JP6984128B2 - Manufacturing method of polyethylene resin, solar cell encapsulant and solar cell module using polyethylene resin manufactured by the method. - Google Patents

Description

The present invention relates to a method for producing a polyethylene resin, a solar cell encapsulant, a solar cell module, and an insulator using the polyethylene resin produced by the method, and more specifically, from an ethylene / α-olefin copolymer or the like. The present invention relates to a polyethylene resin having excellent cross-linking characteristics, insulating properties, and cost, and a solar cell encapsulant, a solar cell module, and an insulator using the polyethylene resin.

Polyethylene resin is used for electronic materials such as solar cells and cables because of its good workability, moisture resistance, flexibility, and insulation. Further, in many of these applications, polyethylene resin is crosslinked and used in order to improve heat resistance and mechanical strength. The cross-linking reaction is carried out by electron beam irradiation or the use of an additive having high radical reactivity, for example, an organic peroxide.

One of the uses of the resin composition imparted with a crosslinked structure by an organic peroxide is a solar cell encapsulant. Conventionally, a resin composition of an ethylene-vinyl acetate copolymer (EVA) having a high vinyl acetate content has been used (see Patent Document 1). However, when ethylene-vinyl acetate copolymer (EVA) -based resin is used for a long period of time, its moisture resistance deteriorates due to deterioration and deterioration such as yellowing, cracking, and foaming, and power generation due to corrosion of solar cells and the like. It caused a decrease in the amount. It is considered that these are due to the fact that the EVA resin has a highly hydrolyzable ester structure and is therefore easily affected by sunlight and moisture.

Therefore, it has been proposed to use an ethylene / α-olefin copolymer having excellent transparency, moisture resistance, etc. as the resin material used for the encapsulant. For example, Patent Document 2 discloses a sealing material using an amorphous or low crystalline α-olefin copolymer having a crystallinity of 40% or less, and ethylene is used as the α-olefin copolymer. It is described that a cross-linking agent is added to the copolymer as a main component.

Further, in Patent Document 3, as a sealing material, (a) a density of less than about 0.90 g / cc, and (b) a 2% split wire of less than about 150 megapascals (MPa) as measured by ASTM D-882-02. Factors, (c) melting point below about 95 ° C, (d) α-olefin content of at least about 15 and less than about 50% by weight based on the weight of the polymer, (e) Tg below about -35 ° C, and (f). ) A polymer material comprising a polyolefin copolymer satisfying one or more of at least about 50 SCBDIs is disclosed.

In recent years, with the increase in demand for solar cell modules, it is required to improve the production efficiency of solar cell modules, and the cross-linking process of the encapsulant tends to be shortened. In general, an ethylene / α-olefin copolymer is not easy to crosslink with an organic peroxide as compared with EVA, and it is difficult to obtain a high gel fraction by heating for a short time, and the crosslink is about the same as EVA. Difficult to get efficiency. This is because the vinyl acetate moiety, which is a comonomer, can easily become a radical cross-linking point in EVA, whereas the α-olefin comonomer itself used in a general ethylene / α-olefin copolymer does not become a radical cross-linking point. ..

On the other hand, as a polyethylene resin exhibiting high insulating properties, polymerization using a catalyst avoiding a boron-containing co-catalyst has been proposed (see Patent Document 4). Regarding the polyethylene resin exemplified, it is described that the volume resistivity, which is an index of insulation property, is lowered by the boron residue derived from the boron-containing co-catalyst as compared with the sample of the alumoxane co-catalyst alone.

As the insulation decreases, the leakage current from the electronic material increases. For example, in the case of a solar cell, there is an example in which the occurrence of a PID (Positive Induced Degradation) phenomenon in which a decrease in power generation capacity occurs due to the influence of leakage current is reported. Therefore, the PID phenomenon can be suppressed by manufacturing a solar cell encapsulant having a high volume resistivity.

However, when a metallocene catalyst system is used, the boron-containing co-catalyst exhibits higher activity under high temperature and high pressure conditions as compared with alumoxane, so that the production rate of the polyethylene resin is high (see Patent Document 5). Moreover, it is known that the amount of the co-catalyst required for production is smaller in the boron-containing co-catalyst, and the use of the boron-containing co-catalyst is advantageous in terms of the production cost of the polyethylene resin.

As described above, in the conventional technique, a method for producing a polyethylene resin excellent in cross-linking characteristics, insulating properties, and cost, and a solar cell encapsulant and a solar cell module using the same have not been obtained.

Japanese Unexamined Patent Publication No. 58-023870 Japanese Unexamined Patent Publication No. 2006-210906 Special Table 2010-504647A Gazette Japanese Patent Publication No. 2015-508833 Special Table No. 7-508545

An object of the present invention is a method for producing a polyethylene resin, which is composed of an ethylene / α-olefin copolymer and has excellent cross-linking characteristics, insulating properties, and cost, in view of the problems of the prior art, and is produced by this method. It is an object of the present invention to provide a solar cell encapsulant, a solar cell module and an insulator using polyethylene resin.

As a result of diligent studies to solve the above problems, the present inventor has determined characteristics such as specific MFR, density, and boron residue concentration produced by using a catalytic system containing a metallocene compound and a specific type and amount of boron compound. The solar electron encapsulant using a resin composition containing a polyethylene resin made of an ethylene / α-olefin copolymer has good heat resistance and suppresses leakage current from a solar cell. The present invention has been completed.

That is, according to the first aspect of the present invention, there is a method for producing a polyethylene resin composed of an ethylene / α-olefin copolymer, wherein the ethylene / α-olefin copolymer contains the following components (A) and ( Provided is a method for producing a polyethylene resin, which is obtained by carrying out polymerization using a catalytic system containing B).
Component (A): Cross-linked metallocene compound having an indenyl skeleton having a substituent Component (B): A boron compound that reacts with the component (A) to form an ion pair, and heat that causes a weight change in _{an N 2 atmosphere.} Decomposition temperature is less than 200 ° C

Further, according to the second invention of the present invention, in the first invention, the component (A) is a crosslinked metallocene compound having an indenyl skeleton having a substituent or an unsubstituted aryl group. A method for producing a polyethylene resin is provided.

［一般式（Ｉ）中、ＭはＴｉ、Ｚｒ、またはＨｆであり；
Ｒ^１〜Ｒ^１０およびＲ^１１〜Ｒ^２０は、同一または異なっていてもよく、それぞれ水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のハロゲン化アルキル基、炭素数６〜２０のアリール基、炭素数１〜１０のアルコキシ基、炭素数１〜６の炭化水素基を有するシリル基、炭素数１〜６の炭化水素基を有するシリル基で置換された炭素数１〜２０のアルキル基、−Ｎ（Ｒ^２３）_２基、−ＳＲ^２３基、−ＯＳｉ（Ｒ^２３）_３基又は−Ｐ（Ｒ^２３）_２基であり（Ｒ^２３は、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数６〜２０のアリール基であり、Ｒ^２３を２以上有する場合は、それぞれ同じであっても異なっていてもよい）、Ｒ^１〜Ｒ^１０およびＲ^１１〜Ｒ^２０が隣接するＲ基同士でそれらを連結する原子と一緒になって１つ以上の芳香族環又は脂肪族環を形成してもよく、Ｒ^５とＲ^６若しくはＲ^５とＲ^１０、Ｒ^１５とＲ^１６若しくはＲ^１５とＲ^２０がそれらを連結する原子と一緒になって１つの芳香族環または脂肪族環を形成していてもよく；
ＹはＳｉまたはＣであり；
Ｒ^２１とＲ^２２は、同一または異なっていてもよく、それぞれ水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のフルオロアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１０のフルオロアリール基、炭素数６〜１０のアリールオキシ基、炭素数２〜１０のアルケニル基、炭素数７〜４０のアリールアルキル基、炭素数７〜４０のアルキルアリール基、炭素数８〜４０のアリールアルケニル基であり、かつ、Ｒ^２１とＲ^２２が同時に水素原子ではなく、Ｒ^２１とＲ^２２がそれらを連結する原子と一緒になって１つ以上の環を形成してもよく；
Ｘ^１とＸ^２は、同一または異なっていてもよく、それぞれ水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１０のアリールオキシ基、炭素数２〜１０のアルケニル基、炭素数７〜４０のアリールアルキル基、炭素数７〜４０のアルキルアリール基、炭素数８〜４０のアリールアルケニル基、炭素数１〜６の炭化水素基を有するシリル基で置換された炭素数１〜２０のアルキル基、炭素数１〜１０のアミノ基、ＯＨ基、ハロゲン原子又は配位可能な中性配位子であり、Ｘ^１とＸ^２が、それらを連結する原子と一緒になって１つの環を形成していてもよい。］ Further, according to the third aspect of the present invention, the polyethylene resin according to the first or second invention, wherein the component (A) is a metallocene compound represented by the following general formula (I). A manufacturing method is provided.

[In general formula (I), M is Ti, Zr, or Hf;
R ^{1 to} R ¹⁰ and R ^{11 to} R ²⁰ may be the same or different, respectively, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, respectively. 1 carbon number substituted with an aryl group of 6 to 20, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 6 carbon atoms. ~ 20 alkyl groups, -N (R ²³ ) ₂ groups, -SR ²³ groups, -OSi (R ²³ ) ₃ groups or -P (R ²³ ) ₂ groups (R ²³ is a halogen atom, 1 carbon number) It is an alkyl group of 10 to 10 and an aryl group having 6 to 20 carbon atoms, and ^{when it has 2 or more R 23} , it may be the same or different from each other), R ^{1 to} R ¹⁰ and R ^{11 to} R ^20. There may form one or more aromatic or aliphatic ring together with the atoms connecting them with R groups adjacent to each other, R ⁵ and R ⁶ or R ⁵ and R ^10, R ¹⁵ R ¹⁶ or R ¹⁵ and R ²⁰ may be combined with the atoms connecting them to form one aromatic or aliphatic ring;
Y is Si or C;
R ²¹ and R ²² may be the same or different, respectively, and have a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, respectively. Aryl groups with 6 to 20 carbon atoms, fluoroaryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, arylalkyl groups with 7 to 40 carbon atoms, and carbon atoms. It is an alkylaryl group of 7 to 40, an arylalkenyl group of 8 to 40 carbon atoms, and R ²¹ and R ²² are not hydrogen atoms at the same time, but R ²¹ and R ²² are combined with an atom connecting them. One or more rings may be formed;
X ¹ and X ² may be the same or different, respectively, and have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 6 carbon atoms, respectively. 10 aryloxy groups, 2-10 carbon alkenyl groups, 7-40 carbon arylalkyl groups, 7-40 carbon alkylaryl groups, 8-40 carbon arylalkenyl groups, 1-6 carbons It is an alkyl group having 1 to 20 carbon atoms, an amino group having 1 to 10 carbon atoms, an OH group, a halogen atom or a coordinable neutral ligand substituted with a silyl group having a hydrocarbon group of X ^1. And X ² may be combined with the atoms connecting them to form a ring. ]

Further, according to the fourth aspect of the present invention, in any one of the first to third inventions, the ethylene / α-olefin copolymer has the following characteristics (a1) to (a5). A method for producing a featured polyethylene resin is provided.
(A1) The content ratio of the structural unit derived from ethylene is 80 to 97 mol%, and the content ratio of the structural unit derived from α-olefin having 3 to 20 carbon atoms is 3 to 20 mol%.
(A2) MFR (190 ° C., 21.18N load) is 0.1 to 100 g / 10 minutes (a3) Density is 0.860 to 0.920 g / cm ³
(A4) Volume resistivity measured at a temperature of 23 ° C. and an applied voltage of 500 V is 1.0 × 10 ¹⁶ Ω · cm or more (a5) Boron residue concentration (M) in the resin is 0 <M <1 wtppm.

Further, according to the fifth aspect of the present invention, in any one of the first to fourth inventions, the ethylene / α-olefin copolymer is characterized by having the following property (a6). A method for producing a resin is provided.
(A6) No melting peak is shown at a temperature 20 ° C. or higher higher than the temperature showing the maximum melting peak of differential scanning calorimetry (DSC).

Further, according to the sixth aspect of the present invention, in any one of the first to fifth inventions, the ethylene / α-olefin copolymer is characterized by having the following property (a7). A method for producing a resin is provided.
(A7) The ratio (Mz / Mn) of the Z average molecular weight (Mz) to the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 8.0 or less.

Further, according to the seventh aspect of the present invention, the solar cell encapsulant using the polyethylene resin produced in any one of the first to sixth inventions and the polyethylene resin composition containing the following component (D) is used. Provided.
Component (D): Organic peroxide

Further, according to the eighth aspect of the present invention, in the seventh invention, the content of the component (D) is 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyethylene resin. Provided is a solar cell encapsulant using a featured polyethylene resin composition.

On the other hand, according to the ninth invention of the present invention, in the seventh or eighth invention, the solar cell module using the solar cell encapsulant is provided.

Further, according to the tenth aspect of the present invention, there is provided an insulator using a polyethylene resin composition containing the polyethylene resin produced in any one of the first to sixth inventions.

The polyethylene resin of the present invention has specific MFR, density, boron residue concentration and other properties polymerized using a catalytic system containing a crosslinked metallocene compound having an indenyl skeleton having a substituent and a boron compound. The ethylene / α-olefin copolymer is used for a relatively short time in the solar cell encapsulant sheet using a polyethylene resin composition containing an olefin copolymer as a main component and an organic peroxide mixed therein. Can be crosslinked with, and the PID phenomenon can be suppressed. In addition, the obtained solar cell module has excellent heat resistance, transparency, and weather resistance, and can maintain stable conversion efficiency for a long period of time.

