JP4887753B2 - Cyclic olefin polymer, process for producing the same, and optical component for blue laser - Google Patents

Description

  The present invention relates to a cyclic olefin polymer, a method for producing the same, and an optical component for a blue laser. More specifically, even if the integrated irradiation amount of blue laser light having a wavelength of around 400 nm is large, the cyclicity of the light transmittance due to white turbidity is small. The present invention relates to an olefin polymer, a process for producing the same, and an optical component for a blue laser using the cyclic olefin polymer.

An optical component is a component that utilizes optical phenomena such as refraction, reflection, diffraction, and birefringence. Optical components include, for example, convex lenses, concave lenses, Fresnel lenses, collimating lenses, lenticular lenses, pickup lenses, grating lenses, geodesic lenses, fθ lenses, aspheric lenses, lenses for optical devices; prisms; MO, DVD, CD, etc. And an optical sheet or plate for a display device such as a retardation plate, a polarizing plate, a light reflecting plate, a light diffusing plate, a light guide plate, and a prism sheet.
Among these, optical components used in information equipment that writes and reads information by light, such as pickup lenses and prisms, do not change their characteristics even when the cumulative amount of light irradiation increases. It has been demanded. In particular, information devices using blue laser light capable of realizing a high recording density have been developed, and development of optical components for blue lasers corresponding to this has been demanded.

Patent Document 1 discloses a resin containing a cyclic olefin polymer obtained by polymerizing and hydrogenating an α-olefin having 2 to 20 carbon atoms and a norbornene monomer, an antioxidant, and a surfactant. A plastic optical component formed by molding a material is disclosed. Patent Document 1 states that even when an optical element formed of a resin material containing an antioxidant is irradiated with light having a wavelength of about 400 nm for 1000 hours, the deterioration of light transmittance is 1% or less.
Cyclic olefin polymers are used in optical materials because they give molded products with excellent transparency and good optical properties, but in order to obtain more stable optical properties, in general, antioxidants and surfactants are used. The agent is blended. However, it is known that a compound such as an antioxidant may cause foreign matters during molding, and the amount of the antioxidant or the surfactant to the optical element material is as small as possible. It is hoped to do.
Patent Document 2 proposes to apply a novel polymer resin containing a norbornene-based monomer having a fused cyclohexane ring as a monomer unit to the optical field or the like.

Japanese Patent Laid-Open No. 2004-197067 International Publication No. WO99 / 09085

However, as a result of the inventor's investigation, in an optical component using a resin specifically disclosed in the examples of Patent Documents 1 and 2, the light transmittance decreases as the accumulated dose of blue laser increases. I found it easy.
An object of the present invention is to provide a cyclic olefin polymer in which the decrease in light transmittance due to white turbidity is small even when the integrated irradiation amount of blue laser light having a wavelength of around 400 nm increases, a method for producing the same, and an optical component for blue laser. It is in.

  As a result of intensive studies to achieve the above object, the present inventor has detected an addition polymer of a cyclic olefin (A) and an α-olefin (B) having 2 to 20 carbon atoms with an ultraviolet spectroscopic detector. The cyclic olefin polymer in which the ratio between the peak area detected by the differential refractometer and the peak area detected by the differential refractometer is in a specific range allows light transmission due to white turbidity even when the integrated dose of blue laser light having a wavelength of around 400 nm increases. We found that there was little decline in rate. The present invention has been completed based on this finding.

Thus, according to the present invention,
(1) An addition polymer of a cyclic olefin (A) and an α-olefin (B) having 2 to 20 carbon atoms, and an ultraviolet spectroscopic detector having a wavelength of 210 nm as analyzed by gel permeation chromatography (GPC) The percentage ((UV peak area) / (RI peak area) × 100) of the peak area (UV peak area) detected at 1 to the peak area (RI peak area) detected by the differential refractometer is 2.5 or less. Certain cyclic olefin polymers are provided.

Also according to the invention,
(2) There is provided a process for producing the above cyclic olefin polymer, which comprises addition polymerization of a cyclic olefin (A) and an α-olefin (B) having 2 to 20 carbon atoms and then contacting with hydrogen.

And according to the present invention,
(3) An optical component for a blue laser comprising the above cyclic olefin polymer is provided.

