JP2015199930A - Method for manufacturing resin composition for solar cell sealing material, and solar cell sealing material and solar cell module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for manufacturing a resin composition for a solar cell sealing material having excellent crosslinking properties; and a solar cell sealing material and a solar cell module using the method.SOLUTION: A method is intended for manufacturing a resin composition for a solar cell sealing material containing an ethylene-α-olefin copolymer and an organic peroxide. The ethylene-α-olefin copolymer is obtained by carrying out copolymerization under the following condition (a1) using an olefin polymerization catalyst containing the following ingredient (A). The ingredient (A): 10-49 mol% in propylene concentration of a reaction system of a metallocene compound (a1).

Description

  The present invention relates to a method for producing a resin composition for a solar cell encapsulant, and a solar cell encapsulant and a solar cell module using the same.

  As global environmental issues such as an increase in carbon dioxide are highlighted, solar power generation has come into focus again along with the effective use of hydropower, wind power, and geothermal heat. Although solar power generation is smaller than hydropower, wind power, etc., it can be distributed in places where power is needed, so research and development aimed at improving performance such as power generation efficiency and reducing prices are being promoted. . In addition, the government and local governments are gradually promoting the spread of measures by substituting installation costs as a residential solar power generation system introduction promotion project. However, further cost reduction is necessary for further spread, so that not only the development of solar cell elements using new materials to replace conventional silicon and gallium arsenide, but also the manufacturing cost of solar cell modules Efforts to further reduce this are continuing.

  Photovoltaic power generation generally protects solar cell elements such as silicon, gallium-arsenic, copper-indium-selenium with an upper transparent protective material and a lower substrate protective material, and the solar cell element and the protective material are sealed with resin. A solar cell module fixed with a material and packaged is used.

  As a condition of the sealing material constituting the solar cell module, in order to ensure the incident amount of sunlight so as not to decrease the power generation efficiency of the solar cell, good transparency is required. Moreover, since a solar cell module is usually installed outdoors, it is exposed to sunlight for a long period of time and the temperature rises. Therefore, in order to avoid troubles in which the resin sealing material flows and the module is deformed, it must have heat resistance.

  Conventionally, an ethylene / vinyl acetate copolymer (EVA) having a high vinyl acetate content has been used as a resin material used for a sealing material. And in order to provide heat resistance, the resin composition which mix | blended the organic peroxide with EVA and provided the crosslinked structure is employ | adopted as a sealing material (for example, refer patent document 1). However, ethylene / vinyl acetate copolymer (EVA) resin, when used over a long period of time, has deteriorated moisture resistance due to deterioration / deterioration such as yellowing, cracking and foaming, and power generation due to corrosion of solar cells, etc. The amount was reduced. These are considered to be easily affected by sunlight and moisture because the EVA resin has an ester structure with high hydrolyzability.

  Therefore, it has been proposed to use an ethylene / α-olefin copolymer that is excellent in transparency, moisture resistance, and the like as a resin material used for the sealing material. 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 describes that a cross-linking agent is blended with a copolymer as a main component.

  In Patent Document 3, as a sealing material, (a) a density of less than about 0.90 g / cc, (b) a 2% secant of less than about 150 megapascals (MPa) as measured by ASTM D-882-02. A coefficient, (c) a melting point less than about 95 ° C., (d) an α-olefin content of at least about 15 and less than about 50% by weight based on the weight of the polymer, (e) a Tg of less than about −35 ° C., and (f ) Disclosed is a polymeric material comprising a polyolefin copolymer that meets one or more conditions of at least about 50 SCBDI.

  In recent years, with an increase in demand for solar cell modules, improvement in production efficiency of solar cell modules is required, and the crosslinking process of the sealing material tends to be shortened. In general, ethylene / α-olefin copolymers are not easily crosslinked with organic peroxides compared to EVA, and it is difficult to obtain a high gel fraction by heating in a short time. It is difficult to get efficiency. This is because, in EVA, the vinyl acetate portion which is a comonomer can easily become a radical crosslinking point, whereas the α-olefin comonomer itself used in a general ethylene / α-olefin copolymer does not become a radical crosslinking point. .

  Therefore, in order to improve the crosslinking efficiency of the ethylene α-olefin copolymer, the number of branches and the number of double bonds (vinyl, vinylidene, cis-vinylene, trans-vinylene, trisubstituted olefin) in the copolymer are large. It has been proposed to use an ethylene / α-olefin copolymer (Patent Documents 4 and 5). However, further improvement in crosslinking efficiency is required for a sealing material using an ethylene / α-olefin copolymer.

JP 58-023870 A JP 2006-210906 A JP 2010-504647 A JP 2012-009688 A JP 2012-009691 A

  The object of the present invention is to provide a method for producing a resin composition for a solar cell encapsulant that is excellent in cross-linking properties in view of the problems of the prior art, and further, by using it, heat resistance, transparency, weather resistance It is providing the solar cell sealing material and solar cell module which are excellent in this.

  As a result of intensive studies to solve the above problems, the present inventors have used a metallocene compound or the like as a catalyst component, and an ethylene / α-olefin copolymer produced with a propylene concentration during a polymerization reaction within a specific range, Finding that the copolymer contains many double bonds of vinyl and vinylidene, and further that the solar cell encapsulant using the resin composition containing the copolymer is excellent in crosslinking properties. As a result, the present invention has been completed.

That is, according to 1st invention of this invention, it is a manufacturing method of the resin composition for solar cell sealing materials containing an ethylene-alpha-olefin copolymer and an organic peroxide, Comprising: Said ethylene-alpha-olefin A resin composition for a solar cell encapsulant, wherein the copolymer is obtained by performing copolymerization under the conditions (a1) below using an olefin polymerization catalyst containing the following component (A): A manufacturing method is provided.
Component (A): Metallocene compound (a1) The propylene concentration in the reaction system is 10 to 49 mol%.

Further, according to the second invention of the present invention, in the first invention, the copolymerization is performed under the following condition (a1 ′): A method for producing a resin composition is provided.
(A1 ′) The propylene concentration in the reaction system is 20 to 49 mol%.

［一般式（Ｉ）中、ＭはＴｉ、Ｚｒ、又はＨｆであり；
Ｒ^１−Ｒ^１０及びＲ^１１−Ｒ^２０は同一又は異なって、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、−ＮＲ^２３ _２基、−ＳＲ^２３基、−ＯＳｉＲ^２３ _３基又は−ＰＲ^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^１−Ｒ^１０及び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は同一又は異なって、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は同一又は異なって、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。］ According to the third invention of the present invention, in the first or second invention, the component (A) is a metallocene compound represented by the following general formula (I). A method for producing a resin composition for a material is provided.

[In general formula (I), M is Ti, Zr, or Hf;
R ¹ -R ¹⁰ and R ¹¹ -R ²⁰ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group Group, —NR ²³ ₂ group, —SR ²³ group, —OSiR ²³ ₃ group or —PR ²³ ₂ group (R ²³ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl having 6 to 20 carbon atoms) R ¹ -R ¹⁰ and R ¹¹ -R ²⁰ may form one or more aromatic or aliphatic rings together with the atoms connecting them between adjacent R groups. , ^{R 5} and ^{R 6} or ^{R 5} and ^{R 1} , They may form a single aromatic ring or an aliphatic ring together with the atoms to which R ¹⁵ and R ¹⁶ or R ¹⁵ and R ²⁰ are linked to them;
Y is Si or C;
R ²¹ and R ²² are the same or different and are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, C6-C10 fluoroaryl groups, C6-C10 aryloxy groups, C2-C10 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 An alkylaryl group, an arylalkenyl group having 8 to 40 carbon atoms, and R ²¹ and R ²² are not hydrogen atoms at the same time, and R ²¹ and R ²² together with the atoms connecting them are one or more May form a ring;
X ¹ and X ² are the same or different and are each 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, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms 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 neutral ligand capable of coordination, which is substituted with a silyl group having X ¹ and X ² , Together with atoms connecting them, may form a ring. ]

According to a fourth invention of the present invention, in any one of the first to third inventions, the catalyst for olefin polymerization contains the following component (B): A method for producing a resin composition is provided.
Component (B): Compound or ion-exchangeable layered silicate that reacts with component (A) to form an ion pair

According to a fifth invention of the present invention, in any one of the first to fourth inventions, the olefin polymerization catalyst includes the following component (C): A method for producing a resin composition is provided.
Component (C): Organoaluminum compound

  According to a sixth invention of the present invention, in any one of the first to fifth inventions, the component (B) is a boron compound, and the method for producing a resin composition for a solar cell encapsulant Is provided.

  According to a seventh aspect of the present invention, there is provided a method for producing a resin composition for a solar cell encapsulant, characterized in that, in the third aspect, in the general formula (I), Y is a carbon atom. Provided.

According to an eighth aspect of the present invention, in any one of the first to seventh aspects, the ethylene / α-olefin copolymer has the following characteristic (b1): A method for producing a resin composition for a sealing material is provided.
(B1) The total number of vinyl and vinylidene double bonds in the ethylene / α-olefin copolymer is 0.50 (pieces / 1000 C main chain) or more (however, the number of vinyl and vinylidene is measured by NMR) Is the number of

  Moreover, according to the ninth invention of the present invention, there is provided a solar cell encapsulant characterized by using the resin composition according to the eighth invention.

  Furthermore, according to the 10th invention of this invention, the solar cell module characterized by using the solar cell sealing material which concerns on 9th invention is provided.

  The method for producing a resin composition for a solar cell encapsulant of the present invention is for a solar cell encapsulant having an excellent crosslinking rate by using an ethylene / α-olefin copolymer containing many vinyl and vinylidene double bonds. A resin composition is provided. And since the solar cell sealing material using the resin composition can be crosslinked in a relatively short time, the solar cell module can be easily formed, and the solar cell module is excellent in heat resistance, transparency, and weather resistance. In addition, it can be expected that the manufacturing cost is reduced and the conversion efficiency stable for a long time is maintained.

