JP2009138176A - Rubber-packaging film and packaged rubber body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber-packaging film having good releasability from rubber and good melt-miscibility with the rubber, and to provide packaged rubber bodies provided by packaging the rubber with the film. <P>SOLUTION: A resin composition for extrusion expansion molding, comprising the component (A) and component (B) is provided, wherein the content of the component (A) is 80-20 wt.% and the content of the component (B) is 20-80 wt.% based on 100 wt.% total of the component (A) and the component(B). (A): an ethylenic copolymer comprising a monomer unit based on ethylene and a monomer unit based on a 3-20C α-olefin, and having 0.01-5 g/10min melt flow rate (MFR), ≥5 molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) and ≥40 kJ/mol activation energy of fluidization. (B): high pressure low density ethylene. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a film for rubber packaging and a rubber package formed by packaging rubber with the film.

Rubbers such as ethylene-propylene-diene copolymer rubber are usually polymerized and obtained in a lump. The lump rubber is usually molded into a rectangular parallelepiped of about 10 to 35 kg per piece so that it can be easily transported and stored. In order to prevent the rubbers of the rectangular parallelepiped from adhering to each other, the rubber is made of a plastic film. In many cases, it is transported and stored in a packaged rubber package. As such a rubber packaging film, for example, a film made of high-pressure low-density polyethylene (LDPE) is often used (for example, see Patent Document 1).

JP-A-5-337944

Since the rubber package packaged with a film may be used by peeling the plastic film from the rubber when used, it is required that the film is easily peeled off from the rubber, that is, unpacking properties are required. However, when the rubber is polymerized and obtained in a lump shape, it is immediately molded into a rectangular parallelepiped shape and packaged with a plastic film. Therefore, the unpacking property may be insufficient. In addition, when the outside air temperature is high such as in summer, the temperature of the rubber package becomes high during transportation and storage, and the unpacking property may be insufficient. In particular, ethylene-propylene-diene copolymer rubber has a tendency to increase in tackiness as the temperature rises compared to other rubbers. Therefore, when packaging using conventional rubber packaging films, It became difficult to peel off, and the unpacking property tended to be insufficient.
In addition, when the unpacking property is insufficient and the film must be used while attached to the rubber, it is required that the film also melts and easily mixes with the rubber when the rubber is melt-kneaded. Yes.
Under such circumstances, the problem to be solved by the present invention is that a film for rubber packaging having good releasability from rubber and good melt miscibility with rubber, and packaging the rubber with the film. It is providing the rubber package which becomes.

That is, the first of the present invention contains the following component (A) and component (B), the total amount of component (A) and component (B) is 100% by weight, and the content of component (A) is 20 to It is a film for rubber packaging which has a layer which consists of a resin composition which is 80 weight% and content of a component (B) is 80 to 20 weight%.
(A): an ethylene-α-olefin having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms and satisfying the following requirements (a1) and (a2) Copolymer (a1): Flow activation energy (Ea) is 35 kJ / mol or more.
(A2): The molecular weight distribution (Mw / Mn) is 5-25.
(B): High-pressure low-density polyethylene

A second aspect of the present invention relates to a rubber package formed by packaging rubber with the film.

According to the present invention, when packaging rubber that exhibits adhesiveness at a temperature higher than room temperature, a film for rubber packaging that has good releasability from rubber and good melt miscibility with rubber, and rubber in the film Can be provided.

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

  Examples of the ethylene-α-olefin copolymer of component (A) include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer. A copolymer, an ethylene-1-butene-1-hexene copolymer, an ethylene-1-butene-1-octene copolymer, and the like, preferably an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer. A copolymer, an ethylene-1-butene-1-hexene copolymer, and an ethylene-1-butene-1-octene copolymer.

  The content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer of component (A) is usually 50 to 99 when the total weight of the ethylene-α-olefin copolymer is 100% by weight. % By weight. The content of the monomer unit based on the α-olefin having 3 to 20 carbon atoms is usually 1 to 50% by weight when the total weight of the ethylene-α-olefin copolymer is 100% by weight.

From the viewpoint of film processability and melt miscibility between the film and rubber, the molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer of component (A) is 5 or more, preferably 6 or more. More preferably, it is 8 or more. Further, the molecular weight distribution is preferably 25 or less, more preferably 20 or less, from the viewpoint of enhancing the peelability. The molecular weight distribution (Mw / Mn) is a value obtained by obtaining a weight average molecular weight (Mw) and a number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography, and dividing Mw by Mn ( Mw / Mn).

The ethylene-α-olefin copolymer of component (A) is an ethylene-α-olefin copolymer having a long chain branch, and such an ethylene-α-olefin copolymer is conventionally known. Compared to the ethylene-α-olefin copolymer, the flow activation energy (Ea) is high. The Ea of a conventional ethylene-α-olefin copolymer known conventionally is usually lower than 35 kJ / mol.

From the viewpoint of film processability and melt miscibility of the film and rubber, the Ea of the ethylene-α-olefin copolymer of component (A) is 35 kJ / mol or more, preferably 50 kJ / mol or more, More preferably, it is 55 kJ / mol or more, More preferably, it is 60 kJ / mol or more. Moreover, from a viewpoint of improving peelability, Ea is preferably 100 kJ / mol or less, and more preferably 90 kJ / mol or less.

