JP2008007733A - Spiro ring-containing norbornene derivative, norbornene-based ring-opened polymer, norbornene-based ring-opened polymer hydrogenated product, optical resin material and optical form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical form excellent in low birefringence and low in water absorption. <P>SOLUTION: A spiro ring-containing norbornene derivative of the formula(1) ( wherein, R<SP>1</SP>and R<SP>2</SP>are each H, a 1-20C hydrocarbon group or a group containing halogen atom(s), silicon atom(s), oxygen atom(s) or nitrogen atom(s); Z is a 3-10C bivalent hydrocarbon group optionally having polar group as substituent; and n is 0 or 1 ) is provided. A norbornene-based ring-opened polymer therefrom, a hydrogenated product of the polymer, an optical resin material comprising the hydrogenated product, and the optical form obtained by forming the optical resin material, are also provided, respectively. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel spiro ring-containing norbornene derivative, a norbornene-based ring-opening polymer obtained by ring-opening (co) polymerization of this derivative, a hydrogenated norbornene-based ring-opening polymer obtained by hydrogenating this polymer, The present invention relates to an optical resin material containing the hydride, and an optical molded body having a low birefringence and a low water absorption, which is formed by molding the optical resin material.

  Norbornene-based resins have excellent properties such as transparency, heat resistance, mechanical toughness, low water absorption and low birefringence, and are widely used in various optical applications such as optical lenses and optical films. . For example, tetracyclododecenes and 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer hydrides have been proposed as norbornene-based resins having excellent low birefringence (patents). References 1, 2).

  However, conventionally known norbornene-based resins usually show a negative correlation between retardation and wavelength. Therefore, when this resin is used for a retardation film, a uniform retardation is obtained in the entire visible region. There was a problem that it could not be obtained.

  In recent years, materials with lower birefringence, that is, smaller retardation values, have been demanded with the advancement of functions of optical instruments. For example, an imaging lens is required that has a retardation value of 120 nm or less, an fθ lens of 60 nm or less, and a pickup lens of 10 nm or less.

  As such a low birefringence material, Patent Document 3 proposes an optical resin material made of a hydride of a norbornene-based ring-opening polymer having a spiro ring containing at least one selected from an ester bond and an ether bond. Yes. This material is excellent in low birefringence and is suitable for retardation films and the like.

However, the polymer hydride described in Patent Document 3 contains a large amount of oxygen atoms having a high charge density, and therefore has a high water absorption rate. When an optical lens is used, reading and writing errors due to variations in focal length and wavefront aberration are caused. May occur.
Accordingly, development of an optical resin material having excellent low birefringence and low water absorption has been demanded.
Japanese Patent Publication No. 2-9619 WO96 / 10596 Publication JP 2005-290048 A

  The present invention has been made in view of such a state of the art, and includes a novel spiro ring-containing norbornene derivative, a norbornene-based ring-opening polymer obtained by ring-opening (co) polymerization of this derivative, and this polymer Norbornene-based ring-opening polymer hydride obtained by hydrogenating hydride, optical resin material containing this hydride, and optical molding formed by molding this optical resin material, having excellent low birefringence and low water absorption The purpose is to provide a body.

As a result of diligent research to solve the above problems, the present inventors have obtained a novel spiro ring structure-containing norbornene derivative by Diels-Alder reaction between methylene norcamphor and cyclopentadiene. The norbornene ring-opening polymer hydride obtained by subjecting the norbornene derivative to metathesis ring-opening polymerization and then hydrogenating the main chain carbon-carbon double bond has excellent low birefringence and low water absorption. The present invention has been completed by finding out and generalizing this finding.
Thus, according to the first of the present invention, the formula (1)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group containing a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom, and Z is A spiro-ring-containing norbornene derivative represented by the formula (1) represents a divalent hydrocarbon group having 3 to 10 carbon atoms which may have a polar group as a substituent, and n is 0 or 1.
The spiro ring-containing norbornene derivative of the present invention has the formula (1a)

(Wherein R ¹ and R ² represent the same meaning as described above, Z ¹ represents a C 2-9 divalent hydrocarbon group which may have a polar group as a substituent, and n ¹ represents It is preferably a spiro ring-containing norbornene derivative represented by the following formula: 0 or 1.

  According to the second aspect of the present invention, the spiro ring-containing norbornene derivative of the present invention, or the mixture of the spiro ring-containing norbornene derivative and the norbornene-based monomer copolymerizable with the spiro ring-containing norbornene derivative is used as a metathesis catalyst. It is a norbornene-based ring-opening polymer obtained by ring-opening polymerization in the presence, and the weight average molecular weight determined by gel permeation chromatography is 1,000 to 1,000,000 in terms of polystyrene. A norbornene-based ring-opening polymer is provided.

According to the third aspect of the present invention, there is provided a hydrogenated norbornene ring-opening polymer obtained by hydrogenating 50% or more of the main chain carbon-carbon double bond of the norbornene ring-opening polymer of the present invention.
According to the fourth aspect of the present invention, there is provided an optical resin material containing at least one hydride of the norbornene-based ring-opening polymer of the present invention.
According to the fifth aspect of the present invention, there is provided an optical molded body obtained by molding the optical resin material of the present invention.

The norbornene-based ring-opening polymer hydride obtained by subjecting the spiro ring-containing norbornene derivative of the present invention to metathesis ring-opening polymerization and then hydrogenating is excellent in low birefringence and low in water absorption. It is suitable for optical resin materials having optical characteristics and dimensional stability.
Since the optical resin material of the present invention is composed of the norbornene-based ring-opening polymer hydride of the present invention having a spiro ring structure in the molecule, it is described in Patent Document 3 by using this. Similar to the optical resin material, an optical molded body having a uniform phase difference in the entire visible region can be obtained.
Since the optical molded body of the present invention has excellent optical properties and low water absorption, it is excellent in low birefringence and dimensional stability.

  Hereinafter, the present invention is classified into 1) a spiro ring-containing norbornene derivative, 2) a norbornene-based ring-opening polymer, 3) a norbornene-based ring-opening polymer hydride, 4) an optical resin material, and 5) an optical molded body. And will be described in detail.