The method for producing a resin composition for a solar cell encapsulant of the present invention uses an ethylene / α-olefin copolymer obtained by using a catalyst for olefin polymerization containing a metallocene compound and a propylene concentration in a polymerization system within a specific range. And an organic peroxide.
Hereinafter, each component used in the present invention, the obtained ethylene / α-olefin copolymer and a resin composition for a solar cell encapsulant, a solar cell encapsulant using the same, a solar cell module, etc., for each item This will be described in detail.

1. Olefin Polymerization Catalyst The olefin polymerization catalyst used in the present invention contains the following component (A), and preferably contains the following components (B) to (C).
Component (A): Metallocene compound Component (B): Compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair Component (C): Organoaluminum compound

(1) Component (A)
Component (A) used in the present invention is a metallocene compound, 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及びＲ^１１−Ｒ^２０は同一又は異なって、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、−ＮＲ^２３ _２基、−ＳＲ^２３基、−ＯＳｉＲ^２３ _３基又は−ＰＲ^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^１−Ｒ^１０及び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は同一又は異なって、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は同一又は異なって、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 -R ¹⁰ and R ¹¹ -R ²⁰ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group Group, —NR ²³ ₂ group, —SR ²³ group, —OSiR ²³ ₃ group or —PR ²³ ₂ group (R ²³ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl having 6 to 20 carbon atoms) R ¹ -R ¹⁰ and R ¹¹ -R ²⁰ may form one or more aromatic or aliphatic rings together with the atoms connecting them between adjacent R groups. , ^{R 5} and ^{R 6} or ^{R 5} and ^{R 1} , They may form a single aromatic ring or an aliphatic ring together with the atoms to which R ¹⁵ and R ¹⁶ or R ¹⁵ and R ²⁰ are linked to them;
Y is Si or C;
R ²¹ and R ²² are the same or different and are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, C6-C10 fluoroaryl groups, C6-C10 aryloxy groups, C2-C10 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 An alkylaryl group, an arylalkenyl group having 8 to 40 carbon atoms, and R ²¹ and R ²² are not hydrogen atoms at the same time, and R ²¹ and R ²² together with the atoms connecting them are one or more May form a ring;
X ¹ and X ² are the same or different and are each 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, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms 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 neutral ligand capable of coordination, which is substituted with a silyl group having X ¹ and X ² , Together with atoms connecting them, may form a ring. ]

  In 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, chlorine atom, bromine atom, iodine atom, fluorine atom, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, A phenyl group, a benzyl group, a dimethylamino group, a diethylamino group, a trimethylsilyl group, etc. can be mentioned.
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. .

In addition, X ¹ and X ² are coordinateable neutral ligands, and specifically, 1,3-butadiene is an atomic group that forms one ring together with 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 -Ditolyl-1,3-butadiene, 1,4-bis (trimethylsilyl) -1,3-butadiene and the like can be mentioned.

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

In general formula (I), R ^{6 to} R ¹⁰ and R ^{16 to} R ²⁰ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a carbon atom having 6 to 10 carbon atoms. An aryl group, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrogen atom , An alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

  In general formula (I), Y is preferably a carbon atom from the viewpoint of the number of vinyl and vinylidene in the ethylene / α-olefin copolymer to be produced.

In general formula (I), preferred R ²³ groups are alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms, and preferred —NR ²³ ₂ groups are dimethylamide groups, diethylamide groups, A diisopropylamide group etc. can be mentioned.

In the general formula (I), specific examples of the —SR ²³ group include a methylsulfanyl group, an ethylsulfanyl group, an isopropylsulfanyl group, and a phenylsulfanyl group.

Specific examples -OSiR ²³ ₃ group, can be mentioned trimethylsiloxy group, triethyl siloxane Shiki group, triisopropylsiloxy group, triphenylsiloxy group, and tert- butyl (dimethyl) siloxy group.

In the formula (I), specifically as a -PR ²³ ₂ radical can be exemplified dimethylphosphino group, diethylphosphino group, diisopropylphosphino group, di-butyl phosphino group, and diphenylphosphino group.

In 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, and an arylalkenyl group having 8 to 40 carbon atoms, more preferably 1 to 1 carbon atom. 10 alkyl groups, aryl groups having 7 to 10 carbon atoms, and alkenyl groups having 2 to 10 carbon atoms. In addition, the total number of carbon atoms contained in R ²¹ and R ²² is preferably 3 or more.
R ²¹ and R ²² preferably form one or more rings together with the connecting atom (Y), and more preferably form a 4-5 membered ring.

Specific examples of each functional group that can be contained in the general formula (I) are shown below.
Specific examples of the alkyl group 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, 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 group in which a halogen atom is substituted on a hydrogen atom on the skeleton of an 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 the halogenated alkyl group 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- Mention may be made of fluoropentyl, 5,5,5-trifluoropentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl, 6-fluorohexyl and 6,6,6-trifluorohexyl.

  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 a group in which a fluorine atom is substituted for 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, Mention may be made of 5,5,5-trifluoropentyl, 6-fluorohexyl, 6,6,6-trifluorohexyl.

  Specific examples of the alkoxy group 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, cyclo Propoxy, cyclopentoxy, cyclohexoxy, n-octoxy, n-deoxy and the like can be mentioned.

  The fluoroaryl group having 6 to 10 carbon atoms is obtained by substituting a fluorine atom for 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, pentafluoroethylphenyl, nonafluoro-t-butylphenyl, 1-perfluoronaphthyl, Examples include 2-perfluoronaphthyl.

  The aryloxy group having 6 to 10 carbon atoms may be substituted with a hydrocarbon group having 1 to 4 carbon atoms. Specific examples include phenoxy, trimethylphenoxy, dimethylphenoxy, ethylphenoxy, t-butylphenoxy, Examples 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, (tert-butylphenyl) methyl, and the like.

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

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

  Specific examples of the alkyl group having 1 to 20 carbon atoms substituted with a silyl group having a hydrocarbon group having 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilylmethyl group, and a triphenylsilylmethyl group. it 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 trimethylsilyl group, triethylsilyl group, tert-butyl (dimethyl) silyl group, and triphenylsilyl group.

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

Isopropylidene bridged metallocene compounds:
Isopropylidenebis (4-phenyl-1-indenyl) dimethylhafnium, isopropylidenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3-isopropylphenyl) -1- Indenyl) dimethylhafnium, isopropylidenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-Isopropylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-trifluoromethyl) Ruphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethylhafnium Isopropylidenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-fluorophenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4- Chlorophenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2-methylphenyl) -1-indenyl) dimethylha , Isopropylidenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3 , 5-dimethoxyphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium,
Isopropylidenebis (4- (3,5-ditrifluoromethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis ( 4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,3 , 5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis ( 4- (4-tert-butyl-2-methyl-phenyl)- -Indenyl) dimethylhafnium, isopropylidenebis (4-biphenylyl1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- ( 2 ', 6'-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2-naphthyl) -1 -Indenyl) dimethylhafnium, isopropylidenebis (4-phenanthryl-1-indenyl) dimethylhafnium

Cyclobutylidene bridged metallocene compounds:
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) dimethylhafnium, cyclobutylidenebis (4- (4-isopropylphenyl)- 1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (4-trifluoromethylphenyl) -1-indenyl) Dimethyl hafnium, cyclobutylidenebis 4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (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) dimethylhafniumcyclo Butylidenebis (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, cyclo Butylidenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (3,5-dimethoxyphenyl) -1-indenyl) dimethylhafnium, cyclo Butylidenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (3,5-ditrifluoromethylphenyl) -1-indenyl) dimethylhafnium, cyclobuty Redenbis (4- (2,3-dimethylphenyl ) -1-Indenyl) dimethylhafnium, cyclobutylidenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (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-biphenylyl1) -Indenyl) dimethylhafnium, cyclobutylidenebis (4- (2,6-dimethylbiphenyl) Enylyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (2 ′, 6′-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4- (1-naphthyl) -1 -Indenyl) dimethylhafnium, cyclobutylidenebis (4- (2-naphthyl) -1-indenyl) dimethylhafnium, cyclobutylidenebis (4-phenanthryl-1-indenyl) dimethylhafnium,

Cyclopentylidene bridged metallocene compounds:
Cyclopentylidenebis (4-phenyl-1-indenyl) dimethylhafnium,
Cyclopentylidenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (3-isopropylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- ( 3-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4-isopropylphenyl)- 1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4-trifluoromethylphenyl) -1-indenyl) Dimethyl hafnium, cyclo Nethylidenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4- Trimethylsilylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4-fluorophenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4-chlorophenyl) -1-indenyl) dimethyl Hafnium, cyclopentylidenebis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4 -(2- Tylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (3,5-diisopropylphenyl) -1 -Indenyl) dimethylhafnium, cyclopentylidenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (3,5-dimethoxyphenyl) -1 -Indenyl) dimethylhafnium, cyclopentylidenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (3,5-ditrifluoromethylphenyl) -1- Indenyl) dimethylhafnium, cyclope N-tylidenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium,
Cyclopentylidenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (2,3,5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium Cyclopentylidenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (4-tert-butyl-2-methyl-phenyl) ) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4-biphenylyl1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, cyclopentyl Redenbis (4- (2 ′, 6′-dimethylbiphenylyl) -1-y Denyl) dimethylhafnium, cyclopentylidenebis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis (4- (2-naphthyl) -1-indenyl) dimethylhafnium, cyclopentylidenebis ( 4-phenanthryl-1-indenyl) dimethylhafnium

Cyclohexylidene bridged metallocene compounds:
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) dimethylhafnium, cyclohexylidenebis (4- (4-tert -Butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, cyclohexylidenebis (4-biphenylyl1-indenyl) dimethylhafnium

Diethylmethylene bridged metallocene compounds:
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-trimethylsilyl) Phenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, Diethylmethylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, diethylmethylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, diethylmethylene Bis (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-biphenylyl1-indenyl) dimethylhafnium

