JPH11302466A - Ethylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene resin composition having sufficient transparency and operability as a film and excellent stability during molding without harming its excellent mechanical properties and moldability. SOLUTION: This composition is obtained by blending 100 pts.wt. of an ethylene resin comprising 70-98 wt.% of an ethylene/α-olefin copolymer which is a copolymer of ethylene and a 3-20C α-olefin satisfying the conditions (a), (b) and the like: (a) the density (D) is not less than 0.85 g/cm<3> and not more than 0.95 g/cm<3> , (b) the melt tension(MT) at 190 deg.C and the melt flow rate(MFR) satisfy the equation: log(MT)>=-0.9l×log(MFR)+0.06 [wherein MT: the melt tension (g); MFR: the melt flow rate (g/10 min)], and 30-2 wt.% of a low density polyethylene prepared by a high pressure radical method having the properties of (c)-(f): (c) MFR is 0.1-20 h/10 min, (d) the density is 0.915-0.935 g/cm<3> , (e) MT is 5-17 g, (f) the memory effect(ME) is 0.6-2.1, with 0.05-1.0 pt.wt. of an antioxidant and 0.01-0.8 pt.wt. of an antiblocking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ethylene resin composition. More specifically, the present invention relates to an ethylene / α-olefin copolymer whose MFR, MT, density and elution behavior in cross fractionation satisfy a specific relational expression, MFR and density, MT, and ME have specific values. A low-density polyethylene produced by a high-pressure radical method within a range, and a specific amount of an antioxidant and an antiblocking agent, which relates to an ethylene-based resin composition, which is used to mold the copolymer of the present invention into a film. In this case, a film having excellent molding stability and excellent transparency, gloss, and opening property can be obtained.

[0002]

2. Description of the Related Art Conventionally, copolymers of ethylene and α-olefin have been used in pouches because films obtained by inflation film molding have excellent mechanical properties such as tensile strength and impact strength. It is used in large quantities for a variety of applications, mainly for applications. However, a film obtained by inflation molding only a copolymer of ethylene and α-olefin has a problem that transparency and opening property are not sufficient for many uses.

On the other hand, ethylene / α-olefin copolymers produced using a metallocene catalyst have recently been proposed, but their transparency and opening properties are somewhat improved as compared with conventional ethylene / α-olefin copolymers. However, the bubble stability at the time of molding is not always preferable because the molecular weight distribution is narrow.
No. 3309).

Therefore, polymerization is carried out in multiple stages (Japanese Patent Laid-Open No.
And Japanese Patent Application Laid-Open (JP-A) No. 5-155932).
To improve the molding characteristics of polyethylene by expanding the molecular weight distribution by the method disclosed in Japanese Patent Application Laid-Open No. A method of mixing polyethylene produced by a high-pressure method with the coalescing has been proposed.

Further, there is an application (International Patent Application Publication No. WO93 / 08221) claimed to be characterized by having excellent fluidity despite its narrow molecular weight distribution. However, although the fluidity and moldability were slightly better than the former proposal, the transparency and the opening property were not sufficient.

[0006] Therefore, in order to obtain excellent molding stability and to obtain a sufficient opening property when formed into a film, a large amount of low-density polyethylene produced by a high-pressure radical method is blended and a large amount of an antiblocking agent is used. Had to be added. However, in this method, the transparency and strength of the film are reduced, and although the transparency is improved when the amount of the antiblocking agent is reduced, the opening property is deteriorated,
A problem arose in terms of product quality.

[0007]

SUMMARY OF THE INVENTION Therefore, ethylene
Without impairing the excellent mechanical properties and processability of the α-olefin copolymer, the ethylene resin composition has sufficient transparency and openability when formed into a film, and has excellent stability during molding. Development was awaited.

[0008]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, the melt tension and the melt flow rate have a specific relationship, and An ethylene / α-olefin copolymer satisfying the elution conditions and a specific low-density polyethylene produced by a high-pressure radical method, a specific amount of an antioxidant, and a specific amount of an antiblocking agent solve the above-mentioned problems. And arrived at the present invention.

That is, the ethylene resin composition according to the present invention is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and satisfies the following conditions (a) to (c). 70 to 98% by weight of olefin copolymer: (a) Density (D) is 0.850 g / cm ³ or more and 0.95
0 g / cm ³ or less (b) The relationship between the melt tension (MT) at 190 ° C. and the melt flow rate (MFR) satisfies the following equation: log (MT) ≧ −0.91 × log (MFR) +0.06 ... (1) MT: melt tension (g) MFR: melt flow rate (g / 10 minutes) (c) Satisfies the following three formulas: Tmax ≦ 972D-813 (2) logW ₆₀ ≦ −0.114 Tmax + 9.48 ... (3) logW ₉₀ ≧ 0.0394 Tmax−2.95 (4) where D: density (g / cm ³ ) Tmax: elution peak temperature (° C.) by cross fractionation measurement W ₆₀ : soluble below 60 ° C. Weight fraction (wt%) W ₉₀ : Low-density polyethylene 30 to 2 produced by a high-pressure radical method having a soluble weight fraction (wt%) of 90 ° C. or higher and the following properties (d) to (g). weight% : (D) MFR is 0.1 to 20 g / 10 min. (E) Density is 0.915 g / cm ^{3 to} 0.935 g / c.
It is m ³ (f) MT to be 5~17g (g) of the ethylene-based resin 100 parts by weight consists of memory effect (ME) is 1.6 to 2.1, antioxidants An ethylene-based resin composition comprising 0.05 to 1.0 part by weight and 0.01 to 0.8 part by weight of an antiblocking agent.

The ethylene / α-olefin copolymer is preferably an ethylene resin composition satisfying the following three formulas. Tmax ≦ 972D-816 (2) ′ logW ₆₀ ≦ −0.114 Tmax + 9.48 (3) logW ₉₀ ≧ 0.0394 Tmax-2.81 ...
(4) ′ Further, the density (D) of the ethylene / α-olefin copolymer is 0.850 g / cm ³ or more and 0.935 g / c.
An ethylene resin composition having an m ³ or less is particularly preferred.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) Ethylene / α-olefin copolymer The copolymer used in the present invention has a density (D) of 0.850.
g / cm ³ or more, 0.950 g / cm ³ or less, preferably 0.850 g / cm ³ or more, 0.935 g / cm ³ or less, particularly preferably 0.900 g / cm ³ or more, 0.9
It is necessary to be 34 g / cm ³ or less (condition (a)). If the density is too low, the stiffness of the film molded product is not sufficient, and the workability in a bag making machine or the like is poor, and the opening property is poor, which is not preferable. If it is too large, sufficient transparency of the film cannot be secured. Note that the density is 100% of the strand obtained at the time of melt index measurement.
This is a value measured by a density gradient tube method after heat treatment at 1 ° C. for 1 hour and further cooling at room temperature for 1 hour.

[0012] The copolymer used in the present invention comprises 19
The relationship between the melt tension (MT) at 0 ° C. and the melt flow rate (MFR) is as follows: log (MT) ≧ −0.91 × log (MFR) +0.06 (1) Preferably, log (MT) ≧ −0 .91 × log (MFR) +0.
12 Particularly preferably, log (MT) ≧ −0.91 × log (MFR) +0.
21 must be satisfied (condition (b)). If this relational expression is not satisfied, when forming a blown film,
Problems such as bubble tearing or wavering (the stability of the bubble cannot be maintained) occur. Among them, MF of copolymer
Preferably, R is 0.1 to 50 g / 10 min, and MFR
Is too low, the fluidity at the time of melting is insufficient, and the surface of the molded article tends to be rough. If the MFR is too high, the strength of the molded article tends to decrease, which is not preferable.

The MFR is a value measured at 190 ° C. under a load of 2.16 kg in accordance with ASTM D1238. The MT is a capillaograph manufactured by Tsukayo Seiki Seisaku-sho, Ltd., having a nozzle diameter of 2.095 mmφ and a nozzle length of 8 mm. At an inflow angle of 180 ° and a temperature of 190 ° C., an extrusion speed of 1.0 cm
/ Min, take-up speed 4.0 m / min, and a distance of 40 cm from the die outlet to the lower end of the V pulley of the tension detector. ME was measured as follows using a melt indexer used in JlSK7210. Under the condition of cylinder temperature of 240 ° C., after filling the sample into the apparatus, only the piston is placed, and after 6 minutes, the melted sample is extruded at a constant speed of 3 g / min. Cut at the outlet immediately below, then place a measuring cylinder containing ethyl alcohol directly below the orifice and the liquid level is 20 m from the bottom of the orifice.
m, a straight extrudate is taken and its diameter is measured in 0.01 mm units. The value is divided by the inner diameter of the orifice 2.095 (mm) to obtain the value of ME.

A particularly important point in the present invention is to have a specific copolymer composition distribution while having a narrow molecular weight, and such a copolymer composition distribution is determined by the maximum peak temperature (e.g., (Tmax) is shifted to a relatively low side in proportion to the density of copolymerization, and the amount of eluted components in a high temperature region is relatively large in proportion to Tmax. That is, in the copolymer used in the present invention,
Density (D), temperature at maximum peak position (Tmax), 60
The soluble fraction weight fraction (W ₆₀ ) below 90 ° C. and the soluble fraction weight fraction (W ₉₀ ) above 90 ° C. simultaneously satisfy the following three formulas:
For example, it is necessary to improve the stability of film formation during the formation of an inflation film and the transparency of the obtained film (condition (c)).