1) Spiro ring-containing norbornene derivative The first of the present invention is a spiro ring-containing norbornene derivative represented by the formula (1).
In Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group containing a halogen atom, a silicon atom, an oxygen atom, or a nitrogen atom.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms of R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an n-pentyl group. An alkyl group having 1 to 20 carbon atoms such as n-hexyl group; an alkenyl group having 2 to 20 carbon atoms such as vinyl group, 1-propenyl group, 2-propenyl group and crotyl group; carbon such as ethynyl group and propargyl group Alkynyl group having 2 to 20 carbon atoms; aryl groups having 6 to 20 carbon atoms such as phenyl group, 1-naphthyl group, and 2-naphthyl group;

Specific examples of the group containing a halogen atom, silicon atom, oxygen atom or nitrogen atom of R ¹ and R ² include a halogen atom such as an alkyl group substituted with a halogen atom or an aryl group substituted with a halogen atom. Group: a group represented by the formula: Sir ³ r ⁴ r ⁵ (wherein, r ^{3 to} r ⁵ each independently represents a hydrogen atom, an alkyl group or an aryl group), and the formula: Sir ³ r ⁴ a group containing a silicon atom such as an alkyl group substituted with a group represented by r ⁵ ; a group containing an oxygen atom such as an alkyl group substituted with a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group or an alkoxy group; amino Group, mono-substituted amino group, di-substituted amino group, alkyl group substituted with amino group, alkyl group substituted with mono-substituted amino group, alkyl group substituted with di-substituted amino group, A group containing a nitrogen atom such as a rubamoyl group, an acylamino group and a cyano group;
The R ¹ and R ² may be the same or different and may be bonded together.
n is 0 or 1, and 0 is preferable.

Z represents a C 3-10 divalent hydrocarbon group which may have a polar group as a substituent.
The divalent hydrocarbon group having 3 to 10 carbon atoms of Z is a divalent saturated hydrocarbon if the carbon number is 3 to 10 and the main skeleton is only a carbon-carbon bond. Even a group may be a divalent unsaturated hydrocarbon group having a carbon-carbon double bond and / or a carbon-carbon triple bond.

  The polar group substituted by the divalent hydrocarbon group having 3 to 10 carbon atoms of Z is an atom having an electronegativity different from that of a carbon atom or a group containing the atom. For example, a halogen atom; an oxygen atom; a sulfur atom; a group containing one or more selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom;

Specific examples of the polar group include divalent polar groups such as an oxo group (═O), an imino group (═NH), and a thioxo group (═S); a fluorine atom (—F), a chlorine atom (—Cl), Hydroxyl group (—OH), amino group (—NH ₂ ), mercapto group (—SH), carboxyl group (—CO ₂ H), sulfonic acid group (—SO ₃ H), cyano group (—CN), nitro group Monovalent polar groups such as (—NO ₂ ) and formyl group (—CHO); and the like, but are not limited thereto.
These polar groups may be the same or different and a plurality of polar groups may be bonded to any position of the divalent hydrocarbon group.

  Specific examples of the spiro ring structure represented by the following (a) (hereinafter sometimes referred to as “spiro ring structure (a)”) include the following. However, the norbornene derivative of the present invention is not limited to the following.

(In the formula, Z represents the same meaning as described above, and * represents a carbon atom of the norbornene ring.)
(I) having a 4-membered ring structure

(Ii) having a 5-membered ring structure

(Iii) having a 6-membered ring structure

(Iv) Those having a ring structure of 7 or more members

(V) Having a bridge structure

  Among these, in the present invention, the spiro ring structure (a) is obtained by taking into account the ease of synthesis of the monomer and the water absorption, birefringence, and transparency of the polymer obtained by polymerizing the monomer. The spiro ring structure shown in b) is preferred.

(In the above formula, * represents the same meaning as described above, and Z ¹ represents a divalent hydrocarbon group having 2 to 9 carbon atoms which may have a polar group as a substituent.)

(Method for producing norbornene derivative)
Of the norbornene derivatives represented by the formula (1), the compound (1-1) in which n is 0 is, for example, a Dials of cyclopentadiene (2-1) and an olefin compound represented by the formula (3). -It can be obtained by alder addition reaction (the following reaction formula).

(In the formula, R ² and Z have the same meaning as described above.)
Preferable specific examples of the olefin compound represented by the formula (3) include the following (3-1) to (3-20).

  Many of the olefin compounds represented by the formula (3) are known compounds and can be produced by a conventionally known method. Moreover, what is marketed can also be used as a starting material as it is.

  In the formula (1), the compound (1-2) in which n is 1 is obtained by reacting the norbornene derivative (1-1) obtained by the Diels-Alder addition reaction with cyclopentadiene (2-2). It can be obtained by Diels-Alder addition reaction (the following reaction formula).

  In any reaction, the reaction temperature is usually 100 to 300 ° C., preferably 150 to 250 ° C., and the reaction time is several minutes to several hours.

  In any reaction, after the completion of the reaction, the usual post-treatment operation in synthetic organic chemistry is performed, and if desired, the reaction product can be separated and purified by known methods such as distillation, column chromatography, and recrystallization. The norbornene monomers represented by the target formulas (1-1) and (1-2) can be efficiently isolated.

  The structure of the target product can be identified and confirmed by using analytical means such as NMR spectrum, IR spectrum, and mass spectrum.

2) Norbornene-based ring-opening polymer The second aspect of the present invention is the spiro-ring-containing norbornene derivative of the present invention, or the spiro-ring-containing norbornene derivative and the norbornene-based monomer copolymerizable with the spiro-ring-containing norbornene derivative. A norbornene-based ring-opening polymer obtained by ring-opening polymerization of a mixture in the presence of a metathesis catalyst, and having a weight average molecular weight determined by gel permeation chromatography of 1,000 to 1, in terms of polystyrene It is a norbornene-based ring-opening polymer characterized by being 000,000.

