JP5227237B2 - α-Olefin / Cyclic Olefin Copolymer, Process for Producing the Same, and Molded Body Containing α-Olefin / Cyclic Olefin Copolymer - Google Patents

Description

  The present invention relates to an α-olefin / cyclic olefin copolymer suitable as an optical material, and more specifically, an α-olefin / cyclic olefin copolymer exhibiting a high refractive index and a low Abbe number, and a method for producing the same, The present invention relates to optical parts such as molded articles, optical lenses, films and the like containing the α-olefin / cyclic olefin copolymer.

  Glass that has been widely used as an optical material / optical component for a long time has characteristics of high transparency, high refractive index, and extremely low birefringence. However, since glass is inferior in moldability and has the disadvantages that it is difficult to reduce the weight, recently, polymer materials such as polymethyl methacrylate (PMMA) and polycarbonate (PC) that are lightweight and excellent in moldability are optical materials. It is used as an optical component.

  However, PMMA is preferable in that it is excellent in transparency and low in birefringence, but has the disadvantages of low refractive index and low heat resistance. Although PC is superior to PMMA in both refractive index and heat resistance, a higher refractive index may be required depending on the application, but it is often difficult to satisfy the requirements.

  On the other hand, an α-olefin / cyclic olefin copolymer obtained by copolymerizing an α-olefin and a specific cyclic olefin is excellent in optical properties, mechanical properties, thermal properties, etc., and has a good balance between these, for example, It is used as an optical material for optical memory disks and optical fibers.

  In the patent documents 1 to 3, the present applicant has excellent transparency, a copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene, low birefringence, heat resistance, and chemical resistance. It has been found and proposed that it is a polymer with balanced mechanical strength and is suitable for optical parts such as optical lenses.

By the way, depending on the application used in the optical lens, even the ethylene / tetracyclododecene copolymer may have insufficient optical characteristics such as refractive index and bleeding.
As a characteristic of the optical lens, if the refractive index is high, the focal length can be shortened, and the thickness of the lens can be reduced. In addition, it is known that if a lens having a low Abbe number is obtained, effects such as a small dispersion of light, an increase in resolution, and no blurring are manifested when used in combination with a lens having a high Abbe number. Such optical characteristics become more prominent as the difference in Abbe number of the combined lenses increases.

JP-A-62-252406 JP 2005-330465 A JP 2004-331965 A

  An object of the present invention is to solve the problems associated with the prior art as described above, and to provide an α-olefin / cyclic olefin copolymer having a high refractive index and a low Abbe number and a method for producing the same. It is. Another object of the present invention is to provide optical components such as optical lenses and films containing the α-olefin / cycloolefin copolymer as described above.

  As a result of diligent studies to solve the above problems, the present inventors have used a cyclic olefin having a specific structure as a constituent monomer of a copolymer, thereby producing an α-olefin / cyclic olefin having a high refractive index and a low Abbe number. We found that it is possible to produce a copolymer, and further found that the α-olefin / cyclic olefin copolymer is useful as an optical material / optical component, more specifically as an optical lens and film. The invention has been completed.

  That is, the α-olefin / cyclic olefin copolymer in the present invention is represented by a structural unit derived from a linear or branched α-olefin having 2 to 30 carbon atoms and the following general formula (I). It is an α-olefin / cyclic olefin copolymer [a] composed of structural units derived from cyclic olefin.

（一般式（Ｉ）中、ｘは０または１以上の整数であり、Ｒ⁸¹〜Ｒ⁸⁸は水素原子、脂肪族炭化水素基、および芳香族炭化水素基から選ばれ、互いに同一でも異なっていてもよい。Ｒ⁹¹〜Ｒ⁹⁴は水素原子、脂肪族炭化水素基、および芳香族炭化水素基から選ばれ、互いに同一でも異なっていてもよく、隣接する２つの基は互いに結合し、単環または複環の芳香族環を形成していてもよい。）
前記環状オレフィンは、ベンゼン環を２つ以上含有していることにより高屈折率の共重合体が得られる点で好ましい。

(In General Formula (I), x is 0 or an integer of 1 or more, and R ^{81 to} R ⁸⁸ are selected from a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group, and may be the same or different from each other. R ^{91 to} R ⁹⁴ are selected from a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group, and may be the same or different from each other, and two adjacent groups are bonded to each other to form a single ring or (It may form a bicyclic aromatic ring.)
The cyclic olefin is preferable in that a copolymer having a high refractive index can be obtained by containing two or more benzene rings.

The α-olefin is preferably ethylene.
In addition, the method for producing an α-olefin / cycloolefin copolymer [a] according to the present invention includes a transition metal compound (A) represented by the following general formula (II):
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair,
In the presence of a catalyst for olefin polymerization comprising: a linear or branched α-olefin having 2 to 30 carbon atoms and a cyclic olefin represented by the above general formula (I). And

（一般式（ＩＩ）中、Ｍは周期表第４〜５族の遷移金属原子を示し、ｍは、１〜４の整数を示し、Ｒ¹〜Ｒ⁵は、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、およびスズ含有基から選ばれ、互いに同一でも異なっていてもよく、これらのうちの２個以上が互いに連結して環を形成していてもよく、Ｒ⁶は、水素原子、１級または２級炭素のみからなる炭素原子数１〜４の炭化水素基、炭素原子数５以上の脂肪族炭化水素基、アリール置換アルキル基、単環性または二環性の脂環族炭化水素基および芳香族炭化水素基から選ばれ、ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合は、Ｘで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）
前記一般式（ＩＩ）で表される遷移金属化合物において、ｍは２であり、Ｍはチタン原子であることが好ましい。

(In General Formula (II), M represents a transition metal atom of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 4, and R ^{1 to} R ⁵ represent a hydrogen atom, a halogen atom, or a hydrocarbon. Selected from a group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Or two or more of them may be connected to each other to form a ring, and R ⁶ is a hydrocarbon having 1 to 4 carbon atoms consisting of only a hydrogen atom, primary or secondary carbon. Group, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group, and n is the valence of M X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen A containing group, a sulfur containing group, a nitrogen containing group, a boron containing group, an aluminum containing group, a phosphorus containing group, a halogen containing group, a heterocyclic compound residue, a silicon containing group, a germanium containing group, or a tin containing group, n When is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)
In the transition metal compound represented by the general formula (II), m is preferably 2, and M is preferably a titanium atom.

In the transition metal compound represented by the general formula (II), R ¹ is preferably an aryl group represented by the following general formula (III), and R ⁶ is preferably a phenyl group.

