JPH0826124B2 - Optical materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is an optical element suitably used as a material for video discs, compact discs, recordable optical discs, recordable / erasable / reproducible optical discs, plastic lenses, and the like. It is about materials.

[Conventional technology]

In recent years, transparent resins have been applied as optical materials that place importance on optical properties, in addition to being used as molding materials that require ordinary transparency such as automobile parts, lighting equipment, electric parts, and sundries. There is. Further, as an optical material, not only mere transparency but also a high level of function which is not satisfied with conventional transparent resins is required more than ever.

For example, as a substrate material of an optical disc as an optical material, polycarbonate resin, polymethylmethacrylate resin, polycyclohexylmethacrylate resin, copolymer resin of alkylmethacrylate and methylmethacrylate, styrene or other monomer, bulky ester group Containing a methacrylic acid ester having ethylene, a copolymer of ethylene and a norbornene-based hydrocarbon compound using a Ziegler-Nutter catalyst (JP-A-61-292601)
Or a polymer obtained by hydrogenating a ring-opening (co) polymer of a tetracyclododecene hydrocarbon compound with a metathesis catalyst or a norbornene hydrocarbon compound (JP-A-60-26024), or An optical material comprising a ring-opening polymer or a ring-opening copolymer of a norbornene derivative having a polar substituent (Japanese Patent Laid-Open No. 62-19801 and Japanese Patent Laid-Open No. 6-19801).
No. 2-19802) is known.

[Problems to be solved by the invention]

However, the above-mentioned optical material does not satisfy all of low birefringence, low hygroscopicity, mechanical strength, and adhesiveness to a recording layer, which are particularly required as a substrate material for an optical disc.

For example, polystyrene resin or polycarbonate resin having a large birefringence has many errors when reproducing information by laser light, and polymethylmethacrylate resin having a large hygroscopic property causes many errors when reproducing information because of deformation due to moisture absorption. At the same time, there is a high possibility that the quality of the recording film will change due to moisture absorption. Polycyclohexyl methacrylate resin also has a problem of poor heat resistance due to its low glass transition point. A copolymer with methyl methacrylate has a high hygroscopicity, while a copolymer with styrene has an increased birefringence. Optical properties are inferior.

Further, a norbornene-based hydrocarbon (co) polymer obtained from a Ziegler-Nutter-based catalyst or a tetracyclododecene-based hydrocarbon compound by metathesis ring-opening polymerization,
Alternatively, a polymer obtained by hydrogenating a norbornene-based hydrocarbon (co) polymer has improved birefringence, hygroscopicity, and heat resistance, but has no polar group involved in adhesion. Therefore, it has a drawback that the adhesiveness to the recording layer is poor.

In addition, an optical material composed of a ring-opening (co) polymer of a norbornene derivative having a polar group improves adhesion to the recording layer due to the presence of the polar group, but a polar substituent group that raises the glass transition temperature. If the saturated water absorption is high, on the other hand, if a polar substituent that lowers the saturated water absorption is selected, the glass transition temperature will be low, so both high glass transition temperature and low water absorption will occur. It was difficult to satisfy both.

Furthermore, since the structure of the polymer contains an unsaturated double bond, there is a problem that long-term durability is a concern.

As described above, conventionally, sufficient optical properties, low hygroscopicity,
At present, most suitable optical materials having heat resistance and excellent adhesion (durability) to the recording layer have not been obtained.

[Means for solving problems]

An object of the present invention is to provide an optical material having excellent optical properties, low hygroscopicity, and heat resistance.

The optical material of the present invention comprises a polymer of at least one compound represented by the following general formula (I), or a polymer obtained by polymerizing the compound and another copolymerizable monomer:
It is characterized by comprising a hydrogenated polymer obtained by hydrogenation.

General formula (1) [In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, Z represents an alkyl group having 1 to 10 carbon atoms, and m is 0 or 1.

