JP2007197560A - Hydride of norbornene addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydride of a norbornene polymer whose light transmittance is hardly diminished by increased irradiation of a blue laser light at a wavelength of around 400 nm, which is capable of yielding a molded product having a low birefringence property and a high light transmittance. <P>SOLUTION: The hydride of the addition polymer having a number average molecular weight of 15,000 or larger is obtained by performing addition polymerization of a norbornene monomer (A) having an aromatic ring, such as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, and a 2-20C α-olefin (B), such as ethylene, and hydrogenating the aromatic ring until the hydrogenation ratio reaches 99% or higher, peaks at 122-128 ppm and 142-148 ppm in<SP>13</SP>C-NMR spectrum measured in deuterated chloroform (using TMS as a standard) disappear and peak area (C) at 50.5-53 ppm and peak area (D) at 55-56.5 ppm satisfy the relation: C/(C+D)≥0.80. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a norbornene-based addition polymer hydride. More specifically, a norbornene-based polymer that is capable of obtaining a molded article having a low birefringence and a high light transmittance even when the integrated dose of blue laser light having a wavelength of around 400 nm is increased. Relates to hydrides.

An optical molded body is a molded body that is applied to various uses by utilizing optical phenomena such as refraction, reflection, diffraction, and birefringence. Examples of the optical molded body include lenses for optical devices such as convex lenses, concave lenses, Fresnel lenses, collimating lenses, lenticular lenses, pickup lenses, grating lenses, geodesic lenses, fθ lenses, aspherical lenses; prisms; MO, DVD, Examples thereof include optical information recording media such as CD; optical sheets or plates for display devices such as retardation plates, polarizing plates, light reflecting plates, light diffusing plates, light guide plates, and prism sheets.
Among these, optical molded bodies used in information equipment that writes and reads information by light, such as pickup lenses and prisms, may not change their characteristics even when the cumulative amount of light irradiation increases. There is a strong demand. In particular, information equipment using blue laser light capable of realizing a high recording density has been developed, and development of an optical molded body for blue laser corresponding to this has been demanded.

A norbornene-based polymer is known as a transparent resin used for an optical molded body. For example, Patent Literature 1 and Patent Literature 2 disclose cyclic olefin polymers obtained by polymerizing and hydrogenating an α-olefin having 2 to 20 carbon atoms and a norbornene monomer. 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. However, the optical element obtained with this cyclic olefin polymer has an inherently low light transmittance because of the addition of an antioxidant and a surfactant, and the birefringence tends to be high depending on molding conditions. Aberrations are likely to occur when a prism is used.
Patent Document 3 discloses a novel polymer resin containing a norbornene monomer having a fused cyclohexane ring as a monomer unit. Here, the peak area (A) on the high magnetic field side and the peak area (B) on the low magnetic field side of the methylene peak observed by ¹³ C-NMR are B / (A + B) ≦ 0.30. It is described that it gives a molded article having excellent properties.

Japanese Patent Laid-Open No. 2004-197067 JP 2005-330465 A International Publication No. WO99 / 09085

However, it has been found that in the optical molded body using the resin specifically disclosed in the examples of Patent Document 2, the light transmittance is likely to decrease as the integrated amount of blue laser irradiation increases.
In addition, in the case of an addition polymer obtained using a norbornene-based monomer, the light transmittance by blue laser irradiation has no correlation with the methylene peak ratio observed by ¹³ C-NMR described in Patent Document 3. I also understood.
An object of the present invention is to provide a norbornene-based material which can obtain a molded article having a low birefringence and a high light transmittance even when the integrated dose of blue laser light having a wavelength of around 400 nm is increased. It is to provide an addition polymer hydride.