The measurement results of thermogravimetric analysis (TG) of tris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and trityl tetrakis (pentafluorophenyl) borate are shown. The DSC measurement results of PE-1 and PE-2 are shown.

The method for producing a polyethylene resin of the present invention uses a catalytic system containing a crosslinked metallocene compound having an indenyl skeleton having a substituent and a boron compound, and a specific ethylene / α-olefin copolymer and organic peroxide as resin components. The present invention relates to a solar cell encapsulant and a solar cell module using a polyethylene resin composition comprising.
Hereinafter, each component used in the present invention, a solar cell encapsulant using them, and the like will be described in detail.

1. 1. Catalyst system The catalyst system used in the present invention contains the following components (A) and (B).
Component (A): Cross-linked metallocene compound having an indenyl skeleton having a substituent Component (B): A boron compound that reacts with the component (A) to form an ion pair, and changes in weight in _{an N 2 atmosphere 200} Has a pyrolysis temperature below ° C

(1) Ingredient (A)
The component (A) used in the present invention is a crosslinked metallocene compound having an indenyl skeleton having a substituent. The component (A) is preferably a crosslinked metallocene compound having an indenyl skeleton having a substituent or an unsubstituted aryl group.
Further, the component (A) is more preferably a metallocene compound having a specific substituent represented by the following general formula (I).

［一般式（Ｉ）中、ＭはＴｉ、Ｚｒ、又はＨｆであり；
Ｒ^１〜Ｒ^１０およびＲ^１１〜Ｒ^２０は、同一または異なっていてもよく、それぞれ水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のハロゲン化アルキル基、炭素数６〜２０のアリール基、炭素数１〜１０のアルコキシ基、炭素数１〜６の炭化水素基を有するシリル基、炭素数１〜６の炭化水素基を有するシリル基で置換された炭素数１〜２０のアルキル基、−Ｎ（Ｒ^２３）_２基、−ＳＲ^２３基、−ＯＳｉ（Ｒ^２３）_３基または−Ｐ（Ｒ^２３）_２基であり（Ｒ^２３は、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数６〜２０のアリール基であり、Ｒ^２３を２以上有する場合は、それぞれ同じであっても異なっていてもよい）、Ｒ^１〜Ｒ^１０およびＲ^１１〜Ｒ^２０が隣接するＲ基同士でそれらを連結する原子と一緒になって１つ以上の芳香族環又は脂肪族環を形成してもよく、Ｒ^５とＲ^６もしくはＲ^５とＲ^１０、Ｒ^１５とＲ^１６若しくはＲ^１５とＲ^２０がそれらを連結する原子と一緒になって１つの芳香族環又は脂肪族環を形成していてもよく；
ＹはＳｉ又はＣであり；
Ｒ^２１とＲ^２２は、同一または異なっていてもよく、それぞれ水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のフルオロアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１０のフルオロアリール基、炭素数６〜１０のアリールオキシ基、炭素数２〜１０のアルケニル基、炭素数７〜４０のアリールアルキル基、炭素数７〜４０のアルキルアリール基、炭素数８〜４０のアリールアルケニル基であり、かつ、Ｒ^２１とＲ^２２が同時に水素原子ではなく、Ｒ^２１とＲ^２２がそれらを連結する原子と一緒になって１つ以上の環を形成してもよく；
Ｘ^１とＸ^２は、同一または異なっていてもよく、それぞれ水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１０のアリールオキシ基、炭素数２〜１０のアルケニル基、炭素数７〜４０のアリールアルキル基、炭素数７〜４０のアルキルアリール基、炭素数８〜４０のアリールアルケニル基、炭素数１〜６の炭化水素基を有するシリル基で置換された炭素数１〜２０のアルキル基、炭素数１〜１０のアミノ基、ＯＨ基、ハロゲン原子又は配位可能な中性配位子であり、Ｘ^１とＸ^２が、それらを連結する原子と一緒になって１つの環を形成していてもよい。］

[In general formula (I), M is Ti, Zr, or Hf;
R ^{1 to} R ¹⁰ and R ^{11 to} R ²⁰ may be the same or different, respectively, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, respectively. 1 carbon number substituted with an aryl group of 6 to 20, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 6 carbon atoms. ~ 20 alkyl groups, -N (R ²³ ) ₂ groups, -SR ²³ groups, -OSi (R ²³ ) ₃ groups or -P (R ²³ ) ₂ groups (R ²³ is a halogen atom, 1 carbon number) It is an alkyl group of 10 to 10 and an aryl group having 6 to 20 carbon atoms, and ^{when it has 2 or more R 23} , it may be the same or different from each other), R ^{1 to} R ¹⁰ and R ^{11 to} R ^20. There may form one or more aromatic or aliphatic ring together with the atoms connecting them with R groups adjacent to each other, R ⁵ and R ⁶ or R ⁵ and R ^10, R ¹⁵ R ¹⁶ or R ¹⁵ and R ²⁰ may be combined with the atoms connecting them to form one aromatic or aliphatic ring;
Y is Si or C;
R ²¹ and R ²² may be the same or different, respectively, and have a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, respectively. Aryl groups with 6 to 20 carbon atoms, fluoroaryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, arylalkyl groups with 7 to 40 carbon atoms, and carbon atoms. It is an alkylaryl group of 7 to 40, an arylalkenyl group of 8 to 40 carbon atoms, and R ²¹ and R ²² are not hydrogen atoms at the same time, but R ²¹ and R ²² are combined with an atom connecting them. One or more rings may be formed;
X ¹ and X ² may be the same or different, respectively, and have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 6 carbon atoms, respectively. 10 aryloxy groups, 2-10 carbon alkenyl groups, 7-40 carbon arylalkyl groups, 7-40 carbon alkylaryl groups, 8-40 carbon arylalkenyl groups, 1-6 carbons It is an alkyl group having 1 to 20 carbon atoms, an amino group having 1 to 10 carbon atoms, an OH group, a halogen atom or a coordinable neutral ligand substituted with a silyl group having a hydrocarbon group of X ^1. And X ² may be combined with the atoms connecting them to form a ring. ]

In the general formula (I), M is Ti, Zr, or Hf, preferably Zr, Hf, and particularly preferably Hf.

In the general formula (I), as X ¹ and X ² , specifically, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, Examples thereof include a phenyl group, a benzyl group, a dimethylamino group, a diethylamino group, a trimethylsilyl group and the like.
Among these, a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group and a trimethylsilyl group are preferable, and a chlorine atom, a methyl group, an i-butyl group, a benzyl group and a trimethylsilyl group are more preferable. ..

Further, X ¹ and X ² are coordinating neutral ligands, and specifically, 1,3-butadiene as an atomic group forming one ring together with the atoms connecting them. , 1,4-Diphenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 2,4-hexadiene, 1,3-pentadiene, 1,4 -Ditril-1,3-butadiene, 1,4-bis (trimethylsilyl) -1,3-butadiene and the like can be mentioned.

In the general formula (I), R ^{1 to} R ⁵ and R ^{11 to} R ¹⁵ are preferably hydrogen atoms.

In the general formula (I), each of R ^{6 to} R ¹⁰ and R ^{16 to} R ²⁰ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms, respectively. It is an alkyl group having 10 to 10 aryl groups, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and an alkyl group having 1 to 20 carbon atoms substituted with a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, more preferably. Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

In the general formula (I), Y is preferably a carbon atom from the viewpoint of the amount of double bonds involved in the cross-linking reaction of the produced ethylene / α-olefin copolymer.

In the formula (I), preferred ^{R 23} groups, alkyl groups having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferable ^{-N (R} _{23) 2} group, dimethylamide group, Examples thereof include a diethylamide group and a diisopropylamide group.

^{Specific examples of the -SR 23} group in the general formula (I) include a methylsulfanil group, an ethylsulfanil group, an isopropylsulfanil group, and a phenylsulfanil group.

_{Specific examples of the three} -OSi (R ²³ ) groups include a trimethylsiloxy group, a triethylsiloxyki group, a triisopropylsiloxy group, a triphenylsiloxy group, a tert-butyl (dimethyl) siloxy group and the like.

In the general formula (I), _{specific examples of the two} ^{-P (R 23} ) groups include a dimethylphosphino group, a diethylphosphino group, a diisopropylphosphino group, a dibutylphosphino group, and a diphenylphosphino group. ..

In the general formula (I), R ²¹ and R ²² are preferably a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aryl group having 7 to 10 carbon atoms, and a fluoroaryl group. , An alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, and more preferably 1 to 1 carbon atoms. It is an alkyl group of 10, an aryl group having 7 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and more preferably, the sum of the carbon atoms contained in ^{R 21} and R ^{22 is 3 or more.}
Further, R ²¹ and R ²² preferably form one or more rings together with the connecting atom (Y), and more preferably form a 4-5 member ring.

Hereinafter, specific examples of each functional group that can be contained in the general formula (I) will be shown.
Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl and cyclo. Examples thereof include propyl, cyclopentyl, cyclohexyl, n-heptyl, n-octyl, n-decyl and the like.

The halogen-containing alkyl group having 1 to 10 carbon atoms is a hydrogen atom substituted with a hydrogen atom on the skeleton of the alkyl group having 1 to 10 carbon atoms. Examples of the halogen atom of the halogenated alkyl group having 1 to 10 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Specific examples of alkyl halide groups having 1 to 10 carbon atoms include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2. 2-Trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, 5-chloropentyl, 5,5,5-trichloropentyl, 5- Fluoropentyl, 5,5,5-trifluoropentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl, 6-fluorohexyl, 6,6,6-trifluorohexyl can be mentioned.

Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl, anthryl and the like.

A fluoroalkyl group having 1 to 10 carbon atoms is one in which a hydrogen atom is substituted with a hydrogen atom on the skeleton of an alkyl group having 1 to 10 carbon atoms.
Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentafluoropropyl, 5-fluoropentyl, and the like. 5,5,5-trifluoropentyl, 6-fluorohexyl, 6,6,6-trifluorohexyl can be mentioned.

Specific examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, and cyclo. Examples thereof include propoxy, cyclopentoxy, cyclohexoxy, n-octoxy, n-detoxy and the like.

A fluoroaryl group having 6 to 10 carbon atoms is a hydrogen atom substituted with a hydrogen atom on the skeleton of an aryl group having 6 to 10 carbon atoms. Specific examples include pentafluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, di (trifluoromethyl) phenyl, pentafluoroethyl phenyl, nonafluoro-t-butyl phenyl, 1-perfluoronaphthyl, 2-Perfluoronaphthyl and the like can be mentioned.

Aryloxy groups having 6 to 10 carbon atoms may be substituted with hydrocarbon groups having 1 to 4 carbon atoms, and specific examples thereof include phenoxy, trimethylphenoxy, dimethylphenoxy, ethylphenoxy, and t-butylphenoxy. Examples thereof include 1-naphthoxy and 2-naphthoxy.

Specific examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 1-propenyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl and the like.

Specific examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl, phenylethyl, (methylphenyl) methyl, and (tert-butylphenyl) methyl.

Specific examples of the alkylaryl group having 7 to 40 carbon atoms include trill, dimethylphenyl, ethylphenyl, trimethylphenyl, and t-butylphenyl.

Specific examples of the arylalkenyl group having 8 to 40 carbon atoms include vinylphenyl and (2-propenyl) phenyl group.

Specific examples of the alkyl group having 1 to 20 carbon atoms substituted with the silyl group having a hydrocarbon group having 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilylmethyl group and a triphenylsilylmethyl group. can.

Specific examples of the amino group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group and a diisopropylamino group.

Specific examples of the silyl group having a hydrocarbon group having 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilyl group, a tert-butyl (dimethyl) silyl group, and a triphenylsilyl group.

(Specific example of metallocene compound)
Specific examples of the metallocene compound of the present invention represented by the general formula (I) are shown below. These are typical examples.