Di-n-propylmethylene bridged metallocene compound:
Di-n-propylmethylenebis (4-phenyl-1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (3-isopropylphenyl) -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- (3,5-dimethylphenyl) -1-indeni ) Dimethylhafnium, di-n-propylmethylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, di-n-propylmethylenebis (4- (3,5-di) Trimethylsilylphenyl) -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 bridged 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-indeni ) Dimethyl hafnium, di -iso- butyl methylene bis (4- (4-trimethylsilyl-phenyl) -1-indenyl) dimethyl hafnium,
Di-iso-butylmethylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, di- iso-butylmethylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, di-iso-butylmethylenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl ) Dimethylhafnium, di-iso-butylmethylenebis (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 bridged metallocene compounds:
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) dimethylhafnium,
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, Benzylmethylenebis (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) dimethylhafnium, dibenzylmethylenebis (4- ( 4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, dibenzylmethylenebis (4-biphenylyl1-indenyl) dimethylhafnium

Methyl (ethyl) methylene bridged 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) Dimethylha Ni, methyl (ethyl) methylene bis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethyl hafnium, methyl (ethyl) methylene bis (4- (2-methylphenyl) -1-indenyl) dimethyl hafnium, 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) methylenebis (4-biphenylyl1-indenyl) ) Dimethyl hafnium

Methyl (n-propyl) methylene bridged 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-bu Ruphenyl) -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- (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)- -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 bridged metallocene compounds:
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-isopropylphenyl) -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) methyl Bis (4- (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) Chirenbisu (4- (4-tert-butyl-2-methyl-phenyl) - 1-indenyl) dimethyl hafnium, methyl (an iso-butyl) methylene bis (4-biphenylyl 1-indenyl) dimethyl hafnium

Methyl (benzyl) methylene bridged metallocene compounds:
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-indeni ) 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 bridged 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) methylenebis (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-dito Methylsilylphenyl) -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-biphenylyl1-indenyl) dimethylhafnium

Dimethylsilylene bridged metallocene compounds:
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-Isopropylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-trifluoromethyl) Ruphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethylhafnium 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) dimethylha 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 , 5-dimethoxyphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3,5-ditrifluoro) Methylphenyl) -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, dimethylsilylenebis (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) Dimethyl hafnium, dimethylsilylene bis (4-biphenylyl-1-y Denyl) 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-phenanthryl-1) -Indenyl) dimethylhafnium,

Diethylsilylene bridged metallocene compounds:
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-Isopropylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-trifluoromethyl) Ruphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethylhafnium , 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) dimethylha Nitrogen, 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 , 5-Dimethoxyphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, diethylsilylenebis (4- (3,5-ditrifluoro) Methylphenyl) -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) Dimethyl hafnium, diethylsilylene bis (4-biphenylyl-1-y Denyl) 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-phenanthryl-1) -Indenyl) dimethylhafnium,

Trimethylenesilylene-bridged metallocene compounds trimethylenesilylenebis (4-phenyl-1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (3-Isopropylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4-tert-butylphenyl) -1-indenyl ) Dimethylhafnium, trimethylenesilylenebis (4- (4-trifluoromethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, trimethylene Silylenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4 -Fluorophenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4-chlorophenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (4-bromophenyl) -1-indenyl) Methylhafnium, trimethylenesilylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis ( 4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (3 , 5-Di-tert-butylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (3,5-dimethoxyphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (3 , 5-Ditrimethylsilylphe L) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (3,5-ditrifluoromethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (2,6-dimethylphenyl) -1-indenyl ) Dimethylhafnium, trimethylenesilylenebis (4- (2,3,5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (2,3,4,5,6-) Pentamethylphenyl) -1-indenyl) dimethylhafnium, trimethyl Rensilylene bis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4-biphenylyl-1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (2,6-Dimethylbiphenylyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (2 ′, 6′-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4- (2-naphthyl) -1-indenyl) dimethylhafnium, trimethylenesilylenebis (4-phenanthryl-1-indenyl) dimethylhafnium

Tetramethylenesilylene bridged metallocene compounds:
Tetramethylenesilylenebis (4-phenyl-1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (3-isopropylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (4-methylphenyl) -1-indenyl) dimethyl Hafnium, tetramethylenesilylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, teto Methylenesilylenebis (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, tetramethylenesilylenebis (4- (2,3-dimethylphenyl) ) -1-I Denyl) dimethylhafnium, tetramethylenesilylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium Tetramethylenesilylenebis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) dimethylhafnium, tetramethylenesilylenebis (4-biphenylyl-1-indenyl) dimethylhafnium

Diphenylsilylene-bridged metallocene compounds Diphenylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (3-isopropyl) Phenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (4-methylphenyl) -1-indenyl) dimethyl Hafnium, diphenylsilylenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafni , Diphenylsilylenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (2-methylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (2 -Ethylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (3,5-di-tert-butyl) Phenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (2,3-dimethylphenyl) -1- Indenyl) dimethyl Funium, diphenylsilylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, diphenylsilylenebis ( 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 preferred from the viewpoint of the vinyl and vinylidene numbers of the ethylene / α-olefin copolymer to be produced.

From the viewpoint that a high molecular weight ethylene / α-olefin copolymer can be produced in the exemplified metallocene compounds, compounds in which R ¹ and R ¹¹ are hydrogen atoms are preferable.

In the exemplified metallocene compounds, M is a compound in which titanium and zirconium are substituted instead of hafnium, X ¹ and X ² are in place of a methyl group, one or both are chlorine atoms, bromine atoms, iodine Compounds in place of atoms, phenyl groups, benzyl groups, dimethylamino groups, diethylamino groups, trimethylsilylmethyl groups and the like can also be exemplified.

[Synthesis of metallocene compounds]
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 substituent or the mode of bonding. An example of a typical synthesis route is shown below.

In the above synthetic route, 2 is obtained by performing a coupling reaction between 1 and phenylboronic acid in the presence of a palladium catalyst. The crosslinking reaction from 2 to 3 can be performed by the method described in the literature (Japanese Patent No. 3835846), and after anionization of 2 with potassium hydroxide or the like, 3 is obtained by reaction with acetone. After metal 3 is dianionized with 2 equivalents of n-butyllithium or the like, metallocene compound 4 can be obtained by reaction with hafnium tetrachloride. Generally, 4 is a mixture of a racemate and a meso isomer, and a racemate having excellent catalytic performance is concentrated by purification. In addition, the meso form can be isomerized into a racemate by the method described in the literature (WO2000 / 017213), and the yield of the racemate can be improved. The dimethyl body 5 can be obtained by treating 4 with 2 equivalents or more of MeMgBr.
A metallocene compound having a substituent introduced therein can be synthesized by using a corresponding substituted raw material, and instead of phenylboronic acid, a corresponding boronic acid such as 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 4-position phenyl group of the indenyl ring.
The synthesis of metallocene compounds having different substituents on the bridging group can be synthesized by using corresponding substitution raw materials, and by using corresponding ketones such as cyclobutanone and 4-heptenone instead of acetone, Substituents (R ¹⁰ , R ²⁰ ) can be introduced on the bridging group.

(2) Component (B)
The component (B) is a compound or ion-exchange layered silicate that reacts with the component (A) to form an ion pair. Examples of the compound that reacts with the component (A) to form an ion pair include an organoaluminum oxy compound, a boron compound, and a zinc compound, preferably an organoaluminum oxy compound or a boron compound, more preferably a boron compound. It is. These components (B) may be used independently and may use 2 or more types.

(I) Organoaluminum oxy compound The organoaluminum oxy compound which is one of the components (B) has an Al-O-Al bond in the molecule, and the number of bonds is usually 1 to 100, preferably 1 to 50. In the range. Such an organoaluminum oxy compound is usually obtained by reacting an organoaluminum compound with water or an aromatic carboxylic acid.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any of compounds represented by the following general formula (II) can be used, but trialkylaluminum is preferably used.
^{_{R a t AlX a 3-t}} (II)
(In the formula, R ^a represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, aralkyl group or the like having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ^a represents a hydrogen atom or a halogen atom. , T represents an integer of 1 ≦ t ≦ 3.)
The alkyl group of the trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. A methyl group and an isobutyl group are preferable, and a methyl group is more preferable.
Two or more of the above organoaluminum compounds can be mixed and used.

The reaction ratio of water to the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is usually It is in the range of −70 to 100 ^° C., preferably −20 to 20 ^° C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.
Of the organoaluminum oxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds can be used in combination, and a solution in which the organoaluminum oxy compound is dissolved or dispersed in the above-described inert hydrocarbon solvent. You may use.

  In an organoaluminum oxy compound, what is represented by the following general formula can also be illustrated.

The compound represented by the general formula (III) is 10: 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula: R ^c B (OH) _2. It can be obtained by a reaction of ˜1: 1 (molar ratio). In the general formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

(Ii) Boron compound Examples of the boron compound that is one of the components (B) include boron compounds such as borane compounds and borate compounds.
Specific examples of the borane compound include triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, 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 ( Perfluoroanthryl) borane, tris (perf) Oro binaphthyl) borane, and the like.
Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenylyl) borane, tris (perfluoroanthryl) borane, tris (perfluorobinaphthyl) borane are more preferred, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (Perfluoronaphthyl) borane and tris (perfluorobiphenylyl) borane are preferred.

When the borate compound is specifically represented, the first example is a compound represented by the following general formula (IV).
^{[L 1 -H] + [BR} d R e X b X c] - (IV)
In formula (IV), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, phosphonium or the like. Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.
Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium.
Furthermore, examples of the phosphonium include triarylphosphonium such as triphenylphosphonium, tributylphosphonium, tri (methylphenyl) phosphonium, and tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

In formula (IV), R ^d and R ^e are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are connected to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine is preferable.
Furthermore, ^Xb and ^Xc are a hydride group, a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom containing 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by halogen atoms. It is a hydrogen group.