As a result of intensive studies to achieve the above object, the present inventors have increased the addition polymer of a norbornene monomer (A) having an aromatic ring and an α-olefin (B) having 2 to 20 carbon atoms. In the presence of an active hydrogenation catalyst, under a high temperature condition, the hydrogenation rate of the aromatic ring structure is 99% or more, the number average molecular weight measured by gel permeation chromatography is 15,000 or more, in heavy chloroform (TMS standard) In the ¹³ C-NMR spectrum measured in Step 1, no peaks were observed at 122 to 128 ppm and 142 to 148 ppm, and a peak area (C) of 50.5 to 53 ppm and a peak area (D) of 55 to 56.5 ppm , By using a hydrogenated polymer until C / (C + D) ≧ 0.80 is satisfied, an integrated dose of blue laser light having a wavelength of around 400 nm is obtained. Less decrease in light transmittance even when many, and low birefringence molded article with a high light transmittance refractive properties were found to be obtained. The present invention has been completed based on these findings.

Thus, according to the present invention, an addition polymer of a norbornene monomer (A) having an aromatic ring and an α-olefin (B) having 2 to 20 carbon atoms is hydrogenated,
The hydrogenation rate of the aromatic ring structure is 99% or more,
The number average molecular weight measured by gel permeation chromatography is 15,000 or more,
In the ¹³ C-NMR spectrum measured in deuterated chloroform (TMS standard),
No peaks are observed at 122-128 ppm and 142-148 ppm, and
A norbornene-based addition polymer hydride characterized in that a peak area (C) of 50.5 to 53 ppm and a peak area (D) of 55 to 56.5 ppm satisfy C / (C + D) ≧ 0.80. Provided,
As a preferred embodiment, the above-mentioned addition polymer hydride in which the norbornene monomer (A) having an aromatic ring is a norbornene monomer having an aromatic ring condensed with an alicyclic ring, or a norbornene single monomer having an aromatic ring The above addition polymer hydride is provided in which the monomer (A) is 1,4-methano-1,4,4a, 9a-tetrahydrofluorene.

  The hydride of norbornene-based addition polymer of the present invention has a low birefringence and has little decrease in light transmittance even when a large amount of blue laser light having a wavelength of around 400 nm is irradiated without adding an antioxidant. A molded product exhibiting high light transmittance can be provided. Since it has such characteristics, a molded article using the norbornene-based addition polymer hydride 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, a non- Lenses for optical devices such as spherical lenses; prisms; optical information recording media such as MO, DVD and CD; optical sheets for display devices such as retardation plates, polarizing plates, light reflecting plates, light diffusing plates, light guide plates, and prism sheets Alternatively, it can be used as an optical member such as a 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 hydride of norbornene-based addition polymer of the present invention is obtained by hydrogenating an addition polymer of a norbornene-based monomer (A) having an aromatic ring and an α-olefin (B) having 2 to 20 carbon atoms. The hydrogenation rate of the aromatic ring structure is 99% or more, the number average molecular weight measured by gel permeation chromatography is 15,000 or more in terms of polyisoprene, and measured in deuterated chloroform (TMS standard) ¹³ In the C-NMR spectrum, no peaks were observed at 122 to 128 ppm and 142 to 148 ppm, and a peak area (C) of 50.5 to 53 ppm and a peak area (D) of 55 to 56.5 ppm were (C + D) ≧ 0.80 is satisfied.

The addition polymer used in the present invention is obtained by addition copolymerization of a norbornene monomer (A) having an aromatic ring and an α-olefin (B) having 2 to 20 carbon atoms.
The norbornene monomer (A) having an aromatic ring is a monomer having at least one norbornene ring structure and having at least one aromatic ring.

Monomers (A) include those having an aromatic ring condensed to an alicyclic ring and those having an aromatic ring bonded to the alicyclic ring as a substituent.
Examples of those having an aromatic ring condensed with an alicyclic ring include 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- Tano-6b, 7,10,10a-Compound with cyclopentadiene added to tetrahydrofluorane, compound with cyclopentadiene added to asanthrylene, compound with cyclopentadiene added 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 . 0 ^12,16 ] -5-eicosane, 5,6-benzo-bicyclo [2.2.1] hept-2-ene and the like.

