JP2005208588A - Wavelength plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wavelength plate for an optical information recording/regenerating device and a liquid crystal projector which has superior initial characteristics, unlikely to receive influence of usage environment and a manufacturing environment and being superior in long period reliability. <P>SOLUTION: The wavelength plate laminates at least two sheets of phase-difference films and laminates a glass board on at least one side of the laminated phase difference film. The wavelength plate laminates and fixes the phase difference films, and the phase difference film and the glass board with each different adhesive, which is selected from between adhesives (A) and (B). (A): the adhesive has 0°C or lower of glass transition temperature and 10 MPa or smaller of Young's modulus at 23°C; (B): the adhesive has 40°C or higher for the glass transition temperature and 30 MPa or higher for the Young's modulus at 23°C. Here, the glass transition temperature difference between the adhesive (A) and the adhesive (B) is 60°C or higher, and the Young's modulus difference between the adhesive (A) and the adhesive (B) at 3°C is 40 MPa or higher. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a wave plate using a polymer film having a function of giving a phase difference to transmitted light (hereinafter referred to as “retardation film”). More specifically, for optical information recording / reproducing apparatus and liquid crystal projector having a structure in which at least two retardation films are laminated and the laminated retardation film and at least one glass substrate are laminated. This relates to the wave plate.

  The optical disk apparatus is an optical information recording / reproducing apparatus whose use has been greatly expanded in recent years due to non-contact, a large amount of information per unit volume, high-speed accessibility, and low cost. Various recording media have been developed utilizing this. For example, information is recorded once by a laser such as a compact disc (CD), laser disc (registered trademark) (LD), CD-ROM, or DVD-ROM that reproduces pre-recorded information as sounds, images, or computer programs. CD-Rs and DVD-Rs that can only be written and reproduced, and magneto-optical disks (MO), DVD-RAMs, and DVD-RWs that can repeatedly record and reproduce information have been developed.

  Various optical system apparatuses for recording and / or reproducing information in such an optical information recording / reproducing apparatus are known. One of them is a rewritable magneto-optical disk apparatus. It has been. In the rewritable magneto-optical disk device, the irradiation light from the laser light source is irradiated to the magneto-optical disk through the polarizer and the polarization beam splitter (PBS), and the return light reflected by the magneto-optical disk passes through the PBS again. A device having an optical pickup device in which a ½λ wave plate (hereinafter also referred to as “½ wave plate”) is arranged in the middle of the optical path leading to the photodetector or a ¼λ wave plate (hereinafter referred to as “¼”). A device having an optical pickup device on which a “wave plate” is also arranged is known.

  Here, the ½ wavelength plate gives an optical path difference of λ / 2 (and therefore a phase difference of π) between two orthogonal polarization components of a specific wavelength. , An optical path difference of λ / 4 (thus, a phase difference of π / 2) is provided between two orthogonal polarization components of a specific wavelength.

  The wave plate used in the liquid crystal projector functions as, for example, a polarization conversion element, and separates natural light incident on the polarization conversion element into P-polarized light and S-polarized light whose polarization planes are orthogonal to each other and separated. By rotating the polarization plane of any one of the P-polarized light and S-polarized light substantially by 90 degrees, the angle of the polarization plane of the polarized light coincides with the polarization plane of the other polarized light. is there. According to such a polarization conversion element, since most of the obtained polarized light has a substantially single polarization plane, high light utilization efficiency can be obtained in the liquid crystal projector. In such a polarization conversion element, a half-wave plate is used as means for rotating the polarization plane of incident polarized light substantially by 90 degrees. Also, in a liquid crystal projector, after being split into three primary colors (RGB) of light by a dichroic mirror, the light is transmitted through the corresponding liquid crystal panel, synthesized by a cross prism, and emitted from a projection lens. A quarter-wave plate may be used between the cross prisms for the purpose of improving luminance. At this time, since the wavelength of the dispersed light has a certain width, there may be a demand for a wave plate having a quarter wavelength in a wide band as well as a specific short wavelength.

Wave plates used for these applications include birefringent mica, quartz, quartz, calcite, wavelength plates formed from single crystals such as LiNbO ₃ and LiTaO _3, and oblique substrates with respect to underlying substrates such as glass substrates Inorganic materials such as a wave plate having a birefringent film on the surface of a base substrate obtained by vapor-depositing an inorganic material from the direction and a wave plate having an LB (Langmuir-Blodget) film having birefringence have been conventionally used. Yes.