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

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

The density of the ethylene-α-olefin copolymer of component (A) is usually 900 to 950 kg / m ³ . The density is preferably 910 kg / m ³ or more, more preferably 920 kg / m ³ or more from the viewpoint of improving peelability, and preferably 940 kg / m ² from the viewpoint of improving melt miscibility and film flexibility. m ³ or less, more preferably 930 kg / m ³ or less. In addition, this density is measured in accordance with the underwater substitution method prescribed | regulated to JISK7112-1980 using the sample which annealed as described in JISK6760-1995.

The melt flow rate (MFR) of the ethylene-α-olefin copolymer of component (A) is usually from 0.1 to 50 g / 10 minutes, and from the viewpoint of improving peelability, it may be 5 g / 10 minutes or less. preferable. The MFR is measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N by the method defined in JIS K7210-1995.

  As a method for producing the ethylene-α-olefin copolymer of component (A), a metallocene system obtained by contact-treating a metallocene complex and an activation promoter component (hereinafter referred to as promoter component (I)). A method of copolymerizing ethylene and an α-olefin using an olefin polymerization catalyst is preferred. More preferably, a method of copolymerizing using a metallocene complex and a solid promoter component in which the promoter component (I) is supported on a fine particle carrier can be mentioned. Examples of the promoter component (I) include boron compounds, zinc compounds, and organoaluminum oxy compounds.

  Examples of the boron compound of the promoter component (I) include tris (pentafluorophenyl) borane, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N -Dimethylanilinium tetrakis (pentafluorophenyl) borate and the like.

  Examples of the zinc compound of the promoter component (I) include a contact-treated product obtained by contact-treating diethylzinc, fluorinated phenol and water.

The organoaluminum oxy compound of the co-catalyst component (I) does not contain a small amount of an organoaluminum compound that has been conventionally treated as an organoaluminum oxy compound, but is a so-called dry organoaluminum oxy compound that does not substantially contain an organoaluminum compound. Examples of the compound include dry methylaluminosan and dry methylisobutylaluminosan.
Examples of the method for preparing the dry organoaluminum oxy compound include a method for drying a commercially available organoaluminum oxy compound under reduced pressure, such as the method described in JP-A-2003-128718, and a solid obtained by depressurization being washed with a hydrocarbon solvent. You can list the methods.

  As the promoter component (I), a boron compound or a zinc compound is preferable.

As the fine particle carrier, a porous material is preferable, and inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; smectite, Clay and clay minerals such as montmorillonite, hectorite, laponite and saponite; organic polymers such as polyethylene, polypropylene and styrene-divinylbenzene copolymer are used. The 50% volume average particle diameter of the particulate carrier is usually 10 to 500 μm, and the 50% volume average particle diameter is measured by a light scattering laser diffraction method or the like. Moreover, the pore volume of the particulate carrier is usually 0.3 to 10 ml / g, and the specific surface area of the particulate carrier is usually 10 to 1000 m ² / g. The pore volume and the specific surface area are measured by a gas adsorption method. The pore volume is obtained by analyzing the gas desorption amount by the BJH method, and the specific surface area by analyzing the gas adsorption amount by the BET method.

The metallocene complex is preferably a transition metal compound represented by the following general formula [1] or a μ-oxo type transition metal compound dimer thereof.
L ² _a M ² X ¹ _b [1]
(In the formula, M ² is a transition metal atom of Groups 3 to 11 of the periodic table or a lanthanoid series. L ² is a group having a cyclopentadiene-type anion skeleton, and are a plurality of L ² linked directly to each other? Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and X ¹ is a halogen atom, a hydrocarbon group (provided that the cyclopentadiene form (Excluding a group having an anion skeleton), or a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8.

In the general formula [1], M ² is a transition metal atom of Group 3 to 11 of the periodic table (IUPAC 1989) or a lanthanoid series. Specific examples thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom. , Samarium atoms, ytterbium atoms, and the like. M ² in the general formula [1] is preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a chromium atom, an iron atom, a cobalt atom or a nickel atom, particularly preferably a titanium atom, a zirconium atom or a hafnium atom. And most preferably a zirconium atom.

In the general formula [1], L ² is a group having a cyclopentadiene type anion skeleton, and a plurality of L ² may be the same or different. The plurality of L ² may be directly connected to each other, or may be connected via a bridging group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Examples of the group having a cyclopentadiene-type anion skeleton in L ² include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group and the like. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -ethylcyclopentadienyl group, η ⁵ -n-butylcyclopentadienyl group, η ⁵ -Tert-butylcyclopentadienyl group, η ⁵ -1,2-dimethylcyclopentadienyl group, η ⁵ -1,3-dimethylcyclopentadienyl group, η ⁵ -1-methyl-2-ethylcyclopenta Dienyl group, η ⁵ -1-methyl-3-ethylcyclopentadienyl group, η ⁵ -1-tert-butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert-butyl-3-methyl Cyclopentadienyl group, η ⁵ -1-methyl-2-isopropylcyclopentadienyl group, η ⁵ -1-methyl-3-isopropylcyclopentadienyl group, η ⁵ -1-methyl-2-n-butyl Cyclopentadienyl group, η ⁵ -1-methyl-3-n-butylcyclopentadienyl group, η ⁵ -1,2,3-trimethylcyclopentadienyl group, η ⁵ -1,2,4-trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ^{5-4,5,6,7-tetrahydroindenyl} group, η ⁵ -2-methylindenyl group, η ⁵ -3-methylindenyl group, η ⁵ -4-methylindenyl group, η ⁵ -5-methylindenyl group, η ⁵ -6-methylindenyl group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, η ⁵ -3-tert- butyl indenyl group, η ⁵ -4-tert- butylindenyl group, eta ⁵ -5 -Tert-butylindenyl group, η ^5-6 -tert-butylindenyl group, η ⁵ -7-tert-butylindenyl group, η ⁵ -2,3-dimethylindenyl group, η ⁵ -4,7-dimethylindenyl group, η ^5- 2,4,7-trimethylindenyl group, η ⁵ -2-methyl-4-isopropylindenyl group, η ⁵ -4,5-benzindenyl group, η ⁵ -2-methyl-4,5-benzindenyl group, η ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ^{5-2-methyl-4-phenyl} indenyl group, eta ^{5-2-methyl-4-naphthyl} indenyl group , Η ⁵ -fluorenyl group, η ⁵ -2,7-dimethylfluorenyl group, η ⁵ -2,7-di-tert-butylfluorenyl group, and substituted products thereof. In the present specification, “η ⁵ −” may be omitted for the names of transition metal compounds.