Examples of those having an aromatic ring bonded as a substituent to an alicyclic ring include 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 . ^{17, 10} ] dodec-3-ene, 5- (naphthalen-1-yl) bicyclo [2.2.1] hept-2-ene, and the like.

  Of these, norbornene monomers having an aromatic ring condensed with an alicyclic ring are preferred, and 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is particularly preferred. The amount of the monomer (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 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 addition polymer used in the present invention may contain other norbornene monomer (C) copolymerizable with the above (A) and (B), if necessary. The norbornene monomer (C) is a monomer having at least one norbornene ring structure and not belonging to the monomer (A).
Examples of the norbornene monomer (C) include norbornene, dicyclopentadiene, and 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 . 1 ^7,10 ] dodec-3-ene, ^{pentacyclopentadecene, pentacyclopentadecadien and the} like.

The addition polymer used in the present invention may further contain a monomer (D) copolymerizable with (A), (B), and (C) in addition to (A) and (B). Good.
As the monomer (D), cyclobutene, 1-methylcyclobutene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclooctene, 1-methylcyclooctene, 5 -Methylcyclooctene, cyclooctatetraene, 1,5-cyclooctadiene, cyclododecene; acetylene, propyne, 1-butyne; 1,4-hexadiene, 1,6-heptadiene, and acrylic acid and methacrylic acid Ethylenically unsaturated monocarboxylic acids such as maleic acid; ethylenically unsaturated dicarboxylic acids such as maleic acid and itaconic acid and their anhydrides; ethylenic such as methyl acrylate, methyl methacrylate, ethyl acrylate and 2-ethylhexyl acrylate Unsaturated carboxylic acid ester; Nitrile, methacrylonitrile; acrylamide, methacrylamide; styrene, alpha-methyl styrene, vinyl naphthalene, vinyl chloride, vinyl fluoride, etc. polytetrafluoroethylene.

  The amount of these monomers (C) and (D) is not particularly limited as long as the effects of the present invention are not impaired. The amount of the monomers (C) and (D) is preferably 0 to 40 mol% with respect to all monomers to be polymerized.

  The addition polymer used in the present invention can be obtained, for example, by addition copolymerization of (A) and (B) and, if necessary, (C) and / or (D) in the presence of a metallocene catalyst. it can.

  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 preferred.

  Examples of the metallocene compound (a) include a bridged metallocene compound and a half metallocene compound. In order to efficiently polymerize the norbornene monomer (A) having an aromatic ring, a crosslinked metallocene compound is preferable.

  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 represented by the formula (1) include isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, isopropyl Riden- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-t-butyl) cyclopentadienyl] zirconium dichloride, isopropyl Riden- (1-indenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (1-indenyl) zirconium dichloride, ethylene-bis (1-indenyl) zirconium dichloride, diphenylmeth Len - bis (1-indenyl) zirconium dichloride, isopropylidene - bis (1-indenyl) zirconium dichloride can be mentioned.

  As the half metallocene compound, (t-butylamido) dimethyl-1-indenylsilane titanium dimethyl, (t-butylamido) dimethyl-1-indenylsilane titanium dichloride, (t-butylamido) dimethyl-9-fluorenyl Silane 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-butylamide) Dimethyl-9- [2,7-di (t-butyl) fluoreni ] Silane 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; and 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 compound (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 adopted from polymerization methods such as solution polymerization, bulk polymerization, and slurry polymerization. The reactor can be either a continuous reactor or a batch reactor. Good.

