JP2001124925A - Wave plate - Google Patents

Abstract

(57) [Problem] To provide an inexpensive wave plate having a synthetic resin film having high heat resistance, low hygroscopicity, high adhesion to various materials, and a stable retardation value. SOLUTION: The cyclic polyolefin-based resin film is bonded to a surface of a wave plate used for changing the polarization state of light composed of a cyclic polyolefin-based resin film or an undersubstrate transparent to a used wavelength. Is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wave plate, particularly to a wave plate having a cyclic polyolefin resin film.

[0002]

2. Description of the Related Art In recent years, non-contact,
Due to the large amount of information per unit volume, etc., optical recording media have been greatly expanded as media for reading and writing information by light. As an optical recording medium, a compact disk (CD), a laser disk (LD), a CD-ROM, a CD-I, etc., which introduces information into an optical recording medium in advance and reproduces the information as sound or an image, and an optical recording medium substrate There is a CD-R or DRAW used by attaching a recording film or the like and writing information with a laser, or an E-DRAW disc capable of repeatedly reading and writing information.

[0003] As an optical system device for reproducing and / or additionally writing data on such an optical recording medium, a polarizing beam splitter (PBS) and a 1 / 4λ wave plate are provided at an intermediate position in an optical path from a laser light source to a photodetector. (QWP)
2. Description of the Related Art An optical pickup device provided with a (hereinafter, also referred to as “１ ／ wavelength plate”) is known. Here, the quarter-wave plate gives an optical path difference of λ / 4 (therefore, a phase difference of π / 2) between two orthogonal polarization components of a specific wavelength. In the optical pickup device, linearly polarized light (S-wave) is emitted from a laser light source,
The linearly polarized light is converted into circularly polarized light by passing through the 波長 wavelength plate, and is irradiated on the optical recording medium by the condenser lens. The return light reflected from the optical recording medium follows the same path again, and
By passing through a four-wavelength plate, the circularly polarized light is converted in the 90-degree direction into linearly polarized light (P wave), passes through the PBS, and is guided to the photodetector. Also, as a rewritable magneto-optical disk device, irradiation light from a laser light source
The return light irradiating the magneto-optical disk through the deflector and the PBS and reflected by the magneto-optical disk again passes through the PBS,
There is also known an arrangement in which a λ wavelength plate (hereinafter, also referred to as “１ ／ wavelength plate”) is disposed at an intermediate position of an optical path to a photodetector. Here, the half-wave plate gives an optical path difference of λ / 2 (therefore, a phase difference of π) between two orthogonal polarization components of a specific wavelength.

Examples of such a wave plate include mica, quartz, quartz, calcite, LiNbO ₃ , and LiT having birefringence.
Wave plate formed from a single crystal such as aO _3, wave plate having a birefringent film on the surface of the base substrate obtained by obliquely depositing an inorganic material on the base substrate such as a glass substrate, birefringence (Langmuir-Blodget)
A wave plate having a film is disclosed. Further, a film obtained by stretching a film of polycarbonate, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyethylene terephthalate (PET), polypropylene (PP), polyarylate, polysulfone, polyethersulfone, acrylic resin, etc., is subjected to flatness, Also known are wave plates that are adhered to a glass substrate in order to maintain their formability, or sandwiched between two glass substrates.

However, in order to produce a single crystal such as a quartz crystal, an expensive single crystal production apparatus is required, so that it cannot be produced at a low cost, and a large-area wave plate cannot be easily obtained. . Further, when processing a single crystal into a wave plate, it is necessary to polish the single crystal, but it is difficult to adjust changes in the thickness and the retardation value of the single crystal during polishing. Further, in the production of a wave plate having a birefringent film by vapor-depositing an inorganic material from an oblique direction with respect to a base substrate, a vacuum vapor deposition apparatus capable of controlling the vapor deposition direction of the inorganic material is necessary. Is expensive. Furthermore, the production of a wavelength plate having an LB film requires the lamination of a monomolecular LB film, which complicates the production and also increases the production cost. Further, when a stretched synthetic resin film such as polycarbonate is used for the wave plate, there is a problem in stability and durability of the retardation value. Further, the conventional synthetic resin film has a low glass transition temperature (Tg) and poor heat resistance, so that a process temperature for manufacturing an optical device for performing reproduction and / or additional recording, for example, a soldering or bonding process There is a problem that limits the temperature at the temperature.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and has a high heat resistance, a low moisture absorption, a high adhesion to various materials, and a stable retardation value. An object is to provide an inexpensive wave plate having a resin film.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a wave plate used for changing the polarization state of light composed of a cyclic polyolefin resin film. Further, the present invention relates to a wavelength plate which is provided with a cyclic polyolefin-based resin film on a surface of an undersubstrate which is transparent to a wavelength to be used and which is used for changing a polarization state of light. This wave plate is preferably formed by bonding a cyclic polyolefin-based resin film to a base substrate.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The wave plate of the present invention comprises a cyclic polyolefin resin film. Here, examples of the cyclic polyolefin-based resin include the following (co) polymers. A ring-opened polymer of a specific monomer represented by the following general formula (I). A ring-opening copolymer of a specific monomer represented by the following general formula (I) and a copolymerizable monomer. Hydrogenation (co) of the above or ring-opened (co) polymers
Polymer. A hydrogenated (co) polymer obtained by cyclizing the above or the ring-opened (co) polymer by Friedel-Crafts reaction. A saturated copolymer of a specific monomer represented by the following general formula (I) and a compound containing an unsaturated double bond. An addition type (co) polymer of at least one monomer selected from a specific monomer represented by the following general formula (I), a vinyl-based cyclic hydrocarbon-based monomer, and a cyclopentadiene-based monomer; The hydrogenated (co) polymer.