Tmax ≦ 972D-813 (2) logW ₆₀ ≦ −0.114 Tmax + 9.48 (3) logW ₉₀ ≧ 0.0394 Tmax−2.95 (4) Preferably, Tmax ≦ 972D-816 (2) ) 'LogW ₆₀ ≦ −0.114 Tmax + 9.48 (3) logW ₉₀ ≧ 0.0394 Tmax−2.81 ...
(4) '

If the above range is not satisfied, bubble stability cannot be maintained when the ethylene-based resin composition of the present invention is formed into a film by inflation molding. Furthermore, the opening property is inferior. The measurement by the cross fractionation method was performed by Mitsubishi Chemical Corporation.
Separation apparatus (CFC) manufactured by Toshiba Corporation was used, the solvent was ortho-dichlorobenzene, and the column size was 0.46 mm diameter x 15
cm, filler is glass beads (0.1 mm diameter), detector is infrared detector (MIRAN IA), measurement wave number is 3.42
The test was performed under the conditions of μm, sample concentration of 3 mg / ml, and injection volume of 0.4 ml. Specifically, the sample solution was introduced into the column at 140 ° C. under the above conditions, cooled to 0 ° C. at a rate of temperature decrease of 1 ° C./min, held for 30 minutes, and then 0, 10, 20, 30, 35,
40, 45, 49, 52, 55, 58, 61, 64, 6
7, 70, 73, 76, 79, 82, 85, 88, 9
Elution was performed at 26, 1, 94, 100, 120, and 140 ° C. temperatures, and the concentration of the polymer was detected by an infrared detector to obtain an elution curve. From the second section onwards, elution was carried out after holding at each temperature for 40 minutes. The flow rate was 1 ml / min.

In order to obtain the copolymer used in the present invention, for example, a method in which an ethylene / α-olefin copolymer separately produced by a so-called metallocene catalyst is blended by kneading, and And a method of obtaining copolymers having different densities by using two kinds of metallocene compounds in combination, and satisfying the above characteristics (a) to (c). If it is not particularly limited, the following [A] ~
A copolymer obtained by polymerization using the catalyst component comprising [C] is preferable. [A] a metallocene-based transition metal compound [B] an ion-exchange layered compound or a non-layered inorganic silicate, and if necessary, [C] an organoaluminum compound

The metallocene transition metal compound as the component (A) has one or two cyclopentadienyl ligands or substituents which may be substituted are bonded to form a condensed ring. And one or two cyclopentadienyl ring-containing ligands and a long period table (I.
It is based on the 18 group system recommended by UPAC. The same applies to the following), an organometallic compound comprising a transition metal belonging to Group 3, 4, 5, or 6, or a cationic complex thereof. Preferred as such a metallocene transition metal compound is a compound represented by the following general formula [1] or [2].

(CpR ⁴ _a H _5-a ) _p (CpR ⁵ _b H _5-b ) _q MR ⁶ _r ... [1] [(CpR ⁴ _a H _5-a ) _p (CpR ⁵ _b H _5-b ) _q MR ⁶ _r L _m] ^{n +} [R ^{7] n} one ... [2] where, CpR ⁴ _a H _5-a and CpR _{⁵ b} H _^5-b show the derivatives of cyclopentadienyl (Cp) groups .

In the above formulas (1) and (2), R ⁴ and R ⁵ are
An optionally substituted hydrocarbon group having 1 to 20 carbon atoms,
Silicon-containing substituents, phosphorus-containing substituents, nitrogen-containing substituents,
Oxygen-containing substituents, which may be the same or different. Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. Alkyl group, phenyl group, p-tolyl group, o-tolyl group, aryl group such as m-tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, Bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, halo-substituted hydrocarbon group such as iodophenyl group,
Trimethylsilyl group, triethylsilyl group, silicon-containing substituents such as triphenylsilyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group,
Alkoxy groups such as isobutoxy group and t-butoxy group, phenoxy group, methylphenoxy group, pentamethylphenoxy group, p-tolyloxy group, o-tolyloxy group, m
And aryloxy groups such as tolyloxy groups. Of these, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a t-butyl group, an alkoxy group such as a trimethylsilyl group and a methoxy group, and an aryloxy group such as a phenoxy group.

R ⁴ and R ⁵ may be bonded to each other to form a crosslinking group. Specifically, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, Silicon-containing crosslinking groups such as propylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t-butylsilylene group, dimethylgermylene group, diethylgermylene Gels such as group, dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, methylisopropylgermylene group, methyl-t-butylgermylene group Sulfonium-containing crosslinking group such as an amino group, Hosufuiniru group and the like.

Further, R ⁴ and R ⁵ may be bonded to each other to form a ring. Specifically, an indenyl group, a tetrahydroindenyl group, a fluorenyl group,
An octahydrofluorenyl group and the like are preferably mentioned, and these may be substituted.

R ⁶ is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, hydrogen, halogen, a silicon-containing substituent, an alkoxy group, an aryloxy group, an amide group, or a thioalkoxy group. Include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl,
Alkyl group such as decyl group, phenyl group, p-tolyl group,
o-tolyl group, aryl group such as m-tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl Group, halo-substituted hydrocarbon group such as iodophenyl group, fluorine, chlorine, bromine, halogen such as iodine, trimethylsilyl group, triethylsilyl group,
Silicon-containing substituents such as triphenylsilyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, alkoxy group such as t-butoxy group, phenoxy group, methylphenoxy group, pentamethylphenoxy group, aryloxy σ 6 groups such as p-tolyloxy group, m-tolyloxy group, o-tolyloxy group,
Amide groups such as dimethylamide group, diethylamide group, dipropylamide group, diisopropylamide group, ethyl-t-butylamide group, bis (trimethylsilyl) amide group, methylthioalkoxy group, ethylthioalkoxy group, propylthioalkoxy group, butyl And thioalkoxy groups such as a thioalkoxy group, a t-butylthioalkoxy group, and a phenylthioalkoxy group. Of these, hydrogen, methyl, ethyl, propyl,
Halogen such as isopropyl group, butyl group, phenyl group and chlorine, methoxy group, ethoxy group, propoxy group, isopropoxy group, dimethylamide group and methylthioalkoxy group are mentioned, and hydrogen, methyl group and chlorine are particularly preferable.

Also, R⁶ Is R^Four Or R^Five Or C
and a specific example of such a ligand.
And CpH_Four (CH_Two )_n O- (1 ≦ n ≦ 5), Cp
Me _Four(CH_Two )_n O- (1 ≦ n ≦ 5), CpH_Four (M
e_Two Si) (t-Bu) N-, CpMe_Four (Me_Two S
i) (t-Bu) N- etc. (Cp is cyclopentadienyl)
Group, Me represents a methyl group, and Bu represents a butyl group).
It is. Further, R⁶ Bind to each other to form a bidentate ligand
You may. Such R⁶ As a specific example of -OCH
_Two O-, -OCH_Two CH_Two O-, -O (o-C₆ H_Four )
O- and the like.

M is an atom belonging to Groups 3, 4, 5, and 6 of the periodic table, and specific examples thereof include scandium, yttrium, lanthanum, cerium, brassodymium, neodymium, samarium, europium, gadolinium, terbium, dysbrosium, and holmium. , Erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, titanium, zirconium,
Hownium, vanadium, niobium, tantalum, chromium,
Molybdenum and tungsten are mentioned. Of these, titanium, zirconium, and hafnium of Group 4 are preferably used. These may be used as a mixture.

L is an electrically neutral ligand, and m is an integer of 0 or more in the number thereof.
Ethers such as tetrahydrofuran and dioxane,
Examples thereof include nitriles such as acetonitrile, amides such as dimethylformamide, phosphines such as trimethylphosphine, and amines such as trimethylamine. Preferred are tetrahydrofuran, trimethylphosphine and trimethylamine.

[R ⁷ ] ^n- is one or more anions that neutralize the cation, and specific examples thereof include tetraphenyl borate, tetra (p-tolyl) borate, carbadodecaborate, and dicarbaoundeca. Examples thereof include borate, tetrakis (pentafluorophenyl) borate, tetrafluoroborate, and hexafluorophosphate. Preferably, tetraphenyl borate,
Tetra (p-tolyl) borate, tetrafluoroborate, and hexafluorophosphate. a and b are 0
Is an integer of up to 5. When the valence of M is V, p, q, and r are 0 or a positive integer satisfying p + q + r = V when the metallocene-based transition metal compound is represented by the formula [1]. Is 0 or a positive integer satisfying p + q + r = V−n in the case of the formula [2].
Usually, p and q are integers of 0 to 3, preferably 0 or 1. r is an integer of 0 to 3, preferably 1 or 2. n
Is an integer satisfying 0 ≦ n ≦ V.

The above-mentioned catalyst can produce any of an isotactic polymer, a syndiotactic polymer and an atactic polymer.