（一般式（ＩＩＩ）中、Ｒ^1A〜Ｒ^1Eは水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれ、互いに同一でも異なっていてもよく、また互いに結合して環を形成していてもよい。）

(In the general formula (III), R ^{1A to} R ^1E are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group. And selected from a germanium-containing group and a tin-containing group, which may be the same as or different from each other, and may be bonded to each other to form a ring.)

In the present invention, the α-olefin / cyclic olefin copolymer [a] is molded and preferably used as an optical lens or film.
Furthermore, the optical component according to the present invention includes a lens containing the α-olefin / cyclic olefin copolymer [a] and a cyclic olefin polymer other than the α-olefin / cyclic olefin copolymer [a] [b]. It is characterized by being obtained in combination with a lens containing

The cyclic olefin polymer [b] preferably has a refractive index of 1.54 or less at 23 ° C. and a wavelength of 598 nm.
The optical component is useful as a lens for a digital camera, a lens for a recording medium, a lens for a measuring instrument, a lens for a CCD camera, or a lens for a CMOS camera.

  The α-olefin / cyclic olefin copolymer [a] in the present invention exhibits a high refractive index and a low Abbe number because an aromatic ring is introduced into the cyclic olefin which is a constituent monomer of the copolymer. By processing the α-olefin / cyclic olefin copolymer [a] of the present invention as an optical component, particularly an optical lens, and using it as a correction lens for chromatic aberration in combination with a high Abbe number lens, the dispersion of light is reduced. The effect of increasing the resolution and preventing blurring appears.

  Hereinafter, the α-olefin / cyclic olefin copolymer [a] according to the present invention and the production method thereof, and the optical lens, optical component, and film using the α-olefin / cyclic olefin copolymer [a] are specifically described. explain.

<Α-Olefin / Cyclic Olefin Copolymer [a]>
The α-olefin / cyclic olefin copolymer [a] in the present invention is a linear or branched α-olefin having 2 to 30 carbon atoms and a cyclic olefin represented by the following general formula (I). It is a copolymer. Hereinafter, the cyclic olefin and the α-olefin, which are constituent monomers of the α-olefin / cyclic olefin copolymer [a] in the present invention, will be described in detail.

[Cyclic olefin]
The cyclic olefin which is a constituent monomer of the α-olefin / cyclic olefin copolymer [a] in the present invention is a compound having a structure represented by the following general formula (I).

一般式（Ｉ）において、ｘは０または１以上の整数である。

In general formula (I), x is 0 or an integer of 1 or more.

R ^{81 to} R ⁸⁸ and R ^{91 to} R ⁹⁴ are selected from a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group, and may be the same as or different from each other.
Among R ^{81 to} R ⁸⁸ and R ^{91 to} R ⁹⁴ , examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and the like. Includes alkyl groups such as methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl; and cycloalkyl groups such as cyclobutyl, cyclohexyl, and cyclooctyl.

  Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and the like. Specifically, phenyl, tolyl, naphthyl, benzyl, phenylethyl, and the like, and these hydrogen atoms are substituted with other carbon atoms. Examples include a group substituted with a hydrogen group.

Further, two adjacent groups of R ^{91 to} R ⁹⁴ may be bonded to each other to form a monocyclic or multicyclic aromatic ring.
Among these, specific examples of the cyclic olefin in which R ⁹¹ and R ⁹² are bonded to form an aromatic ring include the following structures.

また、Ｒ⁹²とＲ⁹³が結合して芳香族環が形成される環状オレフィンとして具体的には、以下のような構造が挙げられる。

Specific examples of the cyclic olefin in which R ⁹² and R ⁹³ are bonded to form an aromatic ring include the following structures.

また、Ｒ⁹¹とＲ⁹²、Ｒ⁹³とＲ⁹⁴が結合して芳香族環が形成される環状オレフィンとして具体的には、以下のような構造が挙げられる。

Specific examples of the cyclic olefin in which R ⁹¹ and R ⁹² , R ⁹³ and R ⁹⁴ are bonded to form an aromatic ring include the following structures.

これらの芳香族環上に脂肪族炭化水素基、および芳香族炭化水素基から選ばれる置換基が置換された環状オレフィンも例として挙げられる。

Examples of the cyclic olefin in which an aromatic hydrocarbon group and a substituent selected from an aromatic hydrocarbon group are substituted on these aromatic rings are also exemplified.

The cyclic olefin used in the present invention preferably contains two or more benzene rings in that a copolymer having a higher refractive index can be obtained.
Specific examples of the cyclic olefin used in the present invention include the following compounds.

これらの環状オレフィンは、Ｒ．Ｗ．Ｈｏｆｆｍａｎｎ著，“Ｄｅｈｙｄｒｏｂｅｎｚｅｎｅ ａｎｄ ｃｙｃｌｏａｌｋｙｎｅｓ”， Ａｃａｄｅｍｉｃ Ｐｒｅｓｓ Ｎｅｗ Ｙｏｒｋ刊（１９７３年），４９９頁、Ｙ．Ｈｉｍｅｓｈｉｍａ，Ｔ．Ｓｏｎｏｄａ，Ｈ，Ｋｏｂａｙａｓｈｉ著 Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ誌 １２１１頁（１９８３年）などに記載の公知の方法によって発生させた対応する構造を有するベンザイン誘導体と、シクロペンタジエン誘導体とをディールス・アルダー反応させることによって製造することができる。

These cyclic olefins are R.I. W. Hoffmann, “Dehydrobenzene and cycloalkynes”, Academic Press New York (1973), p. Himeshima, T .; Producing by Diels-Alder reaction of a benzyne derivative having a corresponding structure generated by a known method described in Sonoda, H, Kobayashi, Chemistry Letters, page 1211 (1983), and a cyclopentadiene derivative. Can do.

[Linear or branched α-olefin having 2 to 30 carbon atoms]
The α-olefin used in the present invention is a linear or branched α-olefin having 2 to 30 carbon atoms.

  Specific examples of the linear or branched α-olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3- Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, Examples include 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. Of these, ethylene and propylene are preferable, and ethylene is particularly preferable.

<Method for Producing α-Olefin / Cyclic Olefin Copolymer [a]>
Such an α-olefin / cyclic olefin copolymer [a] is a linear or branched α-olefin having 2 to 30 carbon atoms and the above in the presence of the olefin polymerization catalyst described below. It can manufacture by copolymerizing the cyclic olefin of this.

[Olefin polymerization catalyst]
The olefin polymerization catalyst used in the production of the α-olefin / cyclic olefin copolymer [a] according to the present invention will be described in detail below.

The olefin polymerization catalyst according to the present invention comprises:
(A) a transition metal compound represented by the following general formula (II);
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound (A) to form an ion pair,
And at least one compound selected from the group consisting of:

[(A) Transition metal compound]
The transition metal compound (A) constituting the olefin polymerization catalyst used in the present invention is a compound represented by the following general formula (II).