Specific examples of the compound represented by the general formula (IV) include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluorophene) L) borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5 -Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium Tetra (pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyl Ammonium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like.
Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.
Of these, most preferred are tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylaniline. Nitrotetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (perfluoronaphthyl) It is borate.

Moreover, the 2nd example of a borate compound is represented by the following general formula (V).
^{[L 2] + [BR d} R e X b X c] - (V)
In the formula (V), L ² is carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. A cation, a proton, etc. are mentioned. R ^d , R ^e , X ^b and X ^c are the same as defined in the general formula (IV).

  Specific examples of the compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 -Ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, sodium tetraphenyl borate, sodium tetra (o-tolyl) borate, sodium tetra (p-tolyl) borate, sodium Tora (m-tolyl) borate, sodium tetra (o-fluorophenyl) borate, sodium tetra (p-fluorophenyl) borate, sodium tetra (m-fluorophenyl) borate, sodium tetra (3,5-difluorophenyl) borate, sodium tetra (pentafluoro) Phenyl) borate, sodium tetra (2,6-ditrifluoromethylphenyl) borate, sodiumtetra (3,5-ditrifluoromethylphenyl) borate, sodiumtetra (perfluoronaphthyl) borate, hydrogentetraphenylborate-2diethylether, hydrogentetra ( 3,5-difluorophenyl) borate-2 diethyl ether, hydrogen tetra (pentafluorophenyl) borate-2 diethyl ether, hydride Examples include logentetra (2,6-ditrifluoromethylphenyl) borate · 2 diethyl ether, hydrogentetra (3,5-ditrifluoromethylphenyl) borate · 2 diethyl ether, hydrogentetra (perfluoronaphthyl) borate · 2 diethyl ether be able to.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, Sodium tetra (pentafluorophenyl) borate, sodium tetra (2,6-ditrifluoromethylphenyl) borate, sodium tetra (3,5-ditrifluoromethylphenyl) borate, soji Mutetra (perfluoronaphthyl) borate, hydrogentetra (pentafluorophenyl) borate-2 diethyl ether, hydrogentetra (2,6-ditrifluoromethylphenyl) borate-2 diethylether, hydrogentetra (3,5-ditrifluoromethylphenyl) ) Borate · 2 diethyl ether and hydrogen tetra (perfluoronaphthyl) borate · 2 diethyl ether are preferred.
More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) Methylphenyl) borate, sodium tetra (pentafluorophenyl) borate, sodiumtetra (2,6-ditrifluoromethylphenyl) borate, hydrogentetra (pentafluorophenyl) borate-2diethyl ether, hydrogentetra (2,6-ditrifluoromethylphenyl) ) Borate-2 diethyl ether and hydrogen tetra (3,5-ditrifluoromethylphenyl) borate-2 diethyl ether.

  As the component (B), a mixture of the organoaluminum oxy compound and the borane compound or borate compound can also be used. Further, two or more of the above borane compounds and borate compounds can be used in combination.

(Iii) Ion-exchange layered silicate The ion-exchange layered silicate component (B) (hereinafter sometimes simply referred to as “silicate”) is bonded to each other by surfaces formed by ionic bonds or the like. It refers to a silicate compound that has a crystal structure that is stacked in parallel by force and that can contain exchangeable ions. Various known silicates are known, and are specifically described in Shiramizu Haruo "Clay Mineralogy" Asakura Shoten (1995).
In the present invention, those preferably used as the component (B) belong to the smectite group, and specific examples include montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, and stevensite. Among these, montmorillonite is preferable in terms of the activity and molecular weight of the rubber component.
Since most silicates are naturally produced mainly as the main component of clay minerals, they often contain impurities (such as quartz and cristobalite) other than ion-exchanged layered silicates. Hybrids may be contained in the smectite silicate.

Granulation of ion-exchange layered silicate:
Silicates may be used in a dry state or in a slurry state in a liquid. In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate. Of these, the use of granulated silicate is particularly preferred because it gives good polymer particle properties.
The shape processing of the ion-exchange layered silicate such as granulation, pulverization, and classification may be performed before the acid treatment, or the shape may be processed after the acid treatment.

Acid treatment:
The silicate used in the present invention is used after being subjected to an acid treatment, but may be treated by combining other chemical treatments. Other chemical treatments include alkali treatment, salt treatment, organic matter treatment, and the like.
The acid treatment of the silicate can change the acid strength of the solid. In addition to the effect of ion exchange and removal of surface impurities, the acid treatment also has an effect of eluting part of cations such as Al, Fe, Mg, Li having a crystal structure.
Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Two or more of these may be used simultaneously. Of these, inorganic acids are preferable, sulfuric acid, hydrochloric acid and nitric acid are preferable, and sulfuric acid is more preferable.
In addition, a method in which acid treatment and salt treatment are combined is particularly preferable, a method in which acid treatment is performed after salt treatment, a method in which salt treatment is performed after acid treatment, a method in which salt treatment and acid treatment are performed simultaneously, salt treatment There is a method of performing salt treatment and acid treatment at the same time after the treatment.

Composition of silicate after acid treatment:
The acid-treated silicate which is the component (B) according to the present invention has an Al / Si atomic ratio of 0.01 to 0.29, preferably 0.03 to 0.25, and more preferably. Is preferably in the range of 0.05 to 0.23 in view of the activity of the polymerization catalyst and the molecular weight of the olefin polymer.
The Al / Si atomic ratio is an index of the acid treatment strength of the clay portion, and the method for controlling the Al / Si atomic ratio is controlled by adjusting the acid species for acid treatment, the acid concentration, the acid treatment time, and the temperature. can do.
Aluminum and silicon in the silicate are measured by a method in which a calibration curve is prepared by a chemical analysis method by JIS method and quantified by fluorescent X-rays.

(3) Component (C)
Component (C) is an organoaluminum compound.
An example of the organoaluminum compound is represented by the following general formula (VI).
AlR _a X _3-a (VI)
In the general formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a halogen, an alkoxy group, or a siloxy group, and a represents a number greater than 0 and 3 or less.
Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum, diethylaluminum monochloride, diethylaluminum mono Mention may be made of halogens such as methoxide or alkoxy-containing alkylaluminums. Of these, trialkylaluminum is preferred, and most preferred is trihexylaluminum or trioctylaluminum. Two or more of the above organoaluminum compounds may be used in combination.

(4) Catalyst Preparation Method In the preparation method of the catalyst for olefin polymerization according to the present invention, the contact method of component (A), component (B) and component (C) is not particularly limited, and a conventionally known method is used. Can be used.

When component (B) is an organoaluminum oxy compound, the molar ratio of component (A) to component (B) is preferably 1: 0.1 to 1: 100,000.
When component (B) is a boron compound, the molar ratio of component (A) to component (B) is preferably in the range of 1: 0.1 to 1: 100.
When component (C) is used, the molar ratio of component (A) to component (C) is preferably in the range of 1: 0.1 to 1: 10,000.

  When the component (B) is a silicate, the amount of the component (A) and the component (B) used is preferably 0.001 to 10 mmol of the metallocene compound of the component (A) with respect to 1 g of the component (B), more preferably 0. The range is 0.001 to 1 mmol. The amount of the component (C) used is such that the molar ratio of Al / metallocene compound is 0.1 or more and 100,000 or less, preferably 1 or more and 10,000 or less. These use ratios show examples of normal ratios, and the present invention is limited by the range of use ratios described above as long as the catalyst meets the purpose of the present invention. Must not.

2. Polymerization Conditions for Ethylene / α-Olefin Copolymer The present invention provides a solar cell by carrying out copolymerization under the following polymerization conditions (a1), preferably (a1 ′), using the above olefin polymerization catalyst. An ethylene / α-olefin copolymer suitable as a resin material for a sealing material is produced.
(A1) The propylene concentration in the reaction system is 10 to 49 mol%.
(A1 ′) The propylene concentration in the reaction system is 20 to 49 mol%.
Hereinafter, each polymerization condition will be described.
(1) Monomer Configuration The ethylene / α-olefin copolymer in the present invention is a random copolymer of ethylene and an α-olefin mainly composed of a structural unit derived from ethylene.
Two or more types of α-olefin can be used as the comonomer, and at least propylene is contained as a comonomer.
The α-olefin other than propylene used as a comonomer is an α-olefin having 4 to 20 carbon atoms, preferably 4 to 12 carbon atoms. Specifically, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene Etc.
Specific examples of such ethylene / α-olefin copolymers include ethylene / propylene copolymers, ethylene / propylene / 1-butene terpolymers, ethylene / propylene / 1-hexene terpolymers, ethylene / propylene copolymers, Examples include propylene / 1-octene terpolymers.

  Further, as comonomer other than propylene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 5-vinyl-2-norbornene, and 5-ethylidene A small amount of a diene such as 2-norbornene can also be used.

(2) Propylene concentration The propylene concentration in the reaction system is 10 to 49 mol%, preferably 20 to 49 mol%, more preferably 25 to 40 mol%.
When the propylene concentration is less than 10 mol%, the amount of vinyl and vinylidene in the produced polymer is small and the crosslinking properties are insufficient. On the other hand, if it exceeds 49 mol%, the propylene-propylene chain in the produced polymer increases, and molecular breakage is likely to occur, making it unsuitable for use as a solar cell encapsulant that requires durability.
In the present invention, by setting the propylene concentration in the reaction system within the above range, an ethylene / α-olefin copolymer having a large total number of vinyl and vinylidene can be obtained. This effect cannot be obtained when an α-olefin such as 1-hexene or 1-octene other than propylene is polymerized as a comonomer main component.

  When propylene is used as a comonomer within the above range, the detailed cause of the increase in the total number of vinyl and vinylidene during ethylene / α-olefin copolymerization is not known, but the results of insertion of propylene into the polymer chain during polymerization are as follows. The possible mechanism for the increase in vinylidene will be described with reference to the following figure.

