Cp₂MR¹ _aR² _b ... (II) (Cp-A_e-Cp) MR¹ _aR² _b ... (III) or general formula MR¹ _aR² _bR³ _cR^Four _d A compound represented by (IV) or a derivative thereof is preferable. The general
In formulas (I) to (IV), M is titanium or zirconium
Or a group IVB transition metal of the periodic table such as hafnium.
Cp is a cyclopentadienyl group, substituted cyclopenta
Dienyl group, indenyl group, substituted indenyl group, tetra
Hydroindenyl group, substituted tetrahydroindenyl group,
Cyclic group such as fluorenyl group or substituted fluorenyl group
A saturated hydrocarbon group or a chain unsaturated hydrocarbon group is shown. R
¹, R², R³And R^FourAre independently σ-connectivity
Ligand, chelating ligand, ligand such as Lewis base
, And as a σ-bonding ligand,
Child, oxygen atom, halogen atom, C1-20 alkyl
Group, C1-C20 alkoxy group, C6-C20
Aryl group, alkylaryl group or aryl group of
Alkyl group, acyloxy group having 1 to 20 carbon atoms, allyl
Group, substituted allyl group, substituent containing silicon atom, etc.
Acetylacetone is a chelating ligand that can be formed.
Tonato group, substituted acetylacetonate group etc.
Wear. A indicates crosslinking by covalent bond. a, b, c and
And d are each independently an integer of 0 to 4. e is an integer from 0 to 6
Indicates. R¹, R², R³And R^FourTwo or more are mutual
They may be bonded to each other to form a ring. The above Cp has a substituent
When it has, the substituent is alkyl having 1 to 20 carbons.
Groups are preferred. Two in formula (II) and formula (III)
Cp may be the same or different from each other
May be

Examples of the substituted cyclopentadienyl group in the above general formulas (I) to (III) include methylcyclopentadienyl group, ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethyl. Cyclopentadienyl group; tetramethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group;
1,2,3-trimethylcyclopentadienyl group; 1,
2,4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group and the like. In addition, the above (I)
Specific examples of R ^{1 to} R ^{4 in} the formulas (IV) to (IV) include, for example, fluorine atom, chlorine atom, bromine atom, iodine atom as halogen atom, methyl group, ethyl group, n- Propyl group, isopropyl group,
n-butyl group, octyl group, 2-ethylhexyl group, methoxy group as an alkoxy group having 1 to 20 carbon atoms, ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or Phenyl group, tolyl group, xylyl group, benzyl group as arylalkyl group, heptadecylcarbonyloxy group as acyloxy group having 1 to 20 carbon atoms, trimethylsilyl group as substituent containing silicon atom, (trimethylsilyl) methyl group, Lewis base Dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; Z, Z-dimethylaniline; pyridine; 2,2'-bipyridine; amines such as phenanthroline; triethylphosphine; phosphines such as triphenylphosphine; chain unsaturated hydrocarbons; ethylene; butadiene; 1-pentene; isoprene; pentadiene; 1-hexene and derivatives thereof, benzene as cyclic unsaturated hydrocarbon;
Toluene; xylene; cycloheptatriene; cyclooctadiene; cyclooctatriene; cyclooctatetraene and derivatives thereof. Also,
Examples of the crosslink by A covalent bond in the above formula (III) include methylene bridge, dimethylmethylene bridge, ethylene bridge, 1,1′-cyclohexylene bridge, dimethylsilylene bridge, dimethylgermylene bridge, dimethylstannylene bridge, etc. Is mentioned.

Examples of the compound represented by the general formula (I) include (pentamethylcyclopentadienyl) trimethyl titanium, (pentamethylcyclopentadienyl) triphenyl titanium, (pentamethylcyclopentadienyl). Tribenzyl titanium, (pentamethylcyclopentadienyl) trichloro titanium, (pentamethyl cyclopentadienyl) trimethoxy titanium, (cyclopentadienyl) trimethyl titanium, (cyclopentadienyl) triphenyl titanium, (cyclopentadiene Enil)
Tribenzyl titanium, (Cyclopentadienyl) trichlorotitanium, (Cyclopentadienyl) trimethoxytitanium, (Cyclopentadienyl) dimethyl (methoxy)
Titanium, (methylcyclopentadienyl) trimethyl titanium, (methylcyclopentadienyl) triphenyl titanium, (methylcyclopentadienyl) tribenzyl titanium, (methylcyclopentadienyl) trichlorotitanium, (methylcyclopentadienyl) ) Dimethyl (methoxy) titanium, (dimethylcyclopentadienyl) trichlorotitanium, (trimethylcyclopentadienyl) trichlorotitanium, (trimethylcyclopentadienyl) trimethyltitanium, (tetramethylcyclopentadienyl) trichlorotitanium, etc. In these,
Examples include compounds in which titanium is replaced with zirconium or hafnium.