  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, and the above (A) and (B) and (C) and / or (D) are added as necessary. Then, a catalyst may be added; (A) and (B) and a part of (C) and / or (D) are added if necessary, a catalyst is added, and then (A) And (B) and, optionally, the remainder of (C) and / or (D) may be added all at once or in small portions; the catalyst is first added to the reactor and then (A) and (B ) And (C) and / or (D) may be added all at once or in small amounts as necessary.
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 method of hydrogenating the addition polymers (A) and (B) and, if necessary, further copolymerizing (C) and / or (D), has the characteristics described below. In addition, the method is not particularly limited as long as it can be thoroughly hydrogenated. The hydrogenation reaction is usually carried out by supplying hydrogen to the addition polymer solution in the presence of a hydrogenation catalyst.
As the hydrogenation catalyst, there are a homogeneous catalyst and a heterogeneous catalyst.
Examples of the homogeneous catalyst include, for example, Wilkinson complex, that is, chlorotris (triphenylphosphine) rhodium (I), cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride. / Sec-butyllithium, tetrabutoxy titanate / transition metal compound such as dimethylmagnesium / alkyl metal compound.

  Examples of the heterogeneous catalyst include those in which a metal known as a hydrogenation catalyst such as nickel or palladium is supported on a carrier. In the present invention, a heterogeneous catalyst is preferable, and a combination of nickel and palladium as a metal or a heterogeneous catalyst using palladium is most preferable. Examples of the carrier include alumina, silica, diatomaceous earth, and the like.

The hydrogenation reaction is usually performed in a solvent. Examples of the solvent include the same solvents that can be used during the polymerization. The hydrogenation reaction is usually in the temperature range of 100 to 200 ° C., preferably 130 to 195 ° C., usually 0.1 to 100 kgf / cm ² , preferably 0.5 to 60 kgf / cm ² , more preferably 1 to 50 kgf / It is performed at a hydrogen pressure (gauge pressure) of cm ² .

By this hydrogenation reaction, the hydrogenation rate of the aromatic ring structure is set to 99% or more. The hydrogenation rate of the aromatic ring structure is determined from the values before and after the hydrogenation reaction by measuring the amount of the aromatic ring structure before hydrogenation and the amount of the aromatic ring structure after hydrogenation by ¹ H-NMR spectrum. It can be calculated. When this hydrogenation rate is small, the blue laser resistance is poor.

Furthermore, in this ¹³ C-NMR spectrum measured in deuterated chloroform (TMS standard) by this hydrogenation reaction, no peaks were observed at 122 to 128 ppm and 142 to 148 ppm, and a peak area of 50.5 to 53 ppm ( C) and a peak area (D) of 55 to 56.5 ppm satisfy C / (C + D) ≧ 0.80.
The peaks at 122 to 128 ppm and 142 to 148 ppm are considered to be peaks derived from the aromatic ring structure or the condensed structure of the aromatic ring and the alicyclic ring. In the norbornene-based addition polymer hydride of the present invention, the aromatic ring structure and the aromatic It is presumed that the condensed structure of the ring and the alicyclic ring disappeared and changed to another structure.
Moreover, although it is not clear what structure the peaks of 50.5 to 53 ppm and 55 to 56.5 ppm are derived from, the value of C / (C + D) depends on the hydrogenation conditions of the addition polymer. May be less than 0.80. When the value of C / (C + D) is so small, the cause is unknown, but the resistance to blue laser tends to be insufficient.

  After the polymerization and hydrogenation reaction, the catalyst and the like are removed. The removal method is not particularly limited, and examples thereof include methods such as centrifugation and filtration. Furthermore, the catalyst removal 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 norbornene-based addition polymer hydride of the present invention has a number average molecular weight of 15,000 or 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. When molecular weight is measured, when cyclohexane is used as a solvent, it is a molecular weight in terms of polyisoprene, and when toluene or tetrahydrofuran is used as a solvent, it is a molecular weight in terms of polystyrene.

  The norbornene-based addition polymer hydride of the present invention is not limited by its glass transition temperature, but the lower limit is usually 100 ° C., preferably 110 ° C., more preferably 120 ° C. in consideration of the moldability of the molded product, The upper limit is usually 250 ° C., preferably 200 ° C.