Isopropyridene cross-linked metallocene compounds:
Isopropyridenebis (4-phenyl-1-indenyl) dimethylhafnium, isopropyridenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (3-isopropylphenyl) -1- Indenyl) dimethylhafnium, isopropyridenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropyridenbis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (4-Isopropyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (4-trifluoro) Methylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethyl Hafnium, isopropyridenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (4-fluorophenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (4) -Chlorophenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium , Isopropylidenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4-( 3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (3,3,3) 5-Dimethoxyphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (3,5-ditrifluoromethyl) Phenyl) -1-indenyl ) Dimethylhafnium, isopropylidenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropyridenbis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidene Bis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,3,5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) Dimethylhafnium, isopropyridenebis (4-biphenylyl 1-indenyl) dimethylhafnium, isopropyridenbis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (2',) 6'-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, isopropyridenebis (4- (2-naphthyl) -1-indenyl) Dimethylhafnium, isopropylidenebis (4-phenanthril-1-indenyl) dimethylhafnium

Cyclobutylidene cross-linked metallocene compound:
Cyclobutylidenebis (4-phenyl-1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (3-isopropylphenyl)) -1-Indenyl) dimethylhafnium, cyclobutylidenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-methylphenyl) -1-indenyl) dimethyl Hafnium, cyclobutylidenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-Trifluoromethylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4- (4- (4-)4-) Isopropoxyphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-fluorophenyl) -1-indenyl ) Dimethylhafnium, cyclobutylidenebis (4- (4-chlorophenyl) -1-indenyl) Dimethylhafnium cyclobutylidenbis (4- (4-bromophenyl) -1-indenyl) Dimethylhafnium, cyclobutylidenebis (4) -(2-Methylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (3,5-dimethylphenyl) ) -1-Indenyl) dimethylhafnium, cyclobutylidenebis (4- (3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (3,5-di-tert-butylphenyl) ) -1-Indenyl) dimethylhafnium, cyclobutylidenebis (4- (3,5-dimethoxyphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (3,5-ditrimethylsilylphenyl) -1 -Indenyl) Dimethylhafnium, cyclobutylidenebis (4- (3,5-ditrifluoromethylphenyl) -1-indenyl) Dimethylhafnium, cyclobutylidenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclo Butylidenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (2,3,5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium, Cyclobutylidenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-tert-butyl-2-methyl-phenyl)) -1-Indenyl) dimethylhafnium, cyclobutylidenebis (4-biphenylyl 1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, cyclobutylidene Bis (4- (2', 6'-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4-) (2-naphthyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4-phenanthril-1-indenyl) dimethylhafnium

Cyclopentylidene cross-linked metallocene compound:
Cyclopentylidenebis (4-phenyl-1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (3-isopropylphenyl)) -1-Indenyl) dimethylhafnium, cyclopentyldenbis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4-methylphenyl) -1-indenyl) dimethyl Hafnium, cyclopentyldenbis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4-Trifluoromethylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4- (4- (4-)4-) Isopropoxyphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4-fluorophenyl) -1-indenyl ) Dimethylhafnium, cyclopentyldenbis (4- (4-chlorophenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis ( 4- (2-Methylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (3,5-dimethyl) Phenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (3,5-di-tert-butyl) Phenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (3,5-dimethoxyphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (3,5-ditrimethylsilylphenyl)- 1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (3,5-di) Trifluoromethylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (2,5-dimethylphenyl) ) -1-Indenyl) dimethylhafnium, cyclopentyldenbis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (2,3,5,6-tetramethyl) Phenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (4- (4- (4- (4-)4-) tert-Butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4-biphenylyl 1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (2,6-dimethylbiphenylyl)- 1-Indenyl) dimethylhafnium, cyclopentyldenbis (4- (2', 6'-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4- (1-naphthyl) -1-indenyl) Dimethylhafnium, cyclopentyldenbis (4- (2-naphthyl) -1-indenyl) dimethylhafnium, cyclopentyldenbis (4-phenanthryl-1-indenyl) dimethylhafnium

Cyclohexylidene cross-linked metallocene compound:
Cyclohexylidenebis (4-phenyl-1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (3-isopropylphenyl)) -1-Indenyl) dimethylhafnium, cyclohexylidenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (4-methylphenyl) -1-indenyl) dimethyl Hafnium, cyclohexylidenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (2-ethylphenyl) ) -1-Indenyl) dimethylhafnium, cyclohexylidenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (3,5-di-tert-butylphenyl) ) -1-Indenyl) dimethylhafnium, cyclohexylidenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (2,3-dimethylphenyl) -1 -Indenyl) dimethylhafnium, cyclohexylidenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethyl Hafnium, cyclohexylidenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4-biphenylyl1-indenyl) dimethylhafnium

Diethylmethylene crosslinked metallocene compound:
Diethylmethylenebis (4-phenyl-1-indenyl) dimethylhafnium, diethylmethylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (3-isopropylphenyl) -1- Indenyl) dimethylhafnium, diethylmethylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (4-Isopropylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (4-trimethylsilylphenyl) ) -1-Indenyl) dimethylhafnium, diethylmethylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, diethyl Methylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (2) , 5-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (4-tert-butyl-2) -Methyl-phenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4-biphenylyl-1-indenyl) dimethylhafnium

Di-n-propylmethylene crosslinked metallocene compound:
Di-n-propylmethylenebis (4-phenyl-1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (3-Isopropyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (4-Methylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4) -(4-tert-Butylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4) -(2-Methylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4-(2-ethylphenyl) -1-indenyl) 3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, di-n-propyl Methylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, di- n-propylmethylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, Di-n-propylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4-biphenylyl1-indenyl) dimethylhafnium

Di-iso-butylmethylene crosslinked metallocene compound:
Di-iso-butylmethylenebis (4-phenyl-1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (3-Isopropylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (4-Methylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4) -(4-tert-Butylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4) -(2-Methylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4-(2-ethylphenyl) -1-indenyl) 3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, di-iso-butyl Methylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, di- iso-butylmethylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, Di-iso-butylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4-biphenylyl1-indenyl) dimethylhafnium

Dibenzylmethylene crosslinked metallocene compound:
Dibenzylmethylenebis (4-phenyl-1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (3-isopropylphenyl)) -1-Indenyl) dimethylhafnium, dibenzylmethylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (4-methylphenyl) -1-indenyl) dimethyl Hafnium, dibenzylmethylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (2-ethylphenyl) ) -1-Indenyl) dimethylhafnium, dibenzylmethylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (3,5-di-tert-butylphenyl) ) -1-Indenyl) dimethylhafnium, dibenzylmethylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (2,3-dimethylphenyl) -1 -Indenyl) dimethylhafnium, dibenzylmethylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethyl Hafnium, dibenzylmethylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4-biphenylyl1-indenyl) dimethylhafnium

Methyl (Ethyl) Methylene Crosslinked Metallocene Compounds:
Methyl (ethyl) methylenebis (4-phenyl-1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (3-) Isopropylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (4-methylphenyl)- 1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (4-tert-butylphenyl) -1-indenyl) Dimethylhafnium, methyl (ethyl) methylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) ) Methylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4) -(3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) Methylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis ( 4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) methylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, methyl (ethyl) ) Methylbis (4-biphenylyl 1-indenyl) dimethylhafnium

Methyl (n-propyl) methylene crosslinked metallocene compound:
Methyl (n-propyl) methylenebis (4-phenyl-1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (3-Isopropylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (4-Methylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4) -(4-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4) -(2-Methylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4-(n-propyl) methylenebis 3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) ) Methylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl ( n-propyl) methylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, Methyl (n-propyl) methylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, methyl (n-propyl) methylenebis (4-biphenylyl1-indenyl) dimethylhafnium

Methyl (iso-butyl) methylene crosslinked metallocene compound:
Methyl (iso-butyl) methylenebis (4-phenyl-1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (3-Isopropyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (4-Methylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4) -(4-tert-Butylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4) -(2-Methylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4-(iso-butyl) 3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) ) Methylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl ( iso-butyl) methylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, Methyl (iso-butyl) methylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, methyl (iso-butyl) methylenebis (4-biphenylyl1-indenyl) dimethylhafnium

Methyl (benzyl) methylene crosslinked metallocene compound:
Methyl (benzyl) methylenebis (4-phenyl-1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (3-) Isopropylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (4-methylphenyl)- 1-Indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (4-tert-butylphenyl) -1-indenyl) Dimethylhafnium, methyl (benzyl) methylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) ) Methylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4) -(3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) Methylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis ( 4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) methylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, methyl (benzyl) ) Methylenebis (4-biphenylyl 1-indenyl) dimethylhafnium

Di (4-methylphenyl) methylene crosslinked metallocene compound:
Di (4-methylphenyl) methylenebis (4-phenyl-1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, di (4-methyl) Phenyl) methylenebis (4- (3-isopropylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, di (4) -Methylphenyl) Methylbis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, di (4) -Methylphenyl) methylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, di (4-Methylphenyl) methylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, di (4-Methylphenyl) methylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (3,5-di-tert-butylphenyl)- 1-Indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (2,3) -Dimethylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4-) (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, di (4-methylphenyl) methylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, di ( 4-Methylphenyl) Methylenebis (4-biphenylyl 1-indenyl) Dimethylhafnium

Dimethylsilylene cross-linked metallocene compound:
Dimethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3-isopropylphenyl) -1- Indenyl) dimethylhafnium, dimethylsilylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-Isopropyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-trifluoro) Methylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethyl Hafnium, dimethylsilylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-fluorophenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4) -Chlorophenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium , Dimethylsilylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4-( 3,5-Diisopropylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3,3) 5-Dimethoxyphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3,5-ditrifluoromethyl) Phenyl) -1-indenyl ) Dimethylhafnium, dimethylsilylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene Bis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (2,3,5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) Dimethylhafnium, dimethylsilylenebis (4-biphenylyl-1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (2') , 6'-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (2-naphthyl) -1-indenyl) ) Dimethylhafnium, dimethylsilylenebis (4-phenanthril-1-indenyl) dimethylhafnium

Diethylsilylene cross-linked metallocene compound:
Diethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3-isopropylphenyl) -1- Indenyl) dimethylhafnium, diethylsilylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-Isopropyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-trifluoro) Methylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethyl Hafnium, diethylsilylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-fluorophenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4) -Chlorophenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium , Diethylsilylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4-( 3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3,3) 5-Dimethoxyphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3,5-ditrifluoromethyl) Phenyl) -1-indenyl ) Dimethylhafnium, diethylsilylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylsilylene Bis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (2,3,5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) Dimethylhafnium, diethylsilylenebis (4-biphenylyl-1-indenyl) dimethylhafnium, diethylsilylenebis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (2') , 6'-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (2-naphthyl) -1-indenyl ) Dimethylhafnium, diethylsilylenebis (4-phenanthril-1-indenyl) dimethylhafnium

Trimethylenesilylene cross-linked metallocene compound:
Trimethylene silylenebis (4-phenyl-1-indenyl) dimethylhafnium, trimethylenecilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, trimethylenecilylenebis (4- (3-isopropylphenyl)) -1-Indenyl) dimethylhafnium, trimethylenecilylene bis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, trimethylenecilylenebis (4- (4-methylphenyl) -1-indenyl) dimethyl Hafnium, trimethylene silylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, trimethylene silylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, trimethylene silylenebis (4- (4-Trifluoromethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (4- (4-)4-indenyl) Isopropoxyphenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (4-fluorophenyl) -1-indenyl) ) Dimethylhafnium, trimethylenecilylene bis (4- (4-chlorophenyl) -1-indenyl) Dimethylhafnium, trimethylenecilylenebis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4-bromophenyl) -1-indenyl) 4- (2-Methylphenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (3,5-dimethyl) Phenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (3,5-di-tert-butyl) Phenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (3,5-dimethoxyphenyl) -1-indenyl) dimethylhafnium, trimethylenesylylenebis (4- (3,5-ditrimethylsilylphenyl)- 1-indenyl) dimethylhafnium , Trimethylene silylenebis (4- (3,5-ditrifluoromethylphenyl) -1-indenyl) dimethylhafnium, trimethylenecilylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, tri Methylene silylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, trimethylenecilylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, trimethylenecilylenebis (4- (2,6-dimethylphenyl) -1-indenyl) 4- (2,3,5,6-tetramethylphenyl) -1-indenyl) Dimethylhafnium, trimethylenecilylenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) Dimethylhafnium, trimethylenesilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) Dimethylhafnium, trimethylenecilylenebis (4-biphenylyl-1-indenyl) dimethylhafnium, trimethylenecilylene Bis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, trimethylenecilylene bis (4- (2', 6'-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, trimethylenecilylene Bis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, trimethylenecilylene bis (4- (2-naphthyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4-phenanthril-1-indenyl) Dimethylhafnium

Tetramethylenesilylene cross-linked metallocene compound:
Tetramethylene silylenebis (4-phenyl-1-indenyl) dimethylhafnium, tetramethylenecilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (3-isopropylphenyl)) -1-Indenyl) dimethylhafnium, tetramethylenecilylene bis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, tetramethylenecilylenebis (4- (4-methylphenyl) -1-indenyl) dimethyl Hafnium, tetramethylenecilylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (2-ethylphenyl) ) -1-Indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (3,5-di-tert-butylphenyl) ) -1-Indenyl) Dimethylhafnium, Tetramethylenesilylenebis (4- (3,5-ditrimethylsilylphenyl) -1-Indenyl) Dimethylhafnium, Tetramethylenecilylenebis (4- (2,3-dimethylphenyl) -1 -Indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, tetramethylenecilylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethyl Hafnium, tetramethylenesilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4-biphenylyl-1-indenyl) dimethylhafnium

Diphenylsilylene cross-linked metallocene compound:
Diphenylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium, diphenylcilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, diphenylcilylenebis (4- (3-isopropylphenyl) -1- Indenyl) dimethylhafnium, diphenylsilylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, diphenylcilylenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (4-Isopropylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (4-trimethylsilylphenyl) ) -1-Indenyl) Dimethylhafnium, Diphenylcilylenebis (4- (2-methylphenyl) -1-Indenyl) Dimethylhafnium, Diphenylcilylenebis (4- (2-ethylphenyl) -1-Indenyl) Dimethylhafnium, Diphenyl Silylenbis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (3,5-Ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (2) , 5-Dimethylphenyl) -1-Indenyl) Dimethylhafnium, Diphenylcilylenebis (4- (2,6-dimethylphenyl) -1-Indenyl) Dimethylhafnium, Diphenylcilylenebis (4- (4-tert-butyl-2) -Methyl-phenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4-biphenylyl-1-indenyl) dimethylhafnium

Among the exemplified metallocene compounds, a compound in which Y is a carbon atom is preferable from the viewpoint of the amount of double bonds involved in the cross-linking reaction of the produced ethylene / α-olefin copolymer.

^{Among the exemplified metallocene compounds, R 1} and R ¹¹ are preferably compounds having a hydrogen atom from the viewpoint of being able to produce a high molecular weight ethylene / α-olefin copolymer.

Further, among the exemplified metallocene compounds, M is a compound that replaces titanium or zirconium instead of phenylnium, and X ¹ and X ² are one or both of chlorine atom, bromine atom, and iodine instead of a methyl group. Compounds in place of an atom, a phenyl group, a benzyl group, a dimethylamino group, a diethylamino group, a trimethylsilylmethyl group and the like can also be exemplified.