Examples of the compound represented by the general formula (II) include bis (cyclopentadienyl) dimethyl titanium, bis (cyclopentadienyl) diphenyl titanium,
Bis (cyclopentadienyl) diethyl titanium, bis (cyclopentadienyl) dibenzyl titanium, bis (cyclopentadienyl) dimethoxy titanium, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) dihydrido Titanium, bis (cyclopentadienyl) monochloromonohydrido titanium, bis (methylcyclopentadienyl) dimethyl titanium, bis (methylcyclopentadienyl) dichlorotitanium, bis (methylcyclopentadienyl) dibenzyl titanium, bis ( Pentamethylcyclopentadienyl) dimethyl titanium, bis (pentamethylcyclopentadienyl) dichlorotitanium, bis (pentamethylcyclopentadienyl) dibenzyl titanium, bis (pentamethylcyclopentadienyl) chloromethyl titanium, Scan (pentamethylcyclopentadienyl) hydridomethylsiloxanes titanium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorotitanium like, furthermore in these include compounds obtained by substituting titanium, zirconium or hafnium.

Examples of the compound represented by the general formula (III) include ethylene bis (indenyl) dimethyl titanium, ethylene bis (indenyl) dichloro titanium,
Ethylene bis (tetrahydroindenyl) dimethyl titanium, ethylene bis (tetrahydroindenyl) dichloro titanium, dimethyl silylene bis (cyclopentadienyl) dimethyl titanium, dimethyl silylene bis (cyclopentadienyl) dichloro titanium, isopropylidene (cyclopentadiene) (Enyl) (9-fluorenyl) dimethyl titanium, isopropylidene (cyclopentadienyl) (9
-Fluorenyl) dichlorotitanium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethyl titanium, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl titanium, ethylene (9-fluorenyl) ( Cyclopentadienyl) dimethyl titanium, cyclohexalidene (9-fluorenyl) (cyclopentadienyl) dimethyl titanium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethyl titanium, cyclobutylidene (9-
Fluorenyl) (cyclopentadienyl) dimethyl titanium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethyl titanium, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) dichlorotitanium, dimethylsilylene bis ( 2,3,5-trimethylcyclopentadienyl) dimethyl titanium, dimethyl silylene bis (indenyl) dichloro titanium and the like, and further, compounds in which titanium is substituted with zirconium or hafnium in these compounds can be mentioned.

Further, examples of the compound represented by the general formula (IV) include tetramethyl titanium, tetrabenzyl titanium, tetramethoxy titanium, tetraethoxy titanium, tetrabutoxy titanium, tetrachloro titanium, tetrabromo titanium, butoxy trichloro. Titanium, butoxydichlorotitanium, bis (2,5-di-t-butylphenoxy) dimethyltitanium, bis (2,5-di-t-butylphenoxy) dichlorotitanium, titanium bis (acetylacetonate), and the like. In the above, a compound in which titanium is replaced with zirconium or hafnium is mentioned.

Further, as the component (a), in the above general formula (III), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is a substituted cyclopentadienyl group). ) Is preferably a titanium compound having a ligand of a multicoordinating compound bonded to each other through an element selected from Group IVA of the periodic table.
Examples of such a compound include those represented by the general formula (V)

[0031]

[Chemical 4]

Examples thereof include compounds represented by: and derivatives thereof.

Y in the general formula (V) is carbon, silicon,
Germanium or tin atom, R^Five _t-C_FiveH_4-tAnd
And R^Five _u-C_FiveH_4-uAre each substituted cyclopentadiene
The nyl group, t and u each represent an integer of 1 to 4. Where R
^FiveAre hydrogen atoms, silyl groups or hydrocarbon groups,
May be the same or different. Also, at least
Also, the cyclopentadienyl group on one side is bound to Y
R on at least one carbon next to the carbon^FiveExists
It R⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or
Is an aryl group having 6 to 20 carbon atoms or an alkylaryl group
Specifically, it represents an arylalkyl group. X is a hydrogen atom, halo
Gen atom, alkyl group having 1 to 20 carbon atoms, 6 to 2 carbon atoms
0 aryl group, alkylaryl group or aryl
Indicates an alkyl group or an alkoxyl group having 1 to 20 carbon atoms
You X may be the same or different from each other, and R
⁶May be the same as or different from each other.