  Also, polycarbonate (PC), triacetyl acetate (TAC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyethylene terephthalate (PET), polypropylene (PP), polyarylate, polysulfone, polyethersulfone, acrylic resin, etc. By stretching and orienting the transparent resin film, the retardation film, which is an organic thin film imparted with birefringence (function to give a retardation to transmitted light), can be adhered to a glass substrate to maintain flatness and shape. A wave plate sandwiched between two glass substrates is also used. Furthermore, a wave plate is used in which a polymer liquid crystal film is formed on a glass substrate to maintain flatness, regularity and molecular orientation, or is held between two glass substrates to give birefringence. ing.

Recently, DVD is rapidly spreading as a high-density information recording medium. On the other hand, read-only and write-type optical discs such as CD, CD-ROM and CD-R are already widely used in the market. For this reason, optical disc apparatuses are strongly required to be able to perform recording and reproduction on various optical discs having different systems, and are also required to be downsized and reduced in price as application fields expand. And in order to respond | correspond to these requirements, use of the broadband wavelength plate (phase difference plate) for respond | corresponding to the laser for several reading / writing is proposed (patent documents 1-3). Among these, for example, in Patent Document 3 (Japanese Patent Laid-Open No. 2002-14228), two types of incident linearly polarized light whose polarization planes are parallel to each other are polarized after the wave plate passes, A wave plate has been proposed in which is orthogonalized. In such a wave plate, in order to obtain desired optical characteristics, two or more retardation films are used. Therefore, not only the retardation films are adhesively fixed to the glass substrate but also the retardation films need to be adhesively fixed to each other. There was also. However, the wavelength plate having a structure in which the films are bonded to each other has a problem that the in-plane aberration is changed by continuous use over a long period of time, and good characteristics obtained in the initial stage cannot be maintained. In addition, because the physical properties of the retardation film are reflected as the characteristics of the wave plate, the retardation value (retardation) of the wave plate may gradually change over a long period of use depending on the usage environment, and the thickness of the film It has been pointed out that in-plane aberrations may increase due to unevenness, and as a result, good characteristics obtained in the initial stage may not be maintained.
JP 2001-101700 A JP 2001-208913 A Japanese Patent Laid-Open No. 2002-14228

  The object of the present invention is based on the above-mentioned problems of the prior art, and has excellent initial characteristics, is not easily affected by the use environment and manufacturing environment, and has excellent long-term reliability. The object is to provide a wave plate for a projector.

As a result of earnest studies to solve the above-described problems of the prior art, the present inventors have laminated at least two retardation films, and laminated a glass substrate on at least one side of the laminated retardation films. A wave plate in which the retardation films and the retardation film and the glass substrate are selected from the following adhesives (A) and (B) and are laminated and fixed with different adhesives, respectively. As a result, the present invention has been completed by finding that it is optimal as a wave plate for optical information recording / reproducing devices and liquid crystal projectors, which have excellent initial characteristics, are not easily affected by the use environment and manufacturing environment, and have excellent long-term reliability. It was.
Adhesive (A): Adhesive with a glass transition temperature of 0 ° C. or lower and a Young's modulus at 23 ° C. of 10 MPa or lower (B): A glass transition temperature of 40 ° C. or higher and a Young at 23 ° C. An adhesive having a rate of 30 MPa or more (however, the difference in glass transition temperature between the adhesive (A) and the adhesive (B) is 60 ° C. or more, and the adhesive (A) and the adhesive (B The difference in Young's modulus from the above is 40 MPa or more.)
In addition, the present inventors have developed a film (hereinafter referred to as “cyclic olefin”), which is made of a cyclic olefin resin having excellent heat resistance, low hygroscopicity, excellent retardation stability, and low retardation wavelength dependency. Retardation film that is stretched and oriented is particularly excellent in initial characteristics, is not easily affected by the use environment or manufacturing environment, and has excellent long-term reliability. For liquid crystal projectors. As a result, the present invention has been completed.