(Synthesis method of metallocene compound)
The method for synthesizing the metallocene compound of the present invention is not particularly limited, and the metallocene compound can be synthesized by any method depending on the mode of substituent or bond. The following is an example of a typical synthetic route.

In the above synthetic route, 1 and phenylboronic acid are coupled to each other in the presence of a palladium catalyst to obtain 2. The cross-linking reaction of 2 to 3 can be carried out by the method described in Document (Patent No. 3835846), and after anionizing 2 with potassium hydroxide or the like, 3 is obtained by reaction with acetone. After dianionizing 3 with 2 equal amounts of n-butyllithium or the like, the metallocene compound 4 can be obtained by reaction with hafnium tetrachloride. In general, 4 is obtained as a mixture of racemate and meso, and the racemate having excellent catalytic performance is concentrated by purification. Further, the meso compound can be isomerized to a racemate by the method described in the document (WO2000 / 017213), and the yield of the racemate can be improved. The dimethyl form 5 can be obtained by treating 4 with 2 equivalents or more of MeMgBr or the like.
Synthesis of substituent-introduced metallocene compounds can be performed by using the corresponding substituents and instead of phenylboronic acid, the corresponding boronic acid, eg 4-isopropylphenylboronic acid, 3,5- ^{By using dimethylphenylboronic acid or the like, a (R 5-} R ⁹ , R ^15- R ¹⁹ ) substituent can be introduced on the phenyl group at the 4-position of the indenyl ring.
The synthesis of metallocene compounds having different substituents on the cross-linking group can be synthesized by using the corresponding substituents, and by using the corresponding ketones such as cyclobutanone and 4-heptenone instead of acetone. ^{Substituents (R 10} , R ²⁰ ) can be introduced on the cross-linking group.

(2) Ingredient (B)
The component (B) is a boron compound that reacts with the component (A) to form an ion pair, and is a compound having a thermal decomposition temperature of less than 200 ° C. Examples of such a compound include borane compounds.

Specific examples of borane compounds include triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, and tris (p-). Fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3) , 5-Ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenylyl) borane, tris ( Examples thereof include perfluoroanthril) borane and tris (perfluorobinaphthyl) borane.
Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthril) borane, tris (perfluorobinaphthyl) borane are more preferred, and even more preferably tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris. (Perfluoronaphthyl) borane and tris (perfluorobiphenylyl) borane are preferred.

(4) Method for preparing a catalyst In the method for preparing a catalyst system according to the present invention, the contact method between the component (A) and the component (B) is not particularly limited, and a conventionally known method can be used.

The molar ratio of the component (A) to the component (B) is preferably used in the range of 1: 0.1 to 1: 100. This usage ratio shows an example of a normal ratio, and if the catalyst is in line with the object of the present invention, the present invention may be limited by the range of the usage ratio described above. It doesn't become.

2. 2. Polymerization conditions of ethylene / α-olefin copolymer In the present invention, the ethylene / α-olefin copolymer weight suitable as a polyethylene resin material for a solar cell encapsulant can be obtained by performing copolymerization using the above-mentioned catalytic system. Manufacture coalescing.
Hereinafter, each polymerization condition will be described.

(1) Polymerization method In the present invention, in the polymerization method, if the polymerization catalyst containing the metallocene compound represented by the general formula (I) and the monomer can efficiently contact each other and the olefin can be polymerized or copolymerized. The high-pressure ion polymerization method, the gas phase method, the solution method, the slurry method and the like can be used without particular limitation.

In the present invention, the polymerization temperature is generally 40 to 300 ° C.
In the vapor phase polymerization method and the slurry polymerization method, the preferable polymerization temperature is 40 to 120 ° C., more preferably 50 to 110 ° C., and the preferable polymerization pressure is 0.1 MPa to 10 MPa, preferably 1 to 5 MPa.
In solution polymerization, the polymerization temperature is preferably 50 to 170 ° C., more preferably 120 to 170 ° C., and the preferred polymerization pressure is 0.1 to 10 MPa, more preferably 1 to 5 MPa.

In high-pressure ion polymerization, the preferred polymerization temperature is 125 to 300 ° C., more preferably 160 to 280 ° C., further preferably 180 to 280 ° C., and the preferred polymerization pressure is 40 to 150 MPa, more preferably 50 to 125 MPa. Is.
Among these, in order to obtain an ethylene / olefin copolymer having an adjusted amount of double bonds related to cross-linking characteristics, it is desirable to carry out polymerization at a high temperature, so it is preferable to use a high-pressure ion polymerization method (“polyethylene technology”). Readers, Chapter 4, edited by Kazuo Matsuura and Naotaka Mikami, 2001).

(2) Other conditions Further, even if a component for the purpose of removing water, a so-called scavenger, is added to the polymerization system, it can be carried out without any problem.
The scavenger includes organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum, the organoaluminum oxy compound, and modification of the organoaluminum compound with alcohols or phenols. Organoaluminium compounds, organozinc compounds such as diethylzinc and dibutylzinc, organomagnesium compounds such as diethylmagnesium, dibutylmagnesium and ethylbutylmagnesium, and glinal compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum are preferable, and triisobutylaluminum, trihexylaluminum and trioctylaluminum are particularly preferable.

The molecular weight of the produced polymer can be adjusted by changing the polymerization conditions such as the polymerization temperature, the concentration of the olefin monomer, and the molar ratio of the catalyst. Further, the molecular weight can be effectively adjusted by adding hydrogen, the above-mentioned scavengers, or the like as a chain transfer agent to the polymerization reaction system.

It can also be applied without hindrance to a two-stage or higher-stage polymerization method in which polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature are different from each other.

As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. Further, the combination of polymerization types is not particularly limited, and a mode such as solution polymerization 2 steps, bulk polymerization 2 steps, bulk polymerization post-vapor phase polymerization, and gas phase polymerization 2 steps is possible, and the number of polymerization steps is more than that. It is also possible to manufacture with.

3. 3. Polyethylene resin The polyethylene resin of the present invention is an ethylene / α-olefin copolymer obtained by copolymerizing one or more of ethylene and α-olefin and having the following characteristics (a1) to (a5).
(A1) The content ratio of the structural unit derived from ethylene is 80 to 97 mol%, and the content ratio of the structural unit derived from α-olefin having 3 to 20 carbon atoms is 3 to 20 mol%.
(A2) MFR (190 ° C., 21.18N load) is 0.1 to 100 g / 10 minutes (a3) Density is 0.860 to 0.920 g / cm ³
(A4) Volume resistivity measured at a temperature of 23 ° C. and an applied voltage of 500 V is 1.0 × 10 ¹⁶ Ω · cm or more (a5) Boron residue concentration (M) in the resin is 0 <M <1 wtppm
The polyethylene resin of the present invention has good cross-linking characteristics and insulating properties by satisfying the above characteristics.

(1) Monomer composition of polyethylene resin The polyethylene resin in the present invention is a random copolymer of ethylene and α-olefin containing a structural unit derived from ethylene as a main component.
The α-olefin used as a comonomer has 3 to 20 carbon atoms, and is preferably an α-olefin having 3 to 12 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- The first prize can be mentioned. Specific examples of such ethylene / α-olefin copolymers include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / Examples thereof include 4-methyl-pentene-1 copolymer. Of these, ethylene / 1-butene copolymers and ethylene / 1-hexene copolymers are preferable. Further, the α-olefin may be one kind or a combination of two or more kinds. When combining two types of α-olefins into a ternary copolymer, ethylene / propylene / 1-hexene ternary copolymer, ethylene / 1-butene / 1-hexene ternary copolymer, ethylene / propylene -Examples include 1-octene ternary copolymer, ethylene / 1-butene / 1-octene ternary copolymer and the like.
As the comonomer, a diene compound such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadien, 1,8-nonadien, and 1,9-decadien may be added to the α-olefin in a small amount. When these diene compounds are blended, long-chain branches can be formed, which lowers the crystallinity of the ethylene / α-olefin copolymer, improves transparency, flexibility, adhesiveness, etc., and also serves as a cross-linking agent between molecules. Therefore, the mechanical strength is increased. Further, since the terminal group of the long-chain branch is an unsaturated group, it is possible to easily carry out a cross-linking reaction with an organic peroxide, a copolymerization reaction with an acid anhydride group-containing compound or an epoxy group-containing compound, and a graft reaction. can.

(A1) Content ratio of ethylene and α-olefin-derived structural units The polyethylene resin in the present invention has an α-olefin content ratio of 3 to 20 mol%. Within this range, the flexibility of the sheet and the like and the heat resistance after crosslinking are good. If the α-olefin content is less than 3 mol%, the flexibility of polyethylene may deteriorate. On the other hand, if it exceeds 20 mol%, the softening point of polyethylene is lowered too much, so that the obtained sheet or the like is poorly blocked and the handleability is poor.

(2) Characteristics of polyethylene resin (a2) MFR
The polyethylene resin in the present invention has an MFR of 0.1 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, and more preferably 2 to 40 g / 10 minutes. If the MFR of the polyethylene resin is less than 0.1 g / 10 minutes, the molecular weight is too high and extrusion becomes difficult at the time of kneading, while if the MFR exceeds 100 g / 10 minutes, the melt viscosity becomes too low and the handleability is poor. It becomes a thing. The MFR of the polyethylene resin is measured according to JIS-K6922-2: 1997 Annex (190 ° C., 21.18N load).

(A3) Density The polyethylene resin in the present invention has a density of 0.860 to 0.920 g / cm ³ , preferably 0.865 to 0.915 g / cm ³ , and more preferably 0.870 to 0.900 g / cm 3. It is cm ^3. If the density of the polyethylene resin ^{is less than 0.860 g / cm 3} , the processed sheet will block, while if the density ^{exceeds 0.920 g / cm 3} , the rigidity of the processed sheet will be too high and it will be easy to handle. Will be lacking.
In order to adjust the density of the polymer, for example, a method of appropriately adjusting the α-olefin content, the polymerization temperature, the catalyst amount and the like is adopted. The density of the polyethylene resin is measured in accordance with JIS-K6922-2: 1997 Annex (in the case of low density polyethylene) (23 ° C.).

(A4) Volume resistivity The polyethylene resin in the present invention has a volume resistivity of 1.0 × 10 ¹⁶ Ω · cm or more, preferably 1.0 × 10 ¹⁷ Ω · cm, measured at a temperature of 23 ° C. and an applied voltage of 500 V. Is. Polyethylene resin with a volume resistivity of 1.0 × 10 ¹⁶ Ω · cm or more has excellent insulation performance. For example, in solar cell encapsulant applications, PID is generated in a solar cell module using an n-type cell. It can be suppressed.

(A5) Boron residue concentration The concentration (M) of the boron compound residue contained in the polyethylene resin in the present invention satisfies 0 <M <1 wtppm.
The concentration of the boron residue depends on the type of the boron compound added as a co-catalyst in the polymerization process of the ethylene / α-olefin copolymer and the concentration thereof used. When the boron residue concentration is less than the above range, the concentration of the boron compound cocatalyst in the polymerization process of the ethylene / α-olefin copolymer is small, and the catalytic activity is not sufficiently exhibited. On the other hand, when the boron residue concentration is above the above range, the insulating property tends to deteriorate.

Feature of the present invention, further the boron residue is in thermal decomposition temperature by weight change under N ₂ atmosphere occurs is the thermal history of the boron compound is less than 200 ° C.. That is, as the boron compound to be added as a co-catalyst during polymerization, a boron compound having a thermal decomposition temperature of less than 200 ° C. is selected, and the heat-heated history material after receiving the thermal history during polymerization at about 180 to 230 ° C. is contained. Means to do. It is preferably a history of being heated by a boron compound having a thermal decomposition temperature of less than 180 ° C. By using a boron compound having a thermal decomposition temperature of less than 200 ° C., the chemical structure of the original boron compound is lost due to the thermal history at the time of production, so that the effect of preventing deterioration of the insulating property due to boron can be obtained.

The thermal decomposition temperature of the boron compound is measured by thermogravimetric analysis (TG), and the measurement conditions are as follows.
Equipment: EXSTAR6000 / TG / DTA6200 manufactured by Seiko Instruments Inc.
Measurement temperature range: 30-400 ° C
Heating rate: 10 ° C. / weighed min sample 10 mg, heated at the temperature range under a N ₂ atmosphere, the temperature was measured to the weight loss occurs from weight change and baseline.

Further, the concentration (M) of the boron residue can be measured, for example, under the following measurement conditions.
Approximately 10 g of polyethylene resin is collected in a Teflon (registered trademark) container, nitric acid is added, and the mixture is decomposed by a microwave decomposition apparatus, the decomposition liquid is constant volume, and measured by ICP-MS.
Equipment: Millestone General ETHOS One type PerkinElmer NextION300S type

(A6) Melting peak When the ethylene / α-olefin copolymer used in the present invention is used in an application requiring transparency, it is higher than the temperature showing the maximum melting peak measured by differential scanning calorimetry (DSC). It is preferable not to show a melting peak at a temperature higher than 20 ° C. Since the component having a melting point higher than that of the main component is not present, the high crystal component is not present in the resin, so that the transparency is high. In order to adjust so that the melting peak is not shown at a temperature 20 ° C. or higher higher than the temperature showing the maximum melting peak, a method of selecting an appropriate catalyst system or the like can be used.