  Even if the cyclic olefin polymer of the present invention is not blended with an antioxidant, even if a large amount of blue laser light having a wavelength of about 400 nm is irradiated, it does not become cloudy and has little decrease in light transmittance, and has low birefringence. A molded product exhibiting high light transmittance can be provided. Since it has such characteristics, the optical component for a blue laser using the cyclic olefin polymer of the present invention is, for example, a convex lens, a concave lens, a Fresnel lens, a collimating lens, a lenticular lens, a grating lens, a geodesic lens, an fθ lens, Optical device lenses such as aspherical lenses; prisms; optical information recording media such as MO, DVD, and CD; optical devices for display devices such as retardation plates, polarizing plates, light reflecting plates, light diffusing plates, light guide plates, and prism sheets It can be used as a sheet or plate; In particular, it is suitable as an optical element used in information equipment for writing and reading information with blue laser light, such as a pickup lens and a prism.

The cyclic olefin polymer of the present invention is an addition polymer of a cyclic olefin (A) and an α-olefin (B) having 2 to 20 carbon atoms.
Typical examples of the cyclic olefin (A) include monocyclic cycloalkenes and monomers having a norbornene ring structure (hereinafter referred to as norbornene monomers).

  Monocyclic cycloalkenes include cyclobutene, 1-methylcyclobutene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclooctene, 1-methylcyclooctene, 5- Examples include methylcyclooctene, cyclooctatetraene, cyclododecene; 1,5-cyclooctadiene, cyclopentadiene, cyclohexadiene, and the like.

As norbornene monomers, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-methyl-1,4,4a, 9a-tetrahydrofluorene, 1,4- Methano-8-chloro-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-bromo-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 9a-tetrahydrodibenzofuran, 1,4-methano-1,4,4a, 9a-tetrahydrodibenzothiazine, 1,4-methano-1,4,4a, 9a-tetrahydrocarbazole, 1,4-methano-9-phenyl -1,4,4a, 9a-tetrahydrocarbazole, 7,10-methano-6b, 7,10,10a-tetrahydrofluoranthene, 7,10-methano-6b Compound obtained by adding cyclopentadiene to 7,10,10a-tetrahydrofluorane, compound obtained by adding cyclopentadiene to acanthrylene, compound obtained by adding cyclopentadiene to acephenanthrylene, 11,12-benzo-pentacyclo [6 .5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, 11,12-benzo - pentacyclo [6.6.1.1 ^{3, 6.} 0 ^2,7 . 0 ^9,14] -4-hexadecene, 14,15-benzo - heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^{11, 17} . 0 ^3,8 . Having an aromatic ring condensed to an alicyclic ring such as 0 ^12,16 ] -5-eicosane;

5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-o-tolyl-bicyclo [2.2.1] hept-2-ene, 5-m-tolyl-bicyclo [2.2. 1] hept-2-ene, 5-p-tolyl-bicyclo [2.2.1] hept-2-ene, 5-o-ethylphenyl-bicyclo [2.2.1] hept-2-ene, 5 -M-ethylphenyl-bicyclo [2.2.1] hept-2-ene, 5-p-ethylphenyl-bicyclo [2.2.1] hept-2-ene, 5-p-isopropylphenyl-bicyclo [ 2.2.1] hept-2-ene, 8-phenyltetracyclo [4.4.0.1 ^2,5 . Having an aromatic ring bonded as a substituent to an alicyclic ring such as 1 ^{7, 10} ] dodec-3-ene, 5- (naphthalen-1-yl) bicyclo [2.2.1] hept-2-ene;

Norbornene, dicyclopentadiene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (also called tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isobutyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-stearyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 2,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 2,7,9-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 9-ethyl-2,7-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 9-isobutyl-2,7-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 9-isobutyl-2,7-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 9,11,12-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 9-ethyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 9-isobutyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5,8,9,10-tetramethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-bromotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-dichlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . And those having no aromatic ring, such as ^{17, 10} ] dodec-3-ene, pentacyclopentadecene, pentacyclopentadedecadiene.
The amount of the cyclic olefin (A) is preferably 15 to 55 mol%, more preferably 20 to 50 mol%, based on all monomers to be polymerized.