In the upper side of the above figure, an intermediate is obtained by inserting an α-olefin such as 1-hexene or 1-octene into the polymer chain (P) in the polymerization reaction, and subsequently extracting the hydrogen at the β-position of the complex metal (M). 1 is generated. In this intermediate 1, the elimination reaction of (a) or (b) from hydrogen can be considered. However, due to steric and electronic factors, the hydrogen of (a) is preferentially eliminated and intermediate 2 becomes Arise. Further, a trisubstituted olefin or vinylidene is generated from the intermediate 2 depending on the insertion position of the next monomer, but the route in which the vinylidene is generated is sterically inserted between the complex metal (M) and the secondary carbon. Is difficult. Therefore, the intermediate 2 preferentially produces a trisubstituted olefin body through insertion of the complex metal (M) and primary carbon.
On the other hand, the lower side of the above figure shows that intermediate 3 is formed when propylene is inserted into the polymer chain (P) during the polymerization reaction and subsequently hydrogen at the β-position of the complex metal (M) is withdrawn. . In this intermediate 31 as well, the elimination reaction of (a) or (b) from hydrogen is conceivable. However, due to steric and electronic factors, hydrogen of (b) is preferentially eliminated and 4 is produced. Furthermore, vinylidene is generated regardless of which of the following monomers is inserted into intermediate 4.

  As shown in the above figure, after insertion of propylene, vinylidene is preferentially produced as compared with after insertion of α-olefin such as 1-hexene and 1-octene. In the present invention, the mechanism of occurrence of double bonds such as vinylidene is not limited to the above mechanism.

(3) Polymerization method In the present invention, the polymerization method can be carried out if the polymerization catalyst containing the metallocene compound represented by the general formula (I) and the monomer can efficiently come into contact with each other to polymerize or copolymerize the olefin. Although not particularly limited, a high pressure ion polymerization method, a gas phase method, a solution method, a slurry method, or the like can be used.

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

In the high-pressure ion polymerization, a preferable polymerization temperature is 125 to 300 ° C, more preferably 160 to 280 ° C, still more preferably 180 to 280 ° C, and a preferable polymerization pressure is 40 to 150 MPa, more preferably 50 to 125 MPa. It is.
Among these, in order to obtain an ethylene / olefin copolymer with adjusted double bonds according to the present invention, it is desirable to perform polymerization at a high temperature. "Chapter 4, edited by Kazuo Matsuura and Naotaka Mikami, 2001).

(4) Other conditions Moreover, even if a component for removing water, a so-called scavenger, is added to the polymerization system, it can be carried out without any trouble.
Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum, the organoaluminum oxy compound, and modified by modifying the organoaluminum compound with alcohols or phenols. Organic aluminum compounds, organic zinc compounds such as diethyl zinc and dibutyl zinc, organic magnesium compounds such as diethyl magnesium, dibutyl magnesium and ethyl butyl magnesium, and Grignard compounds such as ethyl magnesium chloride and butyl magnesium 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 adjusted effectively by adding hydrogen, the above-mentioned scavengers or the like as a chain transfer agent to the polymerization reaction system.

  The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature without any trouble.

  As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. The combination of the polymerization formats is not particularly limited, and a solution polymerization two-stage, bulk polymerization two-stage, gas phase polymerization after bulk polymerization, and two-stage gas phase polymerization are possible. It is also possible to manufacture with.

3. Characteristics of ethylene / α-olefin copolymer The ethylene / α-olefin copolymer in the invention preferably satisfies the following characteristics (b1).
(B1) The total number of vinyl and vinylidene double bonds in the ethylene / α-olefin copolymer is 0.50 (pieces / 1000 C main chain) or more (however, the number of vinyl and vinylidene is measured by NMR) Is the number of

(1) Each characteristic (i) Total number of vinyl and vinylidene The ethylene / α-olefin copolymer in the present invention is the total number of vinyl and vinylidene double bonds per 1000 carbon atoms measured by NMR. Is 0.50 (pieces / main chain 1000C) or more, preferably 0.50 to 5.0 (pieces / main chain 1000C), more preferably 0.60 to 4.5 (pieces / main chain 1000C). More preferably 0.70 to 4.0 (pieces / main chain 1000C), and most preferably 0.80 to 4.0 (pieces / main chain 1000C).
When the total number of vinyl and vinylidene is in the above range, a sealing material having an excellent crosslinking rate is obtained, and when it is less than 0.50, the crosslinking rate is not sufficient. The total number of vinyl and vinylidene can be controlled within the above range by appropriately selecting the appropriate metallocene catalyst, the polymerization temperature, and the type of comonomer.
In addition, the number of these double bonds is the number per 1000 carbon atoms of the main chain, and was calculated using the integrated intensity of the characteristic peaks of the ¹ H-NMR spectrum and ¹³ C-NMR spectrum.

(Ii) MFR
The MFR of the ethylene / α-olefin copolymer in the present invention is preferably 0.1 to 100 g / 10 minutes, more preferably 1 to 50 g / 10 minutes, and further preferably 2 to 40 g / 10 minutes. When the MFR of the ethylene / α-olefin copolymer is less than 0.1 g / 10 min, the molecular weight is too high and extrusion becomes difficult during kneading, and when the MFR exceeds 100 g / 10 min, the melt viscosity becomes too low, It becomes lacking in handleability.
In order to adjust the MFR of the polymer, for example, a method of appropriately adjusting the polymerization temperature, the catalyst amount, the supply amount of hydrogen as a molecular weight regulator, and the like is employed. The MFR of the ethylene / α-olefin copolymer is measured according to JIS-K6922-2: 1997 appendix (190 ° C., 21.18 N load).

(Iii) Density The ethylene / α-olefin copolymer in the present invention preferably has a density of 0.860 to 0.920 g / cm ³ , more preferably 0.865 to 0.910 g / cm ³ , and still more preferably. Is 0.870-0.900 g / cm ³ . When the density of the ethylene / α-olefin copolymer is less than 0.860 g / cm ³ , the processed sheet is blocked, and when the density exceeds 0.920 g / cm ³ , the transparency of the processed sheet is deteriorated. It is not preferable.
In order to adjust the density of the polymer, a method of appropriately adjusting the content of the α-olefin as a comonomer, the polymerization temperature, the amount of catalyst and the like is employed. The density of the ethylene / α-olefin copolymer is measured according to JIS-K6922-2: 1997 appendix (in the case of low density polyethylene) (23 ° C.).

  In addition, since the ethylene / α-olefin copolymer in the present invention is excellent in radical crosslinking properties, it can be used as a substitute for a crosslinked olefin rubber (EPDM). In other words, using the EPDM utilization method such as 1) crosslinking by using an organic peroxide or sulfur as a crosslinking agent, and 2) combining with other thermoplastic resins to form a dynamically crosslinked thermoplastic elastomer, A material having a crosslinked structure can be produced. The materials obtained by these methods have long-term durability, and are excellent in light resistance and heat resistance, so that they are used for applications such as automobile parts, electric wires and cables.

4). Resin Composition for Solar Cell Encapsulant The resin composition for a solar cell encapsulant of the present invention has excellent crosslinkability by including the ethylene / α-olefin copolymer. Moreover, the resin composition in this invention can contain an organic peroxide, a hindered amine light stabilizer, etc. as components other than a resin component.
Specific examples of additive components that can be used will be described below.

(1) Organic peroxide As the organic peroxide used in the present invention, an organic peroxide having a decomposition temperature (temperature at which the half-life is 1 hour) is 70 to 180 ° C, particularly 90 to 160 ° C. Can do. Examples of such organic peroxides include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, 2 , 5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1 , 1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5- Diperoxybenzoate, t-butyl hydroperoxide, p-menthane hydroperoxy Id, benzoyl peroxide, p- chlorobenzoyl peroxide, t- butyl peroxy isobutyrate, hydroxyheptyl peroxide, and di cyclohexanone peroxide.

  The blending ratio of the organic peroxide is preferably 0.2 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, further preferably 1 when the resin component is 100 parts by weight. ~ 2 parts by weight. When the blending ratio of the organic peroxide is less than the above range, crosslinking is not performed or it takes time for crosslinking. Moreover, when larger than the said range, dispersion | distribution will become inadequate and it will be easy to become non-uniform | crosslinked.

(2) Hindered amine light stabilizer The hindered amine light stabilizer captures radical species harmful to the polymer and prevents generation of new radicals. There are many types of hindered amine light stabilizers from low molecular weight compounds to high molecular weight compounds, and the hindered amine light stabilizers used in the present invention are particularly known as long as they are conventionally known. It can be used without limitation.

  Low molecular weight hindered amine light stabilizers include decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and Consists of 70% by weight of a 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] butyl malonate (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 ( 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-butane Mixture of tetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate (molecular weight 900); 1,2,2,6,6-pentamethyl-4-piperidyl-1,2,3,4-butane Examples thereof include a mixture (molecular weight 900) of tetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate.

  As the high molecular weight hindered amine 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 Polymer of dimethyl and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (molecular weight 3,100 to 4,000); N, N ′, N ″, N ″ ′-tetrakis- ( 4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10- Diamine (molecular weight 2,286) and above A mixture of 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 polycondensate (molecular weight 2,600-3) 400) and 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-pentamethyl Peridine, 4-methacryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy Examples include copolymers of cyclic aminovinyl compounds such as -2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-1-propyl-2,2,6,6-tetramethylpiperidine and ethylene. The above-mentioned hindered amine light stabilizers may be used alone or in combination of two or more.

  Among these, as the hindered amine 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); Polymer of dimethyl acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (molecular weight 3,100 to 4,000); N, N ′, N ″, N ″ ′-tetrakis- (4,6-Bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10 -Diamine (molecular weight 2,286) A mixture of 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 polycondensate (molecular weight 2,600) ~ 3,400) It is preferable to use a copolymer of a cyclic aminovinyl compound and ethylene, because the hindered amine light stabilizer is prevented from bleeding out over time when the product is used. An agent having a melting point of 60 ° C. or higher is preferably used from the viewpoint of easy preparation of the composition.