In the above general formula (I), specific examples of the tetracyclodecene derivative in which the value of m is 1 include 8-methyl-8-carboxymethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxyethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxy n-propyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxyisopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxy n-butyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxy sec-butyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxy t-butyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxycyclohexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxy (4′-t-butylcyclohexyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 3-
Dodecene, 8-methyl-8-carboxymenthyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxybornyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxyisobornyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxyadamantyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxybicyclo [2.2.1] -2
-Heptyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8-methyl-8-carboxytetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3- ^{Dodecyltetracyclo} [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxytricyclo [5.2.1.
0 ^2,6 ] -8-decyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxypentacyclo [6.5.1.1
^3,6 . 0 ^2,7 . 0 ^9,13] -4-penta decyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxytricyclo [6.2.1.
0 ^2,7 ] -9-undecyl tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8-methyl-8-carboxypentacyclo [6.6.1.1
^3,6 . 0 ^2,7 . 0 ^9,14] -4-hexadecyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, and the like.

In the above general formula (I), specific examples of bicyclo [2.2.1] -2-heptene in which the value of m is 0 include 5-methyl-5-carboxymethylbicyclo [2.2.
1] -2-heptene, 5-methyl-5-carboxycyclohexylbicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxy (4'-t-butylcyclohexyl) bicyclo [2.2.1] -2 -Heptene, 5-methyl-5-carboxymenthylbicyclo [2.2.
1] -2-heptene, 5-methyl-5-carboxybornylbicyclo [2.2.
1] -2-heptene, 5-methyl-5-carboxyadamantylbicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxybicyclo [2.2.1] -2
-Heptylbicyclo [2.2.1] -2-heptene, 5-methyl-2-carboxytetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-Dodecylbicyclo [2.2.1] -2-
Heptene, 5-methyl-5-carboxytricyclo [5.2.1.
0 ^2,6 ] -8-decyl-bicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxypentacyclo [6.5.1.1]
^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-Pentadecylbicyclo [2.2.
1] -2-heptene, 5-methyl-5-carboxytricyclo [6.2.1.
0 ^2,7 ] -9-Undecylbicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxypentacyclo [6.6.1.1]
^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-Hexadecylbicyclo [2.2.
1] -2-heptene, and the like.

In the compound represented by the above general formula (I),
Since the polar substituent consisting of the carboxylic acid ester group represented by the formula —COOR is bonded, the obtained polymer has a high glass transition temperature and low hygroscopicity.

Further, this monomer is easy to synthesize, and the resulting polymer has good characteristics. R is a hydrocarbon group having 1 to 20 carbon atoms, and it is preferable that the carbon number increases, because the hygroscopicity of the polymer decreases. However, a chain hydrocarbon group having 1 to 4 carbon atoms or a (poly) cyclic hydrocarbon group having 5 or more carbon atoms is preferable from the viewpoint of the balance with the glass transition temperature of the obtained polymer.

Furthermore, since the alkyl group having 1 to 10 carbon atoms is bonded to the carbon atom to which the carboxylic acid ester group is bonded, hygroscopicity can be reduced without lowering the glass transition temperature of the obtained polymer, and particularly, The one in which the alkyl group is a methyl group is preferable because it is easy to synthesize the raw material monomer.

Hydrogenated polymer obtained by hydrogenating a polymer of at least one compound represented by the above general formula (I) or obtained by hydrogenating a copolymer of the derivative and another copolymerizable monomer. The resulting hydrogenated polymer constitutes the optical material of the present invention. In the case of a copolymer, the proportion of the monomer of general formula (I) contained in the copolymer is
It is 5 mol% or more, preferably 20 mol% or more. And as a copolymerizable monomer in the case of a copolymer, a monomer that can be ring-opening polymerized by a metathesis catalyst and a partially polymerized low molecular weight having a carbon-carbon double bond in the main chain of the polymer Polymers of