Further, the two retardation films are laminated so that the optical axes thereof intersect, and one retardation film has a retardation of λ / 2 with respect to light having a wavelength λ (nm) defined by the following formula (1). The other retardation film gives a retardation of λ / 4 to the light of wavelength λ (nm) defined by the following formula (1), and one retardation film has the following: A phase difference of λ is given to light having a wavelength λ (nm) defined by the equation (1), and the other retardation film is applied to light having a wavelength λ (nm) defined by the following equation (1). A wave plate made of a material that gives a retardation of λ / 4 or (3λ) / 4, and both retardation films are λ / 2 with respect to light having a wavelength λ (nm) defined by the following formula (1) A wave plate made of a material that gives a phase difference of 1 or one of the phase difference films in the following formula (1) A phase difference of λ is given to the light of the wavelength λ (nm) defined more, and the other retardation film has a wavelength of λ / 2 for the light of the wavelength λ (nm) defined by the following formula (1). By using a wave plate made of a material that gives a phase difference, monochromatic light with different wavelengths is given the same polarization characteristics, especially excellent initial characteristics, and it is not affected by the use environment or manufacturing environment, and is long-term reliable. The present invention has been completed by finding that it is optimal as a wave plate for an excellent optical information recording / reproducing apparatus and liquid crystal projector.
[(Λ _S + λ _L ) / 2] −200 ≦ λ ≦ [(λ _S + λ _L ) / 2] +200 (1)
λ _S : wavelength of monochromatic light on the shortest wavelength side (nm)
λ _L : wavelength of monochromatic light on the longest wavelength side (nm)

  The wave plate of the present invention is an inexpensive and long-performance wave plate. When the wave plate of the present invention is used, an optical information recording / reproducing apparatus and a liquid crystal projector apparatus which are inexpensive and have high performance over a long period of time can be manufactured.

  The optical information recording / reproducing apparatus using the wave plate of the present invention can be applied to any of a reproduction-only recording medium, a write-once recording medium, and a rewritable recording medium, as described above, with respect to audio and image recording. -ROM, CD-R, rewritable DVD and other recording devices and OA equipment using them, CD and other sound reproducing devices, DVD and other image reproducing devices and AV equipment using them, and the above CD and DVD, etc. It can be used for the game machine used. The wave plate of the present invention can also be used for a liquid crystal projector device.

Hereinafter, the present invention will be described more specifically.
Examples of the retardation film used in the present invention include polycarbonate (PC), triacetyl acetate (TAC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyethylene terephthalate (PET), polypropylene (PP), polyarylate, and polysulfone. And a transparent resin film such as polyethersulfone, acrylic resin, and cyclic olefin-based resin stretched and oriented. Especially, what extended | stretched and oriented the cyclic olefin resin film is used preferably.

The following (co) polymer is mentioned as cyclic olefin resin preferably used for retardation film use by this invention.
(1) A ring-opening polymer of a cyclic olefin represented by the following general formula (I) (hereinafter referred to as “specific monomer”).
(2) A ring-opening copolymer of a specific monomer and a copolymerizable monomer.
(3) A hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) above.
(4) A (co) polymer obtained by cyclization of the ring-opening (co) polymer of the above (1) or (2) by Friedel-Craft reaction and then hydrogenation.
(5) A saturated copolymer of a specific monomer and an unsaturated double bond-containing compound.
(6) Addition type (co) polymers of one or more monomers selected from specific monomers, vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers, and their hydrogenated (co) weights Coalescence.
(7) An alternating copolymer of a specific monomer and an acrylate.

[In formula, R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, respectively, and may be same or different, respectively. 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
Alternatively, R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. ]
<Specific monomer>
Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene,
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-methoxycarbonylbicyclo [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-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3
-Dodecene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [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-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [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 (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 difluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 pentafluoroethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-tetracyclo [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- tetrafluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8,8,9,9- tetrakis (trifluoromethyl) tetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethoxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-pentafluoro propoxy tetracyclo [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-heptafluoro-iso- propyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Chloro -8,9,9- trifluoro tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-Dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
, And the like 8-methyl-8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene.
These can be used alone or in combination of two or more.

Among the specific monomers, in the general formula (1), R ¹ and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 10, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms. R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom or a hydrocarbon group, and m is 0 An integer of ˜3, p is an integer of 0 to 3, more preferably m + p = 0 to 4, more preferably 0 to 2, particularly preferably m = 1 and p = 0. The specific monomer in which m = 1 and p = 0 is preferable in that the cyclic olefin resin obtained has a high glass transition temperature and excellent mechanical strength.