Examples of the substituted cyclopentadienyl group in the above general formula (V) include methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group. Group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X include halogen atoms such as F, Cl, Br and I, and alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, octyl group and 2 -Ethylhexyl group, a methoxy group as an alkoxy group having 1 to 20 carbon atoms,
Examples of the ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group include phenyl group, tolyl group, xylyl group and benzyl group. Specific examples of R ⁶ include methyl group, ethyl group, phenyl group, tolyl group, xylyl group, and benzyl group. Examples of the compound of the general formula (V) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, and further compounds in which titanium is replaced with zirconium or hafnium.

As the component (b), a compound which reacts with a transition metal compound to form an ionic complex is used. As this compound, any compound can be used as long as it can react with the titanium compound as the component (a) to form an ionic complex, and is composed of a cation and an anion in which a plurality of groups are bound to an element. It is possible to preferably use a complex compound, especially a coordination complex compound comprising a cation and an anion in which a plurality of groups are bound to an element. Examples of the compound such cations and a plurality of groups consisting of bound anions to elemental general formula ([L ¹ -R ^{7] k +)} _p ^{([M 3 Z 1 Z 2 ·· Z} n ] ^{(nm) -} ) _Q・ ・ ・ (VI) or ([L ² ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² ··· Z ⁿ ] ^(nm)- ) _q・ ・ ・ (VII) (However, L ² is M ⁵ , R ⁸ R ⁹ M ⁶ , R ¹⁰ ₃ C or R
^{11 is} M ⁶ ) (wherein L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group, VIIB group, VIII group, IB group, II of the periodic table, respectively)
An element selected from Group B, Group IIIA, Group IVA and Group VA, preferably an element selected from Group IIIA, Group IVA and Group VA,
M ⁵ and M ⁶ are IIIB group, IVB group, and
VB, VIB, VIIB, VIII, IA, IB, IIA
Elements selected from Group I, IIB and VIIA, Z ^{1 to} Z ⁿ
Are hydrogen atom, dialkylamino group, and 1 to 1 carbon atoms, respectively.
An alkoxy group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group,
C1-C20 halogen-substituted hydrocarbon group, C1-C1
20 represents an acyloxy group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷ is hydrogen atom, carbon number 1
To an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, R
⁸ and R ⁹ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. m is an valence of M ³ and M ⁴ , an integer of 1 to 7, n is an integer of 2 to 8, and k is [L ¹ −
R ⁷ ] and [L ² ] have an ionic valence of 1 to 7 and p is 1.
The above integer, q = (p × k) / (nm). ) Is a compound represented by.

Specific examples of the Lewis base represented by L ¹ are ammonia, methylamine, aniline, dimethylamine, diethylamine, Z-methylaniline, diphenylamine, trimethylamine, triethylamine, tri-n-butylamine, Z. , Z-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-Z, Z-dimethylaniline, p-nitro-Z, Z
-Amines such as dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, thioethers such as diethylthioether and tetrahydrothiophene, ethylbenzoate And the like.

As specific examples of M ³ and M ⁴ ,
Specific examples of B, Al, Si, P, As, Sb, and preferably B or P, M ³ include Li, Za, Ag, and C.
Specific examples of M ⁴ , such as u, Br and I, include Mn and F.
e, Co, Zi, Zn, and the like. Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group and a C 6 to 20 carbon atom as an alkoxy group having 1 to 20 carbon atoms. Phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as aryloxy group, methyl group as alkyl group having 1 to 20 carbon atoms,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms, phenyl group as alkylaryl group or arylalkyl group, p-tolyl group , Benzyl group, 4-t-butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-
Dimethylphenyl group, 2,3-dimethylphenyl group, p-fluorophenyl group as halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluoro group Phenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, F, C as halogen atom
1, Br, I, pentamethylantimony group as an organic metalloid group, trimethylsilyl group, trimethylgermyl group,
Examples thereof include diphenylarsine group, dicyclohexylantimony group, and diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include the same as those mentioned above.
Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Be done.
Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups is an integer of 1 to 5.