  The groups having a cyclopentadiene type anion skeleton may be directly connected to each other, and are connected via a bridging group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Also good. Examples of such cross-linking groups include: alkylene groups such as ethylene groups and propylene groups; substituted alkylene groups such as dimethylmethylene groups and diphenylmethylene groups; or substituted silylenes such as silylene groups, dimethylsilylene groups, diphenylsilylene groups, and tetramethyldisilylene groups. Groups; heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom.

X ¹ in the general formula [1] is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group here does not include a group having a cyclopentadiene type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Examples of the hydrocarbon oxy group include an alkoxy group, an aralkyloxy group, and an aryloxy group.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, amyl group, n -Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, and these alkyl groups are all fluorine atom, chlorine atom, bromine atom, It may be substituted with a halogen atom such as an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Examples thereof include a fluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group. Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group.

  Examples of the aralkyl group include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2, 4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl Group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) ) Methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) Nyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl Group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexyl) Phenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc., and these aralkyl groups Are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group An alkoxy group such as ethoxy group; a portion at an aralkyl group such as aryloxy or benzyloxy group, such as phenoxy group may be substituted.

  Examples of the aryl group include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, and 2,6-xylyl group. Group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,4 6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6- Tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentyl Phenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. All of the aryl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; and aralkyloxy groups such as benzyloxy group May be partially substituted.

  Examples of the alkenyl group include an allyl group, a methallyl group, a crotyl group, and a 1,3-diphenyl-2-propenyl group.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n -Octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, and these alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methoxy group, An alkoxy group such as an ethoxy group; an aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

  Examples of the aralkyloxy group include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, ( 2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) ) Methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5- Trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy , (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, Pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert -Butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group, etc. All of the aralkyloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. Emissions atoms; an alkoxy group such as methoxy group and ethoxy group; a portion at an aralkyl group such as aryloxy or benzyloxy group, such as phenoxy group may be substituted.

  Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, and 2,5-dimethylphenoxy group. Group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6- Trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2- tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl- 3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3, 4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6- Trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl group -3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n -Butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group, etc. These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; and benzyloxy groups. Partially placed with an aralkyloxy group, etc. It may be replaced.

In the general formula [1], a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M ² . When M ² is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

As a specific example of a metallocene complex,
Bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butyl) Cyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadienyl) titanium dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadi) Enyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n) -Butylcyclopentadi Nyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methyl) Cyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methylcyclopentadienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,2 4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6, 7-tetra Doroindeniru) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenyl indenyl) titanium dichloride,

Bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride , Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindene) Nil) titanium dichloride,

Dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2, 3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) titanium Dichloride, dimethylsilylene bis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylene bis (4,5-benzindenyl) titanium dichloride, dimethyl Silylene bis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylene bis (2-phenylindenyl) titanium dichloride, dimethylsilylene bis (4-phenyl) Indenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-naphthyl) Indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl (Indenyl) (fluorenyl) titanium dichloride, dimethylsilylenebis (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) ) Titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) ) Titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethyl) Phenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) thi Njikuroraido, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2) -Phenoxy Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-) 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Id, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) 5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl Down (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (n- Tilcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) ( 3,5-diamil- -Phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium Dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (tert-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1- Naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadi) Enyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl) Rudimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamil-2-phenoxy) titanium dichloride Dimethylsilylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) ( -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamil-2-phenoxy) ) Titanium dichloride, dimethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1-naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyltitanium dichloride, (tert-butylamide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphide) tetramethylcyclopentadi Enyldimethylsilane titanium dichloride, (tert-butylamido) indenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) tetrahydroyl Denyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium Dichloride, (tert-butylamido) fluorenyldimethylsilane titanium dichloride,

(Dimethylaminomethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyl titanium (III) dichloride (N-pyrrolidinylethyl) tetramethylcyclopentadienyl titanium dichloride, (B-dimethylaminoborabenzene) cyclopentadienyl titanium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) titanium dichloride, Or compounds in which titanium of these compounds is changed to zirconium or hafnium, (2-phenoxy) is changed to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-ter -Butyldimethylsilyl-2-phenoxy), dimethylsilylene changed to methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride changed to difluoride, dichloride Compound, trichloride changed to bromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide), diphenoxide, or di (pentafluorophenoxide) Trifluoride, tribromide, triiodide, trimethyl, triethyl, triisopropyl, triphenyl, tribenzyl, trimethoxide, trieth Sid, tri (n- propoxide), tri (isopropoxide), tri phenoxide or a compound was changed to tri (pentafluorophenyl phenoxide), etc., can be exemplified.