[0009]

Embedded image

Wherein R ^{1 to} R ⁴ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or another monovalent organic group, which may be the same or different. . R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a monocyclic or It may form a polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. ]

The cyclic polyolefin resin of the present invention includes:
A ring-opened polymer of a specific monomer is included. <Specific monomer> Among the specific monomers, the above-mentioned one is preferable.
In the general formula (I), R¹And R^ThreeIs a hydrogen atom or carbon number
1 to 10, more preferably 1 to 4, particularly preferably 1
~ 2 hydrocarbon groups;^TwoAnd R^FourIs a hydrogen atom
Or a monovalent organic group, ^TwoAnd R^FourAt least
One of which has a polarity other than hydrogen and hydrocarbon
Represents a polar group, m is an integer of 0 to 3, p is an integer of 0 to 3
Yes, more preferably m + p = 0-4, even more preferably
Is a number from 0 to 2, particularly preferably 1. the above
Halogen, carboxyl
Group, hydroxyl group, alkyl ester group and aromatic ester group
Ester group, amino group, amide group, cyano group, d
-Tel group, acyl group, silyl ether group, thioether
Groups, and the like. Among these, carboxyl
Group and an ester group are preferable, and an alkyl ester group is particularly preferable.
preferable.

Among the specific monomers, particularly, R ² and R ⁴
At least one polar group has the formula of - (CH ₂₎ nCOOR
Is preferred in that the resulting cyclic polyolefin-based resin has a high glass transition temperature, low hygroscopicity, and excellent adhesion to various materials. In the above formula relating to the specific polar group, R represents 1 to 1 carbon atoms.
2, more preferably 1-4, particularly preferably 1-2 hydrocarbon groups, preferably alkyl groups. In addition, n is generally 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the obtained cyclic polyolefin-based resin is higher. This is preferred in that the above-mentioned process is easy and the obtained cyclic polyolefin-based resin has a high glass transition temperature.

Further, the specific monomer is represented by the above general formula (I)
In the formula, R ¹ or R ³ is preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms,
And preferably an alkyl group of the formula ( ₂ ), especially a methyl group.
It is preferable that the specific polar group represented by OR is bonded to the same carbon atom as the bonded carbon atom. Further, the specific monomer in which m is 1 in the general formula (I) is preferable in that a cyclic polyolefin-based resin having a high glass transition temperature can be obtained.