  The norbornene-based addition polymer hydride of the present invention contains a coloring agent such as a pigment or a dye, a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, a lubricant, a solvent, etc. Can be blended. The norbornene-based addition polymer hydride of the present invention can obtain an optical molded article excellent in blue laser resistance without blending an antioxidant, but if necessary, an antioxidant is blended. Also good. The blending method is not particularly limited. For example, a method of adding the compounding agent while kneading the addition polymer hydride with a kneader such as a roll, a kneader, an extrusion kneader, a Banbury mixer, or a feeder ruder; dissolving the solution and compounding agent of the addition polymer hydride Or 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 norbornene-based addition polymer hydride of the present invention can be molded by a known molding method to obtain a molded body. 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 has high resistance to blue lasers, and is therefore suitable for optical components that use blue lasers, particularly optical members that increase the cumulative amount of blue laser light such as pickup lenses and prism lenses. .

  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. In the following, parts and% are based on weight unless otherwise specified.

The evaluation methods performed in the examples and comparative examples are as follows.
(1) Molecular weight The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the addition polymer hydride were measured by gel permeation chromatography (GPC) using cyclohexane as a developing solvent, and obtained as standard polyisoprene equivalent values.
(2) Repeating unit composition The repeating unit composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene / ethylene addition copolymer is determined by ¹ H-NMR spectrum in deuterated chloroform solvent (TMS standard). Asked.
Based on the integrated value of the peak (6.7-7.6 ppm) of the aromatic ring derived from the 1,4-methano-1,4,4a, 9a-tetrahydrofluorene unit, an aliphatic peak (0.4 The proportion of ethylene units in (˜4.0 ppm) was determined, and the molar ratio of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene units to ethylene units was determined.

(3) Hydrogenation rate of aromatic ring The hydrogenation rate of the aromatic ring of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene / ethylene addition copolymer was measured in deuterated chloroform solvent (TMS standard). ^It calculated | required from the < ¹ > H-NMR spectrum.
Using tetramethylsilane (TMS) as an internal standard, the reduction rate of the peak of the aromatic ring (6.7 to 7.6 ppm) before and after the hydrogenation reaction on the basis of the integrated value of the 0 ppm peak, the hydrogenation rate Asked.
(4) Glass transition temperature The glass transition temperature (Tg) of the addition polymer hydride was determined by differential scanning calorimetry (DSC) when the temperature was raised at 10 ° C per minute.
(5) Birefringence A disk having a thickness of 1.2 mm and a diameter of 85 mm at 280 ° C. was injection molded. The birefringence value at a position having a radius of 25 mm from the center of the disk was measured using a polarizing microscope (Nikon Corporation, 546 nm Senarmon Compensator). The closer the birefringence value is to zero, the lower the birefringence.

(6) Light transmittance A resin plate having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm was molded. The light transmittance of this resin plate was measured with a visible spectrophotometer (manufactured by JASCO Corporation, V-570).
(7) Laser resistance Using a spectral aging tester (XSP type, manufactured by Suga Test Instruments Co., Ltd.), a laser beam having a wavelength of 400 ± 10 nm is applied to a resin plate used for measurement of light transmittance by an integrated light amount of 520 kJ / Irradiated cm ² . The light transmittance of the resin plate after laser beam irradiation was measured in the same manner as described above. It shows that it is excellent in laser resistance, so that the value | valence (light transmittance retention) which remove | divided this measured value by the measured value obtained by said (6) is high.
(8) ¹³ C-NMR analysis A 4.8 wt% deuterated chloroform solution was prepared, and the ¹³ C-NMR spectrum was obtained using an NMR measurement apparatus “JNM-EX400WB” manufactured by JEOL Ltd. at an integration number of 16,000 times. Got.