In addition, the tetracyclododecene derivative in which m is 1 in the above general formula (I) is more preferable than m = 0 in that a polymer having a high glass transition point can be obtained, and it is subjected to ring-opening copolymerization with a cyclic olefin compound. It is also possible to form a copolymer. Specific examples of such cyclic olefin compounds include cyclopentene, cyclooctene, 1,5-cyclooctadiene, cycloolefins such as 1,5,9-cyclododecatriene, bicyclo [2.2.1] -2-heptene, tricyclo [5.2.1.0 ^2,6 ] -8-decene, tricyclo [5.
2.1.0 ^2,6 ] -3-decene, tricyclo [6.2.1.0 ^1,8 ]-
9-undecene, tricyclo [6.2.1.0 ^1,8 ] -4-undecene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]-
4-pentadecene, pentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 .
0 ^9,14 ] -4-Hexadecene, Pentacyclo [6.5.1.1
^3,6 . 0 ^2,7 . 0 ^9,13 ] -11-pentadecene, dicyclopentadiene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]
Mention may be made of polycycloalkenes such as pentadeca-4,11-diene.

The above polycycloalkene is useful for lowering the hygroscopicity of the copolymer and controlling the glass transition temperature of the copolymer. Therefore, when the glass transition temperature of a tetracyclodecene homopolymer or a copolymer with bicycloheptene is high and close to the thermal decomposition temperature, or higher, it is copolymerized with a cycloolefin to reduce the glass transition temperature. In fact, the temperature can be lowered to a temperature at which molding can be easily performed.

In addition, the glass transition temperature of the obtained polymer is low and 100
When the temperature is lower than 0 ° C, the hygroscopicity of the polymer can be lowered and the glass transition temperature can be raised by copolymerizing the polycycloalkene.

Further, the compound represented by the general formula (I) is a polymer such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene non-conjugated diene copolymer rubber, polynorbornene, and polypentenamer. It is also possible to copolymerize with an unsaturated hydrocarbon polymer containing a double bond.

The (co) polymer obtained as described above preferably has a saturated water absorption of 1.8% or less and a glass transition temperature of 100 ° C or more. The saturated water absorption is more preferably 1.2% or less, most preferably 0.8% or less. Glass transition temperature is 120 ℃
The above is more preferable.

The metathesis catalyst used for producing a ring-opening (co) polymer is usually (a) at least one selected from W, Mo and Re compounds, and (b) Deming's periodic table I.
A catalyst composed of a compound of A, IIA, IIB, IIIA, IVA or IVB group elements and at least one selected from the group having at least one element-carbon bond or element-hydrogen bond. It may be one to which an additive for enhancing the above is added.

Suitable W, Mo or Re compounds as the component (a) include halides, oxyhalides, alkoxyhalides, alkoxides and carboxylates of these compounds.
(Oxy) acetylacetonate, carbonyl complex, acetonitrile complex, hydride complex, and derivatives thereof,
Alternatively, although it is a combination thereof, compounds of W and Mo, particularly halides, oxyhalides and alkoxyhalides thereof are preferable from the viewpoint of polymerization activity and practicality. Further, it may be a mixture of two or more kinds of compounds which produce the above compounds by the reaction. These compounds may be complexed with a suitable complexing agent such as P (C ₆ H ₅ ) ₅ , C ₅ H ₅ N and the like.

Specific examples include WCl ₆ , WCl ₅ , WCl ₄ , WBr ₆ , WF ₆ , W
I ₆ , MoCl ₅ , MoCl ₄ , MoCl ₃ , ReCl ₃ , WOCl ₄ , MoOCl ₃ , ReO
_{Cl 3, ReOBr 3, W (} OC 6 H 5) 6, WCl 2 (OC 6 H 5) 4, Mo (OC 2 H 5) 2 Cl
₃ , Mo (OC ₂ H ₅ ) ₅ , MoO ₂ (acac) ₂ , W (OCOR) ₅ , W (OC ₂ H ₅ ) ₂ C
l ₃ , W (CO) ₆ , Mo (CO) ₆ , Re ₂ (CO) ₁₀ , ReOBr ₃・ P (C ₆ H ₅ ) ₃ ,
WCl ₅・ P (C ₆ H ₅ ) ₃ , WCl ₆・ C ₅ H ₅ N, W (CO) ₅・ P (C ₆ H ₅ ) ₃ , W
Examples include (CO) ₃ and (CH ₃ CN) ₃ . The _{MoCl 5, Mo (OC 2 H} 5) 2 Cl 3 Particularly preferred compounds of the above, WCl _6,
W (OC ₂ H ₅ ) ₂ Cl _{3 and the} like can be mentioned.