The above specific monomers include the following compounds
Things. Specifically, bicyclo [2.2.1]
Hept-2-ene, tricyclo [5.2.1.0^2,6]
-8-decene, 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,
Black [7.4.0.1^2,5. 1^9,12. 0^8,13] -3-pe
Ntadecene, tricyclo [4.4.0.1^2,5] -3-
Undecene, 5-methylbicyclo [2.2.1] hept
-2-ene, 5-ethylbicyclo [2.2.1] hept
-2-ene, 5-methoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-methyl-5-methoxy
Carbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.1
^2,5. 1^7,10-3-Dodecene, 8-ethoxycarboni
Letetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8-n-propoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Isopropoxycarbonyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8-n-butoxyca
Rubonyltetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-methyl-8-methoxycarbonyl
Tetracyclo [4.4.0.1^2,5. 1^{7, Ten}] -3-do
Decene, 8-methyl-8-ethoxycarbonyltetracy
Black [4.4.0.1^2,5. 1^{7, Ten}-3-dodecene,
8-methyl-8-n-propoxycarbonyltetracyclic
B [4.4.0.1^2,51^7,10] -3-dodecene, 8-
Methyl-8-isopropoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Methyl-8-n-butoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, dime
Tanooctahydronaphthalene, ethyl tetracyclodode
Sen, 6-ethylidene-2-tetracyclododecene,
Limethanooctahydronaphthalene, pentacyclo [8.
4.0.1.^2,5. 1^9,12. 0^8,13] -3-Hexadece
Heptacyclo [8.7.0.1^3,6. 1^10,17. 1
^12,15. 0^2,7. 0^11,16-4-Eicosene, hepta
Cyclo [8.8.0.1^4,7. 1^11,18. 1^13,16. 0
^3,8. 0^12,17] -5-Hen-eicosene, 5-ethylidene
Bicyclo [2.2.1] hept-2-ene, 8-ethyl
Lidentetracyclo [4.4.0.1^2,5. 1^7,10]-
3-dodecene, 5-phenylbicyclo [2.2.1]
Put-2-ene, 8-phenyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 5-fluorobi
Cyclo [2.2.1] hept-2-ene, 5-fluoro
Methylbicyclo [2.2.1] hept-2-ene, 5-
Trifluoromethylbicyclo [2.2.1] hept-2
-Ene, 5-pentafluoroethylbicyclo [2.2.
1] Hept-2-ene, 5,5-difluorobicyclo
[2.2.1] Hept-2-ene, 5,6-difluoro
Bicyclo [2.2.1] hept-2-ene, 5,5-bi
(Trifluoromethyl) bicyclo [2.2.1] hep
To-2-ene, 5,6-bis (trifluoromethyl) bi
Cyclo [2.2.1] hept-2-ene, 5-methyl-
5-trifluoromethylbicyclo [2.2.1] hept
-2-ene, 5,5,6-trifluorobicyclo [2.
2.1] Hept-2-ene, 5,5,6-tris (full
Oromethyl) bicyclo [2.2.1] hept-2-e
5,5,6,6-tetrafluorobicyclo [2.
2.1] Hept-2-ene, 5,5,6,6-tetraki
(Trifluoromethyl) bicyclo [2.2.1] hep
To-2-ene, 5,5-difluoro-6,6-bis (to
(Fluoromethyl) bicyclo [2.2.1] hept-2
-Ene, 5,6-difluoro-5,6-bis (trifur
Oromethyl) bicyclo [2.2.1] hept-2-e
, 5,5,6-trifluoro-5-trifluoromethyl
Rubicyclo [2.2.1] hept-2-ene, 5-fur
Oro-5-pentafluoroethyl-6,6-bis (tri
Fluoromethyl) bicyclo [2.2.1] hept-2-
Ene, 5,6-difluoro-5-heptafluoro-is
o-propyl-6-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-chloro-5,6,6-
Trifluorobicyclo [2.2.1] hept-2-e
, 5,6-dichloro-5,6-bis (trifluorome
Tyl) bicyclo [2.2.1] hept-2-ene, 5,
5,6-trifluoro-6-trifluoromethoxybis
Black [2.2.1] hept-2-ene, 5,5,6-to
Trifluoro-6-heptafluoropropoxybicyclo
[2.2.1] Hept-2-ene, 8-fluorotetra
Cyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
8-fluoromethyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-difluoromethyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8-trifluoromethyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8-pentane
Fluoroethyltetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8,8-difluorotetracycline
B [4.4.0.1^2,5. 1^7,10-3-dodecene,
8,9-difluorotetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,8-bis (tri
Fluoromethyl) tetracyclo [4.4.0.1^2,5.
1^{7, Ten}] -3-dodecene, 8,9-bis (trifluoro
Methyl) tetracyclo [4.4.0.1^2,5. 1^{7, Ten}]
-3-dodecene, 8-methyl-8-trifluoromethyl
Tetracyclo [4.4.0.1^2,5. 1^{7, Ten}] -3-do
Decene, 8,8,9-trifluorotetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8,8,9
-Tris (trifluoromethyl) tetracyclo [4.
4.0.1.^2,5. 1^7,10-3-dodecene, 8,8,
9,9-tetrafluorotetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8,8,9,9-tetra
Laquis (trifluoromethyl) tetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8,8-diflu
Oro-9,9-bis (trifluoromethyl) tetracycl
B [4.4.0.1^2,5. 1^7,10-3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl
Le) tetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8,8,9-trifluoro-9-trifur
Oromethyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8,8,9-trifluoro-
9-trifluoromethoxytetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,8,9-triff
Fluoro-9-pentafluoropropoxytetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Fluoro-8-pentafluoroethyl-9,9-bis
(Trifluoromethyl) tetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8,9-difluoro-
8-heptafluoroiso-propyl-9-trifluoro
Romethyltetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-chloro-8,9,9-trifluoro
Rotetracyclo [4.4.0.1^2,5. 1 ^7,10] -3-
Dodecene, 8,9-dichloro-8,9-bis (triflu
(Oromethyl) tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8- (2,2,2-trifluoro)
Roethoxycarbonyl) tetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-methyl-8-
(2,2,2-trifluoroethoxycarbonyl) tetra
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
And the like. These are one kind alone,
Alternatively, two or more kinds can be used in combination.

Among them, from the viewpoint of heat resistance of the obtained ring-opened polymer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10]} -3-dodecene, 8-ethylidene tetracyclododecene [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Pentacyclo [7.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ]
-3-Pentadecene is preferred.