The α-olefin (B) having 2 to 20 carbon atoms is an unsaturated hydrocarbon compound having an unsaturated double bond between the terminal carbon and the adjacent carbon. Examples of the α-olefin (B) include ethylene, propylene, but-1-ene, penta-1-ene, hexa-1-ene, octa-1-ene, deca-1-ene, and dodec-1-ene. Tetradec-1-ene, hexadec-1-ene, octadec-1-ene, eicosa-1-ene; 3-methylbut-1-ene, 3-methylpent-1-ene, 3-ethylpent-1-ene, 4 -Methylpent-1-ene, 4-methylhex-1-ene, 4,4-dimethylhex-1-ene, 4,4-dimethylpent-1-ene, 4-ethylhex-1-ene, 3-ethylhexa-1 -Ene, vinylcyclohexane, vinylcyclohexene, 1,4-pentadiene, 1,5-hexadiene and the like. Of these, ethylene is preferred.
The amount of the α-olefin (B) is preferably 45 to 85 mol%, more preferably 50 to 80 mol%, based on all monomers to be polymerized.

The cyclic olefin polymer of the present invention may further contain a copolymerizable monomer (C) in addition to the above (A) and (B).
Monomers (C) include acetylene, propyne, 1-butyne; 1,4-hexadiene, 1,6-heptadiene and the like, and ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; Ethylenically unsaturated dicarboxylic acids such as acids and itaconic acids and acid anhydrides thereof; ethylenically unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate; acrylonitrile, methacrylonitrile Acrylamide, methacrylamide; styrene, α-methylstyrene, vinylnaphthalene; vinyl chloride, vinyl fluoride, tetrafluoroethylene, and the like.
The amount of the monomer (C) is not particularly limited as long as the effect of the present invention is not impaired. The amount of the monomer (C) is preferably 0 to 40 mol% with respect to all monomers to be polymerized.

The cyclic olefin polymer can be obtained, for example, by addition copolymerization of the cyclic olefin (A) and the α-olefin (B) and, if necessary, the monomer (C) in the presence of a metallocene catalyst. .
A metallocene catalyst is a well-known catalyst conventionally used for addition polymerization reaction. In the present invention, a catalyst comprising a transition metal metallocene compound (a) and an organoaluminum oxy compound (b) or a borate or borane compound (c) is particularly preferable.
Examples of the metallocene compound (a) include a bridged metallocene compound and a half metallocene compound.
Examples of the bridged metallocene compound include those represented by the general formula (1).

In formula (1), M1 is a metal atom selected from the group consisting of titanium, zirconium, and hafnium, and zirconium is preferred because of its excellent catalytic activity.
X1 and X2 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen group.
R6 and R7 are each independently a cyclopentadienyl group, an indenyl group, or a fluorenyl group, substituted with an alkyl group such as a methyl group, an ethyl group, an isopropyl group, or a t-butyl group; a phenyl group or a benzyl group May be.
R5 represents a lower alkylene group such as a methylene group, an ethylene group or a propylene group; an alkylidene group such as an isopropylidene group; a substituted alkylene group such as diphenylmethylene; a substituted silylene group such as a dimethylsilylene group or a diphenylsilylene group; or a silylene group. is there.

  Examples of the bridged metallocene compound include isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene- (9-fluorenyl) [ 1- (3-methyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-t-butyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (1-indenyl) ( Cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (1-indenyl) zirconium dichloride, ethylene-bis (1-indenyl) zirconium dichloride, diphenylmethylene-bis (1- Ndeniru) zirconium dichloride, isopropylidene - bis (1-indenyl) zirconium dichloride can be mentioned.

  Examples of the half metallocene compound include those represented by the general formula (2).

In Formula (2), M2 is a metal atom selected from the group consisting of titanium, zirconium, and hafnium. Z1 and Z2 are each independently a hydrocarbon group having 1 to 12 carbon atoms or a halogen group. Cp is an indenyl group or a fluorenyl group, and these may be substituted with a hydrocarbon group having 1 to 12 carbon atoms.
R8, R9 and R10 are each independently a hydrogen atom or an alkyl group, aryl group, silyl group, halogenated alkyl group or aryl group having up to 20 carbon atoms.