  Examples of the polar group of the specific monomer include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These polar groups are connected via a linking group such as a methylene group. May be combined. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Furthermore, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) _n COOR is obtained by using a cyclic olefin-based resin having a high glass transition temperature, a low hygroscopic property, and various materials. It is preferable at the point from which it has the outstanding adhesiveness. In the formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. In addition, n is usually 0 to 5, but the smaller the value of n, the higher the glass transition temperature of the resulting cyclic olefin resin, which is preferable, and the specific monomer having n of 0 is It is preferable in that the synthesis is easy.

In the general formula (I), R ¹ or R ³ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly preferably a methyl group. In particular, the fact that this alkyl group is bonded to the same carbon atom as that to which the specific polar group represented by the formula — (CH ₂ ) _n COOR is bonded is that of the obtained cyclic olefin-based resin. It is preferable at the point which can make hygroscopicity low.

<Copolymerizable monomer>
Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The number of carbon atoms of the cycloolefin is preferably 4-20, and more preferably 5-12. These can be used alone or in combination of two or more.

A preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50, more preferably 100/0 to 60/40, in weight ratio.
<Ring-opening polymerization catalyst>
In the present invention, (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening polymerization reaction for obtaining a ring-opening copolymer of a specific monomer and a copolymerizable monomer are metathesis It is carried out in the presence of a catalyst.

This metathesis catalyst comprises (a) at least one selected from W, Mo and Re compounds, (b) a Deaming periodic table group IA element (for example, Li, Na, K, etc.), IIA group element (for example, , Mg, Ca, etc.), group IIB elements (eg, Zn, Cd, Hg, etc.), group IIIA elements (eg, B, Al, etc.), group IVA elements (eg, Si, Sn, Pb, etc.), or group IVB A catalyst comprising a combination of at least one element selected from compounds having elements (for example, Ti, Zr, etc.) and having at least one element-carbon bond or the element-hydrogen bond. In this case, in order to increase the activity of the catalyst, an additive (c) described later may be added.

Representative examples of W, Mo or Re compounds suitable as component (a) include WCl ₆ ,
The compounds described in JP-A-1-132626, page 8, lower left column, line 6 to page 8, upper right column, line 17 such as MoCl ₆ and ReOCl _{3 can be} exemplified.

(B) Specific examples of the _{component, n-C 4 H 9 Li} , (C 2 H 5) 3 Al, (C 2 H 5) 2 AlCl
(C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH, etc. JP-A-1-132626, page 8, upper right column, line 18 to page 8, lower right column, column 3 Mention may be made of the compounds described in the row.

  As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, but further, JP-A-1-132626, page 8, lower right column, The compounds shown in line 16 to page 9, upper left column, line 17 can be used.

The amount of the metathesis catalyst used is a range in which “(a) component: specific monomer” is usually 1: 500 to 1: 50,000 in terms of the molar ratio of the component (a) to the specific monomer. , Preferably 1
The range is from 1,000 to 1: 10,000.

The ratio of the component (a) to the component (b) is such that (a) :( b) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atomic ratio.
The ratio of the component (a) to the component (c) is such that the molar ratio (c) :( a) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. The

<Solvent for polymerization reaction>
Examples of the solvent used in the ring-opening polymerization reaction (solvent constituting the molecular weight regulator solution, solvent for the specific monomer and / or metathesis catalyst) include alkanes such as pentane, hexane, heptane, octane, nonane and decane. , Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene , Halogenated alkanes such as chloroform and tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane ; Dibutyl ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, they can be used singly or in combination. Of these, aromatic hydrocarbons are preferred.

As the amount of the solvent used, “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. The
<Molecular weight regulator>
The molecular weight of the resulting ring-opening (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is adjusted by allowing the molecular weight regulator to coexist in the reaction system. To do.

Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable.
These molecular weight regulators can be used alone or in admixture of two or more.

The amount of the molecular weight regulator 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.
(2) In order to obtain a ring-opening copolymer, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization in the ring-opening polymerization step, and further, polybutadiene, polyisoprene, etc. In the presence of unsaturated hydrocarbon polymers such as conjugated diene compounds, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, polynorbornene and the like containing two or more carbon-carbon double bonds in the main chain. The specific monomer may be subjected to ring-opening polymerization.