Among the compounds of the above general formulas (VI) and (VII), those in which M ³ and M ⁴ are boron are preferable. Among the compounds of the general formulas (VI) and (VII), the following compounds can be used particularly preferably. For example, as the compound of the general formula (VI), triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) tetraphenylborate can be used. Ammonium, benzyltri (n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), tetraphenylborate trimethylsulfonium, tetraphenylborate benzene Rumethylsulfonium, triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate , Tetra (pentafluorophenyl)
Tetraethylammonium borate, tetra (pentafluorophenyl) borate [methyltri (n-butyl) ammonium], tetra (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], tetra (pentafluorophenyl) borate methyldiphenylammonium, tetra Methyltriphenylammonium (pentafluorophenyl) borate, Dimethyldiphenylammonium tetra (pentafluorophenyl) borate, Anilinium tetra (pentafluorophenyl) borate, Methylanilinium tetra (pentafluorophenyl) borate, Dimethyl tetra (pentafluorophenyl) borate Anilinium, trimethylanilinium tetra (pentafluorophenyl) borate, dimethyl tetra (pentafluorophenyl) borate (m-ni Roanilinium), dimethyl (p-bromoanilinium) tetra (pentafluorophenylmethyl) borate, pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (Z-methylpyridinium), tetra (pentafluorophenyl) borate (Z-benzylpyridinium), tetra (pentafluorophenyl) borate (O
-Cyano-Z-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-Z-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-Z-benzylpyridinium), tetra (pentafluorophenyl) ) Trimethylsulfonium borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetrafelphosphonium tetra (pentafluorophenyl) borate, tetra (3,5-
Examples thereof include dimethylanilinium ditrifluoromethylphenyl) borate and triethylammonium tow hexafluoroarsenate.

On the other hand, as the compound of the general formula (VII), ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetra (pentafluorophenyl) borate, tetra Decamethylferrocenium (pentafluorophenyl) borate, Acetylferrocenium tetra (pentafluorophenyl) borate, Formylferrocenium tetra (pentafluorophenyl) borate, Cyanoferrocenium tetra (pentafluorophenyl) borate, Tetra ( Silver pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl)
Sodium borate, tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate , Silver hexafluoroarsenate, silver hexafluoroantimonate, and the like. Examples of compounds other than the general formulas (VI) and (VII) include, for example,
Tri (pentafluorophenyl) boric acid, tri [3,5-
Di (trifluoromethyl) phenyl] boric acid, triphenylboric acid, etc. can also be used.

The organoaluminum compound which is the component (c) is represented by the general formula (VIII) R ¹² _r AlQ _3-r (VIII) (wherein R ¹² has 1 to 20 carbon atoms, preferably 1 carbon atom). ~ 12
Is a hydrocarbon group such as an alkyl group, an alkenyl group or an arylalkyl group, Q is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is a number from 1 to 3. ), A compound represented by the general formula (IX)

[0041]

[Chemical 5]

(In the formula, R ¹² is the same as above. S is the degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40.), and a chain aluminoxane Formula (X)

[0043]

[Chemical 6]

The cyclic alkylaluminoxane represented by the formula (wherein R ¹² and s are the same as above) can be mentioned.

Among the compounds represented by the above general formulas (VIII), (IX) and (X), preferred are aluminum compounds containing an alkyl group having at least one alkyl group having 3 or more carbon atoms, and particularly at least one branched alkyl group. It is an aluminoxane. Particularly preferred is triisobutylaluminum or aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof is used, high activity can be obtained. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, an organoaluminum compound is dissolved in an organic solvent, a method of contacting it with water, a method of initially adding an organoaluminum compound at the time of polymerization, and a method of adding water later, water of crystallization contained in a metal salt, There are a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water.

Specific examples of the compound represented by the general formula (III) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum. Examples include dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride.

In producing the copolymer of the component (B) in the present invention, the above-mentioned catalyst is used as a copolymerization catalyst. In addition, (1) the component (a),
A catalyst obtained by separately adding the component (b) and the component (c) to the reaction system may be used, or (2) the component (a), the component (b) and the component (c) may be contacted with each other in advance. You may use the obtained reaction product. The carrier may be supported on the carrier as described above. Regarding the amount of each catalyst component used in the above (1), the component (a) is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter.
Liter, the component (b) is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, and the component (c) is 0.01 to 500 mmol / liter in terms of Al atom, preferably 0.05. ˜100 mmol / liter, and the molar ratio of component (b) / component (a) is 0.01 to 100, preferably 0.5 to 10 and (c).
It is desirable to use each component so that the component / (a) component molar ratio is in the range of 0.1 to 2000, preferably 5 to 1000.