  That is, the norbornene-based ring-opening polymer of the present invention includes (α) one or more spiro ring-containing norbornene derivatives of the present invention, or (β) the spiro ring-containing norbornene derivative of the present invention and the spiro ring-containing norbornene. A mixture of a derivative and a norbornene monomer copolymerizable with the derivative can be obtained by ring-opening polymerization in the presence of a metathesis catalyst.

  Examples of the norbornene-based monomer copolymerizable with the spiro ring-containing norbornene derivative of the present invention used in the case of (β) include compounds represented by the following formula (4).

In Formula (4), R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group containing a halogen atom, a silicon atom, an oxygen atom, or a nitrogen atom, and R ³ And R ⁵ may combine to form a ring. m is 0 or 1.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms of R ^{3 to} R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an n-pentyl group. An alkyl group having 1 to 20 carbon atoms such as n-hexyl group; an alkenyl group having 2 to 20 carbon atoms such as vinyl group, 1-propenyl group, 2-propenyl group and crotyl group; carbon such as ethynyl group and propargyl group Alkynyl group having 2 to 20 carbon atoms; aryl groups having 6 to 20 carbon atoms such as phenyl group, 1-naphthyl group, and 2-naphthyl group;

Specific examples of the group containing a halogen atom, silicon atom, oxygen atom or nitrogen atom of R ^{3 to} R ⁶ include a halogen atom such as an alkyl group substituted with a halogen atom or an aryl group substituted with a halogen atom. Group: a group represented by the formula: Sir ¹ r ² r ³ (wherein, r ^{1 to} r ³ each independently represents a hydrogen atom, an alkyl group or an aryl group), and the formula: Sir ¹ r ² a group containing a silicon atom such as an alkyl group substituted with a group represented by r ³ ; a group containing an oxygen atom such as an alkyl group substituted with a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group or an alkoxy group; amino Group, mono-substituted amino group, di-substituted amino group, alkyl group substituted with amino group, alkyl group substituted with mono-substituted amino group, alkyl group substituted with di-substituted amino group, A group containing a nitrogen atom such as a rubamoyl group, an acylamino group and a cyano group;

The ring formed by combining R ³ and R ⁵ is usually a ^3- to 8-membered ring, preferably a 5- to 8-membered ring, and includes an oxygen atom, a sulfur atom, and a nitrogen atom in the ring. You may go out.

Specific examples of the norbornene monomer represented by the above formula (4) include 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-ethylidene-2-norbornene, 5- Phenyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-cyclohexenyl-2-norbornene, dicyclopentadiene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, tetracyclo [6 2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] norbornene monomer having no substituent such as dodeca-4-ene or having a hydrocarbon group as a substituent; 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl 2-norbornene, 2-norbornene-5,6-dicarboxylic acid anhydride, 2-norbornene-5,6-dicarboxylic acid imide, 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] norbornene monomers having a functional group such as dodec-4-ene; and the like.

  Among these, a norbornene-based monomer having no substituent or having a hydrocarbon group as a substituent can easily obtain a copolymer having a desired composition ratio and molecular weight, and has a hygroscopic property. Since it is low, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is particularly preferable because a ring-opening polymer hydride having low birefringence can be obtained.

  Examples of the metathesis catalyst used in the production of the ring-opening polymer of the present invention include (i) a ring-opening metathesis polymerization catalyst comprising a combination of a transition metal halogen compound and an alkylating agent or a Lewis acid that functions as a co-catalyst, (ii) Examples include periodic group 4-8 transition metal-carbene complex catalyst, (iii) metallacyclobutane complex catalyst, and the like. These metathesis reaction catalysts can be used alone or in admixture of two or more. Among these, since a cocatalyst is not required and the activity is high, it is preferable to use a transition metal-carbene complex catalyst belonging to groups 4 to 8 of the periodic table of (ii), and use of a ruthenium carbene complex catalyst. Is particularly preferred.

Specific examples of the transition metal halogen compound (i) include molybdenum halides such as MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , MoF ₄ , MoOCl ₄ , MoOF ₄ , etc .; WBr ₂ , WCl ₂ , WBr ₄ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WOBr ₄ , WOCl ₄ , WOF ₄ , WCl ₄ (OC ₆ H ₄ Cl ₂ ) _2, etc .; VOCl ₃ , VOBr ₃ And vanadium halides such as TiCl ₄ and TiBr ₄ .

  Specific examples of alkylating agents or Lewis acids that function as cocatalysts include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminum monochloride. Organic aluminum compounds such as di-n-butylaluminum monochloride, diethylaluminum monoiodide, diethylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane, isobutylaluminoxane;

  Tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin, tetraoctyltin, trioctyltin fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride, dibutyltin Organotin compounds such as dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trichloride, butyltin trichloride, butyltin tribromide, dibutyltin triiodide;

  Organolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium and phenyllithium; Organic sodium compounds such as n-pentylsodium; methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium bromide, n-propyl Organic magnesium compounds such as magnesium bromide, t-butylmagnesium chloride and arylmagnesium chloride; Organic zinc compounds such as diethyl zinc; Organic cadmium compounds such as diethyl cadmium; Trimethyl boron, Triethyl boron, Tri-n-butyl boron, Triphenyl boron , Tris (perfluorophenyl) boron, N, N-dimethylanilinium tetrakis (perfluorophenyl) borate, trityltetrakis (perf Orofeniru) organoboron compounds such borate and the like.

  Examples of the periodic table group 4-8 transition metal-carbene complex catalyst of (ii) include a tungsten alkylidene complex catalyst, a molybdenum alkylidene complex catalyst, a rhenium alkylidene complex catalyst, and a ruthenium carbene complex catalyst.

Specific examples of the tungsten alkylidene complex ^{_{catalysts, W (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, W (N-2,6-Pr i 2 C 6 ^{_{H 3) (CHBu t) (}} OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, W (N-2 ^{_{, 6-Pr i 2 C 6}} H 3) (CHCMe 2 Ph) (OBu t) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2 ^{_{, W (N-2,6-Pr}} i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 and the like.