Suitable compounds as the component (b) are IA and II of the periodic table.
A compound of group A, IIB, IIIA, IVA or IVB having at least one element-carbon junction or a hydride thereof. Specific examples, n-C ₄ H ₅
Li, n-C ₅ H ₁₁ Na, C ₅ H ₅ Na, CH ₃ MgI, C ₂ H ₅ MgBr, CH ₃ MgB
_{r, n-C 3 H 7} MgCl, (C 6 H 5) 3 Al, t-C 4 H 9 MgCl, CH 2 = CHC
_{H 2 MgCl, (C 2 H} 5) 2 Zn, (C 2 H 5) 2 Cd, CaZn (C 2 H 5) 4, (CH 3) 3
_{B, (C 2 H 5)} 3 B, (nC 4 H 9) 3 B, (CH 3) 3 Al, (CH 3) 2 AlCl,
_{(CH 3) 3 Al 2 Cl} 3, CH 3 AlCl 2, (C 2 H 5) 3 Al, LiAl (C 2 H 5) 2, (C
_{2 H 5) 3 Al-O} (C 2 H 5) 2, (C 2 H 5) 2 AlCl, C 2 H 5 AlCl 2, (C 2 H 5)
₂ AlH, (iso-C ₄ H ₉ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (iso-C ₄ H ₉ ) ₃ A
_{l, (C 2 H 5)} 3 Al 2 Cl 3, (CH 3) 4 Ga, (CH 3) 4 Sn, (n-C 4 H 9) 4
_{Sn, (C 2 H 5)} 3 SiH, (n-C 6 H 13) 3 Al, (n-C 4 H 17) 3 Al,
_{LiH, NaH, B 2 H 6} , NaBH 4, AlH 3, LiAlH 4, BiH 4 and TiH
₄ and so on. It is also possible to use a mixture of two or more compounds which produce these compounds by the reaction.

Particularly preferred examples include (CH ₃ ) ₃ Al, (CH ₃ ) ₂ Al
_{Cl, (CH 3) 3 Al} 2 Cl 3, CH 3 AlCl 2, (C 2 H 5) 3 Al, (C 2 H 5) 2 AlC
_{l, (C 2 H 5)} 1.5 AlCl 1.5, C 2 H 5 AlCl 2, (C 2 H 5) 2 AlH, (C 2 H 5)
₂ AlOC ₂ H ₅ , (C ₂ H ₅ ) ₂ AlCN, (C ₃ H ₇ ) ₃ Al, (iso-C ₄ H ₉ ) ₃ A
_{l, (iso-C 4 H} 9) 2 AlH, (C 6 H 13) 3 Al, (C 8 H 17) 3 Al, (C
₆ H ₅ ) ₅ Al and the like.

Regarding the quantitative relationship between the component (a) and the component (b), the metal atom ratio (a) :( b) is used in the range of 1: 1 to 1:20, preferably 1: 2 to 1:10.

The catalyst prepared from the above two components (a) and (b) usually has a high activity in the polymerization reaction for obtaining the optical material of the present invention, but if desired, as described below ( By adding the component c) (activator), it is possible to obtain a catalyst with higher activity.

Although various compounds can be used as the component (c), the following compounds are particularly preferably used.