The above-mentioned metallocene transition metal compound, specifically, taking zirconium as an example, bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclohexane) are equivalent to the formula [1]. (Pentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dihydride, bis (ethylcyclopentadienyl) Zirconium dihydride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (ethyltetramethylcyclopentadienyl) zirconium dichloride, bis (ethyl-n-butyl-cyclopentadienyl) zirconium dichloride, bis (ethyl-methyl-cyclopentadienyl) zirconium dichloride, bis (n-butyl-methyl) -Cyclopentadienyl) zirconium dichloride, bis (indenyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (trimethylcyclopentadienyl) zirconium dimethyl, bis (tetramethylcyclopentadienyl) zirconium dimethyl, bis (ethyltetramethylcyclopentadienyl)
Zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium dihydride, bis (trimethylcyclopentadienyl) zirconium dihydride, bis (ethyltetramethylcyclopentadienyl) zirconium dihydride , Bis (trimethylcyclopentadienyl) zirconium dimethyl, bis (trimethylsilylcyclopentadienyl) zirconium dihydride, bis (trifluoromethylcyclopentadienyl) zirconium dichloride, bis (trifluoromethylcyclopentadienyl)
Zirconium dimethyl, bis (trifluoromethylcyclopentadienyl) zirconium dihydride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dimethyl, isopropylidene-bis (indenyl) zirconium dihydride, Pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, ethyltetramethyl Cyclopentadienyl (cyclopentadienyl) zirconium dihydride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride Lido, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dihydride, bis (cyclopentane) Dienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium dipropyl, bis (cyclopentadienyl) zirconium diphenyl, methylcyclopenta Dienyl (cyclopentadienyl) zirconium dichloride, ethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, methylcyclopentadi Nyl (cyclopentadienyl) zirconium dimethyl, ethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, methylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, ethylcyclopentadienyl (cyclopentadienyl) zirconium Dihydride, dimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclo Pentadienyl) zirconium dichloride, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, indenyl (cyclo Pentadienyl) zirconium dichloride, dimethylcyclopentadienyl (cyclopentadienyl)
Zirconium dimethyl, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, ethyltetramethylcyclopentadi Enyl (cyclopentadienyl)
Zirconium dimethyl, indenyl (cyclopentadienyl) zirconium dimethyl, dimethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, bis (pentamethylcyclo (Pentadienyl) zirconium dihydride, indenyl (cyclopentadienyl) zirconium dihydride, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium dihydride , Trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, trifluoromethylcyclopentadienyl (cyclopentadienyl) Zirconium dimethyl, trifluoromethyl cyclopentadienyl (cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl)
(Trimethylsilyl) (methyl) zirconium, bis (cyclopentadienyl) (triphenylsilyl) (methyl) zirconium, bis (cyclopentadienyl)
[Tris (trimethylsilyl) silyl] (methyl) zirconium, bis (cyclopentadienyl) [bis (methylsilyl) silyl] (methyl) zirconium, bis (cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis (cyclo Pentadienyl) (trimethylsilyl) (benzyl) zirconium, methylene-bis (cyclopentadienyl) zirconium dichloride, ethylene-bis (cyclopentadienyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl) zirconium dichloride, dimethyl Silyl-bis (cyclopentadienyl) zirconium dichloride, methylene-bis (cyclopentadienyl) zirconium dimethyl, ethylene-bis (cyclopentadienyl) di Conium dimethyl, isopropylidene-bis (cyclopentadienyl) zirconium dimethyl, dimethylsilyl-bis (cyclopentadienyl) zirconium dimethyl, methylene-bis (cyclopentadienyl) zirconium dihydride, ethylene-bis (cyclopentadiene) (Enyl) zirconium dihydride, isopropylidene-bis (cyclopentadienyl) zirconium dihydride, dimethylsilyl-bis (cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl) zirconium bis (methanesulfonate) ), Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (cyclopentadienyl) zircon Trifluoromethanesulfonatochloride, bis (cyclopentadienyl) zirconiumbis (benzenesulfonato), bis (cyclopentadienyl) zirconiumbis (pentafluorobenzenesulfonato), bis (cyclopentadienyl) zirconiumbenzenesulfonate Chloride, bis (cyclopentadienyl) zirconium (ethoxy) trifluoromethanesulfonate, bis (tetramethylcyclopentadienyl) zirconiumbis (trifluoromethanesulfonato), bis (indenyl) zirconiumbis (trifluoromethanesulfonato), ethylene Bis (indenyl) zirconium bis (trifluoromethanesulfonato), isopropylidene-bis (indenyl)
Zirconium bis (trifluoromethanesulfonate),
(Tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silanedibenzylzirconium, (tertiary-butylamido) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silanedibenzylzirconium, indenyl Zirconium tris (dimethylamide), indenyl zirconium tris (diethylamide), indenyl zirconium tris (di-n-propylamide), cyclopentadienyl zirconium tris (dimethylamide), methylcyclopentadienyl zirconium tris (dimethylamide) , (Tertiary butylamide) (tetramethylcyclopentadienyl) -1,2
-Ethanediyl zirconium dichloride, (methylamide) -1- (tetramethylcyclopentadienyl) -1,2
-Ethanediyl zirconium dichloride, (ethylamide) (tetramethylcyclopentadienyl) methylene zirconium dichloride, (tertiary butylamido) dimethyl-(tetramethylcyclopentadienyl) silane zirconium dichloride, (benzylamido) dimethyl (tetramethylcyclo (Pentadienyl) silane zirconium dichloride, (phenylphosphido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dibenzyl, (phenylamido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride,
(2-methoxyphenylamide) dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, (4-fluorophenylamido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, ((2,6-di (1- Methylethyl) phenyl) amido) dimethyl (tetramethylcyclobenzodienyl) amido zirconium dichloride.

Examples of the compound corresponding to the general formula [2] include bis (methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex and bis (ethylcyclopentadienyl) zirconium (chloride) ( Tetraphenylborate) tetrahydrofuran complex, bis (methylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (methyl) Cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
Bis (dimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (trimethylcyclopentadienyl)
Zirconium (chloride) (tetraphenylborate)
Tetrahydrofuran complex, bis (tetramethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethyltetramethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) Zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
Bis (dimethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (tetramethylcyclopentadienyl) zirconium (Methyl) (tetraphenylborate) tetrahydrofuran complex, bis (ethyltetramethylcyclopentadienyl) zirconium (methyl)
(Tetraphenyl borate) tetrahydrofuran complex,
Bis (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
Bis (trimethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (ethyltetramethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (trimethylcyclopentadienyl) Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (trimethylsilylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (trifluoromethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate ) Tetrahydrofuran, bis (trifluoromethylcyclopentadienyl) zirconium (hydride) (tetraphenyl vole ) Tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (indenyl) Zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclopendadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) ) Zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclope Tajieniru)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclopentadienyl) Zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (Chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconi (Methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (chloride) (tetraphenyl (Borate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (ethyl) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) Zirconium (propyl) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (phenyl) (tetraphenyl Rate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex , Bis (ethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (methyl)
(Tetraphenyl borate) tetrahydrofuran complex,
Ethylcyclopentadienyl (cyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
Ethylcyclopentadienyl (cyclopentadienyl)
Zirconium (hydride) (tetraphenylborate)
Tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
Trimethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (pentane Methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, indenyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium ( Methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconi Beam (methyl) (tetraphenylborate) tetrahydrofuran complex, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetramethyl-phenylalanine borate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, cyclopentadienyl (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate ) Tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, indenyl (Cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, trimethylsilane Lecyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, trifluoromethylcyclo Pentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (trimethylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (triphenyl) (Silyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) [tris (trimethylsilyl) [Silyl] zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (trimethylsilyltyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (benzyl) zirconium (tetraphenylborate) tetrahydrofuran complex, Methylene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadiene) Enyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadi (Enyl) zirconium (chloride) (tetraphenyl borate) tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenyl borate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (methyl) ( Tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
Ethylene-bis (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentane) Dienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
Bis (cyclopentadienyl) zirconium (methanesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (p-toluenesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) ) Zirconium (trifluoromethanesulfonate)
(Tetraphenyl borate) tetrahydrofuran complex,
Bis (cyclopentadienyl) zirconium (benzenesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (pentafluorobenzenesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (tetramethylcyclopenta Dienyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex, ethylenebis (indenyl) zirconium (trifluoromethanesulfonate) (Tetraphenyl borate) tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (trifluoro Tansuruhonato) (tetraphenylborate) tetrahydrofuran complex, and the like.

In the above examples, disubstituted cyclopentadienyl rings include 1,2- and 1,3-substituted compounds, and tri-substituted ones are 1,2,3- and 1,2,4- Including substitutions. In addition, the same compounds as those described above for other Group 3, 4, 5, and 6 metal compounds such as titanium compounds and hafnium compounds can also be used. Further, a mixture of these compounds may be used.

As the component (B), (1) an ion-exchange layered compound or (2) an inorganic silicate having no layered structure, that is, a non-layered inorganic silicate is used. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force to each other, and means a compound whose contained ions are exchangeable. Most clays are ion exchangeable underlying compounds.
Clay is usually based on clay minerals. These clays, clay minerals or ion-exchange layered compounds are not limited to natural products, but may be artificially synthesized products.

Specific examples of clays and clay minerals include allophane group such as allophane, kaolin group such as deckite, nacrite, kaolinite and anoxite, halloysite group such as metahaloysite and halloysite, chrysotile, lizardite, and antigolite. Serpentinite, montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, etc., smectite, vermiculite, etc., vermiculite minerals, helicite, sericite, mica minerals, such as chlorite, attapulgite, sepiolite, paigorskite, Examples include bentonite, kibushi, gairome clay, hisingelite, pyrophyllite, and ryokudeite. These may form a mixed layer. Among these, smectites such as montmorillonite, zaukonite, hyderite, nontronite, saponite, hectonite, bentonite, teniolite, and mica are preferred.