  Specific examples of the transition metal compound of the transition metal compound represented by the general formula [1] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chloride], μ-oxobis [ Sopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) chita Chloride], .mu. Okisobisu [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], and the like. Examples include compounds in which the chloride of these compounds is changed to fluoride, bromide, iodide, methyl, ethyl, isopropyl, phenyl, benzyl, methoxide, ethoxide, n-propoxide, isopropoxide, phenoxide, or pentafluorophenoxide. can do.

  As the method for producing the ethylene-α-olefin copolymer of component (A), it is particularly preferable to use a promoter support (a) on which the following promoter component (I) is supported, and an alkylene group or a silylene group. In the presence of a polymerization catalyst obtained by contacting a metallocene complex (b) having a ligand having a structure in which two cyclopentadienyl type anion skeletons are bonded with a bridging group such as an organoaluminum compound (c) And a method of copolymerizing ethylene and an α-olefin.

[Cocatalyst support (I)]
Component (a) diethyl zinc, component (b) fluorinated phenol, component (c) water, component (d) inorganic particulate carrier and component (e) trimethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH) A carrier obtained by contact.

  Component (b) is preferably 3,4,5-trifluorophenol, 3,4,5-tris (trifluoromethyl) phenol, 3,4,5-tris (pentafluorophenyl) phenol, 3,5- Difluoro-4-pentafluorophenylphenol or 4,5,6,7,8-pentafluoro-2-naphthol.

  More preferably, component (b) is 3,4,5-trifluorophenol or 4,5,6,7,8-pentafluoro-2-naphthol, more preferably 3,4,5-trifluorophenol. It is.

  The inorganic particulate carrier of component (d) is preferably silica gel.

Component (a) diethylzinc, component (b) fluorinated phenol, component (c) The amount of each component used is the molar ratio of the amount of each component used (component (a) diethylzinc: component (b) fluorinated When phenol: component (c) water = 1: y: z, y and z preferably satisfy the following formula.
| 2-y-2z | ≦ 1 (2)
z ≧ −2.5y + 2.48 (3)
y <1 (4)
(In the above formulas (2) to (4), y and z represent numbers greater than 0.)
The molar ratio y of the usage amount of the component (b) to the usage amount of the component (a) and the molar ratio z of the usage amount of the component (c) to the usage amount of the component (a) are the above formulas (2) and (3). As long as the above and (4) are satisfied, there is no particular limitation. When the value of z is smaller than the value on the right side of Formula (3), the flow activation energy (Ea) of the resulting ethylene-α-olefin copolymer may be low, and the value of y may be Formula (4). When the value is larger than the value on the right side, the flow activation energy (Ea) of the ethylene-α-olefin copolymer may be low. Specifically, y usually takes a value of 0.55 to 0.99, more preferably 0.55 to 0.95, still more preferably 0.6 to 0.9, and most preferably 0. .7 to 0.8.

  The amount of component (d) inorganic fine particle carrier used for component (a) diethyl zinc is included in the particles obtained by contacting component (a) diethyl zinc and component (d) inorganic fine particle carrier. The amount of the zinc atom derived from the component (a) diethylzinc is preferably 0.1 mmol or more and 0.5 to 20 mmol in terms of the number of moles of zinc atoms contained in 1 g of the obtained particles. It is more preferable that The amount of component (e) trimethyldisilazane used for component (d) inorganic particulate carrier is such that component (e) trimethyldisilazane is 0.1 mmol or more per gram of component (d) inorganic particulate carrier. The amount is preferably 0.5 to 20 mmol, and more preferably 0.5 to 20 mmol.

  The metal atom of the metallocene complex (b) having a ligand having a structure in which two cyclopentadienyl type anion skeletons are bonded by a bridging group such as an alkylene group or a silylene group, includes group IV atoms in the periodic table. Zirconium and hafnium are preferred. The ligand is preferably an indenyl group, a methylindenyl group, a methylcyclopentadienyl group, or a dimethylcyclopentadienyl group, and the crosslinking group is preferably an ethylene group, a dimethylmethylene group, or a dimethylsilylene group. Furthermore, as a remaining substituent which a metal atom has, a diphenoxy group and a dialkoxy group are preferable. Preferred examples of the metallocene complex (b) include ethylene bis (1-indenyl) zirconium diphenoxide.

  Examples of the organoaluminum compound (c) include trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, and trinormaloctylaluminum, with triisobutylaluminum and trinormaloctylaluminum being preferred.

The amount of the metallocene complex (b) used is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol with respect to 1 g of the promoter support (a). The amount of the organoaluminum compound (c) is preferably expressed as a ratio (Al / M) of the number of moles of aluminum atoms in the organoaluminum compound (c) to the number of moles of metal atoms in the metallocene complex (b). 1 to 2000.

  In the polymerization catalyst obtained by contacting the promoter support (a), the metallocene complex (b) and the organoaluminum compound (c), the promoter support (a) and the metallocene complex (b) ) And the organoaluminum compound (c) may be a polymerization catalyst obtained by contacting the electron donating compound (d). Preferred examples of the electron donating compound (d) include triethylamine and trinormaloctylamine.