(Comparative Example 1)
A pressure-resistant reactor equipped with a stirrer was charged with 860 parts of toluene, 200 parts of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, and 0.840 parts of triethylaluminum dissolved in 5.18 parts of toluene.
A glass container was charged with 43.5 parts of toluene, 0.04 part of rac-ethylenebis (1-indenyl) zirconium dichloride, and 0.510 parts of methylaluminoxane dissolved in 2.7 parts of toluene and mixed. This mixed solution was added to the pressure-resistant reactor.
0.2 MPa of ethylene gas was introduced into the pressure-resistant reactor, and a polymerization reaction was started at 40 ° C. After 40 minutes, the pressure was released and 5 parts of methanol was added to stop the polymerization reaction. This solution was filtered through Radiolite # 800, and then poured into a large amount of hydrochloric acid-methanol to precipitate a polymer. The precipitated polymer was collected, washed, and dried under reduced pressure at 100 ° C. for 15 hours. The weight average molecular weight of the addition polymer was 62,000, and the number average molecular weight was 31,000. The 1,4-methano-1,4,4a, 9a-tetrahydrofluorene unit / ethylene unit molar ratio in the addition polymer was 40/60, and the glass transition temperature was 150 ° C. The molecular weight was determined by gel permeation chromatography (converted to standard polystyrene) using tetrahydrofuran as a solvent.
In this polymer, “C / (C + D)” measured by ¹³ C-NMR spectrum was 0.90, and signals based on aromatic rings were observed at 122 to 128 ppm and 142 to 148 ppm. Further, no signal was observed at 21 to 22.5 ppm.

  This addition polymer was injection-molded to obtain a disk for birefringence measurement and a resin plate for light transmittance measurement and the like and evaluated. The birefringence value was 17 nm. The light transmittance (T0) at a wavelength of 400 nm of the resin plate was 86%. The light transmittance (T1) at 400 nm after laser beam irradiation was 48%. The retention of light transmittance (T1 / T0) was 55.8%.

Example 1
150 parts of the addition polymer obtained in Comparative Example 1 was dissolved in a mixed solvent of 283 parts of toluene and 567 parts of cyclohexane, 50 parts of a nickel-silica supported catalyst (product name “E22U”, manufactured by JGC Chemical Co., Ltd.), and palladium-silica. 15 parts of supported catalyst was added and stirred. The solution was charged into a stainless steel autoclave equipped with an electric heating device and an electromagnetic stirring device. Hydrogen was supplied while maintaining the internal pressure of the autoclave at 4.5 MPa and a temperature of 180 ° C., and a hydrogenation reaction was performed for 12 hours. The reaction solution was filtered through Radiolite # 800 to obtain a colorless and transparent solution. This solution was poured into a large amount of methanol to precipitate a polymer hydride. The precipitated polymer hydride was collected, washed, and dried under reduced pressure at 100 ° C. for 15 hours. The polymer hydride had a weight average molecular weight of 40,000, a number average molecular weight of 22,000, and a glass transition temperature of 145 ° C. ^No aromatic ring peak was observed in the ¹ H-NMR spectrum, and the hydrogenation rate of the aromatic ring was 99% or more.
“C / (C + D)” of the polymer hydride measured by ¹³ C-NMR spectrum was 0.98, and no peaks were observed at 122 to 128 ppm and 142 to 148 ppm. Further, almost no peak was observed at 21 to 22.5 ppm.

  This polymer hydride was injection molded by the same method as in Comparative Example 1 to obtain a disk and a resin molded plate and evaluated. The birefringence value was 6 nm. The light transmittance (T0) at a wavelength of 400 nm of the resin molded plate was 90%. The light transmittance (T1) at 400 nm after laser beam irradiation was 86%. The retention of light transmittance (T1 / T0) was 95.5%.