Specific examples of molybdenum alkylidene complex _{^{catalyst, Mo (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H _{^{3) (CHBu t) (OCMe}} 2 CF 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2, _{^{6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, _{^{Mo (N-2,6-Pr i}} 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (BIPHEN), Mo ( N-2,6-Pr i 2 C ₆ H ₃ ) (CHCMe ₂ Ph) (BINO) (THF) and the like.

Specific examples of rhenium alkylidene complex ^{catalyst, Re (CBu t) (CHBu} t) (O-2,6-Pr i 2 C 6 H 3) 2, Re (CBu t) (CHBu t) (O-2- _{^{Bu t C 6 H 4) 2}} , Re (CBu t) (CHBu t) (OCMe 2 CF 3) 2, Re (CBu t) (CHBu t) (OCMe (CF 3) 2) 2, Re (CBu t) (CHBu ^t ) (O-2,6-Me ₂ C ₆ H ₃ ) _{2 and the} like.

In the above formula, the Pr ⁱ isopropyl group, a Bu ^t is tert- butyl group, Me is a a methyl group, Ph refers to a phenyl group, BIPHEN is 5,5 ', 6,6'-tetramethyl-3, 3′-di-tert-butyl-1,1′-biphenyl-2,2′-dioxy group, BINO represents 1,1′-dinaphthyl-2,2′-dioxy group, and THF represents tetrahydrofuran. .

  Specific examples of the ruthenium carbene complex catalyst include compounds represented by the following formula (A) or formula (B).

In the above formulas (A) and (B), ═CR ^a R ^b and ═C═CR ^a R ^b are carbene compounds containing a carbene carbon at the reaction center, and these carbene compounds contain a heteroatom. You don't have to. R ^a and R ^b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom.

L ¹ represents a heteroatom-containing carbene compound, and L ² represents a heteroatom-containing carbene compound or any neutral electron-donating compound. Both L ¹ and L ² or L ¹ is a heteroatom-containing carbene compound, and a ruthenium metal atom is directly bonded to the carbene carbon contained therein, and a group containing a heteroatom is bonded.

  Here, the hetero atom-containing carbene compound refers to a compound containing a carbene carbon and a hetero atom. Specific examples of the hetero atom include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atom is particularly preferable.

When L ² is a neutral electron donating compound, L ² may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines and pyridines are preferable, and trialkylphosphine is more preferable.

L ³ and L ⁴ each independently represent an arbitrary anionic ligand.
The L ³ and L ⁴ anionic (anionic) ligands are ligands having a negative charge when separated from the central metal. For example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydrocarbon groups containing oxygen such as diketonate group, alkoxy group, aryloxy group and carboxyl group; halogen atoms such as cyclopentadienyl chloride group Examples thereof include substituted alicyclic hydrocarbon groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

Also, 2, 3, 4, 5 or 6 of R ^a , R ^b , L ¹ , L ² , L ³ and L ⁴ are bonded to each other to form a multidentate chelating ligand. May be.

  Examples of the ruthenium carbene complex catalyst represented by the formula (A) include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl). Imidazolidine-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) Ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazole-2 Ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) Ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride, etc. A ruthenium carbene complex in which a heteroatom-containing carbene compound and a neutral electron donating compound are bonded;

  Ruthenium in which two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride are bonded. Carbene complex; and the like.

  Examples of the ruthenium carbene complex catalyst represented by the formula (B) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene). ) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  Specific examples of the metallacyclobutane complex catalyst (iii) include titanacyclobutanes.

  The amount of the metathesis reaction catalyst used is the molar ratio of the norbornene monomer to the catalyst. Catalyst: monomer = 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000,000. 000, more preferably 1: 1,000 to 1: 500,000. If the amount of catalyst is more than the molar ratio, it may be difficult to remove the catalyst, and if it is too small, sufficient polymerization activity may not be obtained.

  The ring-opening polymerization of a norbornene monomer using a metathesis reaction catalyst can be performed in a solvent or without a solvent. When the hydrogenation reaction is carried out as it is without isolating the produced polymer after completion of the polymerization reaction, the polymerization is preferably carried out in a solvent.

The solvent used is not particularly limited as long as it dissolves the produced polymer and does not inhibit the polymerization reaction.
Examples of the solvent used include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicyclo Alicyclic hydrocarbons such as heptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing compounds such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile Hydrocarbons; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, ethyl methyl ketone, cyclopentanone and cyclohexanone; methyl acetate; Ethyl, ethyl propionate, methyl benzoate, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as chlorobenzene; and the like. Among these, the use of aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters is preferable.

  The concentration of the norbornene monomer in the solvent is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and still more preferably 5 to 40% by weight. When the concentration of the norbornene monomer is less than 1% by weight, the productivity of the polymer may be deteriorated, and when it exceeds 50% by weight, the viscosity after polymerization is too high, and subsequent hydrogenation becomes difficult. There is.

  The metathesis reaction catalyst may be dissolved in a solvent and added to the reaction system, or may be added as it is without being dissolved. Examples of the solvent for preparing the catalyst solution include the same solvents as those used in the polymerization reaction.

  In the polymerization reaction, a molecular weight modifier can be added to the reaction system in order to adjust the molecular weight of the polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. A polymer having a desired molecular weight can be obtained by using 0.1 to 100 mol% of a molecular weight modifier with respect to the norbornene-based monomer represented by the formula (2).

  The polymerization temperature is not particularly limited, but is usually −100 ° C. to + 200 ° C., preferably −50 ° C. to + 180 ° C., more preferably −30 ° C. to + 160 ° C., and further preferably 0 ° C. to + 140 ° C. The polymerization time is usually from 1 minute to 100 hours, and can be appropriately adjusted according to the progress of the reaction.

A norbornene-based ring-opening polymer can be produced as described above.
The weight average molecular weight calculated | required by the gel permeation chromatography of the norbornene-type ring-opening polymer obtained is 1,000-1,000,000 normally in polystyrene conversion, Preferably it is 3,000-500,000. Preferably it is 5,000-50,000.