  From the viewpoint of increasing the molecular weight distribution of the obtained ethylene-α-olefin copolymer, it is preferable to use the electron donating compound (d), and the amount of the electron donating compound (d) used is an organoaluminum compound. More preferably, it is 0.1 mol% or more, and more preferably 1 mol% or more, relative to the number of moles of aluminum atoms in (c). The amount used is preferably 10 mol% or less, more preferably 5 mol% or less, from the viewpoint of increasing the polymerization activity.

  As a method for producing the ethylene-α-olefin copolymer of the present invention, a small amount of olefin is polymerized (hereinafter referred to as prepolymerization) using a solid promoter component in which the promoter component (I) is supported on a particulate carrier. A prepolymerized solid catalyst component obtained by polymerizing a small amount of olefin using a solid promoter component, a metallocene complex, and an organoaluminum compound, A method of copolymerizing ethylene and an α-olefin using the catalyst component or catalyst is preferred.

  Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, and trinormaloctylaluminum, with triisobutylaluminum and trinormaloctylaluminum being preferred.

As a method for producing the prepolymerized solid catalyst component, from the viewpoint of improving molding processability, a co-catalyst carrier, a metallocene complex, an organoaluminum compound, and a process comprising the following steps (1), (2) and (3): A method of subjecting to a contact treatment is preferred.
Step (1): A step of heat-treating a saturated aliphatic hydrocarbon compound solvent containing a metallocene complex at 40 ° C. or higher.
Step (2): A step of contacting the heat-treated product obtained by heat treatment in step (1) with the promoter support.
Step (3): a step of contact-treating the contact-treated product obtained by the contact treatment in Step (2) and the organoaluminum compound.

  Step (1) is a step of heat-treating a saturated aliphatic hydrocarbon compound solvent containing a metallocene complex at 40 ° C. or higher. The saturated aliphatic hydrocarbon compound solvent containing the metallocene complex is prepared by a method of introducing the metallocene complex into the saturated aliphatic hydrocarbon compound solvent. The metallocene complex is usually charged as a powder or a slurry of a saturated aliphatic hydrocarbon compound liquid.

  Examples of the saturated aliphatic hydrocarbon compound used for the preparation of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane and the like. It is done. These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or less at normal pressure, more preferably 90 ° C. or less at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane. More preferred is cyclohexane.

  The heat treatment of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex may be performed by adjusting the temperature of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex to a temperature of 40 ° C. or higher. Further, during the heat treatment, the solvent may be allowed to stand or the solvent may be stirred. The temperature is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of improving molding processability. Moreover, from a viewpoint of improving a catalyst activity, Preferably it is 100 degrees C or less, More preferably, it is 80 degrees C or less. The heat treatment time is usually 0.5 to 12 hours. The time is preferably 1 hour or more, and more preferably 2 hours or more, from the viewpoint of improving molding processability. Moreover, from stability of catalyst performance, Preferably it is 6 hours or less, More preferably, it is 4 hours or less.

  Step (2) is a step of contact-treating the heat-treated product (that is, a saturated aliphatic hydrocarbon compound solvent containing a metallocene complex) obtained by heat treatment in step (1) above and a promoter support. In the contact treatment, the heat-treated product and the co-catalyst support may be in contact with each other. Usually, the method of introducing the co-catalyst support into the heat-treated product, and the method of adding the heat-treated product and the co-catalyst support into the saturated aliphatic hydrocarbon compound. Is used. The cocatalyst carrier is usually charged as a powder or a slurry of a saturated aliphatic hydrocarbon compound solvent.

  The temperature of the contact treatment in the step (2) is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, preferably 10 ° C. or higher, more preferably 20 ° C. or higher. The time for the contact treatment is usually 0.1 to 2 hours.

  In the step (3), the contact-treated product obtained by the contact treatment in the above-described step (2) (that is, the contact-treated product of the heat-treated product obtained by heat-treating in the step (1) and the promoter support) and the organoaluminum compound are combined. It is a process of contact processing. In the contact treatment, the contact treatment product formed in the step (2) may be brought into contact with the organoaluminum compound. Usually, the organoaluminum compound is introduced into the contact treatment product obtained in the contact treatment in the step (2). A method is used in which a contact-treated product obtained by contact treatment in step (2) and an organoaluminum compound are introduced into a saturated aliphatic hydrocarbon compound.

  The temperature of the contact treatment in the step (3) is preferably 70 ° C. or lower, more preferably 60 ° C. or lower. Further, from the viewpoint of efficiently expressing the prepolymerization activity, the temperature is preferably 10 ° C or higher, more preferably 20 ° C or higher. The time for the contact treatment is usually 0.01 hours to 0.5 hours.

  The contact treatment in the step (3) is preferably performed in the presence of an olefin. As the olefin, an olefin that is a raw material in prepolymerization is usually used. The amount of olefin is preferably 0.05 to 1 g per 1 g of the promoter support.

  In the above steps (1) to (3), the saturated aliphatic hydrocarbon compound, the cocatalyst carrier, the metallocene complex and the organoaluminum compound are separately charged into the prepolymerization reactor, so that all the steps are spared. You may perform in a polymerization reactor, you may perform a process (2) and (3) in a prepolymerization reactor, and you may perform a process (3) in a prepolymerization reactor.

  In the prepolymerization, an olefin is added in the presence of a contact-treated product obtained by contact-treating a cocatalyst carrier, a metallocene complex, and an organoaluminum compound by the treatment step having the steps (1), (2) and (3). Pre-polymerization (polymerization of a small amount of olefin). The prepolymerization is usually performed by a slurry polymerization method, and the prepolymerization may be performed by any of batch, semi-batch, and continuous methods. Furthermore, the prepolymerization may be performed by adding a chain transfer agent such as hydrogen.