上記一般式（ＩＩ）において、Ｎ…Ｍは、一般的にはＮがＭに配位していることを示すが、本発明においては配位していてもしていなくてもよい。

In the above general formula (II), N... M generally indicates that N is coordinated to M, but may or may not be coordinated in the present invention.

  In the general formula (II), M represents a transition metal atom of Groups 4 to 5 of the periodic table, and specifically includes a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, a tantalum atom, and the like. M is preferably a metal atom of Group 4 of the periodic table, specifically a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom.

R ^{1 to} R ⁵ are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing Selected from a group and a tin-containing group, and may be the same or different from each other, and two or more of these may be bonded to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
The hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl. 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl, isopropenyl, etc .; carbon atoms such as ethynyl, propargyl, etc. A linear or branched alkynyl group having 2 to 30 and preferably 2 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and adamantyl, having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms A cyclic saturated hydrocarbon group of 5 to 5 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl, etc. 0 cyclic unsaturated hydrocarbon group; aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; tolyl, iso-propylphenyl, t Examples include alkyl-substituted aryl groups such as -butylphenyl, dimethylphenyl, and di-t-butylphenyl.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen, such as monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, chlorophenyl, etc. The halogenated hydrocarbon group of 1-30, Preferably 1-20 is mentioned.

The hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl-substituted alkyl groups such as benzyl and cumyl.
Further, the hydrocarbon group is a heterocyclic compound residue; oxygen such as alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group, etc. Containing group: amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group and ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group, Isothiocyanate group, sulfone ester group, sulfo group Sulfur-containing groups such as amide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, silicon-containing groups A germanium-containing group; or a tin-containing group.

  Examples of the hydrocarbon group include 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl, preferably 1 A linear or branched alkyl group of -20; a cyclic group having 3 to 50 carbon atoms, preferably 3 to 30 carbon atoms, such as cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, tetracyclododecyl, etc. Hydrocarbons; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; halogen atoms, 1 to 30 carbon atoms, preferably these aryl groups 1-20 alkyl or alkoxy groups, 6-6 carbon atoms 0, preferably including a substituted aryl group substituents, such as 6 to 20 aryl group or aryloxy group is 1-5 substituents is preferred.

  Examples of the heterocyclic compound residue include cyclic groups containing 1 to 5 heteroatoms, and examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a boron atom. Examples of the ring include 4 to 7-membered monocyclic and polycyclic rings, preferably 5 to 6-membered monocyclic and polycyclic rings. Specifically, residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, residues of oxygen-containing compounds such as furan and pyran, residues of sulfur-containing compounds such as thiophene, etc. Examples of the group include a group further substituted with a substituent such as an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  Examples of the oxygen-containing group include groups containing 1 to 5 oxygen atoms, specifically, alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Aryloxy groups such as phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and naphthoxy; ester groups such as acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl; ether groups; Examples include acyl groups such as formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group and p-methoxybenzoyl group; carboxyl group; carbonate group; hydroxy group; peroxy group; carboxylic anhydride group. Among these, an alkoxy group, an aryloxy group, an acyl group, an ester group, and the like are preferable in terms of easy synthesis of the transition metal compound. When the oxygen-containing group contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 30, preferably 1 to 20.

  Examples of the nitrogen-containing group include groups containing 1 to 5 nitrogen atoms. Specifically, methylamino, dimethylamino, diethylamino, dipropylamino, ethylmethylamino, dibutylamino, dicyclohexylamino, diphenylamino Alkylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino and other arylamino groups or alkylarylamino groups; methylimino, ethylimino, propylimino, butylimino, phenylimino and other imino groups; acetamide, Amide groups such as N-methylacetamide and N-methylbenzamide; Imido groups such as acetimide and benzimide; Hydrazino group; Hydrazono group; Nitro group; Nitroso group; Cyano group; Isocyano group; Ester group; amidino group; diazo groups; such as an amino group becomes ammonium salts. Of these, an amino group, an imino group, an amide group, an imide group, a nitro group, and a cyano group are preferable in terms of easy synthesis of the transition metal compound. In addition, when a nitrogen-containing group contains a carbon atom, it is desirable that the number of carbon atoms is in the range of 1 to 30, preferably 1 to 20.

Examples of the boron-containing group include groups containing 1 to 5 boron atoms. Specifically, (Et) ₂ B-, (iPr) ₂ B-, (iBu) ₂ B-, (nC Alkyl-substituted boron such as ₅ H ₁₁ ) ₂ B-, C ₈ H ₁₄ B- (9-borabicyclononyl group); aryl-substituted boron such as (C ₆ H ₅ ) ₂ B-; halogenation such as BCl ₂ — Boron; groups such as alkyl-substituted boron halides such as (Et) BCl- and (iBu) BCl-. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

  Examples of the sulfur-containing group include groups containing 1 to 5 sulfur atoms. Specifically, mercapto groups; thioester groups such as acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl; dithioester groups; Alkylthio groups such as ethylthio; arylthio groups such as phenylthio, methylphenylthio and naphthylthio; thioacyl groups; thioether groups; thiocyanate groups; isothiocyanate groups; sulfones such as methyl sulfonate, ethyl sulfonate and phenyl sulfonate Group; sulfonamide group such as phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide; thiocarboxyl group; dithiocarboxyl group; sulfo group; sulfonyl group; Group; a sulfenyl group; sulfonato group; and sulfinate groups. Among these, an alkylthio group, an arylthio group, a thioester group, a sulfone ester group, and a sulfonamide group are preferable in terms of easy synthesis of the transition metal compound. In addition, when a sulfur containing group contains a carbon atom, it is desirable that the number of carbon atoms is in the range of 1 to 30, preferably 1 to 20.

Examples of the phosphorus-containing group include groups containing 1 to 5 phosphorus atoms, and specific examples include a phosphino group; a phosphoryl group; a phosphothioyl group; and a phosphono group.
Specific examples of the silicon-containing group include silyl groups; siloxy groups, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl And hydrocarbon-substituted silyl groups such as (pentafluorophenyl) silyl; hydrocarbon-substituted siloxy groups such as trimethylsiloxy and the like. Of these, hydrocarbon-substituted silyl groups such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, and triphenylsilyl are preferred. Trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are particularly preferable in that a transition metal compound can be easily synthesized.

Examples of the germanium-containing group and the tin-containing group include those obtained by replacing silicon of the silicon-containing group with germanium and tin.
Moreover, the preferable aspect of R < ¹ > is group which shows aromaticity (aromaticity), More preferably, it is an aryl group represented by the following general formula (III).