Further, the ion-exchangeable layered compound includes hexagonal close-packed type, antimony type, CdCl ₂ type, CdI ₂
An ionic crystalline compound having a layered crystal structure such as a mold can be exemplified. Specific examples of the ion-exchange layered compound having such a crystal structure include α-Zr (H
AsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-
Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ )
₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (H
PO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-T
i (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂
Crystalline acidic salts of polyvalent metals such as O are mentioned. Non-layered inorganic silicates include zeolite and diatomaceous earth.

The component (B) is preferably subjected to a chemical treatment. Here, the chemical treatment may be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure of the clay. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. The acid treatment increases the surface area by removing impurities on the surface and eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay.
In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like are formed, and the surface area and the interlayer distance can be changed. By utilizing the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, it is also possible to obtain a layered material in which the layers are expanded. That is, the bulky ions play a pillar-like role of supporting the layered structure, and are called pillars. Introducing another substance between layered substance layers is called intercalation.

Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR) ₄ and PO (OR)
_3, B (OR) ₃ wherein R is alkyl, aryl, etc.] metal alcoholate such as [Al ₁₃ 0 ₄ (OH) _24] ^7+, [Zr ₄
(OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₅ ] ^{+, and} other metal hydroxide ions. These compounds may be used alone or in combination of two or more.

When intercalating these compounds, Si (OR) ₄ , Al (OR) ₄ , Ge
A polymer obtained by hydrolyzing a metal alcoholate such as (OR) ₄ or the like, a colloidal inorganic compound such as SiO _2, or the like can be coexisted. Examples of pillars include oxides formed by intercalating the hydroxide ions between layers and then heating and dehydrating.

The component [B] may be used alone or as a mixture of two or more of the above solids. As the component (B), those having a wide range of average particle size can be used. In particular, in the case of gas phase polymerization or slurry polymerization, it is preferable to use spherical particles having an average particle size of 5 μm or more. More preferably, spherical particles having an average particle size of 10 μm or more are used. Most preferably, the average particle size is 10 μm or more and 100 μm
The following spherical particles are used. The average particle size here is SE
Laser micronizer LMS-24 manufactured by ISHIN
And obtained by measuring in ethanol using As the component (B), a natural product or a commercially available product may be used as it is as long as it is in the form of particles. May be used.

The granulation method used here includes, for example, stirring granulation, spray granulation, tumbling granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, and emulsion granulation. And a submerged granulation method and a compression molding granulation method, but are not particularly limited as long as the method can granulate the component [B]. Preferable examples of the granulation method include stirring granulation method, spray granulation method, tumbling granulation method and fluidized bed granulation method, and particularly preferable examples include stirring granulation method and spray granulation method, and spray granulation. Is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene and xylene is used as a dispersion medium for the raw material slurry. Preferably, water is used as the dispersion medium. The concentration of the component [B] in the slurry slurry for spray granulation from which spherical particles can be obtained is 0.1 to 70%, preferably 1 to 5%.
0%, particularly preferably 5 to 30%. The inlet temperature of the hot air of the spray granulation for obtaining spherical particles varies depending on the dispersion medium, but is 80 to 260 ° C., preferably 100
Perform at ~ 220 ° C.

At the time of granulation, an organic substance, an inorganic solvent, an inorganic salt, and various binders may be used. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethyl celluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein,
Latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, sodium alginate and the like.

As the component (B), preferred are (1) an ion-exchange layered compound having a water content of 3% by weight or less, obtained by salt treatment and / or acid treatment, or (2) ) At least one compound selected from the group consisting of non-layered inorganic silicates. These can be obtained by treating at least one compound selected from the group consisting of an ion-exchangeable layered compound or a non-layered inorganic silicate with a salt and / or an acid. The acid strength of the solid can be changed by the salt treatment and / or the acid treatment, and the details are as described above.

In addition, before being treated with a salt, at least one compound selected from the group consisting of an ion-exchangeable layered compound and a non-layered inorganic silicate contains a group 40 metal cation of an exchangeable Group 1 metal. % Or more, preferably 60% or more, is preferably ion-exchanged with a cation dissociated from the following salts. The salt used in the salt treatment for the purpose of ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of Group 2 to 14 atoms, preferably 2 to 14 A compound comprising at least one cation containing at least one atom selected from the group consisting of group atoms and a halogen atom, at least one anion selected from the group consisting of inorganic acids and organic acids, more preferably A cation containing at least one atom selected from the group consisting of Group 4 to 6 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , C
O ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ CO
CHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (Cl
O ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl
₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and at least one anion selected from the group consisting of C ₆ H ₅ O ₇ .

Specifically, CaCl_Two , CaSO_Four , Ca
C_Two O_Four , Ca (NO_Three )_Two , Ca _Three (C₆ H_Five O₇ )
_Two , MgCl_Two , MgBr_Two , MgSO_Four , Mg (PO
_Four ) _Two , Mg (ClO_Four )_Two , MgC_Two O_Four , Mg (N
O_Three )_Two , Mg (OOCCH _Three )_Two , MgC_Four H_Four O
_Four , Sc (OOCCH_Three )_Two , Sc_Two (CO_Three )_Three , S
c_Two (C_Two O_Four )_Three , Sc (NO_Three )_Three , Sc_Two (SO
_Four )_Three , ScF_Three , ScCl_Three , ScBr_Three , ScI
_Three , Y (OOCCH_Three )_Three , Y (CH_Three COCHCOC
H_Three )_Three , Y_Two (CO_Three )_Three , Y_Two (C_Two O_Four )_Three , Y
(NO_Three )_Three , Y (ClO_Four )_Three , YPO_Four , Y_Two (S
O_Four )_Three , YF_Three , YCl_Three , La (OOCCH_Three )
_Three , La (CH_Three COCHCOCH_Three )_Three , La_Two (C
O_Three )_Three , La (NO_Three )_Three , La (ClO_Four )_Three , L
a_Two (C_Two O_Four )_Three , LaPO_Four , La _Two (SO_Four )
_Three , LaF_Three , LaCl_Three , LaBr_Three , LaI_Three , S
m (OOCCH_Three )_Three , Sm (CH_Three COCHCOCH
_Three )_Three , Sm_Two (CO_Three )_Three , Sm (NO_Three )_Three , Sm
(Cl0_Four )_Three , Sm_Two (C_Two O_Four )_Three , Sm_Two (SO
_Four ) _Three , SmF_Three , SmCl_Three , SmI_Three , Yb (OO
CCH_Three )_Three , Yb (NO_Three)_Three , Yb (ClO_Four )
_Three , Yb (C_Two O_Four )_Three , Yb_Two (SO_Four )_Three , YbF
_Three , YbCl_Three , Ti (OOCCH_Three )_Four , Ti (CO
_Three )_Two , Ti (NO_Three ) _Four , Ti (SO_Four )_Two , TiF
_Four , TiCl_Four , TiBr_Four , TiI_Four , Zr (OOC
CH_Three )_Four , Zr (CO_Three )_Two , Zr (NO_Three )_Four , Z
r (SO_Four )_Two , ZrF_Four , ZrCl_Four , ZrBr_Four ,
ZrI_Four , ZrOCl_Two , ZrO (NO_Three)_Two , ZrO
(ClO_Four )_Two , ZrO (SO_Four ), Hf (OOCCH)
_Three )_Four , Hf (CO_Three )_Two , Hf (NO_Three )_Four , Hf
(SO_Four )_Two , HfOCl_Two , HfF _Four , HfCl_Four ,
HfBr_Four , HfI_Four , V (CH_Three COCHCOCH
_Three )_Three , VOSO_Four , VOCl_Three , VCl_Three , VCl
_Four , VBr_Three , Nb (CH_Three COCHCOCH_Three )₆ ,
Nb_Two (CO_Three )₆ , Nb (NO_Three )₆ , Nb_Two (SO
_Four ) ₆ , NbF₆ , NbCl₆ , NbBr₆ , NbI
₆ , Ta (OOCCH_Three )₆ , Ta_Two (CO_Three )₆ , T
a (NO_Three )₆ , Ta_Two (SO_Four )₆ , TaF₆ , Ta
Cl₆ , TaBr₆ , TaI₆ , Cr (CH_Three COCH
COCH_Three )_Three , Cr (OOCH)_Two OH, Cr (NO
_Three )_Three , Cr (ClO_Four )_Three , CrPO_Four , Cr _Two (S
O_Four )_Three , CrO_Two Cl_Two , CrF_Three , CrCl_Three , C
rBr_Three , CrI _Three , CrO_Two Cl_Two , CrF_Three , Cr
Cl_Three , CrBr_Three , CrI_Three , MoOCl_Four , MoC
l_Three , MoCl_Four , MoCl₆ , MoF₆ , MoI_Two ,
WCl_Four , WCl₆ , WF₆ , WBr₆ , Mn (OOC
CH_Three )_Two , Mn (CH_Three COCHCOCH_Three )_Two , M
nCO_Three , Mn (NO_Three )_Two , MnO, Mn (ClO
_Four )_Two, MnF_Two , MnCl_Two , MnBr_Two , MnI
_Two , Fe (OOCCH_Three )_Two , Fe (CH_Three COCHC
OCH_Three )_Three , FeCO_Three , Fe (NO_Three )_Two , Fe
(NO_Three )_Three , Fe (ClO_Four )_Three , FePO_Four , Fe
SO_Four , Fe_Two (SO_Four )_Three, FeF_Three , FeCl_Three ,
FeBr_Three , FeI_Two , FeC₆ H_Five O₇ , Co (OO
CCH_Three )_Two , Co (CH_Three COCHCOCH_Three )_Two ,
CoCO_Three , Co (NO_Three )_Two , CoC_Two O_Four , Co
(ClO_Four )_Two , Co_Three (PO_Four )_Two , CoSO _Four , C
OF_Two , CoCl_Two , CoBr_Two , CoI_Two , NiCO
_Three , Ni (NO_Three)_Two , NiC_Two O_Four , Ni (ClO
_Four )_Two , NiSO_Four , NiCl_Two , NiBr _Two , CuC
l_Two , CuBr_Two , Cu (NO_Three )_Two , CuC_Two O_Four ,
Cu (ClO _Four )_Two , CuSO_Four , Cu (OOCCH
_Three )_Two , Zn (OOCCH_Three )_Two , Zn (CH_Three COC
HCOCH_Three )_Two , Zn (OOCH_Three )_Two , ZnCO
_Three , Zn (NO_Three )_Two , Zn (ClO_Four )_Two , Zn_Three 
(PO_Four )_Two , ZnSO_Four , ZnF_Two, ZnCl_Two , Z
nBr_Two , ZnI_Two , Cd (OOCCH_Three )_Two , Cd
(CH_ThreeCOCHCOCH_Three )_Two , Cd (OOCCH_Two 
CH_Three )_Two , Cd (NO_Three )_Two , Cd (ClO_Four )_Two ,
CdSO_Four , CdF_Two , CdCl_Two , CdBr_Two , Cd
I _Two , AlF_Three , AlCl_Three , AlBr_Three , AlI_Three ,
Al_Two (SO_Four )_Three , Al _Two (C_Two O_Four )_Three , Al (C
H_Three COCHCOCH_Three )_Three , Al (NO_Three )_Three , Al
PO_Four , GeCl_Four , GeBr_Four , GeI_Four , Sn (O
OCCH_Three )_Four , Sn (SO_Four )_Two , SnF_Four , SnC
l_Four , SnBr_Four , SnI_Four , Pb (OOCCH_Three )
_Two , Pb (OOCCH_Three )_Four , Pb (CO_Three )_Two , Pb
CO_Three , Pb (NO_Three )_Two , PbHPO_Four , Pb (Cl
O_Four )_Two , PbSO_Four , PbF_Two , PbCl_Two , PbB
r_Two , PbI_Two And the like.