  When the prepolymerization is performed by a slurry polymerization method, a saturated aliphatic hydrocarbon compound is usually used as the solvent, and examples thereof include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane and the like. . These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or less at normal pressure, more preferably 90 ° C. or less at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane. More preferred is cyclohexane.

  When the prepolymerization is performed by the slurry polymerization method, the slurry concentration is usually 0.1 to 600 g, preferably 0.5 to 300 g, of the promoter support per liter of the solvent. The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed, but the temperature at which the prepolymerization is started is preferably 45 ° C. or less, and preferably 40 ° C. or less. Moreover, the partial pressure of olefins in the gas phase part during prepolymerization is usually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

  Examples of the olefin used for the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene, cyclohexene and the like. These may be used alone or in combination of two or more, preferably ethylene alone, or ethylene and α-olefin in combination, more preferably ethylene alone, or 1-butene, 1-hexene and 1 -It is used in combination with at least one α-olefin selected from octene and ethylene.

  The content of the prepolymerized polymer in the prepolymerization catalyst component is usually 0.01 to 1000 g, preferably 0.05 to 500 g, more preferably 0.1 to 200 g, per 1 g of the cocatalyst carrier. It is.

  As a manufacturing method of the ethylene-α-olefin copolymer of component (A), a gas phase polymerization method is preferable, and a continuous gas phase polymerization method is more preferable. The gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method for supplying the prepolymerized prepolymerized solid catalyst component to the continuous polymerization reaction tank accompanied by the formation of ethylene-α-olefin copolymer particles, it is usually an inert gas such as nitrogen or argon, hydrogen, ethylene, etc. And a method of supplying in a water-free state, and a method of supplying each component in a solution or slurry after dissolving or diluting each component in a solvent.

  The polymerization temperature for vapor phase polymerization of the ethylene-α-olefin copolymer of component (A) is usually less than the temperature at which the ethylene-α-olefin copolymer melts, preferably 0 to 150 ° C. More preferably, it is 30-100 degreeC. More preferably, the temperature is lower than 90 ° C, specifically in the range of 70 ° C to 87 ° C. Further, hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the ethylene-α-olefin copolymer. An inert gas may coexist in the mixed gas. In addition, when using a prepolymerization solid catalyst component, you may use promoter components, such as an organoaluminum compound, suitably.

The density of the high pressure method low density polyethylene of component (B) is usually 910 to 935 kg / m ³ . The density is preferably 910 kg / m ³ or more from the viewpoint of enhancing peelability, more preferably 920 kg / m ³ or more, and from the viewpoint of film flexibility, preferably 935 kg / m ³ or more. Preferably it is 930 kg / m ³ or less. In addition, this density is measured in accordance with the underwater substitution method prescribed | regulated to JISK7112-1980 using the sample which annealed as described in JISK6760-1995.

The melt flow rate (MFR) of the high-pressure method low-density polyethylene of component (B) is usually 0.1 to 50 g / 10 minutes, and preferably 5 g / 10 minutes or less from the viewpoint of improving peelability. The MFR is measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N by the method defined in JIS K7210-1995.

The film for rubber packaging of the present invention has a layer comprising a resin composition containing the component (A) and the component (B). As content of the component (A) and component (B) in this resin composition, the total amount of a component (A) and a component (B) is 100 weight%, and content of a component (A) is 20-80. % By weight, and the content of component (B) is 80 to 20% by weight. Considering the balance between peelability and moderate tackiness, the content of component (A) is preferably 30 to 70% by weight, and the content of component (B) is 30 to 70% by weight.

The film for rubber packaging of the present invention is a film having a layer comprising a resin composition containing the above components (A) and (B) as a rubber coating layer. That is, when the film for rubber packaging of the present invention is a single layer film, it becomes a film composed of a layer composed of the resin composition containing the above components (A) and (B), and when it is a multilayer film, The layer made of the resin composition containing the component (A) and the component (B) is a film having at least one surface layer, and the layer is a rubber coating layer.

When the film for rubber packaging of the present invention is a multilayer film, the layer other than the layer composed of the resin composition containing the component (A) and the component (B) is not particularly limited. ) Or only the component (B), a layer made of a polyethylene resin other than the components (A) and (B), and a layer made of polypropylene. Moreover, from a viewpoint of preventing discoloration of rubber, a multilayer film having a light shielding layer made of a resin composition containing a light shielding material may be used. Examples of the light shielding material include powders such as carbon black, aluminum powder, and titanium oxide. From the viewpoint of melt miscibility, the rubber packaging film of the present invention is preferably a single layer.

In the rubber packaging film of the present invention, if necessary, a lubricant, an antiblocking agent, an ultraviolet absorber, an antioxidant, a flame retardant, a colorant, an antistatic agent, and a reinforcement are within the range not impairing the object of the present invention. Agents, fillers, softeners, resins such as polyethylene and polybutene may be added.

Examples of the lubricant include fatty acids such as stearic acid, oleic acid, and lauric acid; fatty acid amides such as oleylamide, erucylamide, ricinolamide, and behenamide; glycerin esters of higher fatty acids; fatty acid esters such as sorbitan ester and n-butyl stearate Etc. can be used.