(1) Elemental boron, BF ₃ , BCl ₃ , B (OnC ₄ H ₉ ) ₃ , (C ₂ H
₅ O ₃ ) ₂ , BF, B ₂ O ₃ , H ₃ BO ₃ and other non-organometallic compounds of boron, Si (OC ₂ H ₅ ) ₄ and other non-organometallic compounds of silicon, (2) alcohols, hydro Peroxides and peroxides, (3) water, (4) oxygen, (5) carbonyl compounds such as aldehydes and ketones and polymers thereof, (6) cyclic ethers such as ethylene oxide, epichlorohydrin and oxetane, (7) N , N-diethylformamide, N, N-dimethylacetamide and other amides, aniline, morpholine, amines such as piperidine and azo compounds such as azobenzene, (8) N-nitrosodimethylamine, N-nitrosodiphenylamine and other N- Nitroso compounds, (9) S-Cl such as trichloromelamine, N-chlorosuccinimide, and phenylsulfenyl chloride Others include such compounds including N-Cl group.

Further, the quantitative relationship between the component (a) and the component (b) cannot be uniformly defined because it varies extremely depending on the type of the component (c) to be added, but in many cases (c)
/ (A) (molar ratio) is 0.005 to 10, preferably 0.05 to 1.0
Used in the range of.

The molecular weight of the obtained ring-opening (co) polymer can be adjusted by changing the reaction conditions such as the kind and concentration of the catalyst, the polymerization temperature, the kind and amount of the solvent, and the monomer concentration. Preferably α-olefins,
Suitable compounds having at least one carbon-carbon double bond or carbon-carbon triple bond in the molecule such as α, ω-diolefins or acetylenes, or polar allyl compounds such as allyl chloride, allyl acetate and trimethylallyloxylan Adjusted by adding the amount to the reaction system.

The solvent used in the polymerization reaction, for example, pentane, hexane, heptane, octane, nonane, alkanes such as decane, cyclohexane, cycloheptane, cyclooctane, decalin, cycloalkanes such as norbornane, benzene, toluene, xylene, ethylbenzene. , Aromatic compounds such as cumene, chlorobutane, bromhexane, methylene chloride, dichloroethane,
Hexamethylene dibromide, halogenated alkanes such as chlorobenzene, compounds such as aryl, ethyl acetate,
Examples include saturated carboxylic acid esters such as methyl propionate and ethers.

The hydrogenation reaction of the polymer obtained by the metathesis ring-opening polymerization is carried out by a usual method. As the catalyst used in this hydrogenation reaction, those used in ordinary hydrogenation reactions of olefinic compounds can be used.

For example, as the heterogeneous catalyst, palladium, platinum,
A solid catalyst in which a catalyst substance such as nickel, rhodium or ruthenium is supported on a carrier such as carbon, silica, alumina or titania can be used.

Further, as a homogeneous catalyst, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium Examples thereof include rhodium catalysts.

The hydrogenation reaction is carried out at atmospheric pressure to 300 atm, preferably 3 to 150 atm.
It can be carried out at 0 to 180 ° C., preferably 20 to 150 ° C. under a hydrogen gas atmosphere at atmospheric pressure.

By hydrogenating in this way, the resulting hydrogenated (co) polymer has excellent thermal stability, and as a result, its properties deteriorate due to heating during molding and use as a product. There is no. The hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably
80%. When the hydrogenation rate is less than 50%, the effect of improving thermal stability is small.

The optical material of the present invention is a known antioxidant, for example, 2,6
-Di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, phenyl-β-naphthylamine, or an ultraviolet absorber, for example 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
It can be stabilized by adding 2'-hydroxy-4-methoxy-2'-carboxybenzophenone or the like. Further, in order to improve the processability, additives such as lubricants which are conventionally used in resin processing can be added.

The optical material of the present invention can be made into an optical product by applying various known molding means. That is, an injection molding method, a compression molding method, an extrusion molding method or the like can be used.

The optical material according to the present invention has, on its surface, a thermosetting method,
Inorganic compounds, organic silicon compounds such as silane coupling agents, acrylic monomers, vinyl monomers, melamine resins, epoxy resins, fluororesins, by methods such as ultraviolet curing, vacuum deposition, sputtering, and ion plating. By hard coating a silicone resin or the like, heat resistance, optical characteristics, chemical resistance, abrasion resistance, moisture permeability, etc. can be improved.