The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid. The salt and the acid used for the treatment may be two or more. When the salt treatment and the acid treatment are combined, there are a method of performing the salt treatment and then performing the acid treatment, a method of performing the acid treatment and then performing the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment.

The treatment conditions with salts and acids are not particularly limited, but usually, the salt and acid concentrations are 0.1 to 30% by weight, the treatment temperature is from room temperature to the boiling point, and the treatment time is from 5 minutes to 24 minutes.
It is preferable to select the time condition and to elute at least a part of a substance constituting at least one compound selected from the group consisting of an ion-exchange layered compound and a non-layered structure inorganic silicate. . Further, salts and acids are generally used in an aqueous solution.

When the salt treatment and / or the acid treatment is performed, the shape may be controlled by pulverization and granulation before, during, or after the treatment. Further, a chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. The component (B) thus obtained preferably has a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, having a pore volume of a radius of 20 ° or more measured by a mercury porosimetry.

A compound having a water content of 3% by weight or less is preferable because at least one compound selected from the group consisting of the ion-exchangeable layered compound and the non-layered inorganic silicate is usually adsorbed. Water and interlayer water are included, which means that it is preferable to remove these adsorbed water and interlayer water by heat treatment.

Here, the adsorbed water is water adsorbed on the surface of the ion-exchangeable layered compound or the non-layered structure inorganic silicate particles or the crystal fracture surface, and the interlayer water is water existing between crystal layers. The method of heat-treating the ion-exchanged layered compound or the non-layered structure inorganic silicate with the adsorbed water and the interlayer water is not particularly limited. A method such as dehydration is used. The temperature at the time of heating is set to 1 so that no interlayer water remains.
The temperature is higher than or equal to 00 ° C., preferably higher than or equal to 150 ° C., but high temperature conditions that cause structural destruction are not preferable. Further, a heat dehydration method for forming a crosslinked structure such as heating under air flow is not preferable because the polymerization activity of the catalyst is reduced. The heating time is at least 0.5 hour, preferably at least 1 hour. The water content was determined at a temperature of 200 ° C. and a pressure of 1
The water content when dehydrated for 2 hours under the condition of mmHg was measured as 0% by weight, and as described above,
It is preferably 3% by weight or less, preferably 1% by weight or less, and the lower limit is preferably 0% by weight or more. The component [B], which has been dehydrated and adjusted to have a water content of 3% by weight or less in this manner, has the same water content as the component [A] and, if necessary, the component [C]. Need to be treated to keep

If necessary, an organoaluminum compound may be used as the component (C), for example, AlR ⁸ _j X _3-j (where R ⁸ is a C1-20 hydrocarbon group, and X is hydrogen , A halogen, an alkoxy group, j is a number of 0 <j ≦ 3), trimethylaluminum, triethylaluminum,
Trialkylaluminum such as tripropylaluminum and triisobutylaluminum; or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride and diethylaluminum methoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkyl aluminum is particularly preferred.

It is preferable to make a catalyst by preliminarily polymerizing by contacting ethylene with the component [A], the component [B] and, if necessary, the component [C]. The method of contacting the component [A], the component [B] and, if necessary, the component [C] is not particularly limited, but they can be brought into contact in the following contact order. The component (A) is brought into contact with the component (B). After the component [A] and the component [B] are brought into contact, the component [C] is added. After the component [A] is brought into contact with the component [C], the component [B] is added. After the component [B] is brought into contact with the component [C], the component [A] is added. In addition, two components may be contacted simultaneously.

Upon or after the contact of each component of the catalyst, a polymer such as polyethylene or polypropylene, silica,
Solids of inorganic oxides such as alumina may coexist or may be brought into contact. The contact may be performed in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene. The contact temperature is -20
C. to the boiling point of the solvent, preferably from room temperature to the boiling point of the solvent.

The amount of each component of the catalyst used is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol of the component [A] per gram of the component [B], and 0.1 to 5 mmol of the component [C].
01 to 10000 mmol, preferably 0.1 to 100
mmol. Further, the atomic ratio of the transition metal in the component [A] to the aluminum in the component [C] is 1: 0.01 to
1,000,000, preferably 0.1-100,000.

Preliminary polymerization with ethylene is carried out by contacting the above components with each other in an inert solvent and subjecting the ethylene to 0.01 to 1000 g, preferably 0.1 to 1000 g per 1 g of the solid catalyst component.
It is desirable to carry out so as to produce ~ 100 g of polymer. The prepolymerization temperature is -50 to 100C, preferably 0 to 100C.
100 ° C., the prepolymerization time is 0.1 to 100 hours,
Preferably, it is 0.1 to 20 hours. The solid catalyst component thus obtained may be used for the polymerization reaction without washing, or may be used after washing. Further, when the reaction is carried out in a solvent such as an inert hydrocarbon, the slurry may be used as it is, or the solvent may be distilled off and dried to form a powder, and then used.

The copolymer of the present invention can be obtained by using the solid catalyst component as described above and an organoaluminum compound as required. At this time, as the organoaluminum compound to be used, the same compounds as the above-mentioned component [C] can be mentioned. The amount of the organoaluminum compound used at this time is such that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the organoaluminum compound is 1: 0 to 1000.
It is chosen to be zero.

The ethylene / α-olefin copolymer used in the present invention can be obtained by using the above-mentioned catalyst to prepare ethylene and propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 3-methyl It is obtained by copolymerizing a linear α-olefin having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms, such as -1-butene and 4-methyl-1-pentene. Although not particularly limited, the ratio of α-olefin is preferably about 0.5 to 40%, because the above-mentioned conditions (a) to (c) of the present invention are easily satisfied.

The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene and cyclohexane and a liquefied α-olefin. The temperature is −50 to 250 ° C., and the pressure is not particularly limited.
It is in the range of about 2000 kgf / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

(2) High density radical method low density polyethylene The low density polyethylene produced by the high pressure radical method used in the present invention has an MFR of 0.1 to 20 g / 10
Min, preferably 0.15 to 10 g / 10 min (condition (d)). The density is 0.91
5 to 0.935 g / cm ³ , preferably 0.918 to
It is necessary to be 0.932 g / cm ³ (condition (e)). Furthermore, MT is 5 to 17 g, preferably 7 to
14 g, ME 1.6-2.1, preferably 1.
It is necessary to be 7 to 2.0 (condition (f) and condition (g)).

If the MFR of the low-density polyethylene is less than the above range, the transparency and gloss may be rather deteriorated.
On the other hand, if it exceeds the above range, sufficient transparency, gloss and molding stability cannot be obtained. If the density of the low-density polyethylene is less than the above range, the stiffness becomes insufficient. Also,
If it exceeds the above range, transparency, gloss and strength will be insufficient. Next, if the MT of the low-density polyethylene is less than the above range, sufficient transparency, gloss, and molding stability cannot be obtained. Further, when the ratio exceeds the above range, transparency and gloss deteriorate. Further, if the ME of the low-density polyethylene is less than the above range, sufficient transparency, gloss and molding stability cannot be obtained. Further, when the ratio exceeds the above range, transparency and gloss deteriorate.