  Examples of the half metallocene compound include (t-butylamido) dimethyl-1-indenylsilane titanium dimethyl, (t-butylamido) dimethyl-1-indenylsilane titanium dichloride, (t-butylamido) dimethyl-9-fluorenylsilane titanium. Dimethyl, (t-butylamido) dimethyl-9-fluorenylsilane titanium dichloride, (t-butylamido) dimethyl-9- (3,6-dimethylfluorenyl) silane titanium dimethyl, (t-butylamido) dimethyl-9- [3,6-di (i-propyl) fluorenyl] silanetitanium dimethyl, (t-butylamido) dimethyl-9- [3,6-di (t-butyl) fluorenyl] silanetitanium dimethyl, (t-butylamido) dimethyl- 9- [2,7-di (t-butyl) fluorenyl] Emissions titanium dimethyl, and as (t-butylamido) dimethyl-9- (2,3,6,7-tetramethyl-fluorenyl) as silane titanium dimethyl is preferred.

The organoaluminum oxy compound (b) or borate or borane compound (c) constituting the metallocene catalyst is an activator for activating the metallocene compound.
The organoaluminum oxy compound (b) may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-78687.

The borate or borane compound (c) is an activator capable of reacting with the metallocene compound to convert the metallocene compound into a cationic species.
Examples of the borate or borane compound (c) include triethylammonium tetrakis (pentafluorophenyl) borate, trityltetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocete. Borate compounds such as nium tetra (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) borate; tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) Examples thereof include borane compounds such as boron and tris (pentafluorophenyl) boron.

  The metallocene catalyst may contain an organoaluminum compound (d) as necessary. Examples of the organoaluminum compound (d) include organoaluminum compounds other than the above organoaluminum oxy compounds. Specific examples of the organoaluminum compound (d) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and trisec-butylaluminum; dimethylaluminum chloride and diisobutylaluminum chloride. Dialkylaluminum halides such as diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide; dialkylaluminum aryloxides such as diethylaluminum phenoxide.

The concentration of the metallocene compound (a) during the polymerization reaction is preferably 0.00005 to 1 mmol / liter, more preferably 0.0001 to 0.3 mmol / liter. The organoaluminum oxy compound (b) or borate or borane compound (c) is preferably 1 to 10,000 equivalents relative to the metallocene compound (a).
The organoaluminum (d) is preferably 0.1 to 1,000 equivalents relative to the metallocene compound (a).

  The addition polymerization reaction is not limited by the form of the polymerization reaction, and can be employed from polymerization methods such as solution polymerization, bulk polymerization, and slurry polymerization, and may be either continuous type or batch type.

  Solvents used in the polymerization reaction include chain aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; aromatic hydrocarbons such as benzene, toluene and xylene. And the like. These solvents can be used alone or in combination of two or more.

  The polymerization reaction is usually carried out in the temperature range of −50 to + 230 ° C., preferably −30 to + 200 ° C., more preferably −20 to + 150 ° C., usually 2 minutes to 5 hours, preferably 5 minutes to 3 hours. The pressure (gauge pressure) during the reaction is usually 10 MPa or less, preferably 5 MPa or less.

The procedure for adding the monomer, catalyst, and solvent used in the polymerization reaction to the reactor is not particularly limited. Add (A) and (B) and (C) as necessary, and then add the catalyst. And (A) and (B) and a part of (C) may be added if necessary, a catalyst is added, and then (A) and (B) and optionally (C). The catalyst may be added all at once or in small portions; the catalyst is added to the reactor first, and then (A) and (B) and (C) are added all at once or dividedly as necessary. May be.
In the metallocene catalyst, the metallocene compound (a), the organoaluminum oxy compound (b) or the borate or borane compound (c), and the organoaluminum compound (d), which constitute the metallocene catalyst, are separately added to the polymerization reactor. Alternatively, these may be mixed outside the reactor and then added to the polymerization reactor.