The melting peak is measured by differential scanning calorimetry (DSC), and the measurement conditions are as follows.
Equipment: DSC7020 manufactured by Seiko Instruments
Lifting temperature conditions: First temperature rise 30 ° C to 200 ° C, 40 ° C / min
Temperature drop 200 ℃ ～ -30 ℃, 10 ℃ / min
Second temperature rise -30 ° C to 200 ° C, 10 ° C / min Temperature retention time: 5 minutes after the first temperature rise, 5 minutes after the temperature drop Sample volume: 5 mg
Temperature calibration: Indium Reference: Aluminum

(A7) Ratio (Mz / Mn) of Z average molecular weight (Mz) to number average molecular weight (Mn)
The ethylene / α-olefin copolymer used in the present invention has a Z average molecular weight (Mz) and a number average molecular weight (Mn) determined by gel permeation chromatography (GPC) when used in applications requiring transparency. ) Is 8.0 or less, preferably 5.0 or less, and more preferably 4.0 or less. Further, Mz / Mn is 2.0 or more, preferably 2.5 or more, and more preferably 3.0 or more. However, if Mz / Mn exceeds 8.0, the transparency deteriorates. In order to adjust Mz / Mn to a predetermined range, a method of selecting an appropriate catalyst system or the like can be used.

The measurement of Mz / Mn is performed by gel permeation chromatography (GPC), and the measurement conditions are as follows.
Device: Waters GPC 150C type detector: MIRAN 1A infrared spectrophotometer (measurement wavelength 3.42 μm)
Column: Measurement of 3 AD806M / S manufactured by Showa Denko (calibration of the column is 0.5 mg / ml solution of monodisperse polystyrene manufactured by Toso (A500, A2500, F1, F2, F4, F10, F20, F40, F288)). The logarithmic value of the elution volume and the molecular weight was approximated by a quadratic equation. The molecular weight of the sample was converted to polyethylene using the viscosity equations of polystyrene and polyethylene. Here, the coefficient of the viscosity equation of polystyrene is α. = 0.723, logK = -3.967, and polystyrene is α = 0.733, logK = -3.407.)
Measurement temperature: 140 ° C
Concentration: 20 mg / 10 mL
Injection amount: 0.2 ml
Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min

Since the Z average molecular weight (Mz) greatly contributes to the average molecular weight of the high molecular weight component, it is easier to confirm the presence of the high molecular weight component in Mz / Mn than in Mw / Mn. The high molecular weight component is a factor that affects the transparency, and if the high molecular weight component is large, the transparency deteriorates. Therefore, it is preferable that Mz / Mn is small for applications that require transparency.

(3) Double bond in ethylene / α-olefin The ethylene / α-olefin copolymer used in the present invention contains a double bond (vinyl, vinylidene, cis-vinylene, trans-vinylene, trisubstituted-vinylene). ..
In the present invention, the total amount of vinyl, vinylidene, cis-vinylene, trans-vinylene, and trisubstituted-vinylene in the ethylene / α-olefin copolymer is preferably 0.22 (pieces / total 1000C) or more. Here, the number of vinyl, vinylidene, cis-vinylene, trans-vinylene, and trisubstituted-vinylene is the number per 1000 carbon atoms in total of the main chain and the side chain measured by NMR. The total amount is more preferably 0.25 or more, further preferably 0.30 or more, particularly preferably 0.40 or more, and most preferably 0.50 or more. Examples of the method for adjusting the total number of double bonds include selection of an appropriate catalyst, a method for appropriately adjusting the polymerization temperature and the type of comonomer, and the like.
Since these groups have unsaturated bonds, their presence in the ethylene / α-olefin copolymer can enhance the cross-linking characteristics.

Here, the number of double bonds can be measured by the ^{1 H-NMR method.}
The total number of vinyl, vinylidene, cis-trans-vinylene and trisubstituted-vinylene in the polymer is ^{measured by 1} H-NMR, and the total number of main chain and side chain is determined by 1000 carbons.
Specifically, the number of vinylidene per 1000 carbon atoms was calculated from the ratio of the peak area derived from the saturated alkyl chain appearing between the chemical shifts of 0.4 to 2.8 ppm and the peak area derived from vinylidene near 4.7 ppm. The intensity of each characteristic peak is used at around 4.9 ppm for vinyl, around 5.2 ppm for trisubstituted vinylene, and around 5.4 ppm for cis and trans-vinylene.

4. Polyethylene Resin Composition The polyethylene resin composition of the present invention (hereinafter, also simply referred to as “resin composition”) is characterized by containing the above-mentioned polyethylene resin and the following organic peroxide (D).

(1) Ingredient (D)
The organic peroxide of the component (D) in the present invention is mainly used for cross-linking a polyethylene resin.
As the organic peroxide, an organic peroxide having a decomposition temperature (a temperature having a half-life of 1 hour) of 70 to 180 ° C., particularly 90 to 160 ° C. can be used. Examples of such organic peroxides include t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-butylperoxyacetate, t-butylperoxybenzoate, dicumyl peroxide, 2 , 5-Dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, 1, , 1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, methylethylketone peroxide, 2,5-dimethylhexyl-2,5- Diperoxybenzoate, t-butylhydroperoxide, p-menthan hydroperoxide, benzoyl peroxide, p-chlorbenzoyl peroxide, t-butylperoxyisobutyrate, hydroxyheptyl peroxide, diclohexanone peroxide, etc. Can be mentioned.

The blending ratio of the component (D) is preferably 0.2 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, and further preferably 1 to 2 parts by weight when the polyethylene resin is 100 parts by weight. It is a department. If the blending ratio of the component (D) is less than the above range, no cross-linking is performed or cross-linking takes time. On the other hand, if it is larger than the above range, the dispersion is insufficient and the degree of cross-linking tends to be non-uniform.

(2) Hindered Amine-based Light Stabilizer In the present invention, a hindered amine-based light stabilizer can be added to the resin composition. Hindered amine-based light stabilizers capture radical species that are harmful to the polymer and prevent the generation of new radicals. There are many types of hindered amine-based light stabilizers, from low molecular weight compounds to high molecular weight compounds, but conventionally known compounds can be used without particular limitation.

Low molecular weight hindered amine light stabilizers include bisdecanoate (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethylhydroperoxide and It consists of 70% by weight of the reaction product of octane (molecular weight 737) and 30% by weight of polypropylene; bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1) -Dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate (molecular weight 685); bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6 6-Pentamethyl-4-piperidyl sebacate mixture (molecular weight 509); bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (molecular weight 481); tetrakis (2,2,6,6-tetramethyl) -4-piperidyl) -1,2,3,4-butanetetracarboxylate (molecular weight 791); tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4- Butanetetracarboxylate (molecular weight 847); 2,2,6,6-tetramethyl-4-piperidyl-1,2,3,4-butanetetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate Mix of rates (molecular weight 900); 1,2,2,6,6-pentamethyl-4-piperidyl-1,2,3,4-butanetetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate Examples include a mixture of rates (molecular weight 900).

As a high-molecular-weight hindered amine-based light stabilizer, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (molecular weight 2,000-3,100); succinic acid Polymers of dimethyl and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (molecular weight 3,100-4,000); N, N', N ", N"'-tetrakis- ( 4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10- A mixture of diamine (molecular weight 2,286), the above dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol; dibutylamine, 1,3,5-triazine, N. , N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine weight Condensates (molecular weight 2,600-3,400), as well as 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine , 4-Acryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1- Butyl-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine , 4-methacryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2 , 2,6,6-tetramethylpiperidine, 4-crotonoyloxy-1-propyl-2, 2,6,6-tetramethylpiperidine and other cyclic aminovinyl compounds and ethylene copolymers. The above-mentioned hindered amine-based light stabilizer may be used alone or in combination of two or more.

Among these, as a hindered amine-based photostabilizer, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2) , 2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (molecular weight 2,000-3,100); Polymers of dimethyl acid acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (molecular weight 3,100-4,000); N, N', N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10 -A mixture of diamine (molecular weight 2,286), the above-mentioned dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol; dibutylamine, 1,3,5-triazine. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine It is preferable to use a copolymer of a polycondensate (molecular weight 2,600 to 3,400) cyclic aminovinyl compound and ethylene, because the bleed-out of the hindered amine-based light stabilizer over time is hindered when the product is used. Further, it is preferable to use a hindered amine-based light stabilizer having a melting point of 60 ° C. or higher from the viewpoint of ease of preparation of the composition.

In the present invention, the content of the hindered amine-based photostabilizer is 0.01 to 2.5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer. It is preferably 0 parts by weight, more preferably 0.01 to 0.5 parts by weight, still more preferably 0.01 to 0.2 parts by weight, and most preferably 0.03 to 0.1 parts by weight.
When the content is 0.01 parts by weight or more, the effect on stabilization is sufficiently obtained, and when the content is 2.5 parts by weight or less, the discoloration of the resin due to excessive addition of the hindered amine light stabilizer is caused. It can be suppressed.
Further, in the present invention, the weight ratio of the organic peroxide (D) to the hindered amine-based light stabilizer is set to 1: 0.01 to 1:10, preferably 1: 0.02 to 1: 6. Let it be 5.5. This makes it possible to remarkably suppress the yellowing of the resin.

(3) Crosslinking aid A crosslinking aid can be added to the resin composition of the present invention. The cross-linking aid is effective in promoting the cross-linking reaction and increasing the degree of cross-linking of the ethylene / α-olefin copolymer, and specific examples thereof include polyallyl compounds and poly (meth) acryloxy compounds. Saturated compounds can be exemplified.
More specifically, polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate. Examples thereof include poly (meth) acryloxy compounds and divinylbenzene. The cross-linking aid can be blended in a ratio of about 0 to 5 parts by weight with respect to 100 parts by weight of the polyethylene resin.

(4) Ultraviolet absorber The resin composition of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include various types such as benzophenone type, benzotriazole type, triazine type and salicylic acid ester type.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2-hydroxy-4. -N-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone , 2,4-Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, etc. Can be mentioned.

Examples of the benzotriazole-based ultraviolet absorber include hydroxyphenyl-substituted benzotriazole compounds, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-t-butylphenyl). Benzotriazole, 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-methyl-5-t- Butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, etc. Can be mentioned. Examples of the triazine-based ultraviolet absorber include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- (octyloxy) phenol and 2- ( 4,6-Diphenyl-1,3,5-triazine-2-yl) -5- (hexyloxy) phenol and the like can be mentioned. Examples of the salicylic acid ester system include phenylsalicylate and p-octylphenylsalicylate.
These ultraviolet absorbers are blended in an amount of 0 to 2.0 parts by weight based on 100 parts by weight of the ethylene / α-olefin copolymer, preferably 0.05 to 2.0 parts by weight, more preferably 0.1 to 1. It is preferable to add 0 parts by weight, more preferably 0.1 to 0.5 parts by weight, and most preferably 0.2 to 0.4 parts by weight.

(5) Silane Coupling Agent In the resin composition of the present invention, a silane coupling agent can be used for the purpose of modifying the resin.
Examples of the silane coupling agent in the present invention include γ-chloropropyltrimethoxysilane; vinyltricrolsilane; vinyltriethoxysilane; vinyltrimethoxysilane; vinyl-tris- (β-methoxyethoxy) silane; γ-methacryloxypropyl. Trimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane; vinyltriacetoxysilane; γ-mercaptopropyltrimethoxysilane; γ-aminopropyltrimethoxysilane; Examples thereof include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane. Preferred are vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane.
These silane coupling agents are used in an amount of 0 to 5 parts by weight, preferably 0.01 to 4 parts by weight, and more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer. , More preferably used in 0.05 to 1 part by weight.

(6) Other Additive Components The resin composition of the present invention may contain other additional optional components as long as the object of the present invention is not significantly impaired. Such optional components include antioxidants, crystal nucleating agents, clearing agents, lubricants, colorants, dispersants, fillers, fluorescent whitening agents, ultraviolet absorbers, etc., which are used in ordinary polyolefin resin materials. Examples include light stabilizers.

Further, in order to impart flexibility and the like to the resin composition of the present invention, a crystalline ethylene / α-olefin polymerized by a lubricating oil, a Cheegler-based or a metallocene-based catalyst, as long as the object of the present invention is not impaired. It is also possible to blend 3 to 75 parts by weight of a copolymer and / or a rubber compound such as an ethylene / α-olefin elastomer such as EBR and EPR or a styrene elastomer such as SEBS and a hydrogenated styrene block copolymer. Further, in order to impart melt tension and the like, 3 to 75 parts by weight of high-pressure low-density polyethylene can be blended.

5. Solar cell encapsulant and solar cell The solar cell encapsulant of the present invention (hereinafter, also simply referred to as “encapsulating material”) is a pellet or sheet of the above resin composition. By using this solar cell encapsulant, a solar cell module can be manufactured by fixing the solar cell element together with the upper and lower protective materials. Various types of such solar cell modules can be exemplified. For example, an upper transparent protective material / encapsulant / solar cell element / encapsulant / lower protective material sandwiched between both sides of the solar cell element, formed on the inner peripheral surface of the lower substrate protective material. On a solar cell element formed on the inner peripheral surface of the upper transparent protective material, for example, a fluororesin-based transparent protective material, which is configured to form a sealing material and an upper transparent protective material on the solar cell element. Examples thereof include an amorphous solar cell element having a structure in which a sealing material and a lower protective material are formed on the one produced by sputtering or the like.

The solar cell element is not particularly limited, and is limited to silicon-based devices such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and group III-V and group II-VI such as gallium-arsenide, copper-indium-selenium, and cadmium-tellur. Various solar cell elements such as compound semiconductor devices can be used. In the present invention, a substrate using glass is preferable.

Examples of the upper protective material constituting the solar cell module include glass, acrylic resin, polycarbonate, polyester, and fluorine-containing resin. The lower protective material is a single or multi-layer sheet such as a metal or various thermoplastic resin films, for example, a metal such as tin, aluminum or stainless steel, an inorganic material such as glass, polyester, an inorganic vapor-deposited polyester, or fluorine. A single-layer or multi-layer protective material such as a contained resin or polyolefin can be exemplified. Such upper and / or lower protective materials can be primed in order to enhance their adhesiveness to the encapsulant. In the present invention, glass is preferable as the upper protective material.