The low-density polyethylene produced by the above high-pressure radical method may be a polymerizable monomer such as ethylene and other α-olefins, vinyl acetate, acrylates and the like, as long as the object of the present invention is not impaired. It may be a copolymer with a body.

(3) Antioxidant The antioxidant used in the present invention may be a known antioxidant for polyolefin, and various antioxidants such as phosphorus, phenol and sulfur can be used.

Specifically, as the phosphorus-based antioxidant,
Triphenyl phosphite, diphenyl phosphite,
Trinonylphenyl phosphite, distearylpentaerythritol diphosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Phyte, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4 ′
-Biphenylenediphosphonite and the like.

The phenolic antioxidants include 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene,
2,2'-methylenebis (4-methyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], octadecyl-8- (8,5-di-
t-butyl-4-hydroxyphenyl) propionate, tris [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl] isocyanurate and the like.

Examples of the sulfur-based antioxidants include tetrakis (laurylmercaptopropionyloxymethylene) methane, dilaurylthiodipropionate, distearylthiodipropionate, and the like.

The antioxidants may be used alone or in combination of two or more. However, a combination of a phosphorus antioxidant and a phenolic antioxidant, or a combination of a sulfur antioxidant and a phenolic antioxidant Are preferred.

(4) Antiblocking Agent Examples of the antiblocking agent used in the present invention include silicon dioxide, talc, zeolite and the like. More specifically, natural silica, synthetic silica, talc, A-type zeolite, Pc-type zeolite, X-type zeolite and the like,
Any of them may be subjected to treatment such as acid modification and ion exchange. The anti-blocking agent may be used alone or in combination of two or more, and preferably has an average particle size of 8 μm or less.

(5) Other Compounding Agents (Optional Components) The ethylene-based resin composition of the present invention contains other ethylene-based resins such as high-density polyethylene as long as the effects of the present invention are not significantly impaired. Or an olefin resin other than polyethylene, such as polypropylene. Further, additional components within a range not significantly impairing the effects of the present invention, for example, a neutralizing agent, an ultraviolet absorber, a lubricant, an antistatic agent, a weather resistance improver, a nucleating agent, an anti-condensation agent, a molecular weight modifier, a coloring agent Agents, impact modifiers, fillers, flame retardants, adhesion improvers, printability improvers, and the like.

Compounding ratio The ethylene / ethylene contained in the ethylene resin composition of the present invention
The mixing ratio of the α-olefin copolymer and the low-density polyethylene produced by the high-pressure radical method is ethylene / α.
-Low-density polyethylene 30-2 prepared by a high-pressure radical method with respect to 70-98% by weight of olefin copolymer
The low-density polyethylene produced by the high-pressure radical method is 20 to 5% by weight, preferably 80 to 95% by weight of the ethylene / α-olefin copolymer. If the blending ratio of the ethylene / α-olefin copolymer is less than the above range, the strength of the formed film is insufficient. Further, if the above range is exceeded, the stability at the time of molding is insufficient,
There is a problem that the transparency and gloss of the formed film are insufficient.

The mixing ratio of the antioxidant and the antiblocking agent contained in the ethylene resin composition of the present invention is 100 parts by weight of the ethylene resin composed of the ethylene / α-olefin copolymer and the high-pressure radical method low-density polyethylene. Parts, the antioxidant is 0.05 to 1.0 part by weight, preferably 0.10 to 0.5 part by weight, and the antiblocking agent is 0.01 to 0.8 part by weight, preferably Should be 0.1 to 0.5 parts by weight. When the compounding ratio of the antioxidant is less than the above range, a problem occurs that gel frequently occurs during molding. In addition, when the above range is exceeded, there is a problem that the film is liable to be discolored. On the other hand, if the compounding ratio of the anti-blocking agent is less than the above range, there arises a problem that a sufficient opening property cannot be obtained. On the other hand, if it exceeds the above range, there arises a problem that sufficient transparency and gloss cannot be obtained.

Kneading / granulation The above (1) ethylene / α-olefin copolymer, (2)
A low-density polyethylene produced by a high-pressure radical method, (3) an antioxidant, and (4) an anti-blocking agent, and if necessary, (5) other compounding agents are compounded in the above compounding ratio and melt-kneaded or dry-blended. Thereby, the ethylene-based resin composition of the present invention can be obtained. However, in the case of dry blending, it is preferable to adopt a master batch method for (3) an antioxidant, (4) an antiblocking agent, and (5) other compounding agents.

The above-mentioned melt kneading is generally carried out at a temperature of 170 to 250 ° C. using a usual kneading machine such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph and a kneader. By suitably granulating, the polyethylene resin composition of the present invention can be obtained. In this case, it is preferable to select a kneading / granulating method capable of improving the dispersion of each component, and usually kneading / granulating is performed using a single-screw extruder or a twin-screw extruder.

The polyethylene resin composition of the present invention thus obtained has excellent stability at the time of molding, and a film molded using the same has excellent transparency, gloss, waist, opening property and strength. Excellent,
In addition, since these are also excellent in quality balance, standard bags, heavy bags, wrap films, sugar bags, various packaging films such as food packaging, infusion bags, bag-in-box,
It is suitable for agricultural materials and the like.

In forming the film, it is preferable to adjust the ethylene resin composition to be used and the obtained film so as to satisfy the following condition (h). (H) Haze <[(382-51log (MFR)) ×
D-345.6 + 57 log (MFR)] × (0.02
67t + 0.2) -2 Here, MFR (g / 10 minutes) and D (g / cm ³ ) are measured for the ethylene-based resin composition used for film molding, and t (μm) and haze (% ) Is the thickness and haze measured for the formed film. If the value of the haze is larger than the value on the right side of the conditional expression (h), the transparency is undesirably reduced.

Further, blown film molding, T
Not limited to ordinary film applications such as die film molding, it can be processed into various containers, pipes, tubes, and the like by extrusion molding, hollow molding, injection molding, and the like. Furthermore, it can be formed into various composite films by extrusion coating or co-extrusion molding on other films, and can be used for applications such as steel pipe coating, electric wire coating, and foam molding.

[0074]

Next, the present invention will be described in detail with reference to examples. However, the present invention is not restricted by these examples unless departing from the gist of the present invention. The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere.
The solvent used was dehydrated and purified with Molecular Sieve-4A.

The measuring method and measuring conditions used in the following Examples and Comparative Examples are the same as those described above for MFR, density, and MFR.
Except for T, ME, Tmax, W ₆₀ and W ₉₀ , it is as follows. (1) Haze Measured according to Jls K7105.

(2) Molding stability During the formation of the blown film, the state of bubbles was visually observed, and the molding stability was evaluated in three steps as follows. ：: Bubble shaking is hardly recognized △: Bubble shaking or meandering is recognized ×: Bubble shakes or meanders and it is difficult to mold

(3) Openability The inflation-molded tube was cut perpendicularly to the axial direction so that the axial length of the tube was 20 cm, to obtain a film sample. The film sample is sandwiched between two rectangular glass plates having a length of 25 cm and a width of 35 cm, a load of 15 kg is placed on the glass plate, and stored in a gear oven set at a temperature of 45 ° C. for 5 days. Thereafter, the load and the glass plate were removed, and the adhered film was peeled off by hand, and the opening property was evaluated in three steps as follows. ：: little resistance and can be peeled off △: resistance when peeling, but whitening or damage is observed on the film surface ×: considerable resistance, peeling off causes whitening or damage on the film surface Is observed or cannot be peeled off

Example 1 (1) Chemical treatment of clay mineral 1 kg of synthetic mica (ME-100 manufactured by Corp Chemical) was dispersed in 3.2 kg of demineralized water in which 0.2 kg of zinc sulfate was dissolved, and stirred at room temperature for 1 hour. Worked up and filtered. After washing with deionized water, the solid content concentration was adjusted to 25%, and the slurry was introduced into a spray drier to obtain spherical granulated particles. The particles were further dried under reduced pressure at 200 ° C. for 2 hours.

(2) Preparation of Catalyst In a reactor equipped with an induction stirrer having a capacity of 10 L, 4.4 L of n-heptane and 150 particles of the synthetic mica obtained in the above (1) were prepared.
g was introduced. 12.0 mmol of dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride dissolved in 600 ml of toluene
Was added and stirred at room temperature for 10 minutes.

(3) Preliminary polymerization Triethylaluminum 7 was added to the above stirred mixture.
1.5 mmol was added and the temperature of the system was brought to 60 ° C. 1
After 0 minute, ethylene gas was introduced, and the reaction was continued for 2 hours. The amount of polyethylene produced during this period was 549 g.

(4) Ethylene / butene copolymerization Gas phase polymerization was carried out using the prepolymerized catalyst obtained in the above (3). That is, a mixed gas of ethylene and 1-butene (1-
446 mg / hr of the above solid catalyst component and 1700 mg / hr of triethylaluminum were intermittently supplied to a continuous gas phase polymerization reactor in which butene / ethylene = 3.0% was circulated. The conditions for the polymerization reaction are 88 ° C. and a pressure of 20 kg / cm.
^2- G, the average residence time was 6.9 hours, and the average polymerization rate of the produced ethylene / butene copolymer was 8.7 kg / hr.
Met. Table 1 shows the basic physical properties of the obtained copolymer A and the results of cross-fractionation measurement.