<Copolymerizable Monomer> Specific examples of the copolymerizable monomer include cyclobutene, cyclopentene, cycloheptene, cyclooctene, and tricyclo [5.2.1.0.
^{Cycloolefins such as 2,6} ] -3-decene, 5-ethylidene-2-norbornene and dicyclopentadiene can be mentioned. The carbon number of the cycloolefin is preferably from 4 to 20, more preferably from 5 to 12.
It is. These can be used alone or in combination of two or more. The preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50 by weight ratio, and more preferably 100/0 to 60/40.

<Ring-opening polymerization catalyst> In the present invention, a ring-opening polymerization reaction for obtaining a ring-opening polymer of a specific monomer and a ring-opening copolymer of a specific monomer and a copolymerizable monomer. Is carried out in the presence of a metathesis catalyst. This metathesis catalyst comprises (a) at least one selected from compounds of W, Mo and Re, (b) a group IA element (eg, Li, Na, K, etc.) of the periodic table of deming, and a group IIA element (eg, , Mg, Ca, etc.), Group IIB elements (eg, Zn,
Cd, Hg, etc.), Group IIIA elements (eg, B, Al
Etc.), a compound of an IVA group element (eg, Si, Sn, Pb, etc.) or a group IVB element (eg, Ti, Zr, etc.), wherein at least one of the element-carbon bond or the element-hydrogen bond is formed. It is a catalyst comprising a combination with at least one member selected from those having. In this case, in order to enhance the activity of the catalyst, an additive (c) described below may be added.

(A) W, Mo or
As a typical example of the compound of Re, WCl₆ , MoCl
_Five , ReOCl_Three JP-A-1-132626, etc.
Conversion from page 8, lower left column, line 6 to page 8, upper right column, line 17
Compounds can be mentioned. (B) As a specific example of the component
Is nC_Four H₉ Li, (C_Two H_Five )_Three Al, (C _Two H
_Five )_Two AlCl, (C_TwoH_Five )_1.5 AlCl_1.5 , (C
_Two H_Five ) AlCl_Two, Methylalumoxane, LiH, etc.
JP-A-1-132626, page 8, upper right column, line 18,
The compounds described on page 8, lower right column, line 3 can be mentioned.
You. A typical example of the additive (c) component is alcohol
Aldehydes, ketones, amines, etc. are preferred
Can be used as described in
No. 6, page 8, right lower column, line 16 to page 9, upper left column, line 17
Can be used.

The amount of the metathesis catalyst to be used is usually from 1: 500 to 1: 50,000 in terms of the molar ratio of the component (a) to the specific monomer. , Preferably 1: 1,000 to 1: 10,000
The range is 0. The ratio of component (a) to component (b) is such that (a) :( b) is 1: 1 to 1: 5 in terms of metal atomic ratio.
0, preferably in the range of 1: 2 to 1:30.
The ratio of the component (a) to the component (c) is a molar ratio of the component (c):
(A) is 0.005: 1 to 15: 1, preferably 0.0
The range is 5: 1 to 7: 1.

<Solvent for Polymerization Reaction> Examples of the solvent used in the ring-opening polymerization reaction (the solvent constituting the molecular weight modifier solution, the solvent for the specific monomer and / or the metathesis catalyst) include, for example, pentane, hexane, heptane and octane. ,
Nonane, alkanes such as decane, cyclohexane, cycloheptane, cyclooctane, decalin, cycloalkanes such as norbornane, benzene, toluene, xylene, ethylbenzene, aromatic hydrocarbons such as cumene,
Compounds such as halogenated alkanes and aryl halides such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform and tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate, and methyl propionate And saturated carboxylic esters such as dimethoxyethane, and ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. These can be used alone or as a mixture. Of these, aromatic hydrocarbons are preferred.
The amount of the solvent used is such that “solvent: specific monomer (weight ratio)” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. You.

<Molecular weight regulator> The molecular weight of the ring-opened (co) polymer obtained can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent.
It is controlled by allowing a molecular weight regulator to coexist in the reaction system. Here, suitable molecular weight regulators include, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-
Examples thereof include α-olefins such as decene and styrene, of which 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

In order to obtain a ring-opening copolymer, in the ring-opening polymerization step, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization. In addition, polybutadiene, polyisoprene, etc. In the presence of unsaturated hydrocarbon-based polymers containing two or more carbon-carbon double bonds in the main chain, such as conjugated diene compounds, styrene-butadiene copolymers, ethylene-non-conjugated diene copolymers, and polynorbornene The specific monomer may be subjected to ring-opening polymerization.

The ring-opened (co) polymer obtained as described above can be used as it is, but the hydrogenated (co) polymer obtained by further hydrogenating it is a resin having high impact resistance. Useful as a raw material for <Hydrogenation catalyst> The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm is added to the solution at 0 to 200 atm. C., preferably at 20-180.degree. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. As this hydrogenation catalyst,
Heterogeneous and homogeneous catalysts are included.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium, ruthenium or the like is supported on a carrier such as carbon, silica, alumina or titania. Examples of the homogeneous catalyst include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt octoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine) rhodium. , Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts have a ring-opening (co) polymer: hydrogenation catalyst (weight ratio) of 1: 1 × 10 ^-6 to 1:
It is used at a ratio of 2. As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties are degraded by heating during molding and use as a product. There is no. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more.