  The norbornene-based ring-opening polymer of the present invention may be referred to as a repeating unit derived from the spiro ring-containing norbornene derivative of the present invention (hereinafter referred to as repeating unit [I]). ), And a norbornene-based monomer-derived repeating unit represented by the above formula (4) (hereinafter sometimes referred to as “repeat unit [II]”). May be a random copolymer or a block copolymer, but a random copolymer is preferred.

When the norbornene-based ring-opening polymer of the present invention is a copolymer containing the repeating unit [I] and the repeating unit [II], the ratio of the repeating unit [I] to the total repeating units is as follows. Although it can be arbitrarily selected depending on the production purpose, it is preferably 1 to 90% by weight and more preferably 1 to 80% by weight in consideration of the balance of heat resistance, electrical characteristics, low water absorption and adhesion, and compatibility. The ratio of the repeating unit [I] contained in the norbornene-based ring-opening copolymer to all repeating units can be determined, for example, by measuring the ¹ H-NMR spectrum of the obtained ring-opening polymer.

3) Hydrogenated Norbornene Ring-Opening Polymer Polymer The third aspect of the present invention is a hydrogenated norbornene ring-opening polymer obtained by hydrogenating the main chain carbon-carbon double bond of the norbornene ring-opening polymer of the present invention. It is.

  In the norbornene-based ring-opening polymer hydride, the hydrogenated ratio of carbon-carbon double bonds (hydrogenation rate) is usually 50% or more, and 70% or more from the viewpoint of heat resistance. Preferably, it is 80% or more, more preferably 90% or more.

Hydrogenation rate of ring-opened norbornene polymer hydrides, for example, carbon in the ^{1 H-NMR} spectrum of the ring-opened norbornene polymer - a peak intensity derived from the carbon-carbon double bond, ^{1 H-NMR} spectrum of the hydride It can obtain | require by comparing with the peak intensity derived from the carbon-carbon double bond in.

  The hydrogenation reaction of the norbornene-based ring-opening polymer is, for example, converting a carbon-carbon double bond in the main chain of the norbornene-based ring-opening polymer into a saturated single bond using hydrogen gas in the presence of a hydrogenation catalyst. This can be done.

  The hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenation of olefin compounds can be used as appropriate.

  Examples of homogeneous catalysts include transitions such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium, etc. Ziegler catalyst comprising a combination of a metal compound and an alkali metal compound; ruthenium carbene complex catalyst, dichlorotris (triphenylphosphine) rhodium described in the above section of ring-opening metathesis reaction catalyst, JP-A-7-2929, JP-A-7 -149823, JP-A-11-109460, JP-A-11-158256, JP-A-11-193323, JP-A-11-109460, etc. Noble metal complex catalyst consisting ruthenium compound; and the like.

  Examples of the heterogeneous catalyst include a hydrogenation catalyst in which a metal such as nickel, palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. More specifically, for example, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more.

  Among these, rhodium and ruthenium can be selectively hydrogenated from carbon-carbon double bonds in the polymer without causing side reactions such as modification of functional groups contained in the norbornene-based ring-opening polymer. It is preferable to use a noble metal complex catalyst such as palladium and a palladium supported catalyst such as palladium / carbon, and it is more preferable to use a ruthenium carbene complex catalyst or a palladium supported catalyst.

  The ruthenium carbene complex catalyst described above can be used as a ring-opening metathesis reaction catalyst and a hydrogenation catalyst. In this case, the ring-opening metathesis reaction and the hydrogenation reaction can be performed continuously.

  In addition, when a ring-opening metathesis reaction and a hydrogenation reaction are continuously performed using a ruthenium carbene complex catalyst, a vinyl compound such as ethyl vinyl ether or a catalyst modifier such as an α-olefin is added to activate the catalyst. Then, the method of starting the hydrogenation reaction is preferably employed. Furthermore, it is also preferable to employ a method for improving the activity by adding a base such as triethylamine, an amide such as N, N-dimethylacetamide, or the like.

  The hydrogenation reaction is usually performed in an organic solvent. As an organic solvent, it can select suitably by the solubility of the hydride to produce | generate, The organic solvent similar to the said polymerization solvent can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added to the reaction solution or the filtrate obtained by filtering the metathesis reaction catalyst from the reaction solution without changing the solvent.

  The conditions for the hydrogenation reaction may be appropriately selected according to the type of hydrogenation catalyst used. The amount of the hydrogenation catalyst used is usually 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ring-opening polymer. . The reaction temperature is usually −10 ° C. to + 250 ° C., preferably −10 ° C. to + 210 ° C., more preferably 0 ° C. to + 200 ° C. If it is less than -10 degreeC, reaction rate will become slow, and conversely when it exceeds 250 degreeC, a side reaction will occur easily. The pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa, more preferably 0.1 to 5.0 MPa. When the hydrogen pressure is less than 0.01 MPa, the hydrogenation rate is slow, and when it exceeds 10.0 MPa, a high pressure reactor is required.

  The time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50% or more, preferably 70% or more, more preferably 80% or more, most preferably, of the carbon-carbon double bonds of the main chain in the polymer. Can hydrogenate more than 90%.

  Since the norbornene-based ring-opening polymer hydride of the present invention is excellent in low birefringence and low in water absorption, an optical resin material having excellent optical characteristics and dimensional stability as described below. Suitable for use.

4) Optical resin material The 4th of this invention is an optical resin material characterized by including 1 or more types of the norbornene-type ring-opening polymer hydride of this invention.

  The optical resin material of the present invention contains at least one norbornene-based ring-opening polymer hydride of the present invention as an essential component, and various additives such as a modifier, an antioxidant, a light stabilizer, if desired. A lubricant, a plasticizer, an antistatic agent, an antiblocking agent, a leveling agent and the like may be contained.

  These modifiers, antioxidants, light stabilizers, lubricants, plasticizers, antistatic agents, antiblocking agents, leveling agents and the like are not particularly limited, and known ones can be used. The amount of these additives to be used is usually 0.001 to 100 parts by weight with respect to 100 parts by weight of the norbornene ring-opening polymer hydride.