(5) Pelletizing Low-density polyethylene “Novatech-LD LF280” manufactured by a high-pressure radical method commercially available from Nippon Polychem Co., Ltd. was used for 80 parts by weight of the powder of the ethylene / butene copolymer A. (HPPEa shown in Table 2)
And octadecyl-3 as an antioxidant
0.10 parts by weight of-(3,5-di-t-butyl-4-hydroxyphenyl) propionate and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite 0.10 part by weight, 0.05 part by weight of calcium stearate as a neutralizing agent, and "Silton JC" manufactured by Mizusawa Chemical Industries as an anti-blocking agent.
-30 "was added in an amount of 0.15 parts by weight, and these were added using a super mixer having a capacity of 50 liters at a rotation speed of 800 rpm.
After mixing for 5 minutes, screw diameter 40mmφ, L / D
26 single screw extruder 200 ° C, screw rotation speed 50r
The mixture was melt-kneaded at pm and pelletized. The MFR and density of the pellet were measured and are shown in Table 3.

(6) Film Forming The pellets were prepared with a screw diameter of 40 mmφ, a die diameter of 75 mmφ equipped with an L / D24 extruder, and a die lip width of 3 mm.
Using a blown film molding machine of
Molded under the conditions of 0 ° C., screw rotation speed 50 rpm, blow-up ratio 2.0, take-up speed 16.5 m / min, frost line height 200 mm, width 230 mm, thickness 30 μ
m of blown film was obtained. During molding,
The molding stability was evaluated, and the haze and the opening property of the formed film were measured and evaluated. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Example 2 (1) Chemical Treatment of Clay Mineral 22.6 kg of commercially available montmorillonite (Kunimine F) was dispersed in an acidic aqueous solution obtained by adding 15 kg of 35% hydrochloric acid to 6.3 L of demineralized water. For 2 hours. After washing this solid component with demineralized water, this aqueous slurry of montmorillonite was adjusted to a solid concentration of 10%,
Spray granulation was performed with a spray dryer to obtain spherical particles.

(2) Preparation of Catalyst Toluene 625 was placed in a 10 L reactor equipped with an induction stirrer.
ml of the montmorillonite particles 1 obtained in the above (1).
50 g were introduced. Here, 450 mmol of triethylaluminum and 34
A total of 3 ml of the mixed solution was added, and the mixture was stirred for 1 hour. The supernatant was extracted, and the remaining solid component was washed with toluene. After adding n-heptane to make the total amount 4.4 L, 12.0 mmol of dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride dissolved in 600 ml of toluene at 25 ° C. The solution was added and stirred for 60 minutes.

(3) Prepolymerization Triethylaluminum 3 was added to the above stirred mixture.
3.0 mmol was added and the temperature of the system was brought to 80 ° C. 1
After 0 minute, ethylene gas was introduced, and the reaction was continued for 2.5 hours. The weight of polyethylene produced during this period was 365 g.

(4) Ethylene / 1-butene copolymerization Ethylene / 1-butene gas phase polymerization was carried out in the same manner as in Example 1 except that the prepolymerized catalyst of the above (3) was used. However, 1340 mg / hr and 860 mg / hr of triethylaluminum were intermittently supplied as a solid catalyst component. The conditions for the polymerization reaction are 88 ° C. and a pressure of 20 kg / cm ² −
G, the average residence time was 7.0 hours, and the average polymerization rate of the produced ethylene / butene copolymer was 8.6 kg / hr. Table 1 shows the basic physical properties and cross-fractionation measurement results of the obtained copolymer B.

(5) Pelletization and Film Forming For 90 parts by weight of the ethylene / butene copolymer B powder, a high-pressure radical method commercially available from Nippon Polychem Co., Ltd. was used instead of low-density polyethylene (HPPEa). Low-density polyethylene "Novatek-LD
Except that 10 parts by weight of “LS162N” (HPPEb shown in Table 2) was used, pelletization and molding were performed in the same manner as in (5) and (6) of Example 1. The MFR and density of the pellet before molding were measured and are shown in Table 3. During molding,
The molding stability was evaluated, and the haze and the opening property of the formed film were measured and evaluated. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Example 3 (1) Chemical treatment of clay mineral Synthetic mica (ME-10 manufactured by Corp Chemical Co., Ltd.) was added to 3.4 kg of demineralized water in which 0.80 kg of chromium (III) nitrate was dissolved.
0) 1 kg was dispersed, stirred at room temperature for 2 hours, and filtered. After washing with demineralized water, the solid content concentration was adjusted to 25%,
The slurry was introduced into a spray dryer to obtain spherical granulated particles. The particles were further dried under reduced pressure at 200 ° C. for 2 hours.

(2) Preparation of Catalyst In a reactor having an induction stirrer having a capacity of 10 L, 4.4 L of n-heptane and 150 particles of the synthetic mica obtained in the above (1) were prepared.
g was introduced. To this was added a solution of 12.0 mmol of bis (n-butylclopentadienyl) zirconium dichloride dissolved in 600 ml of toluene,
Stirred for minutes.

(3) Preliminary polymerization Triethyl aluminum 7 was added to the above stirred mixture.
1.5 mmol was added and the temperature of the system was brought to 60 ° C. 1
After 0 minute, ethylene gas was introduced, and the reaction was continued for 2 hours. The weight of polyethylene produced during this period was 592 g.

(4) Ethylene / 1-butene copolymerization Ethylene / 1-butene gas phase polymerization was carried out in the same manner as in Example 1 except that the preliminary polymerization catalyst of (3) was used. That is, 363 mg / hr as a solid catalyst component and 568 mg / hr of triethylaluminum are intermittently fed into a continuous gas phase polymerization reactor in which a mixed gas of ethylene and 1-butene (1-butene / ethylene = 6.4%) is circulated. Supplied. The conditions of the polymerization reaction were 83 ° C., the pressure was 20 kg / cm ² -G, the average residence time was 14 hours, and the average polymerization rate of the produced ethylene / butene copolymer was 4.3 kg / hr. Table 1 shows the basic physical properties of the obtained copolymer C and the results of cross fractionation measurement.
It was shown to.

(5) Pelletization and Film Forming For 90 parts by weight of the powder of the ethylene / butene copolymer C, 10 parts by weight of a low-density polyethylene (HPPEa shown in Table 2) produced by a high-pressure radical method were added. As an antioxidant, octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate, 0.03 parts by weight of tetrakis (2,4-di-t-butylphenyl) -4,4, -biphenylenediphosphonite, neutralizing agent And 0.050 parts by weight of calcium stearate, and 0.20 parts by weight of "Silton JC-30" manufactured by Mizusawa Chemical Industry Co., Ltd. as an anti-blocking agent. Then, a blown film having a width of 230 mm and a thickness of 30 μm was obtained. MFR of the pellet before molding
And the density were measured and are shown in Table 3. At the time of molding, the molding stability was evaluated.
The mouth opening was measured and evaluated. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Example 4 (1) Preparation of Catalyst and Prepolymerization 800 ml of n-heptane and 24 g of the synthetic mica particles obtained in (1) of Example 3 were introduced into a 1.5 L reactor equipped with an induction stirrer. . A solution of 1.92 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride dissolved in 96 ml of toluene was added thereto, and the mixture was stirred at room temperature for 10 minutes. Then triethyl aluminum 1
1.5 mmol was added and the temperature of the system was brought to 60 ° C. 1
After 0 minute, ethylene gas was introduced, and the reaction was continued for 2 hours. The amount of polyethylene produced during this period was 54.7 g.

(2) Ethylene / Butene Copolymerization Slurry polymerization was carried out using the prepolymerized catalyst obtained in (1). That is, 1.5 L of n-heptane, 2.5 mmol of triethylaluminum, and 200 ml of 1-butene were added to a 3 L autoclave, and the temperature was raised to 65 ° C. Then, 100 mg of the above catalyst component was introduced together with ethylene as a mica component, and polymerization was carried out at 65 ° C. for 2 hours while maintaining the total pressure at 22 kg / cm ² -G. Two hours later, the polymerization was stopped by adding ethanol. The obtained ethylene-1-
The butene copolymer was 285 g. By repeating the above operations, a total of about 5 kg of polymer D was obtained. Table 1 shows the basic physical properties and cross-fractionation measurement results of the obtained copolymer D.

(3) Pelletization and film forming 20 parts by weight of low-density polyethylene (HPPEb shown in Table 2) produced by the high-pressure radical method were added to 80 parts by weight of the powder of the ethylene / butene copolymer D. ,
As an antioxidant, octadecyl-3- (3,5-di-
0.15 parts by weight of t-butyl-4-hydroxyphenyl) propionate and 0.15 parts by weight of tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite 0.05% by weight of calcium stearate as an agent, and 0.10 part by weight of "Silton JC-30" manufactured by Mizusawa Chemical Industry Co., Ltd. as an anti-blocking agent, were added in the same manner as in (5) and (6) of Example 1. Pellets were formed and molded to obtain a blown film having a width of 230 mm and a thickness of 30 μm. MF of the pellet before molding
R and density were measured and are shown in Table 3. At the time of molding, the haze,
The mouth opening was measured and evaluated. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Example 5 (1) Preparation of Catalyst, Prepolymerization, and Ethylene / Butene Copolymerization Bis (n-butylcyclopentadienyl) zirconium dichloride was replaced with biscyclopentadienyl zirconium dichloride in Example 4 (1). , (2). 91.7 g of polyethylene produced during prepolymerization
Met. The amount of the copolymer obtained by ethylene / 1-butene copolymer was 230 g. By repeating the above operation, a total of about 5 kg of the copolymer E was obtained. Table 1 shows the basic physical properties and cross-fractionation measurement results of the obtained copolymer E.