一般式（ＩＩＩ）において、Ｒ^1A〜Ｒ^1Eは水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれ、互いに同一でも異なっていてもよく、また互いに結合して環を形成していてもよい。

In general formula (III), R ^{1A to} R ^1E are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, It is selected from a silicon-containing group, a germanium-containing group, and a tin-containing group, which may be the same as or different from each other, and may be bonded to each other to form a ring.

R ^{1A to} R ^1E halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing Examples of the group include the same groups as those exemplified above for R ^{1 to} R ⁵ .

Among these, R ^{1A to} R ^1E are preferably 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, Preferably 1-20 linear or branched alkyl groups;
Or a benzyl, cumyl, diphenylethyl, or trityl group in which these hydrogen atoms are substituted with other aryl groups;
A cyclic hydrocarbon having 3 to 50 carbon atoms, preferably 3 to 30 carbon atoms, such as cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, tetracyclododecyl;
An aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl;
Alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy;
Aryloxy groups such as phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy; acyl groups such as formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group;
Ester groups such as acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl;
Nitrogen-containing groups such as nitro, acetamide, N-methylacetamide, N-methylbenzamide, dimethylamino, ethylmethylamino, diphenylamino, acetimide, benzimide, methylimino, ethylimino, propylimino, butylimino, phenylimino;
Methylthio, ethylthio, phenylthio, methylphenylthio, naltylthio, acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl, methyl sulfonate, ethyl sulfonate, phenyl sulfonate, sulfonamide, phenylsulfonamide, N-methylsulfonamide, N And sulfur-containing groups such as -methyl-p-toluenesulfonamide.

R ^{1A to} R ^1E may be such that two or more groups, preferably adjacent groups, are bonded to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. These rings may further have the substituents listed above.

In general formula (II), R ⁶ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting of only primary or secondary carbon, an aliphatic hydrocarbon group having 5 or more carbon atoms, or an aryl-substituted alkyl group. Are selected from monocyclic or bicyclic alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

The hydrocarbon group having 4 or less carbon atoms consisting of only primary or secondary carbon is 4 or less carbon atoms in which the carbon directly bonded to the phenoxy ring among the carbon atoms of R ⁶ is a primary or secondary carbon. It is a hydrocarbon group. Specifically, it has 1 to 4 carbon atoms, preferably 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and the like. 3 linear or branched alkyl groups may be mentioned, and methyl, ethyl, isopropyl and n-propyl are more preferable.

The aliphatic hydrocarbon group having 5 or more carbon atoms is a hydrocarbon group having 5 or more carbon atoms in which the carbon directly bonded to the phenoxy ring among the carbon atoms of R ⁶ is not included in the ring structure. Specifically, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and the like have 5 to 30 carbon atoms, preferably Includes 5 to 20 linear or branched alkyl groups, more preferably neopentyl.

Examples of the aryl-substituted alkyl group include benzyl, cumyl, 1-diphenylethyl, triphenylmethyl and the like.
Specific examples of the monocyclic alicyclic hydrocarbon group include a monocyclic aliphatic group having 3 to 30, preferably 3 to 20, carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. And a hydrocarbon group having a ring skeleton, more preferably cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl. , Cyclooctyl and cyclododecyl.

  Specific examples of the bicyclic alicyclic hydrocarbon group include bicyclo [1.1.0] butyl, bicyclo [2.1.0] pentyl, norbornyl, bicyclo [2.2.2] octyl, Examples thereof include hydrocarbon groups having a bicyclic alicyclic skeleton having 5 to 30, preferably 5 to 20 carbon atoms, such as spiro [2.2] pentyl and spiro [2.3] hexyl.

  Specific examples of the aromatic hydrocarbon group include those having 6 to 30 carbon atoms such as phenyl, naphthyl, biphenylyl, triphenylyl, fluorenyl, anthranyl, phenanthryl, and more preferably phenyl, benzyl, naphthyl, and anthranyl. is there.

  The hydrocarbon group having 4 or less carbon atoms, the aliphatic hydrocarbon group having 5 or more carbon atoms, the aryl-substituted alkyl group, the monocyclic or bicyclic alicyclic ring composed of only the primary or secondary carbon. The aromatic hydrocarbon group and the aromatic hydrocarbon group may have a hydrogen atom present in the group substituted with a halogen atom, specifically, trifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluoro Examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as phenyl, trifluorophenyl, pentafluorophenyl, bistrifluorophenyl, and chlorophenyl.

R ⁶ is particularly preferably an aromatic hydrocarbon group such as phenyl, benzyl or naphthyl, and 3,5-difluorophenyl or 3,5-bistrifluoromethylphenyl substituted with these hydrogen atoms.

In the general formula (II), n is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, and more preferably 2.
In general formula (II), X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic ring. In the case where n is 2 or more, a plurality of groups represented by X may be the same as or different from each other, and are represented by X, in the formula compound residue, silicon-containing group, germanium-containing group, or tin-containing group. A plurality of groups may be bonded to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include linear or branched alkyl having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl. Groups; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl , Aryl groups such as dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl and the like. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms is substituted with halogen.

  Among these, alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc .; cyclopentyl, cyclohexyl, norbornyl And cycloalkyl groups such as adamantyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl are preferred.

  Examples of the oxygen-containing group include an oxy group, a peroxy group, a hydroxy group, a hydroperoxy group, an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; phenylmethoxy, phenyl Arylalkoxy groups such as ethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.

  Examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl benzene sulfonate, triisobutyl benzene sulfonate, p- Sulfonate groups such as chlorobenzene sulfonate and pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfite Sulfinate groups such as nate; alkylthio group; arylthio group; sulfate group; sulfide group; polysulfide group; thiolate group and the like.

  Examples of the nitrogen-containing group include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, and the like. Arylamino group or alkylarylamino group; trimethylamine, triethylamine, triphenylamine, N, N, N ′, N′-tetramethylethylenediamine (tmeda), N, N, N ′, N′-tetraphenylpropylenediamine (tppda And alkyl or arylamine groups such as

Examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).
Examples of the aluminum-containing group include AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

  Examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methylphosphite, ethylphosphite, and phenylphosphite. Examples thereof include phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups.

Examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ .
Specific examples of the heterocyclic compound residue include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and residues such as sulfur-containing compounds such as thiophene, and these And a group obtained by further substituting a substituent such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  Specific examples of the silicon-containing group include hydrocarbon-substituted silyls such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilyl, trinaphthylsilyl, and the like. A hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl;

Examples of the germanium-containing group and tin-containing group include groups in which silicon of the silicon-containing group is replaced with germanium and tin.
When n is 2 or more, a plurality of atoms or groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

The bonding mode between X and transition metal atom M is not particularly limited, and examples thereof include a covalent bond, a coordination bond, an ionic bond, and a hydrogen bond.
In general formula (II), m shows the integer of 1-4, Preferably it is 2.