The solar cell encapsulant of the present invention may be used as pellets, but is usually used by molding it into a sheet having a thickness of about 0.1 to 1 mm. If it is thinner than 0.1 mm, the strength is small and the adhesion is insufficient, and if it is thicker than 1 mm, the transparency is lowered, which may cause a problem. The preferred thickness is 0.1 to 0.8 mm.

The sheet-shaped solar cell encapsulant can be manufactured by a known sheet molding method using a T-die extruder, a calendar molding machine, or the like. For example, a cross-linking agent is added to an ethylene / α-olefin copolymer, and if necessary, a hindered amine-based photostabilizer, a cross-linking aid, a silane coupling agent, an ultraviolet absorber, an antioxidant, and a photostabilizer are added. It can be obtained by dry-blending an additive such as an agent in advance, supplying it from a hopper of a T-die extruder, and extruding it into a sheet at an extrusion temperature of 80 to 150 ° C. For these dry blends, some or all of the additives can be used in the form of a masterbatch. Further, in T-die extrusion and calendar molding, a part or all of the additives are previously melt-mixed with the amorphous α-olefin copolymer using a uniaxial extruder, a twin extruder, a Banbury mixer, a kneader, or the like. The resin composition thus obtained can also be used. The molded sheet is wound around a paper tube for easy storage and transportation, but at this time, the sheets may adhere to each other (blocking occurs). If blocking occurs, when the sheet is fed out and used in the next process, it cannot be fed out stably and the productivity is lowered. Therefore, it is generally practiced to avoid blocking by roughening the sheet surface or creating an uneven structure.

In manufacturing the solar cell module, a sheet of the encapsulant of the present invention is prepared in advance, and the resin composition of the encapsulant is pressure-bonded at a melting temperature, for example, 150 to 200 ° C., as described above. Modules with various configurations can be formed. Further, if the method of laminating the sealing material of the present invention with the solar cell element, the upper protective material or the lower protective material by extrusion coating is adopted, the solar cell module can be manufactured in one step without bothering to form a sheet. It is possible. Therefore, if the encapsulant of the present invention is used, the productivity of the module can be significantly improved.

On the other hand, when manufacturing a solar cell module, the sealing material is temporarily applied to the solar cell element or the protective material at a temperature at which the organic peroxide does not substantially decompose and the sealing material of the present invention melts. It is also possible to adhere and then raise the temperature to obtain sufficient adhesion and crosslink the ethylene / α-olefin copolymer. In this case, in order to obtain a solar cell module having a melting point (DSC method) of 85 ° C. or higher and a storage elastic modulus of 103 Pa or higher at 150 ° C. and having good heat resistance, the gel fraction in the sealing material layer is obtained. (1 g of the sample is immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, and then filtered with a 400 mesh wire net to measure the mass fraction of the unmelted portion) is about 50 to 98%, preferably about 70 to 95%. It is better to bridge like this.

In the sealing work of the solar cell element, after covering the solar cell element with the sealing material of the present invention, it is heated to a temperature at which the organic peroxide does not decompose for about several minutes to 10 minutes, and then temporarily bonded. There are methods such as heat treatment at a high temperature of about 150 to 200 ° C. for 5 to 30 minutes in which organic peroxides are decomposed in an oven to bond them.

6. Insulator Another aspect of the present invention is an insulator using a polyethylene resin composition containing a polyethylene resin produced by the production method of the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The evaluation methods and resins used in Examples and Comparative Examples are as follows.

1. 1. Evaluation method of resin physical properties (1) Melt flow rate (MFR)
As described above, the MFR of the ethylene / α-olefin copolymer was measured in accordance with JIS-K6922-2: 1997 Annex (190 ° C., 21.18N load).
(2) Density As described above, the density of the ethylene / α-olefin copolymer was measured in accordance with JIS-K6922-2: 1997 Annex (23 ° C., in the case of low density polyethylene).
(3) Mz / Mn
As described above, it was measured by GPC.
(4) Melting peak As described above, it was measured by DSC.

(5) Volume resistivity A press sheet having a thickness of 0.7 mm was cut into a size of 10 cm × 10 cm, and measured under the following conditions in accordance with IEC60093.
Equipment: ADC micro ammeter R8340A
ADC measurement chamber 12704A
Temperature: 23 ° C
Applied voltage: 500V

(6) Boron residue concentration About 10 g of polyethylene resin was collected in a Teflon (registered trademark) container, nitric acid was added, and the mixture was decomposed by a microwave decomposition apparatus. The decomposition solution was conditioned and measured by ICP-MS.
Equipment: Millestone General ETHOS One type PerkinElmer NextION300S type

(7) Amount of comonomer and number of double bonds The amount of comonomer is determined by ¹³ C-NMR, and the number of double bonds (total of vinyl, vinylidene, cis-trans-vinylene, trisubstituted-vinylene) is determined by ¹ H-NMR. The measurement was carried out under the following conditions, and the number of main chains and side chains was determined by the total number of 1000 carbon atoms.
Equipment: Bruker Biospin Co., Ltd. AVANCE III cryo-400MHz
Solvent: o-dichlorobenzene / layered bromobenzene = 8/2 mixed solution <sample amount>
460mg / 2.3ml
< ¹³ C-NMR>
· ¹ H decoupling, NOE Ali cumulative number of times: 256scan
・ Flip angle: 90 °
-Pulse interval 20 seconds-AQ (capture time) = 5.45s D1 (waiting time) = 14.55s
< ^{1 1} H-NMR>
・ Number of integrations: 1400scan
・ Flip angle: 1.03 °
・ AQ (capture time) = 1.8s D1 (waiting time) = 0.01s

2. 2. Evaluation method of extruded product (sheet) (1) HAZE
The measurement was performed according to JIS-K7136-2000 using a press sheet having a thickness of 0.7 mm. A press sheet piece was set in a cell filled with liquid paraffin (manufactured by Kanto Chemical Co., Inc.) and measured. The press sheet was stored in a hot press for 30 minutes at 150 ° C. and crosslinked to prepare it. The smaller the HAZE value, the better.

(2) Light transmittance Measured according to JIS-K7361-1-1997 using a press sheet having a thickness of 0.7 mm. A press sheet piece was set in a cell filled with liquid paraffin (manufactured by Kanto Chemical Co., Inc.) and measured. The press sheet was stored in a hot press for 30 minutes under the condition of 150 ° C. and crosslinked to prepare it. The light transmittance is 80% or more, preferably 85% or more, and more preferably 90% or more.

(3) Crosslinking characteristics / heat resistance (gel fraction 30 minutes /%)
The resulting pellet, in the conditions of 150 ℃ -0kg / cm ^2, was preheated for 1 minute, then 150 ℃ -100kg / cm 29 min pressure in the ^second condition (press forming for 30 minutes at 0.99 ° C.), then, A crosslinked sheet having a thickness of 0.7 mm was prepared by cooling with a cooling press set at 30 ° C. ^{under a pressure condition of 100 kg / cm 2 for 10 minutes.} It was evaluated by the gel fraction of a sheet having a thickness of 0.7 mm. The higher the gel fraction, the more the cross-linking progresses, and it can be evaluated that the heat resistance is high. Those having a gel fraction of 70 wt% or more were evaluated as "○" for heat resistance. For the gel fraction, cut out about 1 g of the sheet, weigh it precisely, immerse it in 100 cc of xylene, treat it at 110 ° C. for 24 hours, dry the residue after filtration, weigh it finely, and divide it by the weight before treatment. Calculate the gel fraction.

3. 3. Production of polyethylene resin (1) Component (A): Synthesis of metallocene compound-Metallocene compound a: Synthesis of cyclobutylidenebis (4-phenyl-1-indenyl) dimethylhafnium

(I) Synthesis of 4-Phenyl-Indene Synthetic was performed according to the method described in JP-A-2008-10103.

(Ii) Synthesis of 1,1-bis (4-phenyl-inden-1-yl) cyclobutane In a 500 mL glass reaction vessel, 22.4 g (116 mmol) of 4-phenylinden, 1,2-dimethoxyethane (DME). 150 mL and 13.0 g (233 mmol) of potassium hydroxide were added, and the mixture was heated under reflux at 90 ° C. for 1 hour. The reaction mixture was cooled to 0 ° C., 4.00 g (57.2 mmol) of cyclobutanone was added, and then the mixture was heated under reflux at 90 ° C. for 10 hours. The reaction mixture was cooled to room temperature, 200 mL of distilled water was added, the mixture was transferred to a separating funnel, extracted three times with ethyl acetate, and dried over sodium sulfate. The sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (developing solvent, petroleum ether) to obtain 1,1-bis (4-phenyl-inden-). 10.0 g of 1-yl) cyclobutane was obtained as a pale yellow solid (yield 40%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ7.51 (dd, 4H), 7.46-7.39 (m, 6H), 7.36-7.22 (m, 2H), 7.24 ( t, 2H), 7.14 (dd, 2H), 6.07 (t, 2H), 3.49 (d, 4H), 2.78 (t, 4H), 2.11 (quint, 2H).

(Iii) Synthesis of racemic-cyclobutylidenebis (4-phenyl-1-indenyl) hafnium dichloride 4.37 g of 1,1-bis (4-phenyl-indene-1-yl) cyclobutane in a 300 mL glass reaction vessel. (10.0 mmol), 100 mL of diethyl ether was added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. 12.8 mL (20.4 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise thereto, and the mixture was stirred at room temperature for 4 hours. The solvent of the reaction solution was distilled off under reduced pressure, 100 mL of toluene was added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. To that, 3.20 g (10.0 mmol) of hafnium tetrachloride was added. Then, the mixture was stirred for 17 hours while gradually returning to room temperature. At this time, the ratio of racemic mixture to meso compound was 48:52.
The solvent of the reaction solution was distilled off under reduced pressure, 26 mL of DME was added thereto, and the mixture was stirred at 60 ° C. for 5 hours. After cooling the reaction to room temperature, it was filtered through a glass frit and the solid was washed twice with 3 mL of DME. The obtained crude organism was extracted with 150 mL of dichloromethane, filtered through Celite, and then the solvent was distilled off under reduced pressure to turn the racemic mixture of racemic-1,1-cyclobutylidenebis (4-phenyl-indenyl) hafnium dichloride in orange. 4.84 g was obtained as a solid (yield 71%).
^{1 1} H-NMR (400MHz, CDCl ₃ ): δ = 7.57 (d, 4H), 7.52 (d, 2H), 7.42 (t, 4H), 7.35 (t, 2H), 7 .27 (d, 2H), 7.09 (dd, 2H), 6.66 (d, 2H), 6.07 (d, 2H), 3.60 (quartet, 2H), 3.17 (quartet, 2H), 2.49 (quintet, 2H).

(Iv) Synthesis of Racemic-Cyclobutylidenebis (4-Phenyl-1-indenyl) Hafnium Hafnium 1.50 g of 1,1-Cyclobutylidenebis (4-phenyl-Indenyl) hafnium dichloride in a 100 mL glass reaction vessel. (2.19 mmol), 60 mL of toluene was added. A 3.0 mol / L methyl magnesium bromide-diethyl ether solution (6.55 mL (19.7 mmol)) was added dropwise thereto at room temperature, and the mixture was stirred at 80 ° C. for 5 hours. After cooling the reaction solution to 0 ° C. in an ice bath, 2.4 mL (19.0 mmol) of chlorotrimethylsilane is added, and the mixture is stirred at room temperature for 30 minutes, followed by 5.0 mL (58.4 mmol) of 1,4-dioxane. In addition, the mixture was further stirred at room temperature for 30 minutes. After filtering the suspension with Celite, the solvent was distilled off under reduced pressure. The resulting yellow solid was suspended in 5 mL of hexane, filtered through a glass frit, and the solid was further washed twice with 5 mL of hexane to give racemic-cyclobutylidenebis (4-phenyl-1-indenyl) dimethylhafnium. 1.37 g of racemic mixture was obtained as a yellow solid (yield 97%).
_{^{1 H-NMR (400MHz, C}} 6 D 6): δ7.70 (dd, 4H), 7.23 (t, 4H), 7.18-7.08 (m, 6H), 6.80 (dd, 2H), 6.78 (d, 2H), 5.52 (d, 2H), 3.05 (quartet, 2H), 2.60 (quartet, 2H), 2.07 (quartet, 2H), -1 .02 (s, 6H)

-Metallocene compound b: Synthesis of dimethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium

(I) Synthesis of dimethylbis (4-phenylindene-1-yl) silane Synthetic was performed according to the method described in the literature (Oraganametricallics, 1994, Vol. 13, pp. 954-963).

(Ii) Synthesis of racemic-dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride 4.90 g (11.1 mmol) of dimethylbis (4-phenylindene-1-yl) silane in a 200 mL glass reaction vessel. , 110 mL of diethyl ether was added and cooled to −70 ° C. in a dry ice-heptane bath. 14.0 mL (22.7 mmol) of a 1.62 mol / L n-butyllithium-n-hexane solution was added dropwise thereto, and the mixture was stirred at room temperature for 3.5 hours. The solvent of the reaction solution was distilled off under reduced pressure, 100 ml of toluene was added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. To that, 3.56 g (11.1 mmol) of hafnium tetrachloride was added. Then, the mixture was stirred for 17 hours while gradually returning to room temperature. At this time, the ratio of racemic mixture to meso compound was 55:45.
200 mL of dichloromethane was added, the mixture was filtered through Celite, and then recrystallized in toluene to obtain 2.23 g of racemic mixture of dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride as an orange solid (yield 29). %).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ7.63 (d, 4H), 7.53 (d, 2H), 7.42 (t, 4H), 7.38-7.31 (m, 4H) , 7.16 (dd, 2H), 7.01 (d, 2H), 6.10 (d, 2H), 1.18 (s, 6H).