The ring-opened (co) polymer obtained as described above may contain a known antioxidant such as 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-
3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; UV absorber, for example, It can be stabilized by adding 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like. In addition, additives such as a lubricant can be added for the purpose of improving workability.

The hydrogenation rate of the hydrogenated (co) polymer is at least 50%, preferably at least 90%, more preferably at least 98%, as measured by 60 MHz, ¹ H-NMR. The higher the hydrogenation rate, the better the stability to heat and light. The hydrogenated (co) polymer used as the cyclic polyolefin resin of the present invention is:
The gel content in the hydrogenated (co) polymer is preferably 5% by weight or less, more preferably 1% by weight or less.

Further, as the cyclic polyolefin-based resin of the present invention, a (co) polymer obtained by cyclizing the above-mentioned or the ring-opened (co) polymer by a Friedel-Crafts reaction and then hydrogenating it can also be used. <Cyclization by Friedel-Crafts Reaction> The method of cyclizing a ring-opened (co) polymer by the Friedel-Crafts reaction is not particularly limited.
A known method using an acidic compound described in JP-A-154399 can be employed. As the acidic compound, specifically,
AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HC
1, Lewis acids such as CH ₃ ClCOOH, zeolites, activated clay, and Bronsted acids are used. The cyclized ring-opened (co) polymer can be hydrogenated in the same manner as the or the ring-opened (co) polymer.

Further, as the cyclic polyolefin resin of the present invention, a saturated copolymer of the above-mentioned specific monomer and an unsaturated double bond-containing compound can also be used. <Unsaturated double bond-containing compound> Examples of the unsaturated double bond-containing compound include ethylene, propylene, butene and the like, preferably an olefinic compound having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Can be.
The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/10 to 40/60 by weight, and more preferably 85/15 to 50/50.

In the present invention, in order to obtain a saturated copolymer of a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used. <Addition polymerization catalyst> As a catalyst for synthesizing the above-mentioned saturated copolymer, at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a co-catalyst are used.
Here, as the titanium compound, titanium tetrachloride, titanium trichloride and the like can be mentioned, and as the zirconium compound, bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride can be mentioned.

Further, as the vanadium compound, a compound represented by the general formula VO (OR) _{a Xb} or V (OR) _c X _d [where R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3 , 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0
≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ (c + d) ≦ 4. ]
Or an electron donating adduct thereof. Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples include nitrogen-containing electron donors such as nitriles and isocyanates.

Further, as the organoaluminum compound as the co-catalyst, at least one selected from compounds having at least one aluminum-carbon bond or aluminum-hydrogen bond is used. In the above,
For example, when a vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atoms to vanadium atoms (Al / V) is 2
Or more, preferably 2 to 50, particularly preferably 3 to
The range is 20.

The polymerization reaction solvent used for the addition polymerization is as follows:
The same solvent as used in the ring-opening polymerization reaction can be used. Adjustment of the molecular weight of the obtained saturated copolymer is usually performed using hydrogen.

Further, as the cyclic polyolefin resin of the present invention, an addition type of one or more monomers selected from the above-mentioned specific monomers, vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers ( Co) polymers and their hydrogenated (co) polymers can also be used. <Vinyl cyclic hydrocarbon monomer> Examples of the vinyl cyclic hydrocarbon monomer include vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, and 4-vinyl. 5-membered ring hydrocarbon monomer such as vinylcyclopentane monomer such as cyclopentane and 4-isopropenylcyclopentane, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-iso Vinylcyclohexene-based monomers such as propenylcyclohexene, 2-methyl-4-vinylcyclohexene and 2-methyl-4-isopropenylcyclohexene; vinylcyclohexane-based monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane Monomer, styrene, α-methyls Ren, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenyl styrene,
styrene monomers such as p-methoxystyrene, d-terpene, 1-terpene, diterpene, d-limonene, 1
-Terpene monomers such as limonene and dipentene;
Examples include vinylcycloheptene-based monomers such as vinylcycloheptene and 4-isopropenylcycloheptene, and vinylcycloheptane-based monomers such as 4-vinylcycloheptane and 4-isopropenylcycloheptane.
Preferred are styrene and α-methylstyrene. These can be used alone or in combination of two or more.

<Cyclopentadiene-based monomer> Examples of the cyclopentadiene-based monomer used in the addition-type (co) polymer monomer of the present invention include cyclopentadiene, 1-methylcyclopentadiene, Examples thereof include methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, and 5,5-methylcyclopentadiene. Preferred is cyclopentadiene. These can be used alone or in combination of two or more.