(2) Pelletization and Film Formation 5 parts by weight of low-density polyethylene (HPPEa shown in Table 2) produced by the high-pressure radical method was added to 95 parts by weight of the powder of the ethylene / butene copolymer E. , As an antioxidant, octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate in 0.08 parts by weight, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite in 0.07 parts by weight, neutralizing agent 0.05% by weight of calcium stearate and 0.15 part by weight of "Silton JC-30" manufactured by Mizusawa Chemical Industry Co., Ltd. Then, a blown film having a width of 230 mm and a thickness of 30 μm was obtained. MFR of the pellet before molding
And the density were measured and are shown in Table 3. At the time of molding, the molding stability was evaluated, and the haze and opening property of the formed film were measured and evaluated. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Example 6 (1) Preparation of Catalyst, Prepolymerization and Ethylene / Butene Copolymerization Bis (n-butylcyclopentadienyl) zirconium dichloride was converted to dimethylsilylenebis (4,5,6,7-
A prepolymerized catalyst was produced in the same manner as in Example 4 (1) instead of (tetrahydroindenyl) zirconium dichloride, and ethylene / 1-butene copolymerization was carried out in the same manner as in Example 4 (2). The amount of polyethylene produced during the prepolymerization was 93.6 g. The amount of the copolymer obtained by ethylene / 1-butene copolymer was 298 g. By repeating the above operation, a total amount of about 5 kg of the copolymer F was obtained. Table 1 shows the basic physical properties of the obtained copolymer F and the results of the cross fractionation measurement.

(2) Pelletization and Film Forming For 92 parts by weight of the above-mentioned ethylene / butene copolymer F powder, 8 parts by weight of low-density polyethylene (HPPEa shown in Table 2) produced by the high-pressure radical method was used. , As an antioxidant, octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate, 0.05 parts by weight of tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, neutralizing agent 0.05% by weight of calcium stearate and 0.10 part by weight of "Silton JC-30" manufactured by Mizusawa Chemical Industry Co., Ltd. Then, a blown film having a width of 230 mm and a thickness of 30 μm was obtained. MFR of the pellet before molding
And the density were measured and are shown in Table 3. At the time of molding, the molding stability was evaluated, and the haze,
The mouth opening was measured and evaluated. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Comparative Example 1 Octanedecyl-3- (3,5-di-t-) was used as an antioxidant with respect to 100 parts by weight of the ethylene / 1-butene copolymer A obtained in (4) of Example 1 as an antioxidant. Butyl-4-hydroxyphenyl) propionate in an amount of 0.05 part by weight,
Tetrakis (2,4-di-tert-butylphenyl) -4,
0.05 weight part of 4'-biphenylenediphosphonite,
0.05 parts by weight of calcium stearate was added as a neutralizing agent, and pelletized and formed in the same manner as in (5) and (6) of Example 1 to obtain a blown film having a width of 230 mm and a thickness of 30 μm. The MFR and density of the pellet before molding were measured and are shown in Table 3. At the time of molding, the molding stability was evaluated, and the formed film was measured and evaluated for haze and opening property. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Comparative Example 2 Octadecyl-3-amine was added to 100 parts by weight of the powder of the ethylene / 1-butene copolymer A obtained in (4) of Example 1.
(3,5-di-t-butyl-4-hydroxyphenyl)
0.05 parts by weight of propionate and tetrakis (2,
0.05 parts by weight of 4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, 0.05 part by weight of calcium stearate as a neutralizing agent, and "Mizusawa Chemical Industry Co., Ltd." Shilton JC-3
"0" was added in an amount of 0.15 part by weight, and (5) and (6) of Example 1 were added.
Pellets were formed and molded in the same manner as in Example 1 to obtain a blown film having a width of 230 mm and a thickness of 30 μm. The MFR and density of the pellet before molding were measured and are shown in Table 3. At the time of molding, molding stability was evaluated, and the haze and opening property of the formed film were measured and evaluated. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Comparative Example 3 70 parts by weight of the ethylene / 1-butene copolymer A obtained in (4) of Example 1 was mixed with a low-density polymer produced by a high-pressure radical method commercially available from Nippon Polychem. 30 parts by weight of polyethylene "Novatek-LD LH100N" (HPPEc shown in Table 2) was added to octadecyl-
0.05 parts by weight of 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and 0 parts by weight of tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite 0.05 parts by weight, 0.05 parts by weight of calcium stearate as a neutralizing agent, and "Silton JC" manufactured by Mizusawa Chemical Industry Co., Ltd. as an anti-blocking agent.
-30 "was added in an amount of 0.15 part by weight.
Pelletized and molded in the same manner as (6), width 230m
m, an inflation film having a thickness of 30 μm was obtained.
The MFR and density of the pellet before molding were measured and are shown in Table 3. At the time of molding, molding stability was evaluated, and the haze and opening property of the formed film were measured and evaluated.
Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Comparative Example 4 Table 1 shows the basic physical properties and cross-fractionation measurement results of EXACT3030 (ethylene-butene copolymer G shown in Table 1) which is a commercially available metallocene-catalyzed polymerization product manufactured by Exxon Chemical Company.
It was shown to. This was pelletized and formed into a film in the same manner as (5) and (6) of Example 1. At the time of molding, the molding stability was evaluated, and the formed film was measured and evaluated for haze and opening property. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

Comparative Example 5 A commercially available metallocene-catalyzed polymerization product A manufactured by Dow Chemical Company
Table 1 shows the basic physical properties of fifinity FM1570 (ethylene / butene copolymer H shown in Table 1) and the results of cross fractionation measurement. This was pelletized and formed into a film in the same manner as (5) and (6) of Example 1. At the time of molding, for the film formed by evaluating the molding stability,
Haze and mouth opening were measured and evaluated. The condition (h)
The right side of the equation was calculated. The results were as shown in Table 3.

Comparative Example 6 A commercially available Ziegler-catalyzed polymerization product UF240 manufactured by Mitsubishi Chemical Corporation (ethylene-butene copolymer I shown in Table 1)
Are shown in Table 1.
This was pelletized and formed into a film in the same manner as (5) and (6) of Example 1. At the time of molding, the molding stability was evaluated, and the formed film was measured and evaluated for haze and opening property. Further, the right side of the condition (h) was calculated. The results were as shown in Table 3.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

[Table 3]

[0110]

The ethylene resin composition of the present invention has excellent molding stability when it is formed into a film, and the formed film has excellent transparency, gloss, openability and strength. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // (C08L 23/08 23:04)

Claims (6)

[Claims] 1. A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein 70 to 98% by weight of an ethylene / α-olefin copolymer satisfying the following conditions (a) to (c): (A) Density (D) is 0.850 g / cm ³ or more and 0.95
0 g / cm ³ or less (b) The relation between the melt tension (MT) at 190 ° C. and the melt flow rate (MFR) satisfies the following equation: log (MT) ≧ −0.91 × log (MFR) +0.06 ... (1) MT: melt tension (g) MFR: melt flow rate (g / 10 minutes) (c) Satisfies the following three formulas: Tmax ≦ 972D-813 (2) logW ₆₀ ≦ −0.114 Tmax + 9.48 ... (3) logW ₉₀ ≧ 0.0394 Tmax−2.95 (4) where D: density (g / cm ³ ) Tmax: elution peak temperature (° C.) by cross fractionation measurement W ₆₀ : soluble below 60 ° C. Weight fraction (wt%) W ₉₀ : Low-density polyethylene 30 to 2 produced by a high-pressure radical method having a soluble weight fraction (wt%) of 90 ° C. or higher and the following properties (d) to (g). weight : (D) it MFR of 0.1 to 20 g / 10 min (e) density of 0.915g / cm ³ ~0.935g / c
It is m ³ (f) MT to be 5~17g (g) of the ethylene-based resin 100 parts by weight consists of memory effect (ME) is 1.6 to 2.1, antioxidants An ethylene resin composition comprising 0.05 to 1.0 part by weight and 0.01 to 0.8 part by weight of an antiblocking agent. 2. The ethylene resin composition according to claim 1, wherein the ethylene / α-olefin copolymer satisfies the following three formulas. Tmax ≦ 972D-816 (2) ′ logW ₆₀ ≦ −0.114 Tmax + 9.48 (3) logW ₉₀ ≧ 0.0394 Tmax-2.81 ...
(4) ' 3. The ethylene / α-olefin copolymer has a density of not less than 0.850 g / cm ^{3 and not} more than 0.935 g / cm ^3.
The ethylene-based resin composition according to claim 1, which is ³ or less. 4. The ethylene / α-olefin copolymer has a density of 0.900 g / cm ³ or more and 0.934 g / cm ³ or more.
The ethylene-based resin composition according to claim 3, which is ³ or less. 5. The ethylene resin composition according to claim 1, wherein the following condition (h) is satisfied when the film is formed. (H) Haze <[(382-51log (MFR)) ×
D-345.6 + 57 log (MFR)] × (0.02
67t + 0.2) -2 Here, MFR (g / 10 minutes) and D (g / cm ³ ) are measured for the composition before film forming, and t (μm) and haze (%) are The thickness and the haze measured for the obtained film. 6. A film obtained by molding the ethylene-based resin composition according to claim 1 and satisfying the above condition (h).