  The ring-opening (co) polymer obtained as described above can be used as it is, but obtained by hydrogenating an olefinically unsaturated bond in the molecule of this (co) polymer (3) Hydrogenated (co) polymers are preferred because they are excellent in heat resistance colorability and light resistance and can improve the durability of the retardation film.

<Hydrogenation catalyst>
For the hydrogenation reaction, a method of hydrogenating a normal olefinically unsaturated bond can be applied. That is, by adding a hydrogenation catalyst to the ring-opening polymer solution and allowing hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, to act at 0 to 200 ° C., preferably 20 to 180 ° C. Done.

  As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. The homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, 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 are used in such a ratio that the ring-opening (co) polymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.
The hydrogenation rate of the hydrogenated (co) polymer is 500 MHz and the value measured by ¹ H-NMR is 5
It is 0% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more. The higher the hydrogenation rate, the better the stability to heat and light, and when used as the wave plate of the present invention, stable characteristics can be obtained over a long period of time.

  In addition, when the ring-opening (co) polymer molecule has an aromatic group, such an aromatic group is less likely to deteriorate the heat resistance coloring property and light resistance, and conversely optical properties such as refractive index and wavelength dispersion May have an advantageous effect with respect to the optical properties or heat resistance, and hydrogenation is not necessarily required.

The ring-opening (co) polymer obtained as described above contains known antioxidants such as 2,6-
Di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate] methane; UV absorber, eg 2,4
-It can be stabilized by adding dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone or the like. Further, additives such as a lubricant can be added for the purpose of improving processability.

  The hydrogenated (co) polymer used as the cyclic olefin-based resin used in the present invention preferably has a gel content contained in the hydrogenated (co) polymer of 5% by weight or less, Further, it is particularly preferably 1% by weight or less.

Further, as the cyclic olefin-based resin used in the present invention, (4) (1) or (2) the ring-opening (co) polymer is cyclized by Friedel-Craft reaction and then hydrogenated (co) heavy. Merges can also be used.

<Cyclization by Friedel-Craft reaction>
The method for cyclizing the ring-opening (co) polymer of the above (1) or (2) by Friedel-Craft reaction is not particularly limited, but the acidic compound described in JP-A-50-154399 is used. The publicly known method used can be adopted. Specific examples of the acidic compound include AlCl ₃ ,
Lewis acids such as BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₃ ClCOOH, zeolite, activated clay, and Bronsted acid are used.

The cyclized ring-opening (co) polymer can be hydrogenated in the same manner as the ring-opening (co) polymer of (1) or (2) above.
Further, as the cyclic olefin resin used in the present invention, (5) a saturated copolymer of the specific monomer and the unsaturated double bond-containing compound can also be used.

<Unsaturated double bond-containing compound>
As an unsaturated double bond containing compound, ethylene, propylene, butene etc., Preferably it is C2-C12, More preferably, C2-C8 olefin type compound can be mentioned.

The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/10 to 40/60, more preferably 85/15 to 50/50, in weight ratio.
In the present invention, in order to obtain a saturated copolymer of (5) a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used.

<Addition polymerization catalyst>
As the catalyst for synthesizing the (5) saturated copolymer, at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a promoter are used.

  Here, examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride.

Furthermore, as a vanadium compound, general formula VO (OR) _a X _b or V (OR) _c X _d
[Wherein 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 of these compounds.

  Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.

  Furthermore, as the organoaluminum compound as the promoter, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.

In the above, for example, when the vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atom to vanadium atom (Al / V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. Range.

  As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction can be used. Moreover, adjustment of the molecular weight of the (5) saturated copolymer obtained is normally performed using hydrogen.

  Further, as the cyclic olefin resin used in the present invention, (6) one or more monomers selected from the above specific monomer, and a vinyl cyclic hydrocarbon monomer or a cyclopentadiene monomer are used. Addition copolymers and their hydrogenated copolymers 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, 4-vinylcyclopentane, 4-isopropenylcyclopentane and the like. Vinylated 5-membered hydrocarbon monomers such as vinylcyclopentane monomers, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinyl Vinylcyclohexene monomers such as cyclohexene and 2-methyl-4-isopropenylcyclohexene, vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane, styrene, α-methylstyrene, 2-methylstyrene, 3- Styrenic monomers such as styrene styrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene, d-terpene, 1-terpene, diterpene, d-limonene, 1- Terpene monomers such as limonene and dipentene, vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene, 4-vinylcycloheptane, 4-isopropenylcycloheptane, etc. And vinyl cycloheptane monomers. Styrene and α-methylstyrene are preferable. These can be used alone or in combination of two or more.