The cyclic olefin polymer of the present invention is a differential refraction of a peak area (UV peak area) detected by an ultraviolet spectroscopic detector having a wavelength of 210 nm as analyzed by gel permeation chromatography (GPC) among the addition polymers. The percentage ((UV peak area) / (RI peak area) × 100) relative to the peak area (RI peak area) detected by the meter is 2.5 or less, preferably 2.0 or less, more preferably 1.5. It is as follows.
The UV peak area and the RI peak area are determined by the method described in the examples.

The cyclic olefin polymer in which the percentage of the UV peak area to the RI peak area is in the above numerical range is (1) bringing the cyclic olefin polymer obtained by the above-described method into contact with hydrogen, (2) residual metal, etc. Can be obtained by a method such as reducing the number of impurities to several ppb or less. Since it is easy to obtain a molded article excellent in optical properties, (1) a method of contacting with hydrogen is preferable.
A preferable method of bringing hydrogen into contact with the cyclic olefin polymer includes a method of supplying hydrogen to the cyclic olefin polymer solution in the presence of a simple metal.
Examples of the metal simple substance include nickel and palladium, and nickel is most preferable. These simple metals are used by being supported on a carrier. Examples of the carrier include alumina, silica, diatomaceous earth, and the like.

Examples of the solvent that dissolves the cyclic olefin polymer include the same solvents that can be used during the polymerization.
A metal simple substance is added to a solution in which a cyclic olefin polymer is usually dissolved in a solvent in an amount of 1 to 30% by weight, preferably 3 to 20% by weight, with a concentration of 0.5 to 10% by weight based on the polymer. 150 to 200 ° C., preferably 170 to 200 ° C., and hydrogen partial pressure is usually 0.1 to 100 kgf / cm ² , preferably 0.5 to 60 kgf / cm ² , more preferably 1 to 50 kgf / cm ² . .
The contact time is appropriately selected according to the required degree of hue improvement, but is usually selected from 5 minutes to 12 hours, preferably from 5 minutes to 6 hours. If there is an unsaturated bond in the cyclic olefin polymer by this hydrogen contact treatment, the unsaturated bond is hydrogenated. In particular, when a cyclic olefin (A) having an aromatic ring is used, the hydrogenation rate of the aromatic ring structure is preferably 90% or more, more preferably 95% or more, and 99% or more. Is more preferable. The hydrogenation rate of the aromatic ring structure was determined from the values before and after the hydrogen contact treatment by measuring the amount of the aromatic ring structure before the hydrogen contact and the amount of the aromatic ring structure after the hydrogen contact by ¹ H-NMR spectrum. It can be calculated. If this hydrogenation rate is small, oxidation deterioration and burning tend to occur.

  In order to remove the catalyst used in the above addition polymerization reaction and the metal simple substance used in the hydrogen contact treatment, methods such as centrifugation and filtration are usually employed. Furthermore, removal of the catalyst and simple metals can be promoted by adding a catalyst deactivator such as water or alcohol, or by adding an adsorbent such as activated clay, alumina, or silicon earth.

The number average molecular weight of the cyclic olefin polymer of the present invention is preferably 15,000 or more, and more preferably 15,000 to 100,000.
The molecular weight distribution of the polymer represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1.5 to 5.0, more preferably 1.5 to 3. 0.0, particularly preferably 1.5 to 2.5. In the present invention, the number average molecular weight and the weight average molecular weight are standard polymer converted values measured by gel permeation chromatography.

  The cyclic olefin polymer of the present invention is not limited by its glass transition temperature, but considering the moldability, the lower limit is usually 100 ° C., preferably 110 ° C., more preferably 120 ° C., and the upper limit is usually 250 ° C. Preferably it is 200 degreeC.

  In the cyclic olefin polymer of the present invention, a coloring agent such as a pigment or a dye, a fluorescent brightening agent, a dispersing agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, a lubricant, a solvent and the like are added. It can mix | blend suitably. Even if the cyclic olefin polymer of the present invention does not contain an antioxidant, it provides a blue laser optical component having excellent blue laser resistance, but may contain an antioxidant as necessary. The blending method of the compounding agent is not particularly limited. For example, a method of adding the compounding agent while kneading the cyclic olefin polymer with a kneader such as a roll, a kneader, an extrusion kneader, a Banbury mixer, a feeder ruder, or the like; And a method of mixing the dispersed liquid and then removing the solvent from the mixed liquid. The temperature during kneading is preferably 200 to 400 ° C, more preferably 240 to 350 ° C.