Since the optical resin material of the present invention contains the hydride of the norbornene-based ring-opening polymer of the present invention, it is excellent in low birefringence and has a low water absorption.
Therefore, the optical resin material of the present invention can be suitably used as various optical materials such as optical disks, optical lenses, optical films, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates and the like. it can.

5) Optical molded body The fifth aspect of the present invention is an optical molded body obtained by molding the optical resin material of the present invention.
The shape of the optical molded body of the present invention is not particularly limited, and may be a shape and size according to various purposes.
A molding method is not particularly limited, and a known molding method can be employed. For example, an injection molding method, an injection compression molding method, a press molding method, an extrusion molding method, a blow molding method, a vacuum molding method and the like can be mentioned. In the case of forming into a film, an extrusion molding method using a T-die, a calendar molding method, an inflation molding method, or a solution casting method can also be used.

  Since the optical molded body of the present invention uses the optical resin material of the present invention, it is excellent in optical characteristics such as low birefringence and has a low water absorption. Therefore, the optical molded body of the present invention can be suitably used as various optical members such as an optical disc, an optical lens, an optical film, a prism, a light diffusion plate, an optical card, an optical fiber, an optical mirror, a liquid crystal display element substrate, and a light guide plate. it can. Among them, Fθ lenses for laser beam printers, camera lenses, video camera lenses, viewfinder lenses, pickup lenses, collimating lenses, projection lenses for projection televisions, projection lenses for OHP, etc .; polarizing films, retardation films, light diffusion It is particularly preferably used for optical films such as sheets, prism sheets, and light collecting sheets.

Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these examples. In the following examples and comparative examples, “parts” are based on weight unless otherwise specified.
The test and evaluation in an Example and a comparative example were performed with the following method.

(1) Polymer composition ratio The polymer composition ratio of the ring-opening copolymer hydride was determined by ¹ H-NMR spectrum measurement.
(2) Hydrogenation rate The hydrogenation rate (%) of the ring-opened polymer hydride was determined by ¹ H-NMR spectrum measurement.
(3) Weight average molecular weight (Mw) and number average molecular weight (Mn)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were obtained as standard polystyrene conversion values by measuring a hydride of a ring-opening polymer by gel permeation chromatography (GPC).

(4) Glass transition temperature The glass transition temperature of the ring-opened polymer hydride is determined by using a differential scanning calorimeter (DSC 6220, manufactured by SII Nanotechnology Co., Ltd.) based on JIS K7121. It measured on condition of this.
(5) Water absorption Based on JIS K7209, the weight change after being immersed in distilled water of 23 degreeC for 24 hours was measured using the shaping | molding board of thickness 3mm.
(6) Light transmittance of molded product In accordance with ASTM D1003, a molded product (thickness 3 mm, length 65 mm, width 65 mm) formed by an injection molding method is obtained by an ultraviolet-visible spectrophotometer (manufactured by Jusco International; product name). The light transmittance was measured using “V-550”).

(7) Wavelength dependence of retardation A cast film having a thickness of 100 μm is prepared from a solution obtained by dissolving 20 parts of the ring-opened polymer hydride obtained in Examples and Comparative Examples in 80 parts of tetrahydrofuran. The cast film is uniaxially stretched freely at a temperature of 110 ° C. and a stretch ratio of 1.3 to obtain an oriented film.
About the obtained oriented film, a retardation value is measured at measurement wavelength 450nm and 550nm using KOBRA-21ADH by Oji Scientific Instruments, and let each retardation value be R (450) and R (550). If R (550) -R (450) is positive (+), the wavelength dependence of the phase difference indicates a positive correlation, and if negative (−), the wavelength dependence of the phase difference indicates a negative correlation. Represents.

(8) Photoelastic coefficient (CR value)
Using a cast film obtained in the same manner as in (7), it was determined according to the method described in the literature (Polymer Journal, 1995, Vol. 27, page 943). That is, several kinds of constant loads were applied to the cast film at a temperature 15 ° C. lower than the glass transition temperature of the ring-opened polymer hydride, and then the film was allowed to cool slowly and returned to room temperature while being stretched several percent. Measured and calculated from applied stress.

(Example 1)
(1) Production of spiro [norcamphor-3,3′-bicyclo [2.2.1] hept-5-ene] (hereinafter abbreviated as “monomer A”)

  100 parts of methylene norcamphor and 100 parts of cyclopentadiene were added to a SUS autoclave, and the system was purged with nitrogen. After the inside of the system was sealed, it was heated with a mantle heater while stirring with a stirrer, and reacted at 190 ° C. for 2 hours. After completion of the reaction, the reaction mixture was dried under reduced pressure (150 ° C., 66.5 Pa (0.5 mmHg)) to remove unreacted substances to obtain a colorless and transparent liquid with a yield of 85%.

The obtained colorless and transparent liquid was dissolved in deuterated chloroform, and ¹ H-NMR (400 MHz) and ¹³ C-NMR (100 MHz) spectra were measured with an NMR measuring apparatus (JNM-AL series AL400 manufactured by JEOL).
Moreover, the FT-IR spectrum of the obtained colorless and transparent liquid was measured with an FT-IR apparatus (Avatar 360 manufactured by Thermo Electron).
These measurement results confirmed that this compound was monomer A. The spectrum data is shown below.

¹ H-NMR (δ ppm): 1.06 (dd, 1H), 1.26 (d, 1H), 1.46 (d, 3H), 1.58 (m, 1H), 1.80 (dd, 2H), 2.07 (m, 3H), 2.66 (d, 1H), 2.84 (d, 2H), 6.21 (d, 2H)
¹³ C-NMR (δ ppm): 24.1, 26.5, 34.5, 35.5, 42.2, 44.7, 46.2, 48.3, 50.6, 59.8, 134. 4, 139.6, 222.5
FT-IR (neat): 2966.5, 2877.0, 1731.6, 1455.3, 1334.8, 1229.3, 1094.7, 1034.3, 914.1, 715.4, 695.8 (Cm ⁻¹ )

(2) Production of Ring-Opening Polymer of Monomer A In a nitrogen-replaced glass reactor, (1,3-dimesitymimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride 0 as a polymerization catalyst 0.05 part, 120 parts of toluene, 30 parts of monomer A obtained in (1), and 0.2 part of 1-hexene as a chain transfer agent were added and reacted at 70 ° C. for 2 hours to obtain a polymer solution. The polymer yield was 95% based on the monomer amount.