On the other hand, in the above (2), the components (a), (b) and (c) are brought into contact with each other under an inert gas atmosphere in an inert solvent.
The component (a) is 0.01 to 100 mmol / liter,
The component (b) is 0.01 to 100 mmol / liter, and the component (c) is 0.1 to 1000 mmol / liter in terms of Al atom.
It is desirable to use each component so as to be in the range of liters, and in particular, the following conditions 0.5 <[b] / [a] <5 0.5 <[c] / [a] <500 and 0.1 Mmol / L <[a] (where [a] is the molar concentration of component (a) in the contact field, [b] is the molar concentration of component (b) in the contact field, and [c]
Indicates the molar concentration of component (c) (in terms of Al atom) in the contact field. When the above condition (3) is satisfied, the copolymerization activity of the obtained contact product is remarkably improved. If the above [b] / [a] is less than 0.5, the activity improving effect is not observed, and if it exceeds 5, the component (b) is wasted. When [c] / [a] is less than 0.5, the activity improving effect is insufficient, and when it exceeds 500, the component (c) is wasted and a large amount of aluminum component remains in the product polymer. To do. Furthermore, [a] is 0.1
If it is less than millimoles / liter, the contact reaction rate is slow and it is difficult to sufficiently exert the activity improving effect.

Among the above components (a), a compound containing a transition metal selected from Group IVB of the Periodic Table, that is, titanium, zirconium or hafnium ((d))
Ingredients) can be preferably used. As the component (d), compounds represented by the general formulas (I) to (III) or derivatives thereof, or compounds represented by the general formula (IV) or derivatives thereof are preferable.

The above catalyst is supported on a carrier.
You may. The type of carrier (e) that can be used here is limited.
Inorganic oxide carriers, other inorganic carriers and
Any of the organic carriers can be used, but especially inorganic acids
Compound carriers or other inorganic carriers are preferred. inorganic
As the oxide carrier, specifically, SiO 2₂, Al₂O
₃, MgO, ZrO₂, TiO₂, Fe₂O₃, B₂O
₃, CaO, ZnO, BaO, ThO₂Or a mixture of these
Such as silica alumina, zeolite, ferrite,
Examples include glass fiber. Among these,
Especially SiO₂, Al₂O₃Is preferred. The above inorganic
The oxide carrier contains a small amount of carbonates, nitrates, sulfates, etc.
You may have. On the other hand, as an inorganic carrier other than the above, Mg
Cl₂, Mg (OC₂H_Five)₂Magnesium compound
Thing or its complex salt, or MgR¹³ _XX¹ _yRepresented by
Examples include organic magnesium compounds. here
And R¹³Is an alkyl group having 1 to 20 carbon atoms and 1 to 20 carbon atoms
An alkoxy group or an aryl group having 6 to 20 carbon atoms, X
¹Is a halogen atom or an alkyl group having 1 to 20 carbon atoms
As shown, x is 0 to 2 and y is 0 to 2. Also an organic carrier
As polystyrene, polyethylene, polypropylene
Polymers such as styrene, substituted polystyrene, polyarylate,
Starch, carbon, etc. can be mentioned. here
The properties of the carrier (e) used are,
Depending on the method, the average particle size is usually 1 to 300 μm,
It is preferably 10 to 200 μm, more preferably 20 to 10 μm.
It is 0 μm. Small particle size increases fines in the polymer
However, if the particle size is large, the coarse particles in the polymer increase and the bulk density
Cause deterioration of the hopper and clogging of the hopper. Also, the carrier
The specific surface area of (e) is usually 1 to 1000 m.²/ G, preferred
50-500m²/ G, pore volume is usually 0.1-5
cm³/ G, preferably 0.3-3 cm³/ G. ratio
Either surface area or pore volume deviates from the above range
If so, the catalytic activity may decrease. The specific surface area
And pore larvae are, for example, the nitrogen adsorbed according to the BET method.
It can be calculated from the volume of elementary gas (Journal
Bu American Chemical Society, Volume 60, Vol.
See page 309 (1983)). Further, the above carrier
(E) is usually 150 to 1000 ° C., preferably 200
It is desirable to use by firing at ~ 800 ° C.

When the ethylene / α-olefin copolymer is copolymerized using the above raw materials, the components (b) and (d) and the carrier (e), the component (d) and / or the component (b) is used as a carrier. What is carried in (e) is used.
The method of loading the component (d) and / or the component (b) on the carrier (e) is not particularly limited, but the following
The method of can be mentioned. Component (d) and / or component (b) and carrier (e)
How to mix with. A method in which the carrier (e) is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with the component (d) and / or the component (b) in an inert solvent. A method of reacting the carrier (e) with the component (d) and / or the component (b) with an organoaluminum compound or a halogen-containing silicon compound. A method in which the component (d) or the component (b) is supported on the carrier (e) and then mixed with the component (d) or the component (b). A method of mixing a contact reaction product of the component (d) and the component (b) with the carrier (e). A method of allowing the carrier (e) to coexist during the catalytic reaction between the component (d) and the component (b). In addition, in the above reactions (1) to (4), the component (c) may be added.