In the present invention, the content of the hindered amine light stabilizer is preferably 0.01 to 2.5 parts by weight, more preferably 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the resin component. Parts, 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.
By making the content of the hindered amine light stabilizer 0.01 parts by weight or more, a sufficient effect for stabilization can be obtained, and by making the content 2.5 parts by weight or less, an excess of the hindered amine light stabilizer can be obtained. Discoloration of the resin due to the addition can be suppressed.
In the present invention, the weight ratio of the organic peroxide to the hindered amine light stabilizer (organic peroxide: hindered amine light stabilizer) is preferably 1: 0.01 to 1:10, and more Preferably it is set to 1: 0.02 to 1: 6.5. Thereby, it becomes possible to remarkably suppress yellowing of the resin.

(3) Crosslinking aid A crosslinking aid may be added to the resin composition in the present invention. The crosslinking aid is effective in promoting the crosslinking reaction and increasing the degree of crosslinking of the ethylene / α-olefin copolymer. Specific examples thereof include polyaryl 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, etc. Examples include poly (meth) acryloxy compounds and divinylbenzene. The crosslinking aid can be blended at a ratio of about 0 to 5 parts by weight with respect to 100 parts by weight of the resin component.

(4) Ultraviolet absorber An ultraviolet absorber can be mix | blended with the resin composition of this invention. Examples of the ultraviolet absorber include various types such as benzophenone, benzotriazole, triazine, and salicylic acid ester.
Examples of benzophenone-based ultraviolet absorbers 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 2,2-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, etc. To mention Can.

The benzotriazole ultraviolet absorber is a hydroxyphenyl-substituted benzotriazole compound, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 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, and the like. Can be mentioned. Examples of triazine ultraviolet absorbers include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- ( And 4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) phenol. Examples of salicylic acid esters include phenyl salicylate and p-octylphenyl salicylate.
These ultraviolet absorbers are blended in an amount of 0 to 2.0 parts by weight, preferably 0.05 to 2.0 parts by weight, more preferably 0.1 to 1 part, per 100 parts by weight of the ethylene / α-olefin copolymer. 0.0 part by weight, more preferably 0.1 to 0.5 part by weight, and most preferably 0.2 to 0.4 part by weight.

(5) Silane Coupling Agent A silane coupling agent can be used in the resin composition of the present invention mainly for the purpose of improving the adhesion between the solar cell upper protective material and the solar cell element.
Examples of the silane coupling agent in the present invention include γ-chloropropyltrimethoxysilane; vinyltrichlorosilane; vinyltriethoxysilane; vinyltrimethoxysilane; vinyl-tris- (β-methoxyethoxy) silane; γ-methacryloxypropyl. Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane; vinyltriacetoxysilane; γ-mercaptopropyltrimethoxysilane; γ-aminopropyltrimethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane and the like can be mentioned. Vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane are preferable.
These silane coupling agents are used in an amount of 0 to 5 parts by weight, preferably 0.01 to 4 parts by weight, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer. More preferably, it is used at 0.05 to 1 part by weight.

(6) Others As optional components that can be blended in the resin composition of the present invention, other than the above, antioxidants, crystal nucleating agents, clearing agents, lubricants, coloring used in ordinary polyolefin resin materials Agents, dispersants, fillers, fluorescent brighteners, ultraviolet absorbers, light stabilizers and the like.

  Further, in order to impart flexibility and the like to the resin composition of the present invention, a crystalline ethylene / α-olefin copolymer polymerized by a Ziegler-based or metallocene-based catalyst within a range not impairing the object of the present invention. And / or rubber compounds such as ethylene / propylene elastomers such as EBR and EPR, or styrene elastomers such as SEBS and hydrogenated styrene block copolymers may be blended in an amount of 3 to 75 parts by weight. Furthermore, in order to give melt tension etc., 3-75 weight part of high pressure process low density polyethylene can also be mix | blended.

5. Solar cell encapsulant and solar cell module The solar cell encapsulant of the present invention (hereinafter also simply referred to as “encapsulant”) is obtained by pelletizing or forming a sheet of the resin composition.
If this sealing material is used, a solar cell module can be manufactured by fixing a solar cell element with upper and lower protective materials. Examples of such solar cell modules include various types. For example, the upper transparent protective material / encapsulant / solar cell element / encapsulant / lower protective material sandwiched between the solar cell elements from both sides, formed on the inner peripheral surface of the lower substrate protective material A solar cell element formed on the inner peripheral surface of the upper transparent protective material, for example, a fluororesin-based transparent protective material. The thing of the structure which forms a sealing material and a lower protective material on what created the amorphous solar cell element by sputtering etc. can be mentioned.

  The solar cell element is not particularly limited, and is based on silicon such as single crystal silicon, polycrystalline silicon, amorphous silicon, III-V group or II-VI group such as gallium-arsenic, copper-indium-selenium, cadmium-tellurium. Various solar cell elements such as compound semiconductors can be used. In the present invention, those using glass as the substrate are preferred.

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 multilayer 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. Examples of the protective material include a single layer or a multilayer such as a containing resin and polyolefin. Such an upper and / or lower protective material can be subjected to a primer treatment in order to enhance the adhesion to the sealing material. In the present invention, glass is preferred as the upper protective material.

  The solar cell encapsulant of the present invention may be used as a pellet, but is usually used after being formed into a sheet having a thickness of about 0.1 to 1 mm. If the thickness is less than 0.1 mm, the strength is small and the adhesion is insufficient. If the thickness is more than 1 mm, the transparency may be lowered, which may be a problem. A preferred thickness is 0.1 to 0.8 mm.

  The sheet-like solar cell encapsulant can be produced 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 light stabilizer, a cross-linking aid, a silane coupling agent, an ultraviolet absorber, an antioxidant, and a light stabilizer. An additive such as an agent can be dry-blended in advance and supplied from a hopper of a T-die extruder, and extruded into a sheet at an extrusion temperature of 80 to 150 ° C. In these dry blends, some or all of the additives can be used in the form of a masterbatch. In addition, in T-die extrusion or calendar molding, a part or all of the additive is previously melt-mixed into the amorphous propylene copolymer using a single screw extruder, twin screw extruder, Banbury mixer, kneader or the like. The obtained resin composition can also be used.

When manufactured by a T-die extruder, the MFR of the ethylene / α-olefin copolymer is preferably 10 to 50 g / 10 minutes, more preferably 12 to 45 g / 10 minutes, and further preferably 15 to 40 g / minute. 10 minutes. When the MFR of the ethylene / α-olefin copolymer is less than 10 g / 10 min, the molecular weight is too high and extrusion during kneading becomes difficult, and when the MFR exceeds 50 g / 10 min, the melt viscosity becomes too low and the handling property is too high. It will be lacking.
When manufactured by calendar molding, the MFR of the ethylene / α-olefin copolymer is preferably 1 to 10 g / 10 minutes, more preferably 1.5 to 8.5 g / 10 minutes, and further preferably 2 to 7 g. / 10 minutes. If the MFR of the ethylene / α-olefin copolymer is less than 1 g / 10 min, the molecular weight is too high, and shear heat generation occurs during kneading, making it difficult to produce an uncrosslinked sheet. If the MFR exceeds 10 g / 10 min, the melt viscosity Becomes too low, and the handleability in calender molding is lacking.

The formed sheet is wound around a paper tube for easy storage and transportation. At this time, the sheets may adhere to each other (blocking may occur). If blocking occurs, when the sheet is fed out and used in the next step, it cannot be stably fed out, resulting in a decrease in productivity.
In order to avoid blocking between the sheets, the sheet surface may be formed by a conventionally known method so that the surface of the sheet has a mat-like shape. Specifically, in T-die extrusion or calender sheet formation, the molten sheet is cooled by being sandwiched between a cooling roll and a pressing roll whose surface has been processed into a mat / emboss shape, and then cooled on the mat surface. Embossed shape can be transferred.

  In producing the solar cell module of the present invention, a sheet of the sealing material of the present invention is prepared in advance, and the resin composition of the sealing material is melt-bonded at a temperature, for example, 150 to 200 ° C. A module having the above-described configuration can be formed. Moreover, the method of laminating | stacking with a solar cell element, an upper protection material, or a lower protection material by extrusion-coating the sealing material of this invention is also employable. In this method, it is possible to manufacture a solar cell module in one step without bothering to form a sheet, and the productivity of the module can be significantly improved.

  On the other hand, when manufacturing the solar cell module of the present invention, the sealing is performed on the solar cell element or the protective material at a temperature at which the organic peroxide is not substantially decomposed and the sealing material of the present invention is melted. The material can be temporarily bonded and then heated to perform sufficient bonding and cross-linking of the ethylene / α-olefin copolymer. In this case, in order to obtain a solar cell module having good heat resistance, the gel fraction in the sealing material layer (1 g of sample was immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, and then filtered through a 20 mesh wire mesh. Crosslinking is preferably performed so that the mass fraction of unmelted portion is 50 to 98%, preferably about 60 to 95%.

  In the sealing operation of the solar cell element, after the solar cell element is covered with the solar cell sealing material of the present invention, it is temporarily bonded by heating to a temperature at which the organic peroxide is not decomposed for several minutes to 10 minutes. In addition, there is a method in which an organic peroxide is decomposed in an oven at a high temperature of about 150 to 200 ° C. for 5 to 30 minutes for adhesion.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation methods and resins used in the examples and comparative examples are as follows.