The addition type (co) polymer of one or more monomers selected from the above-mentioned specific monomers, vinyl-based cyclic hydrocarbon-based monomers and cyclopentadiene-based monomers may be selected from the above-mentioned specific monomers. And an unsaturated double bond-containing compound. The hydrogenated (co) polymer of the addition type (co) polymer can be obtained by the same hydrogenation method as the hydrogenated (co) polymer of the ring-opened (co) polymer.

The preferred molecular weight of the cyclic polyolefin resin used in the present invention is 0.2 inherent viscosity [η] _inh .
-5, gel permeation chromatography (GP
C) Number average molecular weight (M
n) is preferably from 8,000 to 100,000, and the weight average molecular weight (Mw) is preferably from 20,000 to 300,000. When the intrinsic viscosity [η] _inh or the weight average molecular weight is in the above range, the moldability, heat resistance, water resistance, chemical resistance, mechanical properties, and the like of the cyclic polyolefin-based resin are improved.

The cyclic polyolefin resin used in the present invention includes a ring-opened (co) polymer,
It is composed of a hydrogenated (co) polymer, a saturated copolymer, or an addition type (co) polymer and its hydrogenated (co) polymer, to which a known antioxidant, ultraviolet absorber, etc. is added. To further stabilize. In addition, additives used in conventional resin processing, such as a lubricant, can be added to improve processability.

The cyclic polyolefin-based resin of the present invention can be molded by a casting method, an extrusion method, or the like, and then appropriately stretched to obtain a film for a wave plate.

When the cyclic polyolefin resin film of the present invention is formed by a casting method, preferred organic solvents include:
Chlorine solvents such as methylene chloride, chloroform and carbon tetrachloride; aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene; hydrocarbon solvents such as cyclohexane and n-hexane; acetone, methyl ethyl ketone and methyl isobutyl ketone A ketone solvent,
Tetrahydrofuran and the like. Among these,
Methylene chloride, toluene and cyclohexane are preferred.
These can be used alone or in combination of two or more.

After the solution is filtered through a filter having a pore size of about several μm, a cyclic polyolefin resin film (base film) of the present invention can be obtained by performing a spin coating method, a solution casting method, or the like. The thickness of the obtained base film is usually 10 to 500 μm, preferably 10 to 500 μm.
The retardation value is not particularly limited as long as it is equal to or less than a value required for a wave plate, but is preferably 50 nm or less in consideration of ease of stretching.

When the cyclic polyolefin resin film of the present invention is formed by an extrusion method, the extrusion temperature is preferably 200 to 350 ° C., and more preferably 2 to 350 ° C.
It is 50-330 ° C, particularly preferably 280-320 ° C. The thickness of the base film is usually 10 to 500 μm.
m, preferably 100 to 200 μm, and the retardation value is not particularly limited as long as it is equal to or less than a value required for a wave plate, but is preferably 50 nm or less in consideration of ease of stretching.

Adjustment of the retardation value of the cyclic polyolefin resin film of the present invention is performed by stretching a base film obtained by a casting method, an extrusion method, or the like by an ordinary method and adjusting the stretching ratio. The cyclic polyolefin-based resin film can be used as it is as the wave plate of the present invention.

The wave plate of the present invention may be one in which the above-mentioned cyclic polyolefin-based resin film is provided on the surface of an undersubstrate transparent to the wavelength used. As the material of the base substrate of the optical recording medium of the present invention, a material having transparency to the wavelength of light to be used, such as a glass substrate or a plastic substrate, can be used. As the light to be used, for example, a wavelength of 780 n usually used in an optical pickup device for reproducing a CD.
m laser beam, wavelength 6 normally used for DVD playback
35 nm or 650 nm laser light, and the like. A transparent material such as glass or transparent resin is preferably used as the base substrate material. The shape of the base substrate material is not particularly limited, and may be a plate shape or a shape having an optical function such as a prism shape. The thickness of the undersubstrate is preferably 0.01 to 5 mm, more preferably 0.1 to 0.5 mm. 0.01mm
If it is less than this, the rigidity is insufficient. On the other hand, if it exceeds 5 mm, the size of the wavelength plate becomes large, and it is difficult to reduce the size of the optical system device.

As a method of manufacturing a wave plate of the present invention using an undersubstrate, the above-mentioned cyclic polyolefin-based resin film is laminated on the undersubstrate using an ultraviolet-curable adhesive or a thermosetting adhesive. There is a method of attaching. As a method of attaching a thermoplastic resin film on the base substrate using an adhesive, a commonly used method can be appropriately adopted. That is, a liquid adhesive is applied on the base substrate by spin coating or the like, a cyclic polyolefin-based resin film is laminated thereon, and the adhesive is cured to form a wave plate.

The change in the retardation value when the wave plate is formed using the cyclic polyolefin resin film by the above method is preferably ± 20 nm with respect to the design value.
Hereinafter, it is more preferably ± 10 nm or less, particularly preferably ± 5 nm or less. ± 2 change in retardation value
When the thickness exceeds 0 nm, the function as a wave plate is significantly reduced.