Examples of the anti-blocking agent include synthetic silica such as dry silica and wet silica; natural silica such as diatomaceous earth; silicon resin; polymethyl methacrylate (PMMA) and the like.

The thickness of the film for rubber packaging of the present invention is usually 20 to 100 μm, preferably 30 to 80 μm, more preferably 40 to 60 μm. Moreover, the width | variety of a film is 50-100 cm normally.

Resin containing component (A) and component (B) melts component (A), component (B) and components blended as necessary (the above additives, other resins, etc.) by a known method. By kneading, for example, after mixing with a tumbler blender, Henschel mixer, etc., it is further melt-kneaded with a single-screw extruder or multi-screw extruder, or melt-kneaded with a kneader or Banbury mixer.

The film for rubber packaging of the present invention is produced by a known film molding method, for example, an extrusion molding method such as an inflation film molding method or a T-die cast film molding method. The extrusion temperature is usually 110 to 250 ° C., although it depends on the type of extrusion method used.

The film for rubber packaging of the present invention is suitably used for ethylene-propylene-diene copolymer rubber. The ethylene-propylene-diene copolymer rubber has a tendency to increase in tackiness with an increase in temperature as compared with other rubbers. The film for rubber packaging of the present invention is excellent in peelability even after packaging such an ethylene-propylene-diene copolymer rubber and passing through a high temperature state.
The rubber to be packaged is usually in the shape of a rectangular parallelepiped, and generally has a vertical length of 300 to 400 mm, a horizontal length of 500 to 1000 mm, and a height of 100 to 250 mm. The rubber packaging is performed by a known method.

When the rubber packaging film of the present invention is used to wrap rubber that exhibits adhesiveness when the temperature is higher than room temperature, when peeling the film from the wrapped rubber, the force required for peeling is small, and the film is not easily torn. Good peelability. Even if the film does not peel well and remains attached to the rubber, it does not remain as a contaminant in the rubber because of its excellent melt miscibility with the rubber.

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

(1) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method defined in JIS K 7210-1995, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(2) Density (Unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-11995. The sample was annealed according to JIS K 6760-1995.

(3) Molecular weight distribution (Mw / Mn, unit:-)
Using a gel permeation chromatograph (GPC) method, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured under the following conditions (1) to (9), and the molecular weight distribution (Mw / Mn) was determined.
Measurement condition
(1) Equipment: 150CV ALC / GPC manufactured by Waters
(2) Separation column: Shodex GPC AT-806MS manufactured by Showa Denko KK
(3) Temperature: 140 ° C
(4) Solvent: o-dichlorobenzene
(5) Elution solvent flow rate: 1.0 ml / min
(6) Sample concentration: 1 mg / ml
(7) Measurement injection volume: 400 μl
(8) Molecular weight standard substance: Standard polystyrene (manufactured by Tosoh Corporation; molecular weight = 6000000 to 500)
(9) Detector: Differential refraction

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

(5) Melting point (Tm, unit: ° C)
About 10 mg of a test piece cut out from a sheet having a thickness of about 0.5 mm produced by hot pressing was used as a measurement sample, and measurement was performed using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer). In the measurement, the measurement sample was held at 150 ° C. for 5 minutes, then cooled to 40 ° C. at 1 ° C./minute, then held at 40 ° C. for 5 minutes, and then increased to 150 ° C. at a rate of 10 ° C./minute. Warm up. The melting point was determined from the melting peak of the melting curve obtained when the temperature was raised from 40 ° C. to 150 ° C. at a rate of 10 ° C./min.

(6) Removability 150 × 150 × 80 mm rectangular parallelepiped ethylene-propylene-diene copolymer rubber was affixed to a top surface and a bottom surface, respectively, with a film having a width of 12 cm and a length of 25 cm. A load of 100 kg was applied to the wrapping rubber, and it was placed in an oven at 60 ° C. and conditioned for 3 days. This state is a pseudo reproduction of the state of the lowermost rubber package that is normally stored in 6-7 stacks. After the condition adjustment, the film attached to the upper surface of the rubber was peeled off from the rubber at a peeling speed of 200 mm / min, and the stress (peeling strength) required for peeling was obtained. The lower the peel strength, the better the peelability. Furthermore, the rubber surface at the time of peeling was visually judged as follows for the presence or absence of a film torn.
○: No film tear remaining on the rubber surface.
X: The film is not broken on the rubber surface.

(7) 100 parts by weight of a melt-miscible ethylene-propylene-diene copolymer rubber and 2 parts by weight of a film were kneaded for 2 minutes at an initial temperature of 60 ° C. with a lab plast mill having an internal volume of 100 cc. About the obtained kneaded material, the presence or absence of the insoluble part of a film was determined visually as follows.
○: No insoluble part of the film is observed in the kneaded product.
X: The insoluble part of a film is recognized in a kneaded material.
XX: Many insoluble portions of the film are observed in the kneaded product.

[Example 1]
(1) Preparation of co-catalyst support Silica (Sypolol 948 manufactured by Devison Corp .; 50% volume average particle size = 55 μm; pore capacity = 1.67 ml / g; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 3.46 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 2.05 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 1.54 kg of 3,4,5-trifluorophenol and 2.88 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Then cooled to 5 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O0.221kg the temperature of the reactor to 5 ° C.. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, then heated to 40 ° C, stirred at 40 ° C for 2 hours, further heated to 80 ° C, and stirred at 80 ° C for 2 hours. After stirring, at room temperature, the supernatant was withdrawn to a residual amount of 16 L, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours. After stirring, the supernatant liquid was extracted at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, drying was performed to obtain a solid component (hereinafter referred to as a promoter support (a)).