<Cyclopentadiene monomer>
(6) Examples of cyclopentadiene monomers used as addition copolymer monomers include cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, and 5-methyl. Examples include cyclopentadiene, 5,5-methylcyclopentadiene, and the like. Cyclopentadiene is preferred. These can be used alone or in combination of two or more.

  The addition type (co) polymer of at least one monomer selected from the above specific monomer, vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer is the above (5) specific monomer. It can be obtained by the same addition polymerization method as the saturated copolymer of the 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 hydrogenation (co) polymer of the above 3) ring-opening (co) polymer.
Further, as the cyclic olefin resin used in the present invention, (7) an alternating copolymer of the specific monomer and acrylate can also be used.

<Acrylate>
(7) Examples of the acrylate used for the production of the alternating copolymer of the specific monomer and the acrylate include, for example, straight chain having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate, C2-C20 heterocyclic group-containing acrylate such as branched or cyclic alkyl acrylate, glycidyl acrylate, 2-tetrahydrofurfuryl acrylate, C6-C20 aromatic ring group-containing acrylate such as benzyl acrylate, Examples thereof include acrylates having a polycyclic structure having 7 to 30 carbon atoms such as boronyl acrylate and dicyclopentanyl acrylate.

  In the present invention, (7) In order to obtain an alternating copolymer of the specific monomer and acrylate, when the total of the specific monomer and acrylate is 100 mol in the presence of Lewis acid, The specific monomer is 30 to 70 mol, the acrylate is 70 to 30 mol, preferably the specific monomer is 40 to 60 mol, and the acrylate is 60 to 40 mol, particularly preferably the specific monomer. The body undergoes radical polymerization at a rate of 45 to 55 mol and acrylate at a rate of 55 to 45 mol.

  (7) The amount of Lewis acid used to obtain the alternating copolymer of the specific monomer and acrylate is 0.001 to 1 mol per 100 mol of acrylate. Also, known organic peroxides or azobis radical polymerization initiators that generate free radicals can be used, and the polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. . Moreover, the same solvent as used for the ring-opening polymerization reaction can be used as the solvent for the polymerization reaction.

  The “alternate copolymer” as used herein refers to a structure in which the structural unit derived from the specific monomer is not adjacent, that is, the structural unit derived from the acrylate is always adjacent to the structural unit derived from the specific monomer. It means a copolymer having a structure as a unit, and does not deny a structure in which structural units derived from acrylate are adjacent to each other.

The preferred molecular weight of the cyclic olefin resin used in the present invention is an intrinsic viscosity [η] _inh. 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g, and the number in terms of polystyrene measured by gel permeation chromatography (GPC). The average molecular weight (Mn) is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw) is 20,000 to 300. 30,000, more preferably 30,000 to 25
Those in the range of 0,000, particularly preferably 40,000 to 200,000 are suitable.

Inherent viscosity [η] _inh , number average molecular weight and weight average molecular weight are in the above ranges, so that the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic olefin resin and the wave plate of the present invention were used. The balance with the stability of the phase difference becomes good.

  The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 130 to 250 ° C., and particularly preferably 140 to 200 ° C. When Tg is less than 120 ° C., the change in optical characteristics of the obtained cyclic olefin resin film is undesirably increased by heat from the laser light source or its adjacent parts. On the other hand, when Tg exceeds 350 ° C., there is a high possibility that the resin is thermally deteriorated when heated and processed to the vicinity of Tg such as stretching.

  The saturated water absorption rate at 23 ° C. of the cyclic olefin resin used in the present invention is preferably 0.05 to 2% by weight, more preferably 0.1 to 1% by weight. When the saturated water absorption is within this range, the phase difference is uniform, the adhesiveness between the obtained cyclic olefin resin film and the glass substrate is excellent, peeling does not occur during use, and oxidation is prevented. It is also excellent in compatibility with agents and can be added in a large amount. When the saturated water absorption is less than 0.05% by weight, the adhesion to a support such as a glass substrate or a transparent support is poor, and peeling tends to occur. The resin film is likely to undergo dimensional changes due to water absorption.