1. Evaluation method of resin physical properties (1) Melt flow rate (MFR): MFR of ethylene / α-olefin copolymer is measured according to JIS-K6922-2: 1997 appendix (190 ° C., 21.18 N load). did.
(2) Density: The density of the ethylene / α-olefin copolymer was measured according to JIS-K6922-2: 1997 appendix (in the case of 23 ° C., low density polyethylene).
(3) Number of double bonds, number of comonomers: terminal vinyl, vinylidene, vinylene (including cis-vinylene and trans-vinylene), the number of trisubstituted olefins are as follows according to ¹ H-NMR and ¹³ C-NMR. The amount of comonomer was determined by the number of carbon per 1000 main chains.
Equipment: Bruker BioSpin Corporation AVANCEIII cryo-400MHz
Solvent: o-dichlorobenzene / deuterated bromobenzene = 8/2 mixed solution <sample amount>
460mg / 2.3ml
< ^13C -NMR>
・¹ H decouple and NOE ・ Accumulation count: 256scan
・ Flip angle: 90 °
・ Pulse interval 20 seconds ・ AQ (acquisition time) = 5.45 s D1 (waiting time) = 14.55 s
^<1 H-NMR>
・ Accumulation count: 1400scan
・ Flip angle: 1.03 °
AQ (loading time) = 1.8 s D1 (waiting time) = 0.01 s
(3) Mz / Mn: measured by GPC.
Apparatus: GPC 150C type manufactured by Waters Inc. Detector: 1A infrared spectrophotometer manufactured by MIRAN (measurement wavelength: 3.42 μm)
Column: Showa Denko 3 AD806M / S (column calibration is Tosoh monodispersed polystyrene (0.5 mg / ml solution of each of A500, A2500, F1, F2, F4, F10, F20, F40, and F288) The logarithmic value of the elution volume and molecular weight was approximated by a quadratic equation, and the molecular weight of the sample was converted to polyethylene using the viscosity equation of polystyrene and polyethylene, where the coefficient of the viscosity equation of polystyrene is α = 0.723, log K = -3.967, polyethylene is α = 0.733, log K = -3.407.)
Measurement temperature: 140 ° C
Concentration: 10 mg / 10 mL
Injection volume: 0.2ml
Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min

2. Evaluation method of extruded product (sheet) (1) 150 ° C. gel fraction (crosslinking property)
The sheet produced as a solar cell encapsulant by the method described later was crosslinked at 150 ° C. for 4, 7, 10 and 30 minutes, and evaluated by the gel fraction of the sheet. It can be evaluated that the higher the gel fraction, the more the crosslinking proceeds and the higher the heat resistance. For the gel fraction, about 1 g of the sheet was cut out and weighed accurately, immersed in 100 cc of xylene, treated at 110 ° C. for 24 hours, the residue after filtration was dried and precisely weighed, and the gel fraction was divided by the weight before treatment. Calculate the rate.

3. Preparation of catalyst for olefin polymerization (1) Component (A): Synthesis of metallocene compound Metallocene compound A: Synthesis of isopropylidenebis (4-phenyl-1-indenyl) dimethylhafnium

(I) Synthesis of 4-phenyl-indene Synthesized according to the method described in JP-A-2008-101034.
(Ii) Synthesis of 2,2-bis (4-phenyl-inden-1-yl) propane In a 100 mL glass reaction vessel, 1.00 g (5.21 mmol) of 4-phenyl-indene, 1,2-dimethoxyethane (DME) 10mL and potassium hydroxide 0.583g (10.4mmol) were added, and it heated and refluxed at 90 degreeC for 1 hour. The reaction solution was cooled to 0 ° C., 0.151 g (2.60 mmol) of acetone was added, and the mixture was heated to reflux at 90 ° C. for 6 hours. The reaction solution was cooled to room temperature, 20 mL of distilled water was added, then transferred to a separatory funnel, extracted three times with ethyl acetate, and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (developing solvent, dichloromethane: petroleum ether = 1: 20), whereby 2,2-bis ( 0.45 g of 4-phenyl-inden-1-yl) propane was obtained as a light yellow solid (41% yield).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.52 (dd, 4H), 7.44 (t, 4H), 7.41-7.34 (m, 4H), 7.16 (t, 2H) , 7.11 (dd, 2H), 6.59 (t, 2H), 3.48 (d, 2H), 1.81 (s, 6H).
(Iii) Synthesis of isopropylidenebis (4-phenyl-1-indenyl) hafnium dichloride 2,2-bis (4-phenyl-indene-1- Yl) 1.50 g (3.5 mmol) of propane was added and dissolved by adding 70 ml of toluene and 15 ml of diethyl ether. The solution was cooled to −70 ° C. in a dry ice-isopropyl alcohol bath, 4.7 ml (7.5 mmol) of n-butyllithium / hexane (1.59 M solution) was added, and the mixture was stirred for 40 minutes. The cooling bath was removed, the temperature was raised to 20 ° C., and the solvent was distilled off after maintaining for 1 hour. 70 ml of toluene and 3 ml of diethyl ether were added and dissolved therein, and cooled to -70 ° C. Hafnium tetrachloride (1.25 g, 3.9 mmol) was added, the cooling bath was immediately removed, and the temperature was gradually raised to room temperature. The steric composition of the obtained complex was racemic: meso = 33: 67 from 1H NMR. The solvent was distilled off, 60 ml of DME was added, and the mixture was heated and stirred at 60 ° C. for 3 hours. By this operation, the steric composition of the complex became racemic: meso = 93: 7. The precipitate after removing the supernatant with decant was dissolved in dichloromethane, and the insoluble material was removed by filtration. The solid obtained by concentrating the filtrate was washed with a small amount of toluene and dried under reduced pressure, and yellow powdery solid isopropylidenebis (4-phenyl-1-indenyl) hafnium dichloride was obtained with a racemic purity of 100% and a yield of 1. 25 g, 53% yield.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.78 (d, J = 8.8 Hz, 2H), 7.57 (dd, J = 8.3 Hz, 4H), 7.42 (t, J = 7 .1 Hz, 4H), 7.34 (t, J = 7.3 Hz, 2H), 7.26 (d, J = 6.3 Hz, 2H), 7.13-7.09 (m, 2H), 6 .72 (dd, J = 3.6 Hz, 2H), 6.18 (d, J = 3.6 Hz, 2H), 2.41 (s, 6H).
(Iv) Synthesis of isopropylidenebis (4-phenyl-1-indenyl) dimethylhafnium In a 100 ml branch flask containing a rotator, 0.51 g of isopropylidenebis (4-phenyl-1-indenyl) hafnium dichloride (0. 76 mmol) and 40 ml of toluene were added and dissolved. The mixture was cooled to 0 ° C. in an ice bath, 1.8 ml (5.4 mmol) of methylmagnesium bromide / diethyl ether (3.0 M solution) was added, and the mixture was heated and stirred at 40 ° C. for 11 hours. At room temperature, 0.47 ml (3.7 mmol) of trimethylsilyl chloride was added and stirred for 30 minutes, and then 10 ml of dioxane was added and stirred for 30 minutes. Insoluble matter was removed by filtration, and the filtrate was concentrated to give a yellow solid. This was washed with a small amount of hexane, the supernatant was removed with decant, and dried under reduced pressure. Obtained in 66% yield.
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.69 (dd, J = 8.4 Hz, 4H), 7.35 (d, J = 9.0 Hz, 2H), 7.22 (t, J = 7.6 Hz, 4H), 7.15-7.09 (m, 4H), 6.84-6.80 (m, 4H), 5.57 (d, J = 3.5 Hz, 2H), 1 .77 (s, 6H), -0.99 (s, 6H).

Metallocene compound B: Synthesis of dimethylsilylene bis (4-phenyl-1-indenyl) dimethylhafnium

(I) Synthesis of dimethylbis (4-phenylinden-1-yl) silane The compound was synthesized according to the method described in the literature (Oraganometallics 1994, 13, 954-963).
(Ii) Synthesis of racemic-dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride In a 200 ml glass reaction vessel, 4.90 g (11.1 mmol) of dimethylbis (4-phenylinden-1-yl) silane Then, 110 ml of diethyl ether was added, and the mixture was cooled to −70 ° C. in a dry ice-heptane bath. A 1.62 mol / L n-butyllithium-n-hexane solution (14.0 ml, 22.7 mmol) 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. Thereto was added 3.56 g (11.1 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 17 hours while gradually returning to room temperature. The production ratio of the racemic body and the meso body at this time was 55:45.
After adding 200 mL of dichloromethane and filtering through Celite, recrystallization in toluene gave 2.23 g of a racemic dimethylsilylene bis (4-phenyl-1-indenyl) hafnium dichloride as an orange solid (yield 29). %).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.63 (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 In a 100 ml glass reaction vessel, 1.20 g (1.56 mmol) of dimethylsilylenebis (4-phenyl-1-indenyl) hafnium dichloride ), Toluene (50 mL) was added, and a 3.0 mol / L methylmagnesium bromide-diethyl ether solution (3.6 mL, 10.8 mmol) was added dropwise at room temperature, followed by stirring 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 was added and stirred at room temperature for 30 minutes, followed by 2.0 mL (23.4 mmol) of 1,4-dioxane. The mixture was further stirred at room temperature for 30 minutes. The suspension was filtered through celite, and the solvent was evaporated 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 with 5 mL of hexane three times to obtain a racemic dimethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium. 837 mg was obtained as a yellow solid (yield 85%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.70 (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).

(2) Production of ethylene / α-olefin copolymer High-pressure ion polymerization: ethylene / propylene / 1-hexene copolymer The polymerization reactions of Examples 1 to 10 and Comparative Examples 1 to 8 shown in Table 1 were sufficiently dried. And in a 5.0 L stainless steel autoclave reactor (with a stirrer) substituted with nitrogen. The supply of the raw material is continuously performed so that the total of the raw material gases is 40 kg / hour while maintaining the ratio of ethylene, propylene, and 1-hexene shown in Table 1, and the pressure is adjusted to about 80 MPa with a pressure adjusting valve on the discharge side Kept. The polymerization temperature was controlled by the catalyst feed rate. Moreover, the tri (n-octyl) aluminum (component (C)) / heptane solution prepared to 30 mg / L as a scavenger was supplied continuously.
The metallocene compound (component (A)) and the co-catalyst Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] (component (B)) were separately prepared in toluene solutions (each 20 −50 mg / L, 37-120 mg / L), and the mixture was continuously fed to the polymerization system while being mixed in the piping so that the molar ratio of the metallocene compound to the promoter was 1: 1.5.
Table 1 shows the polymerization conditions such as the metallocene compound used, the molar ratio of each monomer supplied, and the polymerization temperature in each of Examples 1 to 10 and Comparative Examples 1 to 8, and the MFR, density, and NMR measurements of the obtained polymer. The obtained propylene / hexene content and various olefin contents were described.