  The cyclic olefin polymer of the present invention can be formed into a molded body by a known molding method. Examples of the molding method include a solution casting method, a melt extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, and a stretch molding method. The molded body thus obtained is suitable as a material for optical parts, automobile parts, electrical / electronic parts, packaging materials and the like, and particularly suitably used as electronic parts such as packaging materials and fuel tanks for fuel cells. In particular, since the cyclic olefin polymer of the present invention has high resistance to high energy rays such as blue laser, optical components using blue laser, for example, lenses such as pickup lenses and fθ lenses; optical disks such as video disks and memory disks, etc. It is suitable for an optical component in which the accumulated irradiation amount of blue laser light increases.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

The UV peak area and RI peak area were determined by the following method.
The cyclic olefin polymer was added to cyclohexane at 4 mg / ml, and dissolved by warming at 50 ° C. for 30 minutes or more. The solution was allowed to stand at room temperature for 15 minutes and filtered through a sample pretreatment cartridge (manufactured by Tosoh Corporation, Mysholy Disk H-13-2).
A column in which TSKgel G5000HXL, TSKgel G4000HXL, TSKgel G2000HXL, TSKgelGRCXLH, TSKgelGRCXLH, and TSKgelGRCXLH (made by Tosoh Corp.) are connected in series to GPC (HLC-8120GPC, manufactured by Tosoh Corp.) The sample was analyzed by gel permeation chromatography (GPC) using a pump flow rate of 1.0 ml / min, a column temperature of 40 ° C., an injection amount of 100 μl.
The UV peak was detected with an ultraviolet spectroscopic detector (UV-8020, manufactured by Tosoh Corporation) in an environment of 40 ° C. The RI peak was detected with a differential refractometer equipped with GPC. The ultraviolet spectroscopic detector was set at a wavelength of 210 nm. The output range of the ultraviolet spectroscopic detector and the differential refractometer recorder was set to 2.56.
The UV peak area and RI peak area of the cyclic olefin polymer are other than the peaks detected by the differential refractometer and the UV spectroscopic detector when GPC measurement is performed on the same cyclohexane as that used for sample preparation by the above method. It was calculated by integrating the peaks.

Comparative Example 1
Toluene and tetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene was purified by distillation according to a conventional method and sufficiently dried.
Cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium dichloride was synthesized by a known method.
Cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium dichloride (7.30 mg, 12.5 μmol) was weighed into a glass Schlenk. This was dissolved in 15 ml of toluene, and 3.25 ml of a 10 wt% toluene solution of methylaluminoxane (manufactured by Albemarle) was added while stirring at room temperature, followed by stirring at room temperature for 30 minutes to obtain an addition polymerization catalyst.

A stainless steel polymerization reactor was charged with 1200 ml of toluene, and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 100 ml of dodec-3-ene was added and stirred with a stirring blade to raise the temperature of the reactor to 70 ° C. Ethylene gas was supplied to the reactor at a flow rate of 50 liter / hour and stirred for 10 minutes. Next, the addition polymerization catalyst was added to the reactor and polymerized at 70 ° C. for 20 minutes.
The polymerization was stopped by adding 5 ml of isobutyl alcohol. After cooling to room temperature, the reaction solution was poured into a mixed solution of 10 liters of methanol and 10 ml of concentrated hydrochloric acid to precipitate a polymer. The precipitated polymer was filtered, washed with methanol, and dried for 24 hours in a vacuum dryer at 100 ° C. with a reduced pressure of 0.1 kPa or less. The obtained polymer had a glass transition temperature of 137 ° C. Further, the percentage of the UV peak area to the RI peak area of this polymer was 4.5.

The obtained polymer was press-molded to obtain a test piece having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm. This test piece is placed in a room at 60 ° C., and a blue laser beam with a wavelength of 405 ± 10 nm and 200 mW / cm ² is irradiated for 120 hours using a laser diode (“TC4030S-F405ASU” manufactured by Neoarc) on the front side of the test piece. did. After laser irradiation, the side of the test piece was illuminated with strong light (halogen lamp, MORITEX MHF-50L), and the test piece was visually observed. It was confirmed that the specimen was clearly clouded.