FIG. 1 shows the light transmittance of the cyclic polyolefin resin film of the present invention with respect to the wavelength of light. From FIG. 1, it can be seen that the wavelength plate of the present invention has a wavelength
It is clear that the transmittance of a laser beam of 635 nm or 650 nm, which is usually used for reproducing DAD and a wavelength of 635 nm or 650 nm, is 90% or more, so that it can be suitably used for an optical pickup device for reproducing CD and DAD.

As an optical device using the wave plate of the present invention, for example, there is an optical pickup device 10 using a quarter wave plate as shown in FIG. In the optical pickup device 10 shown in FIG. 2, a polarizing beam splitter (PBS) 21, a quarter-wave plate (QWP) 22, and an object are provided at an intermediate position in a forward path from a laser diode (LD) 20 as a laser light source to an optical recording medium 23. A lens 23 is provided. The return path of the return light reflected from the optical recording medium 24 passes through the objective lens 23 and the quarter-wave plate 22, is changed in traveling direction by 90 degrees by the PBS 21, and reaches the photodetector 25. Wave plate of the present invention, high heat resistance, low hygroscopicity, high adhesion to various materials, and for using a cyclic polyolefin-based resin film having a stable retardation value, is an inexpensive, high-performance wave plate, By using the wave plate of the present invention, an inexpensive and high-performance optical recording medium device can be manufactured. The optical recording medium device using the wavelength plate of the present invention can be applied to any of a read-only recording medium, a write-once (write-once) recording medium, and a rewritable recording medium for recording audio and images. Things.

[0049]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, parts and%
Are by weight unless otherwise indicated. Various measurements in the examples are as follows.

Using chloroform or cyclohexane as an intrinsic viscosity ([η] _inh ) solvent,
It was measured with an Ubbelohde viscometer at 30 ° C. at a polymer concentration of 0.5 g / dl. At a temperature of a gel content of 25 ° C., 50 g of a hydrogenated (co) polymer was dissolved in chloroform so as to have a concentration of 1%, and this solution was weighed in advance and a membrane filter having a pore size of 0.5 μm [Advantech Toyo Co., Ltd. And the dried filter was dried, and the gel content was calculated from the increase in weight.

Hydrogenation rate In the case of a hydrogenated homopolymer, 60 MHz, ¹ H-N
The MR was measured, and the hydrogenation rate was measured from the ratio of the respective absorption intensities of methyl hydrogen and olefinic hydrogen of the ester group or the ratio of the respective absorption intensities of paraffinic hydrogen and olefinic hydrogen. In the case of a hydrogenated copolymer, it was calculated by comparing ¹ H-NMR absorption of the copolymer after polymerization with that of the hydrogenated copolymer after hydrogenation. The glass transition temperature was measured by a scanning calorimeter (DSC) at a heating rate of 10 ° C./min in a nitrogen atmosphere.

Film thickness Keyence Co., Ltd., laser focus displacement meter, LT
It measured using -8010. The retardation value was measured at a wavelength of 590 nm using KOBRA-21ADH manufactured by Oji Scientific Instruments.

Reference Example 1 8-methyl-8-methoxycarbonyltetracyclo
[4.4.0.1^2,5. 1 ^7,10] Dodeca-3-ene 10
0 g, 1,2-dimethoxyethane 60 g, cyclohexa
240 g, 1-hexene 25 g, and diethyl alcohol
Minium chloride 0.96 mol / l toluene
3.4 ml of the solution was placed in an autoclave having a volume of 1 liter.
Added. Meanwhile, in another flask, tungsten hexachloride
0.05 mol / l of 1,2-dimethoxyethane
20 ml of solution and 0.1 mol / l of paraaldehyde
Was mixed with 10 ml of a 1,2-dimethoxyethane solution.
4.9 ml of this mixed solution was mixed in the above autoclave.
Added to the mixture. After sealing, heat the mixture to 80 ° C. for 3 hours.
Stirring was performed for hours. The obtained polymer solution is mixed with 1,2-diene.
2/8 (weight ratio) of methoxyethane and cyclohexane
Add a mixed solvent to reduce the polymer / solvent ratio to 1/10 (weight ratio)
Then, add 20 g of triethanolamine and add 10 minutes
While stirring.

To this polymerization solution, 500 g of methanol was added, and the mixture was stirred for 30 minutes and allowed to stand. The upper layer separated into two layers was removed, methanol was added again, and the mixture was stirred and allowed to stand, and then the upper layer was removed. The same operation was further repeated twice, and the obtained lower layer was appropriately diluted with cyclohexane and 1,2-dimethoxyethane to obtain a cyclohexane-1,2-dimethoxyethane solution having a polymer concentration of 10%. 20 g of palladium / silica magnesia (manufactured by Nikki Chemical Co., Ltd., palladium amount = 5%) was added to this solution, and hydrogen pressure was set to 40 in an autoclave.
After reacting at 165 ° C for 4 hours as kg / cm ² ,
The hydrogenation catalyst was removed by filtration to obtain a hydrogenated (co) polymer solution.