(Iii) Synthesis of racemic-dimethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium 1.20 g (1.56 mmol) of dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride in a 100 mL glass reaction vessel. ), Toluene 50 mL was added, and 3.6 mL (10.8 mmol) of a 3.0 mol / L methylmagnesium bromide-diethyl ether solution was added dropwise at room temperature, and the mixture was stirred at 80 ° C. for 1 hour. After cooling the reaction solution to 0 ° C. in an ice bath, 0.98 mL (7.76 mmol) of chlorotrimethylsilane is added, and the mixture is stirred at room temperature for 30 minutes, followed by 2.0 mL (23.4 mmol) of 1,4-dioxane. In addition, the mixture was further stirred at room temperature for 30 minutes. After filtering the suspension with Celite, the solvent was distilled off under reduced pressure. The resulting yellow solid was suspended in 10 mL of hexane, filtered through a glass frit, and the solid was further washed 3 times with 5 mL of hexane to give the dimethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium rasemite. 837 mg was obtained as a yellow solid (yield 85%).
_{^{1 H-NMR (400MHz, C}} 6 D 6): δ7.70 (dd, 4H), 7.27-7.18 (m, 8H), 7.15-7.07 (m, 4H), 6. 90 (dd, 2H), 5.63 (d, 2H), 0.60 (s, 6H), -1.07 (s, 6H).

-Metallocene compound c: Isopropyridenebis [4- (3,5-di-t-butylphenyl) -1-indenyl] Synthesis of dimethylhafnium

(I) Synthesis of 2,2-bis (4-bromo-indene-1-yl) propane In a 500 mL glass reaction vessel, 20.0 g (103 mmol) of 4-bromophenyl indene, 200 mL of DME, and 12.0 g of potassium hydroxide. (206 mmol) was added, and the mixture was heated under reflux at 90 ° C. for 1 hour. The reaction mixture was cooled to 0 ° C., 3.00 g (52.0 mmol) of acetone was added, and then the mixture was heated under reflux at 90 ° C. for 4 hours. The reaction mixture was cooled to room temperature, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solvent, petroleum ether) to obtain 12.0 g of 2,2-bis (4-bromo-inden-1-yl) propane as a yellow solid. (Yield 54%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ); δ7.20 (d, 2H), 7.19 (d, 2H), 6.92 (t, 2H), 6.58 (s, 2H), 3.39 (S, 4H), 1.72 (s, 6H).

(Ii) Synthesis of 3,5-di-t-butylphenylboronic acid 1-bromo-3,5-di-t-butylbenzene and 40 mL of tetrahydrofuran are added to a 100 mL glass reaction vessel, and a dry ice-heptane bath is added. It was cooled to −70 ° C. 16.4 ml (40.9 mmol) of a 2.5 mol / L n-butyllithium-n-hexane solution was added dropwise thereto, and the mixture was stirred for 30 minutes, followed by 4.25 g (40.) of trimethyl borate at −78 ° C. 9 mmol) was added, and the mixture was stirred for 2 hours and further at room temperature for 12 hours. A 1 M aqueous hydrogen chloride solution was added to the reaction solution until the pH reached 3, then the mixture was transferred to a separating funnel, extracted three times with t-butylmethyl ether, and dried over sodium sulfate. The crude product obtained by filtering sodium sulfate and distilling off the solvent under reduced pressure was purified by silica gel column chromatography (developing solvent, petroleum ether: ethyl acetate = 20: 1), and 3,5-di-t-. 8.00 g of butylphenylboronic acid was obtained as a pale yellow solid (yield 91%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ7.72 (d, 1H), 7.57 (s, 2H), 4.61 (s, 2H), 1.32 (s, 18H).

(Iii) Synthesis of dimethylbis (4- (3,5-di-t-butylphenyl) -inden-1-yl) methane 21.6 g (102 mmol) of tripotassium phosphate, distilled in a 500 mL glass reaction vessel. 150 mL of water, 150 mL of DME, 14.3 g (61.3 mmol) of 3,5-di-t-butylphenylboronic acid, 11.0 g (25.5 mmol) of 2,2-bis (4-bromo-indene-1-yl) propane ), Dichlorobis (triphenylphosphine) palladium 358 mg (0.510 mmol), and triphenylphosphine 267 mg (1.02 mmol) were added in this order, and then the mixture was heated under reflux at 90 ° C. for 48 hours. After allowing to cool to room temperature, the reaction solution was poured into 50 mL of distilled water, transferred to a separating funnel, extracted three times with ethyl acetate, and dried over sodium sulfate. The crude product obtained by filtering sodium sulfate and distilling off the solvent under reduced pressure was purified by silica gel column chromatography (developing solvent, petroleum ether) and dimethylbis (4- (3,5-di-t-butyl). 10.0 g of phenyl) -inden-1-yl) methane was obtained as a yellow solid (yield 60%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ7.43 (m, 4H), 7.38 (d, 4H), 7.22-7.12 (m, 4H), 6.59 (s, 2H) , 3.50 (d, 4H), 1.82 (s, 6H), 1.39 (s, 36H).

(Iv) Synthesis of racemic-isopropyridenebis [4- (3,5-di-t-butylphenyl) -1-indenyl] hafnium dichloride In a 200 mL glass reaction vessel, dimethylbis (4- (3,5-) 3.25 g (5.00 mmol) of di-t-butylphenyl) -indene-1-yl) methane and 50 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. 6.2 ml (10.2 mmol) of a 1.64 mol / L n-butyllithium-n-hexane solution was added dropwise thereto, and the mixture was stirred at room temperature for 4 hours. The solvent of the reaction solution was distilled off under reduced pressure, 60 ml of toluene was added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. To that, 1.60 g (5.00 mmol) of hafnium tetrachloride was added. Then, the mixture was stirred for 16 hours while gradually returning to room temperature. At this time, the ratio of racemic mixture to meso compound was 17:83.
The solvent of the reaction solution was distilled off under reduced pressure, 10 mL of DME was added thereto, and the mixture was stirred at 60 ° C. for 5 hours. After cooling the reaction solution to room temperature, the solid is filtered through a glass frit, and the solid is washed twice with 3 mL of DME to contain lithium chloride-containing isopropylidenebis [4- (3,5-di-t-butylphenyl) -1-. Indenyl] A racemic mixture of hafnium dichloride was obtained in an amount of 3.35 g as a yellow solid.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 7.79 (d, 2H), 7.50 (d, 4H), 7.41 (s, 2H), 7.32 (d, 2H), 7 .13 (dd, 2H), 6.80 (d, 2H), 6.19 (d, 2H), 2.42 (s, 6H), 1.31 (s, 36H).

(V) Lasemi-isopropyridenebis [4- (3,5-di-t-butylphenyl) -1-indenyl] Synthesis of dimethylhafnium Isopropyridenebis containing lithium chloride in a 100 mL glass reaction vessel. [4- (3,5-Dimethylphenyl) -1-indenyl] Hafnium dichloride 1.00 g (content is 1.16 mmol or less) and 50 mL of toluene were added. 3.7 mL (11.1 mmol) of a 3.0 mol / L methyl magnesium bromide-diethyl ether solution was added dropwise thereto at room temperature, and then the mixture was stirred at 90 ° C. for 2.5 hours. After cooling the reaction solution to 0 ° C. in an ice bath, 1.15 mL (9.10 mmol) of chlorotrimethylsilane is added, and the mixture is stirred at room temperature for 15 minutes, followed by 2.3 mL (26.9 mmol) of 1,4-dioxane. In addition, the mixture was further stirred at room temperature for 40 minutes. After filtering the suspension with Celite, the solvent was distilled off under reduced pressure. The resulting yellow solid was suspended in 5 mL of hexane, filtered through a glass frit, and the solid was further washed 3 times with 3 mL of hexane to give isopropylidenebis [4- (3,5-di-t-butylphenyl). -1-Indenyl] 611 mg of the dimethylhafnium lasemi form was obtained as a yellow solid. Yield was 48% from the ligand (assuming all dichloro was used).
^{1 1} H-NMR (400 MHz, C ₆ D ₆ ): δ = 7.79 (d, 4H), 7.60 (s, 2H), 7.41 (d, 2H), 7.33 (d, 2H) , 6.94 (d, 2H), 6.90 (dd, 2H), 5.57 (d, 2H), 1.80 (s, 6H), 1.35 (s, 36H), -0.86 (S, 6H).

-Metallocene compound d: Synthesis of dimethylsilylene bisindenylhafnium dimethyl It was prepared by the method described in JP-A No. 10-218921.

-Metallocene compound e: Synthesis of cyclobutylidenebis (1-indenyl) dimethylhafnium

(I) Synthesis of 1,1-bis (1-indenyl) cyclobutane To a 200 mL glass reaction vessel, add 25.0 g (215 mmol) of indene, 250 mL of DME, and 27.0 g (480 mmol) of potassium hydroxide, and add 1 at 90 ° C. The mixture was heated under reflux for hours. The reaction mixture was cooled to 0 ° C., 8.40 g (120 mmol) of cyclobutanone was added, and then the mixture was heated under reflux at 90 ° C. for 6 hours. The reaction mixture was cooled to room temperature, 200 mL of distilled water was added, and the mixture was transferred to a liquid separation funnel and extracted twice with ethyl acetate. The obtained ethyl acetate solution was washed with saturated saline and distilled water in that order, and sodium sulfate was used. It was dried in. The sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (developing solvent, petroleum ether) to obtain 1,1-bis (1-indenyl) cyclobutane. 12.0 g of white solid was obtained (yield 39%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ); δ7.39 (t, 4H), 7.11 (quint, 4H), 6.62 (s, 2H), 3.40 (s, 4H), 2.73 (T, 4H), 2.09 (quint, 2H).

(Ii) Synthesis of racem-cyclobutylidenebis (1-indenyl) hafnium dichloride 2.84 g (10.0 mmol) of 1,1-bis (1-indenyl) cyclobutane and 100 ml of diethyl ether are placed in a 200 mL glass reaction vessel. In addition, it was cooled to −70 ° C. in a dry ice-heptane bath. 12.4 ml (20.5 mmol) of a 1.64 mol / L n-butyllithium-n-hexane solution was added dropwise thereto, and the mixture was stirred at room temperature for 4 hours. The solvent of the reaction solution was distilled off under reduced pressure, 115 ml of toluene was added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. To that, 3.20 g (10.0 mmol) of hafnium tetrachloride was added. Then, the mixture was stirred for 17 hours while gradually returning to room temperature.
The solvent of the reaction solution was distilled off under reduced pressure, 26 mL of DME was added thereto, and the mixture was stirred at 60 ° C. for 5 hours. The reaction mixture was cooled to room temperature, filtered through a glass frit, and the obtained solid was extracted with 130 mL of dichloromethane and filtered through Celite. The filtrate was dried under reduced pressure to obtain 3.76 g of racemic mixture of cyclobutylidenebis (1-indenyl) hafnium dichloride as a yellow solid (yield 71%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 7.51 (d, 2H), 7.48 (d, 2H), 7.27 (dd, 2H), 6.98 (dd, 2H), 6 .53 (d, 2H), 5.97 (d, 2H), 3.54 (quart, 2H), 3.12 (quart, 2H), 2.46 (quint, 2H).

(Iii) Synthesis of cyclobutylidenebis (1-indenyl) dimethylhafnium To a 200 ml glass reaction vessel, 1.50 g (2.82 mmol) of cyclobutylidenebis (1-indenyl) hafnium dichloride and 70 mL of toluene were added. A 3.0 mol / L methyl magnesium bromide-diethyl ether solution (6.6 mL (19.8 mmol)) was added dropwise at room temperature, and the mixture was stirred at 80 ° C. for 7 hours. After cooling the reaction solution to 0 ° C. in an ice bath, 1.75 mL (13.9 mmol) of chlorotrimethylsilane is added, and the mixture is stirred at room temperature for 30 minutes, followed by 3.50 mL (40.9 mmol) of 1,4-dioxane. In addition, the mixture was further stirred at room temperature for 1 hour. After filtering the suspension with Celite, the solvent was distilled off under reduced pressure. The obtained yellow solid was suspended in 10 mL of hexane, filtered through a glass frit, and the solid was further washed twice with 5 mL of hexane to obtain 810 mg of the racemic mixture of cyclobutylidenebis (indenyl) dimethylhafnium as a yellow solid. (Yield 59%).
_{^{1 H-NMR (400MHz, C}} 6 D 6): δ = 7.37 (d, 2H), 7.11 (dd, 2H), 7.05 (dd, 2H), 7.23 (dd, 2H) , 6.33 (d, 2H), 5.42 (d, 2H), 2.98 (quart, 2H), 2.54 (quart, 2H), 2.02 (quint, 2H), -1.16 (S, 6H).

(2) Production of Ethylene / α-olefin Copolymer Examples of ethylene / α-olefin copolymers (PE-1 to PE-3) produced by the following production methods, and comparative examples of PE-4 to PE-8. Used as. The following commercially available ethylene / α-olefin copolymer (PE-9) was also used as a comparative example. The physical characteristics are shown in Table 1.
(PE-9): Toughmer A-4085S manufactured by Mitsui Chemicals, Inc.