The catalyst thus obtained may be used for the copolymerization after the solvent is once distilled off and taken out as a solid, or it may be used for the polymerization as it is. Also, (d)
The catalyst can be produced by carrying out the operation of loading the component and / or the component (b) on the carrier (e) in the copolymerization system. As a specific example of such a method, an inert solvent is put in an autoclave, and (d) component and / or
Alternatively, the component (b), the carrier (e), and optionally the component (c) are added, and an olefin such as ethylene is added in an amount of 0 to 2
Add at 0 kg / cm ² G and at -20 to 100 ° C for 1 minute to 2
A method of preliminarily polymerizing for a time to generate catalyst particles can be mentioned. When copolymerization is performed using the components (b) and (d) and the carrier (e), the mixing ratio (weight ratio) of the component (b) and the carrier (e) is usually 1: 5 to 1: 10000. It is preferably 1:10 to 1: 500. The mixing ratio (weight ratio) of the component (d) and the carrier (e) is usually 1: 5 to 1:10.
000, preferably 1:10 to 1: 500. Here, the mixing ratio of the component (b) and the carrier (e) or (d)
If the mixing ratio of the component and the carrier (e) is out of the above range, the activity may decrease. The average particle size of the catalyst prepared as described above is usually 2 to 200 μm, preferably 1
It is from 0 to 150 μm, particularly preferably from 20 to 100 μm. Here, if the average particle size is less than 2 μm, the fine powder in the copolymer may increase, and if it exceeds 200 μm, the coarse particles in the copolymer may increase. The specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g. Here, the specific surface area is 2
If it is less than 0 m ² / g, the catalytic activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the copolymer may decrease. Further, in the catalyst of the present invention, the amount of transition metal in 100 g of the carrier is usually 0.05 to 10 g, preferably 0.1 to 2 g. If the amount of transition metal in 100 g of the carrier is out of the range of 0.05 to 10 g, the activity may decrease.

Ethylene.α as the component (B) in the present invention
-The copolymerization method for producing the olefin copolymer is not limited, but usually a slurry copolymerization method,
The gas phase copolymerization method, the bulk copolymerization method, the solution copolymerization method, and the suspension copolymerization method can be mentioned. Preferred are the slurry copolymerization method and the gas phase copolymerization method. The copolymerization temperature is usually -100 to
The temperature is 250 ° C, preferably -50 to 200 ° C, particularly preferably 0 to 130 ° C. The amount of the catalyst used with respect to the reaction raw material is usually 1 to 10 ⁸ raw material monomer / (a) or (d) component (molar ratio) or raw material monomer / (b) component (molar ratio), preferably 100 to 10 ^{Is 5} . Further, the copolymerization time is usually 5 minutes to 10 hours, preferably 1
0 minutes to 5 hours. Reaction pressure is 0 to 100 kg / cm
² G, preferably 0 to 30 kg / cm ² G. The molecular weight of the ethylene / olefin copolymer can be controlled by the amount of each catalyst component used, the selection of the copolymerization temperature, and the copolymerization reaction in the presence of hydrogen. In addition, when a copolymerization solvent is used, there is no particular limitation, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, pentane, hexane, heptane, Aliphatic hydrocarbons such as octane and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Also,
A monomer such as α-olefin may be used as a solvent. Further, the copolymerization may be carried out without a solvent. In producing the ethylene / α-olefin copolymer used in the present invention, preliminary polymerization can be carried out using the above catalyst. This prepolymerization can be carried out by contacting the solid catalyst component with a small amount of olefin and can be carried out using conventional techniques. The olefin used in the prepolymerization is not particularly limited, and examples thereof include the same ones as described above, for example, ethylene, α-olefin having 3 to 20 carbon atoms, or a mixture thereof. For this prepolymerization, it is preferable to use the same olefin as that used in the main copolymerization. The prepolymerization temperature is usually -2.
The temperature is 0 to 100 ° C, preferably -10 to 70 ° C, and particularly preferably 0 to 50 ° C. As a solvent for the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon monomer or the like can be used. Of these, aliphatic hydrocarbons are particularly preferable. Further, the preliminary polymerization may be carried out without a solvent. In the prepolymerization, the intrinsic viscosity [η] of the prepolymerized product (measured in decalin at 135 ° C) is
It is preferably 0.2 deciliter / g or more, and particularly preferably 0.5 deciliter / g or more. Further, the amount of the prepolymerized product relative to 1 mmol of the transition metal component in the catalyst is 1 to 10
The range of 000 g is preferable, and it is particularly preferable to adjust the amount to be 10 to 1000 g.