When m is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other. Furthermore, when m is 2 or more, any of R ^{1 to} R ⁵ belonging to one ligand and any of R ^{1 to} R ⁵ belonging to another ligand may be linked. In the case where R ¹ has the structure represented by the general formula (III), any one of R ^{1A to} R ^1E belonging to one ligand and R ^{1 to} R ⁵ (R ¹ may include any ^one of R ^{1A to} R ^1E ). That is, in that case, two ligands are linked (bridged).

  Specific examples of the transition metal compound (A) represented by the general formula (II) are shown below, but the transition metal compound (A) used in the present invention is not limited to these. The titanium atoms in the examples may be replaced with transition metal elements of Groups 4 to 5 of the periodic table such as zirconium atoms, hafnium atoms, vanadium atoms, niobium atoms, and tantalum atoms. The chlorine atom of X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue , A silicon-containing group, a germanium-containing group, or a tin-containing group. In m, 2 may be replaced with 1, 3, and 4, and the number of n may be changed accordingly.

〔（Ｂ−１）有機金属化合物〕
本発明で必要に応じて用いられる（Ｂ−１）有機金属化合物は特開２００４−３３１９６５号公報に記載の（Ｂ−１）有機金属化合物と同様のものが用いられる。

[(B-1) Organometallic compound]
The (B-1) organometallic compound used as necessary in the present invention is the same as the (B-1) organometallic compound described in JP-A-2004-331965.

Among (B-1) organometallic compounds described in the above publication, an organoaluminum compound is preferably used.
Said (B-1) organometallic compound is used individually by 1 type or in combination of 2 or more types.

[(B-2) Organoaluminum oxy compound]
The (B-2) organoaluminum oxy compound used as necessary in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687. It may be. Specifically, compounds described as specific examples of (B-2) organoaluminum oxy compounds in JP-A No. 2004-331965 can also be cited in the present invention.
Said (B-2) organoaluminum oxy compound is used individually by 1 type or in combination of 2 or more types.

[(B-3) Compound that reacts with transition metal compound to form ion pair]
As a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair (hereinafter referred to as “ionized ionic compound”), which is used as necessary in the present invention, JP-A-1- No. 501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. Mention may be made of the Lewis acids, ionic compounds, borane compounds and carborane compounds described. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Specifically, compounds disclosed in Japanese Patent Application Laid-Open No. 2004-331965 as (B-3) a compound that forms an ion pair by reacting with a transition metal compound can also be exemplified in the present invention.

Said (B-3) ionized ionic compound is used individually by 1 type or in combination of 2 or more types.
Of these, compounds represented by the following general formula (IV) are preferably used.

一般式（ＩＶ）中、Ｒ²²としては、Ｈ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。

In general formula (IV), examples of R ²² include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{23 to} R ²⁶ may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.
When an organoaluminum oxy compound (B-2) such as methylaluminoxane is used as the catalyst and promoter component, the transition metal compound according to the present invention exhibits higher activity and higher copolymerization with respect to the olefin compound. When an ionized ionic compound (B-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a promoter component, an olefin polymer having good activity and high molecular weight can be obtained.

  The catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), (B) (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) ionized ion. A support (E) to be described later can be used together with at least one compound selected from the active compounds, if necessary.

[(E) carrier]
The carrier (E) used as necessary in the present invention is an inorganic or organic compound and is a granular or fine particle solid.

Among these, as the inorganic compound, porous oxides, inorganic halides, clays, clay minerals, or ion-exchangeable layered compounds are preferable.
As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or a composite or mixture containing them, for example, using natural or synthetic zeolites, SiO ₂ -MgO, etc. _{SiO 2 -Al 2 O 3, SiO} 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO can do. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

Note that the inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g and the pore volume in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which a plurality of layers are stacked in parallel with each other with a weak binding force by ionic bonds or the like, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

In addition, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And halloysite, and the ion-exchangeable layered compounds include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the clay structure. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Etc. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
Examples of the organic compound carrier include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.

  The catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), (B) (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) ionized ionic compound. A specific organic compound component (F), which will be described later, may be included as necessary together with at least one compound selected from the above, and optionally the carrier (E).

[(F) Organic compound component]
The organic compound component (F) used as necessary in the present invention is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As alcohols and phenolic compounds, those represented by R ³¹ —OH are usually used, wherein R ³¹ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms. A hydrocarbon group is shown. As the alcohol, R ³¹ is preferably a halogenated hydrocarbon. Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As the carboxylic acid, one represented by R ³² —COOH is usually used. R ³² represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

As the phosphorus compound, phosphoric acid having P—O—H bond, P—OR, phosphate having P═O bond, and phosphine oxide compound are preferably used.
As the sulfonate, those represented by the following general formula (V) are used.

一般式（Ｖ）中、Ｍは周期表１〜１４族から選ばれる原子である。

In general formula (V), M is an atom selected from groups 1 to 14 of the periodic table.

R ³³ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
m is an integer of 1 to 7, and n is 1 ≦ n ≦ 7.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(2) A method in which the catalyst component having component (A) supported on carrier (E) and component (B) are added to the polymerization vessel in any order.
(3) A method in which the catalyst component having component (B) supported on carrier (E) and component (A) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (A) supported on carrier (E) and the catalyst component having component (B) supported on carrier (E) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component having components (A) and (B) supported on a carrier (E) is added to a polymerization vessel.

In each of the above methods (1) to (5), at least two or more of the catalyst components may be contacted in advance.
In addition, the solid catalyst component in which the component (A) and the component (B) are supported on the component (E) may be prepolymerized with olefin, and the catalyst is further formed on the prepolymerized solid catalyst component. The component may be supported.

[Production Method of α-Olefin / Cyclic Olefin Copolymer [a]]
In the method for producing an α-olefin / cyclic olefin copolymer [a] according to the present invention, in the presence of the above-mentioned catalyst for olefin polymerization, a linear or branched α-olefin having 2 to 30 carbon atoms and A copolymer can be obtained by copolymerizing the above cyclic olefin.

  As the α-olefin and cyclic olefin copolymerized by the method for producing the α-olefin / cyclic olefin copolymer [a] according to the present invention, the above-mentioned α-olefin and cyclic olefin are preferably used.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
Hereinafter, the conditions of the production method of the α-olefin / cyclic olefin copolymer [a] in the present invention will be described in detail.