(Example 2)
Except for changing the amount of the nickel-silica supported catalyst (product name “E22U”, manufactured by JGC Chemical Co., Ltd.) to 40 parts and changing the amount of the palladium-silica supported catalyst to 5 parts by weight, the same as in Example 1. A polymer hydride was obtained. The polymer hydride had a weight average molecular weight of 43,000, a number average molecular weight of 24,000, and a glass transition temperature of 146 ° C. ^No signal of the aromatic ring was observed in the ¹ H-NMR spectrum, and the hydrogenation rate of the aromatic ring was 99% or more. “C / (C + D)” measured by ¹³ C-NMR spectrum of this hydrogenated product was 0.84, and no signal was observed at 122 to 128 ppm and 142 to 148 ppm. Further, almost no signal was observed at 21 to 22.5 ppm.
This polymer hydride was injection molded by the same method as in Comparative Example 1 to obtain a disk and a resin molded plate and evaluated. The birefringence value was 6 nm. The light transmittance (T0) at a wavelength of 400 nm of the resin molded plate was 89%. The light transmittance (T1) at 400 nm after laser beam irradiation was 84%. The retention of light transmittance (T1 / T0) was 94.4%.

(Comparative Example 2)
Polymer in the same manner as in Example 1 except that the amount of nickel-silica supported catalyst (product name “E22U”, manufactured by JGC Chemical Co., Ltd.) was changed to 10 parts and the amount of palladium-silica supported catalyst was changed to 0 parts. A hydride was obtained. The polymer hydride had a weight average molecular weight of 41,000, a number average molecular weight of 23,000, and a glass transition temperature of 148 ° C. The hydrogenation rate of the aromatic ring was 99%. “C / (C + D)” measured by ¹³ C-NMR spectrum of this hydrogenated product was 0.74, and signals based on aromatic rings were observed at 122 to 128 ppm and 142 to 148 ppm. Peaks A and B were observed in the range of 21 to 22 ppm and 22 to 22.5 ppm, respectively, and the peak area ratio (A / (A + B)) was 0.93.

  This polymer hydride was injection molded by the same method as in Comparative Example 1 to obtain a disk and a resin molded plate and evaluated. The birefringence value was 8 nm. The light transmittance (T0) at a wavelength of 400 nm of the resin molded plate was 85%. The light transmittance (T1) at 400 nm after laser beam irradiation was 62%. The retention of light transmittance (T1 / T0) was 72.9%.

(Comparative Example 3)
150 parts of the addition polymer obtained in Comparative Example 1 was dissolved in a mixed solvent of 283 parts of toluene and 567 parts of cyclohexane. To this solution, 4.33 parts of Raney nickel catalyst (nickel content 40 wt%) was added and stirred. The solution was charged into a stainless steel autoclave equipped with an electric heating device and an electromagnetic stirring device. Hydrogen was supplied while maintaining the internal pressure of the autoclave at 3 MPa and a temperature of 100 ° C., and a hydrogenation reaction was carried out for 4 hours. The reaction solution was filtered through Radiolite # 800 to obtain a colorless and transparent solution. This solution was poured into a large amount of methanol to precipitate a polymer. The precipitated polymer was collected, washed, and dried under reduced pressure at 100 ° C. for 15 hours. The resulting polymer had an aromatic ring hydrogenation rate of 20%.
“C / (C + D)” measured by ¹³ C-NMR spectrum of this hydrogenated product was 0.8, and signals based on aromatic rings were observed at 122 to 128 ppm and 142 to 148 ppm. Moreover, it was (22-22.5 ppm) / (22-22.5 ppm + 21-22 ppm) = 0.9.