The ethylene / α-olefin copolymer composition of the present invention comprises the ethylene / α-olefin copolymer of the above-mentioned components (A) and (B). The ethylene
The composition ratio of the (A) copolymer and the (B) copolymer in the α-olefin copolymer composition is (A) copolymer 60.
˜95% by weight, (B) copolymer 40 to 5% by weight,
It is preferably 70 to 90% by weight of the (A) copolymer and 30 to 10% by weight of the (B) copolymer. Here, when the copolymer (A) exceeds 95% by weight, the film impact strength and haze are poor and the heat-sealing temperature rises, and when the copolymer (B) exceeds 40% by weight, the stiffness of the film decreases. Occurs.

The method for producing the ethylene / α-olefin copolymer composition of the present invention is not limited, and can be favorably produced by kneading each component in a molten state. As the melt-kneading device, conventionally known devices such as an open mixing roll, a non-open Banbury mixer, an extruder, a kneader, and a continuous mixer can be used. A method of adding the additive to the masterbatch of the α-olefin resin can also be preferably used.
As the above-mentioned additive, various kinds can be mentioned, but an anti-blocking agent and a lubricant are particularly preferable. The anti-blocking agent is not particularly limited, and examples thereof include metal oxides, fluorides, nitrides, sulfates, phosphates, carbonates, and complex salts thereof. Specifically, silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, aluminosilicate, zeolite, diatomaceous earth, talc, kaolinite, sericite, montmorillonite, hectorite,
Examples thereof include calcium fluoride, magnesium fluoride, boron nitride, aluminum nitride, calcium sulfate, strontium sulfate, barium sulfate, calcium phosphate, strontium phosphate, barium phosphate, calcium carbonate, strontium carbonate and barium carbonate. The lubricant is not particularly limited, and examples thereof include higher aliphatic hydrocarbon, higher fatty acid, aliphatic amide, fatty acid ester, fatty acid alcohol, polyhydric alcohol and the like. Specifically, liquid paraffin, natural paraffin, polyethylene wax, fluorocarbon oil, lauric acid, palmitic acid, stearic acid, iristearic acid,
Hydroxylauric acid, hydroxystearic acid, oleic acid amide, lauric acid amide, erucic acid amide, methyl stearate, butyl stearate, stearyl alcohol, cetyl alcohol, isocetyl alcohol,
Examples thereof include ethylene glycol, diethylene glycol and fatty acid monoglyceride. Further, other additives can be used if necessary. For example, antioxidants,
Examples include stabilizers such as ultraviolet absorbers, antistatic agents, flame retardants, inorganic and organic fillers, dyes, pigments and the like.

The ethylene / α-olefin copolymer composition of the present invention obtained as described above can be molded into various molded products such as films and sheets by a conventional molding method. Specific examples of the molding method include a single-screw extruder, a vent-type extruder, a twin-screw extruder, a conical twin-screw extruder, a co-kneader, a practicator, a mixer extruder, a twin-screw conical screw extruder, and a planetary screw extrusion Machines, gear type extruders, screwless extruders, etc. are used for extrusion molding, injection molding, compression molding, blow molding, rotational molding and the like. Also, a film or sheet can be prepared by a T-die molding method, an inflation molding method, or the like.

[0057]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples and Comparative Examples. Production Example 1 (Ethylene / 1-octene Copolymer A1) A solution of ethylaluminum sesquichloride, butylethylmagnesium, and tetrabutoxytitanium in n-hexane was 3.3 mmol / hour, 0.825 mmol · hour, and 0.8 mmol / hour, respectively. At a rate of 15 mmol / hour, the content was continuously fed to a polymerization vessel having an internal capacity of 1 liter, and at the same time, 700 g / hour of ethylene,
1-octene 850 g / hour, hydrogen 0.14 g / hour and n-hexane 6 liter / hour were continuously fed to the polymerization vessel at a reaction temperature of 185 ° C. and a reaction pressure of 70 kg / hour.
Copolymerization was carried out under the condition of cm ² G to obtain a copolymer.

Production Example 2 (Ethylene / 1-octene copolymer A2) Copolymerization was performed in the same manner as in Production Example 1 except that the amount of 1-octene supplied was changed to 330 g / hour.

Production Example 3 (1) Synthesis of dimethylanilinium tetra (pentafluorophenyl) borate Pentafluorophenyllithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was added to 45 mmol of boron trichloride in hexane. To give tri (pentafluorophenyl) boron as a white solid. The obtained tri (pentafluorophenyl) boron 41 mmol was reacted with pentafluorophenyllithium 41 mmol to isolate lithium tetra (pentafluorophenyl) boron as a white solid. Next, 16 mmol of lithium tetra (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride were reacted in water to obtain 11.4 mmol of tetra (pentafluorophenyl) boron dimethylanilinium as a white solid. Proton nuclear magnetic resonance measurement ( ¹ H-NM
R), isotope carbon nuclear magnetic resonance measurement ( ¹³ C-NMR).