The use of the optical material of the present invention is not particularly limited and can be used in a wide range, for example,
It can be particularly preferably used for lenses for general cameras, lenses for video cameras, lenses for telescopes, lenses for laser beams and the like, and optical discs such as optical video discs, audio discs, document file discs and memory discs.

〔effect〕

Since the optical material of the present invention comprises a hydrogenated product of a polymer or copolymer of the compound represented by the general formula (I), it has excellent optical properties, that is, high transparency and low birefringence. At the same time, it has excellent heat resistance and high mechanical strength, has sufficient moisture resistance, and has good moldability.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 In a nitrogen atmosphere, in a reaction vessel purged with nitrogen,
Monomer represented by Structural Formula (1) 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene 50 g, 1,2-dichloroethane 200 ml, molecular weight regulator 1-hexene 0.38, catalyst WCl ₆ concentration 0.05 M / l 9.16 ml chlorobenzene solution, paraaldehyde concentration 0.1 M / 6.8 of l of 1,2-dichloroethane solution
7 ml and 3.7 ml of a toluene solution of triisobutylaluminum having a concentration of 0.5 M / l were added and reacted at 60 ° C. for 10 hours,
Intrinsic viscosity (η _inh ) 0.56dl / g (in chloroform, 30 ℃,
A polymer having a concentration of 0.5 g / dl) was obtained.

20 g of this polymer is dissolved in 400 ml of toluene, and 25 g of nickel naphthenate (nickel concentration 5%) and 64 ml of a toluene solution of triethylaluminum at a concentration of 1M / l are added, and a hydrogen gas pressure of 50 kg / cm ^{2 is} charged at 60 ° C for 15 The hydrogenation reaction was carried out for an hour.

The obtained hydrogenated polymer was poured into a large excess amount of hydrochloric acid-acidified methanol, and the catalyst was decomposed and removed to recover the hydrogenated polymer, which was further dried.

The obtained polymer was press-molded at 300 ° C. to prepare a test piece, and various characteristics of this test piece were measured. The results are shown in Table 1.

Example 2 8-Methyl-represented by Structural Formula (1) as a monomer
8-Carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene 42.5 g and 5-methyl-5-carboxycyclohexylbicyclo [2.2.1] -2-heptene 7.5 g represented by the structural formula (2) were used in the same manner as in Example 1. Ring-opening polymerization was performed to obtain a polymer having an intrinsic viscosity (η _inh ) of 0.73 dl / g.

50 g of this polymer was dissolved in 1000 ml of tetrahydrofuran, and 1.0 g of Rh / C catalyst with a Rh concentration of 2% was used and the hydrogen gas pressure was 14
The reaction was carried out at 0 kg / cm ² and a temperature of 120 ° C. for 7 hours to obtain a hydrogenated polymer having a hydrogenation rate of 70%. The catalyst was filtered off, the hydrogenated polymer was solidified and recovered, and molded and processed in the same manner as in Example 1 to prepare a test piece, and various properties were measured in the same manner. The test results are shown in Table 1.

Example 3 8-Methyl-represented by Structural Formula (1) as a monomer
8-Carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1
^A ring-opening polymerization was similarly carried out using 40 g of ^7,10 ] -3-dodecene and 40 g of cyclopentene represented by the structural formula (3) to obtain a polymer having an intrinsic viscosity (η _inh ) of 0.74 dl / g.

This polymer was hydrogenated in the same manner as in Example 2 to prepare a hydrogenated polymer having a hydrogenation rate of 70%.
Molding was performed in the same manner as described above to prepare a test piece, and various characteristics were measured in the same manner. The test results are shown in Table 1.