(Reference example)
Under a nitrogen atmosphere, 720 parts of toluene, 300 parts of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1.0 part of 1-hexene, 11 parts of a 0.3% toluene solution of tungsten chloride and tetrabutyltin 0 6 parts were charged into a reactor and polymerized at 60 ° C. for 1 hour. The number average molecular weight (Mn) of the obtained ring-opening polymer was 19,200, the weight average molecular weight (Mw) was 38,600, and the molecular weight distribution (Mw / Mn) was 2.01. The molecular weight was determined by gel permeation chromatography (converted to standard polystyrene) using tetrahydrofuran as a solvent.
250 parts of this reaction solution contains 5 parts of alumina-supported nickel catalyst (0.7 parts of nickel and 0.2 parts of nickel oxide in 1 part of catalyst; pore volume 0.8 cm ³ / g, specific surface area 300 cm ² / g) And 5 parts of isopropyl alcohol were added, hydrogen was supplied while maintaining the internal pressure of the autoclave at 4.5 MPa and a temperature of 150 ° C., and a hydrogenation reaction was performed for 10 hours.
The reaction solution was filtered to remove the catalyst, and the mixture was poured into a mixed solution consisting of 250 parts of acetone and 250 parts of isopropanol while stirring to precipitate the resin. The precipitated resin was separated by filtration and collected. The yield was 99%. ^{As a result} of measurement by ¹ H-NMR, it was found that 99.9% or more of the double bonds in the main chain of the ring-opening polymer were hydrogenated, and the hydrogenation rate of the aromatic ring structure was 99.8%. It was. The number average molecular weight (Mn) of the ring-opened polymer hydride was 23,000, the weight average molecular weight (Mw) was 44,000, the molecular weight distribution (Mw / Mn) was 1.91, and the glass transition temperature was 165 ° C. The molecular weight was determined by gel permeation chromatography (converted to standard polyisoprene) using cyclohexane as a solvent.
As measured by ¹³ C-NMR spectrum of this hydrogenated product, no signal was observed at 122 to 128 ppm and 142 to 148 ppm. Further, signals were observed at (22 to 22.5 ppm) and (21 to 22 ppm), and the value of (22 to 22.5 ppm) / (22 to 22.5 ppm + 21 to 22 ppm) was 0.13.

This ring-opened polymer hydride was injection molded by the same method as in Comparative Example 1 to obtain a disk and a resin plate and evaluated. The birefringence value was 13 nm. Further, the light transmittance (T0) at 400 nm of the resin plate was 89%.
When the resin plate was irradiated with a laser beam having a wavelength of 400 ± 10 nm until the integrated irradiation amount (integrated light amount) reached 520 kJ / cm ² , the light transmittance (T1) at 400 nm was 76%. The retention of light transmittance (T1 / T0) was 85.4%.

From the above results, the hydrogenation rate of the aromatic ring structure is 99% or more, the number average molecular weight measured by gel permeation chromatography is 15,000 or more, and ¹³ C measured in deuterated chloroform (TMS standard). -In the NMR spectrum, no peaks are observed at 122 to 128 ppm and 142 to 148 ppm, and a peak area (C) of 50.5 to 53 ppm and a peak area (D) of 55 to 56.5 ppm are C / ( It can be seen that the molded article using the hydride of norbornene addition polymer of the present invention satisfying C + D) ≧ 0.80 has high light transmittance and excellent blue laser resistance.

Claims (3)

A hydrogenated addition polymer of a norbornene monomer (A) having an aromatic ring and an α-olefin (B) having 2 to 20 carbon atoms,
The hydrogenation rate of the aromatic ring structure is 99% or more,
The number average molecular weight measured by gel permeation chromatography is 15,000 or more,
In the ¹³ C-NMR spectrum measured in deuterated chloroform (TMS standard),
No peaks are observed at 122-128 ppm and 142-148 ppm, and
A norbornene-based addition polymer hydride characterized in that a peak area (C) of 50.5 to 53 ppm and a peak area (D) of 55 to 56.5 ppm satisfy C / (C + D) ≧ 0.80. The addition polymer hydride according to claim 1, wherein the norbornene monomer (A) having an aromatic ring is a norbornene monomer having an aromatic ring condensed with an alicyclic ring. The addition polymer hydride according to claim 1, wherein the norbornene monomer (A) having an aromatic ring is 1,4-methano-1,4,4a, 9a-tetrahydrofluorene.