(2) Preparation of solid catalyst In a 500 ml flask, 10.0 g of γ-alumina calcined at 500 ° C. for 3 hours, 300 ml of a toluene dispersion of zirconium tetrachloride (0.02 mol / liter), and triisobutyl were added. After adding 30 mmol of aluminum and 6 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate and treating at room temperature for 30 minutes with stirring, toluene was distilled off under reduced pressure to obtain a solid catalyst.

(3) Ethylene / 1-octene Copolymer B Toluene as a solvent was charged at a rate of 1 liter / hour to a 1 liter autoclave which had been dried and replaced with nitrogen, and 700 g / hour of ethylene and 1-octene, respectively. , 800 g / hour, and the solid catalyst prepared in (2) as a catalyst component was used as Zr at 0.1 mmol /
Time and triisobutylaluminum 2 mmol / hour were added and copolymerization was carried out at 80 ° C. The total pressure is 9 kg / cm.
Adjusted to be ² . As a result, an ethylene / 1-octene copolymer was obtained at 720 g / hour. This is 78.9 kg / g as the activity per 1 g of zirconium used.
-It was Zr.

[0062]

[Table 1]

Examples 1 to 4, Comparative Examples 1 and 2 The copolymers A1 and B or A2 and B obtained in Production Examples 1 to 3 were dry blended in the proportions shown in Table 2, and Irganox was used as an additive. 1076 1500ppm, diatomaceous earth 1500ppm and erucic acid acid 1000ppm
In addition, the mixture was kneaded and granulated with a single extruder having a diameter of 20 mm.
Further, a film was formed by the T-die method under the following conditions. Extruder: Diameter 20 mm Molding die: Width 170 mm, Gap 0.5 mm, Air gap 60 mm Resin temperature: 230 ° C. Chill roll temperature: 30 ° C. Film thickness: 25 μm Further, the following physical properties of the obtained molded product were measured. .. The results obtained are shown in Table 2. Tensile modulus (kg / cm ² ): JI using autograph
According to S-Z-7113. Tear strength (kg / cm): based on JIS-Z-1702. Film impact (kg / cm / cm): ASTM-
According to D3430. Haze (%): Based on JIS-Z-1702, a digital haze computer manufactured by Suga Test Instruments Co., Ltd. was used. Heat sealing temperature (° C): in accordance with JIS-Z-1707. Heat-seal width of 4 cm x 20 cm test piece 10
mm × 15 mm, pressure 0.5 kg / cm ² pressure bonding for 1 second and heat sealing, then leave for 30 minutes, pulling speed 20
Temperature at the time of heat sealing at which the strength when peeled at 0 mm / min becomes 300 g.

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

As described above, according to the present invention, transparency,
An ethylene / α-olefin copolymer composition having excellent puncture strength, tear strength, weather resistance, low temperature heat sealability, heat seal strength, impact strength, dielectric properties and the like can be obtained. Therefore, the ethylene / α-olefin copolymer composition of the present invention is used as a sealant film, a pallet stretch film, a commercial wrap film, an agricultural film, a meat packaging film, a shrink film, a covering material, a damping material, a pipe, It can be used for various purposes such as medical infusion packs and toys. In particular, when it is formed into a film or a sheet, it is excellent in transparency and mechanical strength, so that it can be used in various fields such as packaging, medical treatment, and agriculture.

Claims (1)

[Claims] 1. (A) Melt index (MI) is 0.
1 to 25 g / 10 min, density 0.900 to 0.940 g / ml, branch number 10 to 40/1000 carbon and maximum melting point (Tm by differential scanning calorimeter (DSC)
Ethylene having a (max) of 110 to 130 ° C. α-
Olefin copolymer 60 to 95% by weight, (B) melt index (MI) 0.3 to 15 g / 10 min, density
0.890 to 0.910 g / ml, molecular weight distribution defined by weight average molecular weight (Mw) / number average molecular weight (Mn) is 2-5, and molecular weight dependence width of branching number is 0 to 5/10
00 carbon, orthodichlorobenzene (ODCB) soluble content of 10 wt% or less and differential scanning calorimeter (DSC)
And an ethylene / α-olefin copolymer composition having a maximum melting point (Tm (max)) of 115 ° C. or less of 40 to 5% by weight.