(Polymerization solvent)
As the solvent used in the liquid phase polymerization method, an inert solvent that is not subjected to the reaction during the polymerization reaction is used, and in particular, an inert hydrocarbon solvent is used. Specific examples of the inert hydrocarbon include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. Moreover, the olefin itself used for reaction can also be used as a solvent.

(Catalyst concentration)
When the α-olefin and the cyclic olefin are copolymerized using the above olefin polymerization catalyst, the component (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to It is used in such an amount that it becomes 10 ⁻³ mol.

  In the component (B-1), the molar ratio [(B-1) / M] of the component (B-1) and the transition metal atom (M) in the component (A) is usually 0.01 to 100, 000, preferably 0.05 to 50,000. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) of usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) and transition metal atom (M) in component (A) of usually 1 to 10, preferably It is used in such an amount as to be 1-5.

  When the component (B) is the component (B-1), the component (F) has a molar ratio [(F) / (B-1)] of usually 0.01 to 10, preferably 0.1 to 5. When the component (B) is the component (B-2), the molar ratio [(F) / (B-2)] is usually 0.001 to 2, preferably 0.005. When the component (B) is the component (B-3), the molar ratio [(F) / (B-3)] is usually 0.01 to 10, preferably 0.1. It is used as needed in such an amount that it becomes ˜5.

(Polymerization temperature / Polymerization pressure)
Moreover, the polymerization temperature of the copolymerization of α-olefin and cyclic olefin in the present invention is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 9.8 MPa (100 kg / cm ² ) (gauge pressure), preferably from normal pressure to 4.9 MPa (50 kg / cm ² ) (gauge pressure). It can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

(Molecular weight adjustment)
The molecular weight of the resulting α-olefin / cyclic olefin copolymer [a] can be adjusted by allowing hydrogen to exist in the polymerization system or changing the polymerization temperature. Furthermore, it can also adjust by the difference in the component (B) to be used.

(Molecular weight of α-olefin / cyclic olefin copolymer [a])
The weight average molecular weight (Mw) determined by GPC of the α-olefin / cyclic olefin copolymer [a] obtained by the present invention is 1,000 ≦ Mw ≦ 5,000,000, preferably 3,000 ≦ Mw. ≦ 3,000,000, more preferably 5,000 ≦ Mw ≦ 2,000,000, still more preferably 5,000 ≦ Mw ≦ 1,000,000.

When the weight average molecular weight (Mw) of the α-olefin / cyclic olefin copolymer [a] is within the above range, the molded article tends to be excellent in strength and excellent in moldability.
Mw in this specification is a value when measurement is performed under the GPC measurement conditions described later.

(Constitutional unit of α-olefin / cyclic olefin copolymer [a])
The molar ratio (α-olefin / cyclic olefin) of the structural unit derived from the α-olefin and the structural unit derived from the cyclic olefin in the α-olefin / cyclic olefin copolymer [a] according to the present invention is 20 / 80 to 99/1, preferably 30/70 to 90/10, more preferably 40/60 to 80/20, and even more preferably 50/50 to 70/30.

  When the molar ratio of the structural unit derived from α-olefin and the structural unit derived from cyclic olefin in the α-olefin / cyclic olefin copolymer [a] is within the above range, the α-olefin / cyclic olefin copolymer There is a tendency to be excellent in optical characteristics, mechanical characteristics, thermal characteristics, etc., which are the characteristics of [a], and a copolymer can be easily produced.

(Other monomers)
In the production of the α-olefin / cyclic olefin copolymer [a] in the present invention, if necessary, the copolymer may be copolymerized in the presence of a known cyclic olefin in addition to the α-olefin and cyclic olefin described above. good. Known cyclic olefins include bicyclo [2.2.1] hept-2-ene and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is preferred.

<Optical component using α-olefin / cyclic olefin copolymer [a]>
[Molded body]
The α-olefin / cycloolefin copolymer [a] provided in the present invention is molded by a known method. For example, the injection molding is performed by a single screw extruder, a vent type extruder, a twin screw extruder, a conical twin screw extruder or the like.

  The α-olefin / cyclic olefin copolymer [a] used in the present invention includes, in addition to the above-mentioned components, a known weather stabilizer and heat stabilizer as long as the properties of the original good optical component are not impaired. Antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, and the like may be blended.

  For example, UV absorbers for weathering stabilizers blended as optional components include benzophenone compounds, benzotriazole compounds, nickel compounds, and hindered amine compounds. Specifically, 2,2 ′, 4,4 '-Tetrahydroxybenzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3'-t-butyl-5) '-Butylphenyl) benzotriazole, nickel salt of bis (3,5-di-t-butyl-4-hydroxybenzoylphosphoric acid ethyl ester, bis (2,2', 6,6'-tetramethyl-4 -Piperidine) sebacate and the like.

  Moreover, as a heat-resistant stabilizer mix | blended as an arbitrary component, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t Phenol-type antioxidants such as -butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearin Fatty acid metal salts such as zinc acid, calcium stearate, calcium 1,2-hydroxystearate, polyvalent such as glycerin monostearate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate Alcohol fatty acid ester And distearyl pentaerythritol diphosphite, phenyl-4,4′-isopropylidenediphenol-pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methyl) Phosphorus stabilizers such as phenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite may be used.

  These may be blended alone or in combination. As a specific example of the combination, a combination of tetrakis [methylene-3- (3.5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerin monostearate can be exemplified.

  The mixing method of the α-olefin / cyclic olefin copolymer [a] used in the present invention and other polymer components and additives is not limited, and known methods can be applied. For example, a method of mixing each component simultaneously.

〔lens〕
The α-olefin / cyclic olefin copolymer [a] used in the present invention preferably has a refractive index of 1.58 or more at 23 ° C. and a wavelength of 589 nm, an Abbe number of 35 or less, more preferably a refractive index of 1. 60 or more, Abbe number is 30 or less, photoelastic coefficient as an index of birefringence is 25 × 10 ⁻¹⁰ Pa ⁻¹ or less, more preferably 15 × 10 ⁻¹⁰ Pa ⁻¹ or less, and water absorption is 0 20% by weight or less, more preferably 0.10% by weight or less. When the refractive index is within this range, when used as a lens, not only can the thickness of the lens itself be reduced, but the focal length can be shortened, and the device incorporating the lens can be made smaller and lighter. it can. When the Abbe number is in this range, a lens obtained by injection molding of an α-olefin / cycloolefin copolymer [a] and a lens obtained by injection molding of a cyclic olefin polymer [b] described below are combined. As a result, it is possible to form an optical component in which a chromatic aberration is suppressed to be small and an image without color blur is clearly visible. When the photoelastic coefficient is within this range, it is possible to suppress degradation in imaging performance due to deviation of the imaging point of light, and a clear image can be obtained. When the water absorption is in this range, the change in the refractive index can be suppressed, and the molded product is less warped due to deformation, resulting in excellent dimensional stability.