(3) Production of hydrogenated product of ring-opening polymer of monomer A The polymer solution obtained in (2) was placed in an autoclave equipped with a stirrer, and the inside of the autoclave was purged with nitrogen, and then (1,3-dimesitylimidazolidine 2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium 0.2 part and ethyl vinyl ether 0.5 part dissolved in 15 parts of toluene were added, and hydrogenation reaction was performed at a hydrogen pressure of 4.5 MPa and 160 ° C. for 6 hours. Went. After the autoclave was cooled to room temperature, a suspension in which 1 part by weight of activated carbon powder was dispersed in 10 parts by weight of toluene was added to the autoclave and stirred at a hydrogen pressure of 4.0 MPa and 150 ° C. for 3 hours. Next, the solution was taken out, and the activated carbon powder was filtered off with a fluororesin filter having a pore size of 0.2 μm to obtain a hydrogenation reaction solution. This hydrogenation reaction solution was poured into a large amount of methanol to completely precipitate a solid content. The solid content was collected by filtration, washed, and dried under reduced pressure at 100 ° C. for 24 hours to obtain a ring-opened polymer hydride (1).

  Weight average molecular weight (Mw) and weight average molecular weight (Mw) determined by standard polystyrene conversion of the ring-opened polymer hydride (1) obtained by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent. The values (molecular weight distribution (MWD)) divided by the number average molecular weight (Mn) were Mw = 39,000 and MWD = 2.14, respectively.

The ¹ H-NMR, ¹³ C-NMR and FT-IR measurements of the ring-opened polymer hydride (1) show that the ketone moiety is conserved, and the ring-opened polymer hydride (1) It was confirmed to be a ring-opened polymer hydride.
The hydrogenation rate of the ring-opening polymer hydride (1) measured by ¹ H-NMR was 100%.
The ring-opened polymer hydride (1) had a glass transition temperature of 151 ° C.

(4) Production of molded plate 100 parts of ring-opened polymer hydride (1) obtained in (3) and tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-) as an antioxidant 4′-hydroxyphenyl) propionate] methane (trade name: Irganox 1010, manufactured by Ciba Specialty Chemicals) was kneaded with a twin-screw kneading extruder (manufactured by Toshiba Machine Co., Ltd.), and the diameter was 3 mm. Extruded into a strand to obtain a pellet having a length of about 5 mm. The resulting pellets using an injection molding machine (manufactured by α-100, BFANUC Co.), mold temperature 100 ° C., cylinder temperature 290 ° C., a nozzle temperature of 285 ° C., holding pressure 700 Kg / ^{m 2,} the injection speed 20 mm / sec The molded plate (1) having a thickness of 3 mm, a length of 65 mm and a width of 65 mm was obtained by injection molding under the conditions.

Example 2 Production of Ring-Opening Copolymer of Monomer A and 1,4-Methano-1,4,4a, 9a-tetrahydro-9H-fluorene (hereinafter abbreviated as “MTF”) In Example 1, ( As a monomer used in 2), a polymerization solution was obtained in the same manner as in Example 1 except that a mixture of 15 parts of monomer A and 15 parts of MTF was used instead of 30 parts of monomer A. The polymer yield was 97% based on the monomer amount. The composition ratio of the obtained polymer was monomer A / MTF = 50/50.

  Next, in Example 1, instead of 0.2 part of (1,3-dimesitylmimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium used in (3), a palladium catalyst supported on silica 0 The same procedure as in Example (3) was conducted except that 3 parts and 0.6 parts of nickel catalyst were used to obtain a ring-opening copolymer hydride (2).

Weight average molecular weight (Mw) and molecular weight distribution (MWD) obtained by standard polystyrene conversion of the ring-opening copolymer hydride (2) obtained by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent are: Mw = 55,000 and MWD = 2.13, respectively.
The ¹ H-NMR, ¹³ C-NMR and FT-IR measurements of the ring-opening polymer hydride (2) show that the ketone moiety is conserved, and the ring-opening polymer hydride (2) is monomer A And a ring-opening copolymer hydride (2) of MTF.
The hydrogenation rate of the ring-opening copolymer hydride (2) measured by ¹ H-NMR was 100%.
The ring-opening copolymer hydride (2) had a glass transition temperature of 144 ° C.

  Using the obtained ring-opening copolymer hydride (2), a molded plate (2) was obtained in the same manner as in Example 1 (4).

(Comparative Example 1) Production of MTF ring-opening polymer hydrogenated product As Example 2, except that 30 parts of MTF was used instead of the mixture consisting of 6 parts of monomer A and 24 parts of MTF as the monomer used in Example 2. And a polymerization solution was obtained. The polymer yield was 98% based on the monomer amount.

Next, a ring-opened polymer hydride (3) was obtained in the same manner as in Example 2. The weight average molecular weight (Mw) and molecular weight distribution (MWD) in terms of polystyrene of the ring-opened polymer hydride (3) obtained by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent are Mw = It was 49,000 and MWD = 2.24.
The hydrogenation rate of the ring-opening polymer hydride (3) measured by ¹ H-NMR was 100%. The ring-opened polymer hydride (3) had a glass transition temperature of 138 ° C.

  Using the obtained ring-opened polymer hydride (3), a molded plate (3) was obtained in the same manner as in Example 1 (4).