Example 1
50 g of the polymer obtained in Comparative Example 1 was dissolved in 200 g of cyclohexane, and 2.5 g of a diatomaceous earth-supported nickel catalyst (Zude Chemie Catalysts Co., Ltd .: G-96D, nickel support rate: 58% by weight) was added to this solution. Prepared. Hydrogen was supplied to the pressure vessel, and the polymer and hydrogen were brought into contact with each other at a temperature of 200 ° C. and a hydrogen pressure of 4.5 MPa for 6 hours. The hydrogen contact treatment solution was filtered with a pressure filter (made by Ishikawajima-Harima Heavy Industries, Ltd., leaf filter) equipped with diatomaceous earth as a filter aid, and the catalyst was removed from the hydrogen contact treatment solution. Next, the treatment liquid from which the catalyst had been removed was poured into 5 liters of isopropyl alcohol with stirring to precipitate a solid. The precipitated solid was filtered, washed with 50 g of acetone, and dried in a vacuum dryer at 100 ° C. with a reduced pressure of 0.1 kPa or less for 24 hours to obtain a hydrogen contact polymer. The percentage of the UV peak area to the RI peak area of this hydrogen contact polymer was 2.0.
The hydrogen contact polymer thus obtained was press-molded to obtain a test piece having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm. This test piece was irradiated with laser in the same manner as in Comparative Example 1, and the test piece after laser irradiation was visually observed in the same manner as in Comparative Example 1. No cloudiness was observed in the test piece.

Comparative Example 2
50 g of the polymer obtained in Comparative Example 1 was dissolved in 280 g of cyclohexane, and 1.4 g of Raney nickel catalyst (nickel loading 40% by weight) was added to this solution, and charged into a pressure vessel. Hydrogen was supplied to the pressure vessel, and the polymer and hydrogen were brought into contact with each other at a temperature of 100 ° C. and a hydrogen pressure of 4.0 MPa for 4 hours. The hydrogen contact treatment liquid was taken out and filtered through a pressure filter (manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd., leaf filter) equipped with diatomaceous earth as a filter aid, and the catalyst was removed from the treatment liquid. Next, the treatment liquid was poured into 5 liters of isopropyl alcohol with stirring to precipitate a hydrogen contact polymer. The precipitated polymer was filtered, washed with 50 g of acetone, and dried for 24 hours in a vacuum dryer at 100 ° C. with a reduced pressure of 0.1 kPa or less. The percentage of the UV peak area to the RI peak area of this polymer was 2.7.
The hydrogen contact polymer thus obtained was press-molded to obtain a test piece having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm. This test piece was irradiated with laser in the same manner as in Comparative Example 1, and the test piece after laser irradiation was visually observed in the same manner as in Comparative Example 1. Slight cloudiness was observed on the test piece.

  From the above results, the cyclic olefin polymer of the present invention (Example 1) in which the percentage of the UV peak area to the RI peak area is 2.5 or less does not become cloudy even when irradiated with a blue laser for a long time, and transmits light. It can be seen that there is no decrease in rate. In contrast, the cyclic olefin polymer (Comparative Examples 1 and 2) having a percentage of the UV peak area with respect to the RI peak area of more than 0.25 becomes white turbid when irradiated with a blue laser for a long time, resulting in a decrease in light transmittance. Recognize.

Claims (3)

The cyclic olefin (A) and the α-olefin (B) having 2 to 20 carbon atoms are subjected to addition polymerization to obtain an addition polymer, and then the addition polymer and hydrogen are added in the presence of nickel supported on a carrier. Including contacting,
In analysis by gel permeation chromatography (GPC), the percentage of the peak area (UV peak area) detected by an ultraviolet spectroscopic detector with a wavelength of 210 nm to the peak area (RI peak area) detected by a differential refractometer (( (UV peak area) / (RI peak area) × 100) is a process for producing a cyclic olefin polymer of 2.5 or less.   The production method according to claim 1, wherein the addition polymerization is performed in the presence of a metallocene catalyst.   An optical component for a blue laser formed by molding the cyclic olefin polymer obtained by the method according to claim 1 or 2.