[Optical parts]
Furthermore, the optical component in the present invention comprises a lens containing the α-olefin / cyclic olefin copolymer [a] and a cyclic olefin polymer [b] other than the α-olefin / cyclic olefin copolymer [a]. It can be obtained by combining with the contained lens.

  Here, the cyclic olefin polymer [b] in the present invention has a refractive index at 23 ° C. and a wavelength of 589 nm of 1.54 or less, more preferably 1.50 to 1.54. It is done. When the refractive index of the cyclic olefin polymer [b] is within this range, a lens obtained by injection molding the polymer is obtained by injection molding the α-olefin / cyclic olefin copolymer [a]. By combining with a lens, it becomes possible for the first time to form an optical component that has no image distortion, extremely small aberration, and is free from defocusing and color blurring.

  The difference in the Abbe number (used as an index representing the wavelength dependence of the refractive index) between the α-olefin / cyclic olefin copolymer [a] and the cyclic olefin polymer [b] used in the present invention is 10 or more. Preferably it exists in the range of 15 or more. When the difference in Abbe number between the α-olefin / cyclic olefin copolymer [a] and the cyclic olefin polymer [b] is within this range, the α-olefin / cyclic olefin copolymer [a] is injection molded. By combining a lens obtained by injection molding and a lens obtained by injection molding of the cyclic olefin polymer [b], an optical component that further suppresses chromatic aberration and has a clear color blur can be formed. Will be possible for the first time.

  Specific examples of the cyclic olefin polymer [b] include Apel (registered trademark, ethylene / tetracyclododecene copolymer) manufactured by Mitsui Chemicals, Inc. and ZEONEX (registered trademark) manufactured by Nippon Zeon Co., Ltd. , Brand names E48R, 330R, 480R, etc.).

  The optical component obtained by the present invention can be used for a wide range of applications. For example, a digital camera lens, a recording medium lens, a measurement device lens, a camera-equipped cell phone CCD camera lens, a camera-equipped cell phone CMOS camera lens, and an in-vehicle CCD camera lens can be mentioned. Specifically, for example, an aspheric pickup lens used for reading an optical disc such as CD, MO, MD, LD, a reading cylindrical lens, a die lock mirror, a condensing lens, an imaging lens, etc., or a projection television Field lenses and color lenses, spherical lenses and aspheric lenses for camera imaging systems, camera finder lenses, camera finder prisms, telescope lenses, optical fiber connector lenses, lens arrays for 1x imaging elements, roof mirror arrays Examples include lenses, F-theta lenses and polygon mirrors for printers and copiers, prism sheets and light guide plates for liquid crystals, diffusion sheets, polarizing plates, brightness enhancement sheets, viewing angle control films, Furnell lenses, and cylindrical lenses.

  According to a preferred embodiment of the present invention, an α-olefin / cyclic olefin copolymer composed of ethylene and an aromatic-containing norbornene derivative having a specific structure and having a refractive index of 1.58 or more (the α-olefin / cyclic olefin copolymer). Injection molding a lens obtained by injection molding a polymer [a] and a cyclic olefin polymer having a refractive index of 1.54 or less (corresponding to the cyclic olefin polymer [b]). By combining the obtained lenses, it was the first time to provide an optical component that is free from image distortion and that is free from defocusing and color blurring.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all.
[Physical properties of α-olefin / cyclic olefin copolymer [a]]
[Molecular weight]
The molecular weight and molecular weight distribution of the α-olefin / cyclic olefin copolymer were analyzed by GPC measurement. The measurement was performed under the following conditions.
Apparatus: GPC Alliance 2000 (Waters)
Column: TSKgel GMH6-HT × 2 + TSKgel GMH6-HTL × 2 (total 30 cm × 4, Tosoh Corporation)
Detector: differential refraction Measurement solvent: o-dichlorobenzene Measurement flow rate: 1 mL / min
Measurement temperature: 140 ° C
Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation)
Molecular weight conversion: PS conversion / standard conversion method

[Intrinsic viscosity]
Measurements were made at 135 ° C. in decalin.

[Cyclic olefin content]
The cyclic olefin content was determined by ¹ H-NMR measurement (measuring solvent: 1,1,2,2-tetrachloroethane-d2, measuring temperature: 120 ° C.) using an ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL.

[Glass-transition temperature]
The temperature was raised from normal temperature to 250 ° C. at 30 ° C./minute, held for 5 minutes, then lowered to 0 ° C. at 10 ° C./minute, and then obtained from an endothermic curve when the temperature was raised at 10 ° C./minute.

[Refractive index]
In accordance with ASTM D542, a refractive index at a wavelength of 589 nm was measured using a sodium light source using a test piece having a thickness of 1 mm.

[Refractive index, Abbe number]
In accordance with ASTM D542, a refractive index (nd) and an Abbe number (νd) at 23 ° C. were determined using an Abbe refractometer using a test piece having a thickness of 1 mm.
1,4-dihydro-1,4-methanonaphthalene, 1,4-dihydro-1,4-methanoanthracene and complex compounds (A1) and (A2) are known methods (Japanese Patent Laid-Open No. 2004-331965, etc.) ) And synthesized.

[Example 1]
[Ethylene 1,4-dihydro-1,4-methanoanthracene copolymerization with complex compound (A1)]
Into a glass reactor with an internal volume of 500 mL sufficiently purged with nitrogen, 125 mL of toluene was charged, 3.7 g of 1,4-dihydro-1,4-methanoanthracene (Compound 1) was added, ethylene 25 L / hr, nitrogen The liquid phase and gas phase were saturated at 25 L / h. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.001 mmol of the following complex compound (A1) was added to initiate polymerization. Ethylene and nitrogen were continuously supplied at 25 L / hr, respectively, and polymerization was carried out at 50 ° C. for 10 minutes under normal pressure. Then, a small amount of methanol was added to terminate the polymerization.

After completion of the polymerization, the reaction product was added to 1000 mL of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol and drying under reduced pressure at 130 ° C. for 10 hours, 0.740 g of polymer was obtained. The polymerization activity was 4.4 kg / mmol-Ti · hr. When ¹ H-NMR of this polymer was measured, it was found that the polymer obtained was ethylene / 1,4-dihydro in which 16.9 mol% of 1,4-dihydro-1,4-methanoanthracene was contained in the polymer main chain. It was a -1,4-methanoanthracene copolymer (a-1). Measurement of the glass transition temperature T _g of the polymer was 143 ° C..