In addition, said saturated water absorption is a value obtained by immersing in 23 degreeC water for 1 week, and measuring an increase weight according to ASTM D570.
The cyclic olefin resin used in the present invention has a photoelastic coefficient (C _P ) of 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ) and a stress optical coefficient (C _R ) of 1,500 to 4. Those satisfying 1,000 (× 10 ⁻¹² Pa ⁻¹ ) are preferably used.

Here, for the photoelastic coefficient (C _P ) and the stress optical coefficient (C _R ), various documents (Polymer Journal, Vol. 27, No, 9 pp 943-950 (1995), Journal of the Japan Rheological Society, Vol. 19, No. 2, p93-97 (1991), photoelasticity experiment method, Nikkan Kogyo Shimbun, 7th edition of 1975. It is a well-known fact that the former is due to stress in the glassy state of the polymer. The latter represents the degree of occurrence of phase difference, while the latter represents the degree of occurrence of phase difference due to stress in the flow state.

The large photoelastic coefficient (C _P ) is likely to cause a phase difference sensitively in the external factors or the stress generated from the strain generated by freezing when the polymer is used in the glass state. For example, residual stress at the time of bonding when laminated or fixed to a support as in the present invention, and minute stress generated by material shrinkage due to temperature change or humidity change Means that an unnecessary phase difference is likely to be generated. Therefore, it is better that the photoelastic coefficient (C _P ) is as small as possible.

On the other hand, a large stress optical coefficient (C _R ) means that, for example, a desired retardation can be obtained with a small stretch ratio when imparting retardation to a cyclic olefin-based resin film. There is a great merit that it is easy to obtain a film capable of imparting a phase difference, and that when the same phase difference is desired, the film can be thinned as compared with a film having a small stress optical coefficient (C _R ).

From the above viewpoint, the photoelastic coefficient (C _P ) is preferably 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 80 (× 10 ⁻¹² Pa ⁻¹ ), and particularly preferably 0. To 50 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 30 (× 10 ⁻¹² Pa ⁻¹ ), most preferably 0 to 20 (
× 10 ⁻¹² Pa ⁻¹ ). When the photoelastic coefficient (C _P ) exceeds 100 (× 10 ⁻¹² Pa ⁻¹ ), stress generated when the retardation films are bonded together, stress generated when the retardation film is fixed to the support And the phase difference change caused by environmental changes during use, etc., may cause the deviation of the optimum bonding optical axis angle from the allowable error range, and the transmitted light amount may decrease when used as a wave plate. There is not preferable.

The water vapor permeability of the cyclic olefin resin used in the present invention is usually 1 to 400 g / m ² · 2 when a film having a thickness of 25 μm is obtained under the conditions of 40 ° C. and 90% RH.
4 hr, preferably 5 to 350 g / m ² · 24 hr, more preferably 10 hr.
It is -300g / m < ² > * 24hr. By setting the water vapor transmission rate to this range, the water content and wavelength plate of the adhesive (A) and the adhesive (B) used for bonding the support such as a glass plate or a transparent support to the retardation film can be reduced. It is preferable because a change in characteristics due to the humidity of the environment used can be reduced or avoided.

  The cyclic olefin resin used in the present invention includes the above (1) to (2) ring-opening (co) polymer, (3) to (4) hydrogenated (co) polymer, and (5) saturated copolymer. It is composed of a polymer, (6) an addition type (co) polymer, or a hydrogenated (co) polymer thereof, or (7) an alternating copolymer, including known antioxidants, ultraviolet absorbers, etc. Can be further stabilized. Moreover, in order to improve workability, the additive used in conventional resin processings, such as a lubricant, can also be added.

  The cyclic olefin resin film used for the wave plate of the present invention can be obtained by forming the above cyclic olefin resin into a film or sheet by a melt molding method or a solution casting method (solvent casting method). Of these, the solvent casting method is preferred from the viewpoint of good film thickness uniformity and surface smoothness. From the viewpoint of production cost, the melt molding method is preferable.

  The method for obtaining the cyclic olefin-based resin film by the solvent casting method is not particularly limited, and a known method may be applied. For example, the cyclic olefin-based resin is dissolved or dispersed in a solvent to obtain an appropriate concentration. And a method of pouring or coating on a suitable carrier, drying it and then peeling it from the carrier.