Further, this hydrogenated (co) polymer solution is
Antioxidant pentaerythrityl-tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added at 0.1% to the hydrogenated (co) polymer, and the solvent was removed at 380 ° C under reduced pressure. . Next, the molten resin was pelletized by an extruder under a nitrogen atmosphere to obtain a thermoplastic resin A having tricyclodecane as a basic skeleton. Table 1 shows the analysis results of the thermoplastic resin A.

Reference Example 2 As a monomer, 8-ethylidenetetracyclo [4.4.
0.1 ^2,6 . 1 ^7,10 ] -3-dodecene using 100 g,
Polymerization and hydrogenation were performed in the same manner as in Reference Example 1 except that 300 g of cyclohexane was used as a solvent, to obtain a thermoplastic resin B. Table 1 shows the analysis results of the thermoplastic resin B.

[0057]

[Table 1]

Example 1 A base film having a thickness of 10 μm and a retardation value of 15 nm was obtained from the thermoplastic resin A pellet obtained in Reference Example 1 as a raw material by a solution casting method using methylene chloride as a solvent. The obtained base film was uniaxially stretched at a stretching ratio of 150% to obtain a cyclic polyolefin-based resin film. A 0.3 mm thick glass substrate is spin-coated with a UV curable adhesive Photobond manufactured by Kyoritsu Chemical Co., Ltd., and a cyclic polyolefin-based resin film is laminated.
The wavelength plate (a) was prepared by irradiation with ultraviolet rays. FIG. 1 shows light absorption characteristics of the obtained wavelength plate (a) with respect to light wavelength.
The wave plate (a) prepared as described above was heated at 150 ° C. for 1 hour, and the retardation values before and after heating were measured. Table 2 shows the evaluation results. Example 2 A wave plate (b) was produced in the same manner as in Reference Example 1 except that the pellets of the thermoplastic resin B obtained in Reference Example 2 were used as raw materials and cyclohexane was used as a solvent. Table 2 shows the evaluation results.

Example 3 The pellets of the thermoplastic resin A obtained in Reference Example 1 were extruded at a cylinder temperature of 300 ° C. and a die temperature of 300 ° C. using a 40 mmφ extruder manufactured by Hitachi Zosen Corporation. , Thickness 140μm, retardation value 2
A 5 nm base film was obtained. The obtained base film was uniaxially stretched at a stretching ratio of 200% to obtain a cyclic polyolefin-based resin film. Using the obtained cyclic polyolefin-based resin film, a wave plate (c) was produced in the same manner as in Reference Example 1. Table 2 shows the evaluation results.

Comparative Example 1 Polycarbonate A2700 manufactured by Idemitsu Petrochemical Co., Ltd.
[Weight average molecular weight: 32,800 (measured by gel permeation chromatography, converted to polystyrene), glass transition temperature: 155 ° C.]
Extrusion was performed at 80 ° C. and a die temperature of 280 ° C. in the same manner as in Example 3 to a thickness of 10 μm and a retardation value of 40 nm.
Was obtained. The obtained base film was uniaxially stretched at a stretching ratio of 130% to obtain a polycarbonate film having a thickness of 110 µm and a retardation value of 328 nm.
The temperature conditions provided the best optical characteristics for this material. Using the obtained polycarbonate film, a wavelength plate (d) was produced in the same manner as in Reference Example 1. Table 2 shows the evaluation results.

[0061]

[Table 2]

* 1: Equivalent to λλ of 650 nm * 2: Equivalent to λλ of 650 nm

[0063]

The wave plate of the present invention has a high heat resistance, low hygroscopicity, high adhesion to various materials, and a cyclic polyolefin resin film having a stable retardation value. It is a high performance wave plate, and if the wave plate of the present invention is used, an inexpensive and high performance optical recording medium device can be manufactured. The optical recording medium device using the wave plate of the present invention can be applied to any of a read-only recording medium, a write-once recording medium, and a rewritable recording medium for recording audio and images.

[Brief description of the drawings]

FIG. 1 is a diagram showing the light transmittance of a thermoplastic film of Example 1 with respect to the wavelength of light.

FIG. 2 is a schematic configuration diagram of an example of an optical pickup device to which the wavelength plate of the present invention can be applied.

[Explanation of symbols]

 Reference Signs List 10 optical pickup device 21 polarization beam splitter 22 wavelength plate 24 optical recording medium

Claims (3)

[Claims] 1. A wave plate used for changing the polarization state of light composed of a cyclic polyolefin resin film. 2. A wave plate used for changing the polarization state of light, wherein a cyclic polyolefin-based resin film is provided on the surface of a base substrate transparent to the wavelength used. 3. The wave plate according to claim 2, wherein the cyclic polyolefin-based resin film is bonded to a base substrate.