(2) Preparation of pre-polymerization catalyst component After adding 80 liters of butane to an autoclave with a stirrer having an internal volume of 210 liters, which was previously purged with nitrogen, 144 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added, and the autoclave The mixture was heated to 50 ° C. and stirred for 2 hours. Next, 0.5 kg of the cocatalyst carrier (a) is charged and the autoclave is cooled to 31 ° C. to stabilize the system, and then 0.1 kg of ethylene and 0.1 liter of hydrogen (room temperature and normal pressure volume) are charged. Subsequently, 207 mmol of triisobutylaluminum was added to initiate polymerization. After 30 minutes while continuously supplying ethylene and hydrogen at 0.6 kg / Hr and 0.5 liter (room temperature and normal pressure volume), respectively, the temperature was raised to 50 ° C., and ethylene and hydrogen were each 3.6 kg / Hr. And 10.9 liters (normal temperature and normal pressure volume) / Hr were continuously fed to carry out preliminary polymerization for a total of 6 hours. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component containing 37 g of polyethylene per 1 g of the promoter support (a). The [η] of the polyethylene was 1.51 dl / g.

(3) Production of ethylene-1-butene-1-hexene copolymer Using the above prepolymerization catalyst component, copolymerization of ethylene, 1-butene and 1-hexene was performed in a continuous fluidized bed gas phase polymerization apparatus. did. The polymerization conditions were a temperature of 84 ° C., a total pressure of 2 MPa, a molar ratio of hydrogen to ethylene of 1.04%, a molar ratio of 1-butene to ethylene of 2.16%, and a molar ratio of 1-hexene to ethylene of 0.73. %, Ethylene, 1-butene, 1-hexene and hydrogen were continuously fed to keep the gas composition constant during the polymerization. Furthermore, the pre-polymerization catalyst component and triisobutylaluminum were continuously supplied at a constant ratio so that the total powder weight of the fluidized bed was maintained at 80 kg and the average polymerization time was 4 hours. By polymerization, a powder of ethylene-1-butene-1-hexene copolymer (hereinafter referred to as PE-1) was obtained with a polymerization efficiency of 22.9 kg / hr.

(4) Granulation of ethylene-1-butene-1-hexene copolymer powder The PE-1 powder obtained above was fed at a feed rate of 50 kg / hr and screw rotation with an extruder (LCM50 manufactured by Kobe Steel). PE-1 pellets were obtained by granulation under conditions of several 450 rpm, a gate opening of 4.2 mm, a suction pressure of 0.2 MPa, and a resin temperature of 200 to 230 ° C. The evaluation results of PE-1 pellets are shown in Table 1.

(5) Film processing 50% by weight of the PE-1 pellet obtained above and a commercially available high-pressure low-density polyethylene (Sumitomo Chemical Co., Ltd. Sumikasen F218-0 [MFR = 1 g / 10 min, density = 919 kg / m) ³ , molecular weight distribution = 6.8, flow activation energy = 69.0 kJ / mol, melting point = 107.5 ° C.]: hereinafter referred to as LD-1, the basic physical properties of LD-1 are shown in Table 1. ) Was blended and mixed with 50% by weight of the pellets at 150 ° C. using a 50 mmφ inflation machine manufactured by Plako Co., Ltd., to obtain a single layer film having a thickness of 50 μm. Table 2 shows the physical property evaluation results of the obtained film.

[Example 2]
Inflation film processing was carried out in the same manner as in Example 1 except that PE-1 pellets were 30 wt% and LD-1 pellets were 70 wt%. The evaluation results of the obtained film are shown in Table 2.

[Comparative Example 1]
Inflation film processing was performed in the same manner as in Example 1 except that the pellets of PE-1 were 100% by weight and the pellets of LD-1 were 0% by weight. The evaluation results of the obtained film are shown in Table 2.

Comparative Example 2
Inflation film processing was performed in the same manner as in Example 1 except that PE-1 pellets were changed to 0% by weight and LD-1 pellets were changed to 100% by weight. The evaluation results of the obtained film are shown in Table 2.

Comparative Example 3
In inflation film processing, commercially available metallocene linear low density polyethylene (Sumitomo Chemical Co., Ltd. Sumikasen E FV205 [MFR = 2 g / 10 min, density = 921 kg / m ³ , molecular weight distribution = 2.0, flow activation energy] = 30.0 kJ / mol, melting point = 107.5 ° C.]: hereinafter referred to as LL-1, the basic physical properties of LL-1 are shown in Table 1. 50% by weight of pellets and LD-1 pellets Was carried out in the same manner as in Example 1 except that the amount was 50% by weight. The evaluation results of the obtained film are shown in Table 2.

Claims (2)

It contains the following component (A) and component (B), the total amount of component (A) and component (B) is 100% by weight, the content of component (A) is 20 to 80% by weight, A film for rubber packaging having a layer made of a resin composition having a content of B) of 80 to 20% by weight.
(A): an ethylene-α-olefin having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms and satisfying the following requirements (a1) and (a2) Copolymer (a1): Flow activation energy (Ea) is 35 kJ / mol or more.
(A2): The molecular weight distribution (Mw / Mn) is 5-25.
(B): High-pressure low-density polyethylene   A rubber package formed by packing rubber with the rubber packaging film according to claim 1.