(Comparative example 2) Production of ring-opening polymer hydride of cyclopentadiene / diketen adduct The following procedure was carried out with reference to Production Example 1 and Example 1 of JP-A-2005-290048.
A solution obtained by dissolving 50 parts of diketene in 90 parts of tetrahydrofuran was charged into an autoclave equipped with a stirrer, and stirred at 50 ° C. for 2 hours while adding 35 parts of cyclopentadiene little by little. The solvent of the obtained reaction solution was removed under reduced pressure, 90 parts of toluene was added to the residue, and the mixture was stirred well.
The precipitated solid component was removed by filtration, 70 parts of n-hexane was added to the filtrate, and the mixture was allowed to stand at −30 ° C. overnight. The precipitate was washed with n-hexane and dried to obtain a cyclopentadiene / diketen adduct (hereinafter abbreviated as “monomer B”).

  Into a nitrogen-substituted glass reactor, 300 parts of tetrahydrofuran (THF), 30 parts of monomer B, and 0.7 part of 1-hexene as a chain transfer agent were added, and then heated to 80 ° C. To this was added 4.5 parts of a 0.16% THF solution of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride as a polymerization catalyst, and heated at 60 ° C. for 4 hours. The polymer solution was obtained by stirring.

  The obtained polymer solution was put into an autoclave equipped with a stirrer, and the inside of the autoclave was purged with nitrogen, and then 2 parts of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 1.9 parts of ethyl vinyl ether were dissolved in 13 parts of toluene. The hydrogenation catalyst solution was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 4.7 MPa and 160 ° C. for 6 hours. After the autoclave was cooled to room temperature, a suspension in which 1 part of activated carbon powder was dispersed in 20 parts of THF was added to the autoclave and stirred at a hydrogen pressure of 4.0 MPa and 150 ° C. for 3 hours. Next, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm to remove the activated carbon powder to obtain a hydrogenation reaction solution. The hydrogenation reaction solution was poured into a large amount of methanol to completely precipitate a solid content.

  The solid content was collected by filtration, washed, and dried under reduced pressure at 60 ° C. for 24 hours to obtain a ring-opened polymer hydride (4). Using the obtained ring-opened polymer hydride (4), a molded plate (4) was obtained in the same manner as in Example 1 (4).

(Reference Example 1)
100 parts by weight of 5-norbornene-2,2-dimethanol, 95 parts by weight of triethyl orthoformate and 40 parts by weight of acetaldehyde were charged into a glass reactor, and then 0.01 parts by weight of p-toluenesulfonic acid was added, and 40 ° C. For 6 hours.

Then, after adding 300 weight part of diethyl ether and diluting, it wash | cleaned with 2N-sodium hydroxide aqueous solution and water, and confirmed the neutrality of extraction water. The organic layer was recovered, and the solvent was distilled off at 50 ° C. using an evaporator (Rotavapor RE111, manufactured by Shibata Kagaku) and a vacuum pump (A-3S, manufactured by Tokyo Rika Kikai Co., Ltd.). Was dried to obtain a pale yellow liquid. ^{According to 1} H-NMR measurement, this light yellow liquid was converted into 2′-methylspiro [bicyclo [2.2.1] hept-5-ene-2,5 ′-[1,3] dioxane] (hereinafter “monomer C”). ")." The yield of monomer C was 91%.

  Subsequently, the ring-opening polymer was obtained like Example 1 (2). The polymer yield was 93% based on the monomer amount.

  Further, a ring-opened polymer hydride (5) was obtained in the same manner as in Example 1 (3). Weight average molecular weight (Mw) and molecular weight distribution (MWD) in terms of polystyrene of the ring-opening copolymer hydride (5) obtained by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent are Mw = 33, respectively. , MWD = 2.35.

The ¹ H-NMR and ¹³ C-NMR measurements of the ring-opening copolymer hydride (5) show that the acetal group is conserved, and the ring-opening polymer hydride (5) has a ring opening weight of monomer B. It was confirmed to be a combined hydride.
The hydrogenation rate of the ring-opening polymer hydride (5) measured by ¹ H-NMR was 100%.
The ring-opened polymer hydride (5) had a glass transition temperature of 110 ° C.

  Using the obtained ring-opened polymer hydride (5), a molded plate (5) was obtained in the same manner as in Example 1 (4).

  The water absorption, light transmittance, wavelength dependence of the retardation of the cast film, and photoelastic coefficient (CR value) of the molded plates (1) to (5) obtained as described above were measured. These measurement results are shown in Table 1 together with the composition ratios of the ring-opened polymer hydrides (1) to (5) used in the production of the molded plates (1) to (5).

From Table 1, the optical molded body (molded plate) obtained by molding the ring-opened polymer hydride obtained using the spiro ring-containing norbornene derivative of the present invention has a low water absorption and a high light transmittance. The absolute value of the photoelastic coefficient was small, and the birefringence was small.

Claims (6)

Formula (1)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group containing a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom, and Z is polar Represents a C3-C10 divalent hydrocarbon group optionally having a group as a substituent, and n is 0 or 1.)
A spiro ring-containing norbornene derivative represented by: Formula (1a)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, a silicon atom, a group containing an oxygen atom or a nitrogen atom, Z ¹ is (It represents a divalent hydrocarbon group having 2 to 9 carbon atoms which may have a polar group as a substituent, and n ¹ is 0 or 1.)
A spiro ring-containing norbornene derivative represented by:   The spiro ring-containing norbornene derivative according to claim 1 or 2, or a mixture of the spiro ring-containing norbornene derivative and a norbornene monomer copolymerizable with the spiro ring-containing norbornene derivative is opened in the presence of a metathesis catalyst. A norbornene-based ring-opening polymer obtained by ring polymerization, wherein the weight average molecular weight determined by gel permeation chromatography is 1,000 to 1,000,000 in terms of polystyrene. Norbornene ring-opening polymer.   A hydrogenated norbornene-based ring-opening polymer obtained by hydrogenating 50% or more of the main chain carbon-carbon double bond of the norbornene-based ring-opening polymer according to claim 3.   An optical resin material comprising at least one of the norbornene-based ring-opening polymer hydrides according to claim 4. An optical molded body obtained by molding the optical resin material according to claim 5.