(I) Polymerization method of PE-1 A graph of 0.3 mmol of metallocene compound a and 0.6 mmol of tris (pentafluorophenyl) borane (pyrolysis temperature: 166 ° C; thermogravimetric analysis (TG)) is shown in FIG. ) Was dissolved in 30 L of toluene to prepare a catalytic solution.
Using a stirring autoclave type continuous reactor with an internal volume of 5.0 L, the pressure inside the reactor was maintained at 100 MPa, and 55 kg / hour was used so that ethylene was 52 wt%, propylene was 25 wt%, and 1-hexene was 23 wt%. Trioctyl aluminum (TNOA) was continuously supplied at 1.1 g / hour in order to scaveng the raw material gas and impurities in the reaction system at a rate. Further, the above catalyst solution was continuously supplied and the polymerization temperature was adjusted at 230 ° C. to obtain an ethylene / α-olefin copolymer of PE-1.

(Ii) Polymerization method of PE-2 A catalyst solution was prepared by dissolving 0.3 mmol of metallocene compound b and 0.6 mmol of tris (pentafluorophenyl) borane (pyrolysis temperature: 166 ° C.) in 30 L of toluene. ..
Using a stirring autoclave type continuous reactor with an internal volume of 5.0 L, keep the pressure inside the reactor at 80 MPa, and use the raw material gas at a ratio of 55 kg / hour so that ethylene is 40 wt% and 1-hexene is 60 wt%. Trioctyl aluminum (TNOA) was continuously supplied at 1.1 g / hour to scaveng the impurities in the reaction system. Further, the above catalyst solution was continuously supplied and the polymerization temperature was adjusted at 210 ° C. to obtain an ethylene / α-olefin copolymer of PE-2.

(Iii) Polymerization method of PE-3 A catalyst solution was prepared by dissolving 0.3 mmol of metallocene compound c and 0.6 mmol of tris (pentafluorophenyl) borane (pyrolysis temperature: 166 ° C.) in 30 L of toluene. ..
Using a stirring autoclave type continuous reactor with an internal volume of 5.0 L, keep the pressure inside the reactor at 80 MPa, and use the raw material gas at a rate of 55 kg / hour so that ethylene is 46 wt% and 1-hexene is 54 wt%. Trioctyl aluminum (TNOA) was continuously supplied at 1.1 g / hour to scaveng the impurities in the reaction system. Further, the above catalyst solution was continuously supplied and the polymerization temperature was adjusted at 230 ° C. to obtain an ethylene / α-olefin copolymer of PE-3.

(Iv) Polymerization method of PE-4 A catalyst solution was prepared by dissolving 0.3 mmol of metallocene compound d and 0.6 mmol of tris (pentafluorophenyl) borane (pyrolysis temperature: 166 ° C.) in 30 L of toluene. ..
Using a stirring autoclave type continuous reactor with an internal volume of 5.0 L, the pressure inside the reactor was maintained at 100 MPa, and 55 kg / hour was used so that ethylene was 37 wt%, propylene was 27 wt%, and 1-hexene was 36 wt%. Trioctyl aluminum (TNOA) was continuously supplied at 1.1 g / hour in order to scaveng the raw material gas and impurities in the reaction system at a rate. Further, the above catalyst solution was continuously supplied and the polymerization temperature was adjusted at 211 ° C. to obtain an ethylene / α-olefin copolymer of PE-4.

(V) Polymerization method of PE-5 0.3 mmol of metallocene compound d and 0.6 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (pyrolysis temperature: 263 ° C; thermogravimetric analysis (TG)) The graph of (1) is shown in FIG. 1) was dissolved in 30 L of toluene to prepare a catalytic solution.
Using a stirring autoclave type continuous reactor with an internal volume of 5.0 L, the pressure inside the reactor was maintained at 80 MPa, and 55 kg / hour was used so that ethylene was 37 wt%, propylene was 27 wt%, and 1-hexene was 36 wt%. The raw material gas was continuously supplied at a rate. Further, the above catalyst solution was continuously supplied and the polymerization temperature was appropriately adjusted at 190 ° C. to obtain an ethylene / α-olefin copolymer of PE-5.

(Vi) Polymerization method of PE-6 0.3 mmol of metallocene compound a and 0.6 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (pyrolysis temperature: 263 ° C.) are dissolved in 30 L of toluene. To prepare a catalytic solution.
Using a stirring autoclave type continuous reactor with an internal volume of 5.0 L, the pressure inside the reactor was maintained at 80 MPa, and 55 kg / hour was used so that ethylene was 52 wt%, propylene was 25 wt%, and 1-hexene was 23 wt%. Trioctyl aluminum (TNOA) was continuously supplied at 1.1 g / hour in order to scaveng the raw material gas and impurities in the reaction system at a rate. Further, the above catalyst solution was continuously supplied and the polymerization temperature was adjusted at 220 ° C. to obtain an ethylene / α-olefin copolymer of PE-6.

(Vii) Polymerization method of PE-7 A graph of 0.3 mmol of metallocene compound a and 0.6 mmol of trityltetrakis (pentafluorophenyl) borate (pyrolysis temperature: 258 ° C.; thermogravimetric analysis (TG)) is shown in FIG. (Shown) was dissolved in 30 L of toluene to prepare a catalytic solution.
Using a stirring autoclave type continuous reactor with an internal volume of 5.0 L, keep the pressure inside the reactor at 80 MPa, and use the raw material gas at a rate of 55 kg / hour so that ethylene is 43 wt% and 1-hexene is 57 wt%. Trioctyl aluminum (TNOA) was continuously supplied at 1.1 g / hour to scaveng the impurities in the reaction system. Further, the above catalyst solution was continuously supplied and the polymerization temperature was adjusted at ☆ ° C. to obtain an ethylene / α-olefin copolymer of PE-7.

(Viii) Polymerization method of PE-8 A catalyst solution was prepared by dissolving 0.3 mmol of metallocene compound e and 0.6 mmol of tris (pentafluorophenyl) borane (pyrolysis temperature: 166 ° C.) in 30 L of toluene. ..
Using a stirring autoclave type continuous reactor with an internal volume of 5.0 L, keep the pressure inside the reactor at 80 MPa, and use the raw material gas at a rate of 55 kg / hour so that ethylene is 43 wt% and 1-hexene is 57 wt%. Trioctyl aluminum (TNOA) was continuously supplied at 1.1 g / hour to scaveng the impurities in the reaction system. Further, the above catalyst solution was continuously supplied and the polymerization temperature was adjusted at ☆ ° C. to obtain an ethylene / α-olefin copolymer of PE-8.

(3) Organic peroxide: t-butylperoxy2-ethylhexyl carbonate (manufactured by Alchema Yoshitomi, Luperox TBEC)
(4) Hinderdamine-based photostabilizer: Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol (TINUVIN 622LD, manufactured by BASF)
(5) Ultraviolet absorber: 2-hydroxy-4-n-octoxybenzophenone (CYTEC UV531 manufactured by Sun Chemical Co., Ltd.)
(6) Silane coupling agent: γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503)
(7) Antioxidant: n-octadecyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate (manufactured by BASF, IRGANOX1076)

(Example 1)
1.0 part by weight of t-butylperoxy-2-ethylhexyl carbonate (TBEC, manufactured by Alchema Yoshitomi) as an organic peroxide with respect to 100 parts by weight of polyethylene resin (PE-1), hindered amine-based light As a stabilizer, 0.05 part by weight of a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol (TINUVIN 622LD, manufactured by BASF), as an ultraviolet absorber, 2-Hydroxy-4-n-octoxybenzophenone (CYTEC UV531 manufactured by Sun Chemical Co., Ltd.) 0.3 parts by weight, as a silane coupling agent, γ-methacryloxypropyltrimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., KBM503) 0. 3 parts by weight and 0.025 parts by weight of n-octadadecyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate (IRGANOX 1076 manufactured by BASF) were blended as an antioxidant. This was sufficiently mixed and pelletized using a 40 mmφ single-screw extruder under the conditions of a set temperature of 100 ° C. and an extrusion rate (17 kg / hour).
The resulting pellet, in the conditions of 150 ℃ -0kg / cm ^2, after 3 minutes preheat, 150 ℃ -100kg / cm (30 minutes press molding at 0.99 ° C.) 27 minutes pressurization at ² conditions, and then, A crosslinked sheet having a thickness of 0.7 mm was prepared by cooling with a cooling press set at 30 ° C. ^{under a pressure condition of 100 kg / cm 2 for 10 minutes.} The HAZE, light transmittance, heat resistance, and mechanical strength of the sheet were measured and evaluated.
Further, a graph of DSC of polyethylene resin (PE-1) is shown in FIG.

(Example 2)
In Example 1, a sheet was prepared in the same manner as in Example 1 except that PE-2 was used instead of PE-1. The evaluation results are shown in Table 1.

(Example 3)
In Example 1, a sheet was prepared in the same manner as in Example 1 except that PE-3 was used instead of PE-1. The evaluation results are shown in Table 1.

(Comparative Example 1)
In Example 1, a sheet was prepared in the same manner as in Example 1 except that PE-4 was used instead of PE-1. The evaluation results are shown in Table 1.
Moreover, the graph of DSC of PE-4 is shown in FIG.

(Comparative Example 2)
In Example 1, a sheet was prepared in the same manner as in Example 1 except that PE-5 was used instead of PE-1. The evaluation results are shown in Table 1.

(Comparative Example 3)
In Example 1, a sheet was prepared in the same manner as in Example 1 except that PE-6 was used instead of PE-1. The evaluation results are shown in Table 1.

(Comparative Example 4)
In Example 1, a sheet was prepared in the same manner as in Example 1 except that PE-7 was used instead of PE-1. The evaluation results are shown in Table 1.

(Comparative Example 5)
In Example 1, a sheet was prepared in the same manner as in Example 1 except that PE-8 was used instead of PE-1. The evaluation results are shown in Table 1.

(Comparative Example 6)
In Example 1, a sheet was prepared in the same manner as in Example 1 except that PE-9 was used instead of PE-1. The evaluation results are shown in Table 1.

(evaluation)
As a result, as is clear from Table 1, since the polyethylene resin composition of the present invention is used in Examples 1 to 3, the sheet obtained by extrusion molding has good cross-linking characteristics and HAZE. It is small, has a large light transmittance, has excellent heat resistance, and suppresses leakage current.
On the other hand, in Comparative Examples 1 and 5, although the cross-linking characteristics and heat resistance were good and the volume resistivity was high, the transparency was low because there were two melting peaks. In Comparative Examples 2 to 4, although the cross-linking characteristics, transparency, and heat resistance were good, the volume resistivity of the polyethylene resin was low, resulting in the occurrence of leakage current. In Comparative Example 6, the cross-linking characteristics, transparency, heat resistance, and volume resistivity were all low levels.

The polyethylene resin and polyethylene resin composition of the present invention are preferably used as a solar cell encapsulant because they have high insulating properties, good cross-linking characteristics, high heat resistance, and excellent transparency.

Claims (4)

A polyethylene resin composed of an ethylene / α-olefin copolymer and a polyethylene resin containing the following component (D), which are obtained by carrying out polymerization using a catalytic system containing the following components (A) and (B). Solar cell encapsulant using the composition.
Component (A): Metallocene compound represented by the following general formula (I)

[In general formula (I), M is Ti, Zr, or Hf;
R ^{1 to} R ¹⁰ and R ^{11 to} R ²⁰ may be the same or different, and each may have a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, respectively. 1 carbon number substituted with an aryl group of 6 to 20, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 6 carbon atoms. ~ 20 alkyl groups, -N (R ²³ ) ₂ groups, -SR ²³ groups, -OSi (R ²³ ) ₃ groups or -P (R ²³ ) ₂ groups (R ²³ is a halogen atom, 1 carbon number) It is an alkyl group of 10 to 10 and an aryl group having 6 to 20 carbon atoms, and ^{when it has 2 or more R 23} , it may be the same or different from each other), R ^{1 to} R ¹⁰ and R ^{11 to} R ^20. There may form one or more aromatic or aliphatic ring together with the atoms connecting them with R groups adjacent to each other, R ⁵ and R ⁶ or R ⁵ and R ^10, R ¹⁵ R ¹⁶ or R ¹⁵ and R ²⁰ may be combined with the atoms connecting them to form one aromatic or aliphatic ring;
Y is Si or C;
R ²¹ and R ²² may be the same or different, respectively, and have a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, respectively. Aryl groups with 6 to 20 carbon atoms, fluoroaryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, arylalkyl groups with 7 to 40 carbon atoms, and carbon atoms. It is an alkylaryl group of 7 to 40, an arylalkenyl group of 8 to 40 carbon atoms, and R ²¹ and R ²² are not hydrogen atoms at the same time, but R ²¹ and R ²² are combined with an atom connecting them. One or more rings may be formed;
X ¹ and X ² may be the same or different, respectively, and have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 6 carbon atoms, respectively. 10 aryloxy groups, 2-10 carbon alkenyl groups, 7-40 carbon arylalkyl groups, 7-40 carbon alkylaryl groups, 8-40 carbon arylalkenyl groups, 1-6 carbons It is an alkyl group having 1 to 20 carbon atoms, an amino group having 1 to 10 carbon atoms, an OH group, a halogen atom or a coordinable neutral ligand substituted with a silyl group having a hydrocarbon group of X ^1. And X ² may be combined with the atoms connecting them to form a ring. ]
Component (B): a by reacting with component (A) a boron compound to form an ion pair, the thermal decomposition temperature of weight change under N ₂ atmosphere occurs 200 ° C. lower than the component (D): an organic peroxide The solar cell encapsulant according to claim 1, wherein the ethylene / α-olefin copolymer further has the following characteristics (a7).
(A7) The ratio (Mz / Mn) of the Z average molecular weight (Mz) to the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 8.0 or less. The polyethylene resin composition according to claim 1 or 2 , wherein the content of the component (D) is 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyethylene resin (A). The solar cell encapsulant used. A solar cell module using the solar cell encapsulant according to any one of claims 1 to 3.

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