〔参考例２〕
［錯体化合物（Ａ１）によるエチレン・１，４−ジヒドロ−１，４−メタノナフタレン共重合］
充分に窒素置換した内容積５００ｍＬのガラス製反応器に、シクロヘキサン２５０ｍＬを装入し、１，４−ジヒドロ−１，４−メタノナフタレン（化合物２）を１０ｍＬ（１０．６ｇ）加え、エチレン５０Ｌ／ｈｒで液相及び気相を飽和させた。その後、メチルアルミノキサンをアルミニウム原子換算で０．５０ｍｍｏｌ、引き続き下記錯体化合物（Ａ１）を０．００１ｍｍｏｌ加え重合を開始した。エチレンを５０Ｌ／ｈｒで連続的に供給し、常圧下５０℃で１０分間重合を行った後、少量のメタノールを添加することにより重合を停止した。

[ Reference Example 2]
[Ethylene 1,4-dihydro-1,4-methanonaphthalene copolymerization with complex compound (A1)]
A glass reactor having an internal volume of 500 mL that has been sufficiently purged with nitrogen is charged with 250 mL of cyclohexane, 10 mL (10.6 g) of 1,4-dihydro-1,4-methanonaphthalene (compound 2) is added, and 50 L / ethylene is added. The liquid phase and gas phase were saturated with hr. Thereafter, methylaluminoxane was added in an amount of 0.50 mmol in terms of aluminum atom, and then 0.001 mmol of the following complex compound (A1) was added to initiate polymerization. Ethylene was continuously supplied at 50 L / hr, and polymerization was carried out at 50 ° C. under normal pressure for 10 minutes, and then the polymerization was stopped by adding a small amount of methanol.

After completion of the polymerization, the reaction product was added to 1500 mL of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol and drying under reduced pressure at 130 ° C. for 10 hours, 1.893 g of polymer was obtained. The polymerization activity was 11.4 kg / mmol-Ti · hr. As a result of measuring ¹ H-NMR of this polymer, it was found that the obtained polymer was an ethylene / 1,4-dihydro compound containing 39.2 mol% of 1,4-dihydro-1,4-methanonaphthalene in the polymer main chain. It was -1,4-methanonaphthalene copolymer (a-2). Measurement of the glass transition temperature T _g of the polymer was 133 ° C..

[ Reference Example 3]
[Ethylene 1,4-dihydro-1,4-methanonaphthalene copolymerization with complex compound (A2)]
Except using 0.0002mmol complex compound (A2) instead of the complex compound (A1) in Reference Example 2 to obtain a polymer 0.513g Operations in the same manner as in Reference Example 2. The polymerization activity was 15.4 kg / mmol-Ti · hr. When ¹ H-NMR of this polymer was measured, it was found that the polymer obtained was ethylene / 1,4-dihydro with 35.7 mol% of 1,4-dihydro-1,4-methanonaphthalene contained in the polymer main chain. It was a -1,4-methanonaphthalene copolymer. Measurement of the glass transition temperature T _g of the polymer was 119 ° C.. The structure of the complex compound (A2) is shown below.

〔実施例４〕
得られた共重合体（ａ−１）を用いて窒素雰囲気下でプレス成形し、厚さ１ｍｍのプレスシートを得た後、屈折率、アッベ数を測定したところ、屈折率１．６２４、アッベ数２５であった。

Example 4
The obtained copolymer (a-1) was press-molded in a nitrogen atmosphere to obtain a press sheet having a thickness of 1 mm, and the refractive index and Abbe number were measured. It was number 25.

[ Reference Example 5]
The obtained copolymer (a-2) was used to obtain a press sheet by the same method as in Example 4, and the refractive index and Abbe number were measured. The refractive index was 1.584 and the Abbe number was 35. Met.

[Comparative Example 1]
Except for using a copolymer of ethylene and dicyclopentadiene as the olefin copolymer, a press sheet was obtained in the same manner as in Example 4, and the refractive index and Abbe number were measured. The Abbe number was 49.

[Comparative Example 2]
Ethylene and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene was used except that a press sheet was obtained in the same manner as in Example 4, and the refractive index and Abbe number were measured. The Abbe number was 53.

As is apparent from the results of Example 4, Reference Example 5 and Comparative Examples 1 and 2, it can be seen that the olefin copolymer obtained in the present invention is an olefin copolymer having a high refractive index and a low Abbe number.

  The α-olefin / cycloolefin copolymer [a] of the present invention has a high refractive index and a low Abbe number, and a lens obtained by injection molding has excellent dimensional stability after molding and a short focal length. In addition, the deviation of the light image formation point is small, and heat resistance is excellent.

  Further, a lens obtained by injection molding the α-olefin / cyclic olefin copolymer [a] defined in the present invention and a cyclic olefin polymer [b] having a refractive index of 1.54 or less are injection molded. By combining the lenses obtained in this way, it becomes possible for the first time to form an optical component that has no image distortion, extremely small aberration, and is free from defocusing and color blurring.

  The optical component obtained by the present invention can be used for a wide range of applications. For example, it can be suitably used as a lens for a digital camera, a lens for a recording medium, a lens for a measuring instrument, or a lens for a CCD camera lens.

Claims (2)

A transition metal compound (A) represented by the following general formula (II):
(B) (B-1) an organometallic compound,
(B-2) Organoaluminum oxy compound, and (B-3) Olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds that react with transition metal compound (A) to form ion pairs existing under the, characterized in that the copolymerization of a cycloolefin represented by a linear or branched alpha-olefin and the following formula of carbon atoms 2 to 30 (I) alpha-olefin-cyclic Production method of olefin copolymer [a] .

(In General Formula (I), x is 0 or an integer of 1 or more, and R ^{81 to} R ⁸⁸ are selected from a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group, and may be the same or different from each other. R ^{91 to} R ⁹⁴ are selected from a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group, and may be the same as or different from each other, and at least one pair of two adjacent groups is bonded to each other. An aromatic ring is formed, and two or more benzene rings are contained as cyclic olefins.)

(In general formula (II), M represents a titanium atom, m is 2 , R ¹ is an aryl group represented by the following general formula (III), and R ^{2 to} R ⁵ are a hydrogen atom or a halogen atom. , Hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, and tin-containing group, and the same However, they may be different, and two or more of them may be connected to each other to form a ring, R ⁶ is a phenyl group, n is a number satisfying the valence of M, and X Is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group A germanium-containing group, or When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring. Good.)

(In the general formula (III), R ^{1A to} R ^1E are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group. And selected from a germanium-containing group and a tin-containing group, which may be the same as or different from each other, and may be bonded to each other to form a ring.) The method for producing an α-olefin / cyclic olefin copolymer according to claim 1, wherein the α-olefin is ethylene.