Comparative Example 1 8-Carboxymethyltetracyclo [4.4.0.1 ^2,5 . Intrinsic viscosity (η _inh ) 0.7 in the same manner as in Example 1 except that 50 g of 1 ^7,10 ] -3-dodecene was used.
A polymer of 8 dl / g (30 ° C. in chloroform, concentration: 0.5 g / dl) was obtained, and a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain a hydrogenated polymer.

This hydrogenated polymer was molded in the same manner as in Example 1 to prepare a test piece, and various properties were measured in the same manner. The test results are shown in Table 1.

Comparative Example 2 Using 5-carboxymethyl-bicyclo [2.2.1] -2-heptene represented by the structural formula (5) as a monomer,
Using the tungsten hexachloride-triisobutylaluminum-paraaldehyde catalyst used in Example 1 and 1-hexene as a molecular weight modifier, an intrinsic viscosity (η _inh ) of 0.56 dl / g (in chloroform, 30 ℃, concentration
0.5 g / dl) of the polymer was obtained, and this was molded in the same manner as in Example 1 without hydrogenation reaction to prepare a test piece, and various properties were measured in the same manner. The test results are shown in Table 1.

Comparative Example 3 A polymer having the same structure as Comparative Example 2 and an intrinsic viscosity of 0.74 dl / g was hydrogenated under the same conditions as in Example 1 to prepare a polymer having a hydrogenation rate of 90%, and the same as in Example 1. A test piece was prepared by molding into various pieces, and various properties were measured. The test results are shown in Table 1.

Comparative Example 4 8-Methyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene was reacted with a ruthenium trichloride hydrate catalyst in an n-butanol solvent to synthesize a ring-opening polymer, which was molded and processed in the same manner as in Example 1 to give a test piece. It was produced and various properties were measured in the same manner. The test results are shown in Table 1.

Comparative Example 5 A hydrogenated polymer was prepared by using the polymer synthesized in Comparative Example 4 in a tetrahydrofuran solvent with a Pd / diatomaceous earth catalyst having a Pd concentration of 2% under a hydrogen gas pressure of 50 kg / cm ² . The hydrogenation rate was 90%. The catalyst was filtered off and the polymer was solidified and recovered. Molding was performed in the same manner as in Example 1 to prepare a test piece, and various characteristics were measured in the same manner. The test results are shown in Table 1.

The structural formulas of the monomers used above are as follows.

The methods for measuring various properties of the test piece are as follows.

Glass transition temperature 10 by scanning calorimeter (DSC) under nitrogen atmosphere
It was measured at a temperature rising rate of ° C / min.

Saturated water absorption The sample was immersed in water to absorb water into the sample, and the weight w ₁ of the sample after reaching the equilibrium state was measured, and then this sample was heated to 200 ° C under a dry nitrogen stream, The amount w ₂ of water released by was quantified by the Karl Fischer method, and the saturated water absorption was calculated by the following formula.

Birefringence value Measured by an ellipsometer.

Hydrogenation rate Using H-NMR, the rate of disappearance of olefinic protons in the test piece polymer was measured.

Photo-deterioration A test piece having a thickness of 1 mm was irradiated with a carbon arc lamp for 100 hours using a fade meter, and the coloring state of the test piece was examined.

Adhesiveness Aluminum was vapor-deposited on a resin substrate, 100 1mm x 1mm grids were cut with a cutter, and a cellotape peeling test was performed to evaluate the adhesiveness. That is, the number of peeled squares
Those with 10 or less were marked with "O", and those with 11 or more were marked with "X".

As is clear from Table 1, the hydrogenated (co) polymer according to the present invention has excellent optical properties, low hygroscopicity,
An optical material having heat resistance and light resistance can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Iio 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (56) Reference JP-A-63-317520 (JP, A)

Claims (1)

[Claims] 1. Hydrogen obtained by hydrogenating a polymer of at least one compound represented by the following general formula (I) or a polymer obtained by polymerizing the compound and another copolymerizable monomer. An optical material comprising a polymerized polymer. General formula (1) [In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, Z represents an alkyl group having 1 to 10 carbon atoms, and m is 0 or 1.