Solution Polymerization: Ethylene / Propylene Copolymerization (Example 11) To a 2.4 L stainless steel autoclave (stirring with temperature controller) sufficiently dried and substituted with nitrogen, 1000 mL of toluene, tri (n-octyl) aluminum 15 mmol and 10 mL of propylene were added and the temperature was raised to 100 degrees. After the temperature in the reactor was stabilized, the pressure was increased to 0.5 MPaG as the ethylene partial pressure, and the molar ratio of ethylene and propylene in the gas phase was measured by gas chromatography. The composition of ethylene and propylene dissolved in the liquid phase part is calculated from the feed amount of ethylene and propylene, the volume of the gas phase part and the analysis value of gas chromatography, and the monomer composition (molar ratio of ethylene and propylene in the liquid phase is 88 / 12) was calculated. Thereafter, the metallocene compound A 0.3 μmol-toluene 1 mL solution and the cocatalyst [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] 0.3 μmol-toluene 1 mL solution were contacted at room temperature and under nitrogen. Thereafter, the solution stirred for 10 minutes at room temperature was injected with nitrogen to initiate polymerization. Thereafter, ethylene was fed so as to maintain the internal pressure at the start of polymerization, and polymerization was carried out for 15 minutes while stirring. The reaction was stopped by press-fitting ethanol with nitrogen, and the toluene containing the polymer was recovered after the temperature was lowered. 1000 ml of acetone was added thereto to precipitate a polymer, followed by filtration to obtain a polymer. The polymer yield was 7.2 g.

(Comparative Example 9) Polymerization was carried out in the same manner as in Example 11 except that the amount of propylene was changed to 5 ml. The molar ratio of ethylene and propylene in the liquid phase at that time was 94/6. The polymer yield was 7.2 g.
Table 2 shows the MFR, density, and propylene content determined from NMR measurement of the polymers obtained in Example 11 and Comparative Example 9, and various olefin contents.

4). Manufacture of solar cell encapsulant For 100 parts by weight of the ethylene / α-olefin copolymer obtained above, t-butylperoxy-2-ethylhexyl carbonate (manufactured by Arkema Yoshitomi Co., Ltd.) is used as the organic peroxide. , TBEC) as a hindered amine light stabilizer, a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (manufactured by BASF, TINUVIN) 622LD) 0.05 part by weight, as a UV absorber, 2-hydroxy-4-n-octoxybenzophenone (CYTEC UV531 manufactured by Sun Chemical Co., Ltd.) 0.3 part by weight, and as a silane coupling agent, γ-methacryloxypropyltri 0.3 parts by weight of methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503), as an antioxidant, n-octane Decyl-3- (3 ', 5'-di -t- butyl-4'-hydroxyphenyl) propionate (BASF Corp. IRGANOX (R) 1076) was blended 0.025 part by weight. 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 sheet having a thickness of 0.7 mm was produced by cooling for 10 minutes in a cooling press set to 30 ° C. under a pressure of 100 kg / cm ² . The cross-linking properties of the sheet were evaluated. The evaluation results are shown in Table 1.

[Consideration of Comparison Results of Examples and Comparative Examples]
As apparent from Tables 1 and 2, from Examples 1 to 4 and Comparative Examples 1 and 2, and Example 11 and Comparative Example 9 which are polymerization results at the same polymerization temperature, the amount of vinyl + vinylidene was increased during polymerization. It can be seen that it is effective to increase the propylene concentration. It can also be seen that when the propylene concentration is 10% or more, it is possible to obtain a resin composition having a vinyl + vinylidene content exceeding 0.5 per 1000 carbons of the main chain. Further, by comparing Examples 9 and 10 and Comparative Example 8, it can be seen that the content of vinyl + vinylidene exceeds 0.5 per 1000 carbons of the main chain when the propylene concentration is 10% or more even in complex B.
In addition, by comparing Examples 4 and 5 and Examples 6 to 8, it can be seen that increasing the polymerization temperature is effective for increasing the amount of vinyl + vinylidene. In addition, when Examples 1 to 4 were compared with Comparative Examples 5 and 6 and Example 9 and Comparative Example 8 were used other than propylene as a comonomer, the amount of vinyl + vinylidene produced was small, and the comonomer concentration was 10% or more. It can be seen that the number of carbon atoms does not exceed 0.5 per 1000 carbons in the main chain.

  Verification of effect on cross-linking rate: Cross-linking rate depends on MFR of polymer in addition to the number of vinyl / vinylidene, so cross-linking characteristics (heat resistance) of polymers having different vinyl / vinylidene numbers with comparable MFR were compared. . Comparing Example 1 with an MFR of about 2 and Comparative Example 5 and Comparative Example 8, Example 3 with an MFR of about 6.5 and Comparative Example 6, and Example 4 with an MFR of about 25 and Comparative Example 7, It can be seen that the example having a larger number of vinyl + vinylidene has better heat resistance since the gel fraction has a larger value.

  As is apparent from the above, when ethylene / α-olefin copolymerization using metallocene is used with a certain concentration (10 mol%) or more of propylene as a comonomer, the amount of vinyl and vinylidene in the polymer to be produced increases (main chain 1000 The number per carbon is 0.50 or more), and it is possible to produce a resin composition in which the crosslinking characteristics required for the sealing material are greatly improved, and the industrial value is extremely high.

  The method for producing a resin composition for a solar cell encapsulant of the present invention uses a vinyl and ethylene / α-olefin copolymer having a high vinylidene number as a resin material, so that it has excellent cross-linking properties and can be cross-linked in a short time. A possible solar cell encapsulant can be provided. In addition, by using the solar cell encapsulant, it is possible to provide a solar cell module that is excellent in heat resistance, transparency, and weather resistance, and that has a reduced manufacturing cost, and has extremely high industrial value.

Claims (10)

A method for producing a resin composition for a solar cell encapsulant comprising an ethylene / α-olefin copolymer and an organic peroxide,
The above-mentioned ethylene / α-olefin copolymer is obtained by carrying out copolymerization under the conditions of (a1) below using an olefin polymerization catalyst containing the following component (A): A method for producing a resin composition for a stopper.
Component (A): Metallocene compound (a1) The propylene concentration in the reaction system is 10 to 49 mol%. The method for producing a resin composition for a solar cell sealing material according to claim 1, wherein the copolymerization is performed under the following condition (a1 ').
(A1 ′) The propylene concentration in the reaction system is 20 to 49 mol%. Component (A) is a metallocene compound represented by the following general formula (I), The manufacturing method of the resin composition for solar cell sealing materials of Claim 1 or 2 characterized by the above-mentioned.

[In general formula (I), M is Ti, Zr, or Hf;
R ¹ -R ¹⁰ and R ¹¹ -R ²⁰ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. C1-C20 alkyl substituted with an aryl group, a C1-C10 alkoxy group, a silyl group having a C1-C6 hydrocarbon group, or a silyl group having a C1-C6 hydrocarbon group Group, —NR ²³ ₂ group, —SR ²³ group, —OSiR ²³ ₃ group or —PR ²³ ₂ group (R ²³ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl having 6 to 20 carbon atoms) R ¹ -R ¹⁰ and R ¹¹ -R ²⁰ may form one or more aromatic or aliphatic rings together with the atoms connecting them between adjacent R groups. , ^{R 5} and ^{R 6} or ^{R 5} and ^{R 1} , They may form a single aromatic ring or an aliphatic ring together with the atoms to which R ¹⁵ and R ¹⁶ or R ¹⁵ and R ²⁰ are linked to them;
Y is Si or C;
R ²¹ and R ²² are the same or different and are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, C6-C10 fluoroaryl groups, C6-C10 aryloxy groups, C2-C10 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 An alkylaryl group, an arylalkenyl group having 8 to 40 carbon atoms, and R ²¹ and R ²² are not hydrogen atoms at the same time, and R ²¹ and R ²² together with the atoms connecting them are one or more May form a ring;
X ¹ and X ² are the same or different and are each 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, or an aryloxy having 6 to 10 carbon atoms. Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms 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 neutral ligand capable of coordination, which is substituted with a silyl group having X ¹ and X ² , Together with atoms connecting them, may form a ring. ] The said olefin polymerization catalyst contains the following component (B), The manufacturing method of the resin composition for solar cell sealing materials in any one of Claims 1-3 characterized by the above-mentioned.
Component (B): Compound or ion-exchangeable layered silicate that reacts with component (A) to form an ion pair The said olefin polymerization catalyst contains the following component (C), The manufacturing method of the resin composition for solar cell sealing materials in any one of Claims 1-4 characterized by the above-mentioned.
Component (C): Organoaluminum compound   Component (B) is a boron compound, The manufacturing method of the resin composition for solar cell sealing materials in any one of Claims 1-5 characterized by the above-mentioned.   In general formula (I), Y is a carbon atom, The manufacturing method of the resin composition for solar cell sealing materials in any one of Claims 3-5 characterized by the above-mentioned. The method for producing a resin composition for a solar cell encapsulant according to any one of claims 1 to 7, wherein the ethylene / α-olefin copolymer has the following property (b1).
(B1) The total number of vinyl and vinylidene double bonds in the ethylene / α-olefin copolymer is 0.50 (pieces / 1000 C main chain) or more (however, the number of vinyl and vinylidene is measured by NMR) Is the number of   A solar cell encapsulant comprising the resin composition produced by the method according to claim 8.   A solar cell module using the solar cell encapsulant manufactured by the method according to claim 9.