Below, although various conditions of the method of obtaining a cyclic olefin resin film by a solvent cast method are shown, this invention is not limited to these conditions.
When the cyclic olefin-based resin is dissolved or dispersed in a solvent, the concentration of the resin is usually 0.1 to 90% by weight, preferably 1 to 50% by weight, and more preferably 10 to 35% by weight. When the concentration of the resin is less than the above, it becomes difficult to secure the thickness of the film, and problems such as difficulty in obtaining the surface smoothness of the film due to foaming due to solvent evaporation and the like occur. On the other hand, a concentration exceeding the above is not preferable because the viscosity and the surface of the cyclic olefin-based resin film obtained when the solution viscosity becomes too high become difficult to be uniform.

  The viscosity of the solution at room temperature is usually 1 to 1,000,000 mPa · s, preferably 10 to 100,000 mPa · s, more preferably 100 to 50,000 mPa · s, and particularly preferably 1,000. ~ 40,000 mPa · s.

Solvents used include aromatic solvents such as benzene, toluene, xylene, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol, acetone, cyclohexanone, methyl ethyl ketone, 4-methyl. Ketone solvents such as 2-pentanone, ester solvents such as methyl lactate and ethyl lactate, cycloolefin solvents such as cyclohexane, ethylcyclohexane, and 1,2-dimethylcyclohexane, 2,2,3,3-tetrafluoro- Examples thereof include halogen-containing solvents such as 1-propanol, methylene chloride and chloroform, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as 1-pentanol and 1-butanol.

In addition to the above, the SP value (solubility parameter) is usually 10 to 30 (MPa ^1/2 ), preferably 10 to 25 (MPa ^1/2 ), more preferably 15 to 25 (MPa ^1/2 ).
Particularly preferably, when a solvent in the range of 15 to 20 (MPa ^1/2 ) is used, a cyclic olefin resin film having good surface uniformity and optical properties can be obtained.

The said solvent can be used individually or in mixture of multiple. In that case, it is preferable that the range of the SP value when the mixed system is used is within the above range. At this time, the value of the SP value in the mixed system can be predicted by a weight ratio. For example, in the case of mixing two kinds, if the respective weight fractions are W1 and W2, and the SP values are SP1 and SP2, the SP of the mixed system. The value is the following formula:
SP value = W1 · SP1 + W2 · SP2
It can obtain | require as a value calculated by.

As a method for producing a cyclic olefin-based resin film by a solvent casting method, the above solution can be obtained by using a die or a coater to form a metal drum, a steel belt, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), poly Generally, a method of coating on a base material such as a tetrafluoroethylene (trade name; Teflon (registered trademark)) belt, and then drying the solvent to peel the film from the base material is generally used. Moreover, after apply | coating a solution to a base material by spraying, brushing, roll spin coating, dipping etc. and drying the obtained coating film, it can also manufacture by peeling a film from a base material. In addition, you may control thickness, surface smoothness, etc. by apply | coating repeatedly.

  The drying process of the solvent casting method is not particularly limited and can be carried out by a generally used method such as a method of passing through a drying furnace through a number of rollers. If this occurs, the characteristics of the film are remarkably deteriorated. Therefore, in order to avoid this, it is preferable to set the drying step to a plurality of steps of two or more stages and to control the temperature or the air volume in each step.

  Further, the amount of residual solvent in the cyclic olefin-based resin film is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. Here, when the residual solvent amount exceeds 10% by weight, the dimensional change with time becomes large when actually used, which is not preferable. Further, the residual solvent is not preferable because Tg is lowered and heat resistance is also lowered.

  In addition, in order to perform the extending | stretching process mentioned later suitably, it is necessary to adjust the said residual solvent amount suitably within the said range. Specifically, in order to stably and evenly express the phase difference during stretching orientation, the residual solvent amount is usually 10 to 0.1% by weight, preferably 5 to 0.1% by weight, more preferably 1 May be -0.1 wt%.

By leaving a trace amount of the solvent, stretching may be facilitated or phase difference may be easily controlled.
The thickness of the cyclic olefin resin film used in the present invention is usually 0.1 to 500 μm, preferably 0.1 to 300 μm, and more preferably 1 to 250 μm. When the thickness is less than 0.1 μm, handling becomes substantially difficult. On the other hand, when the thickness exceeds 500 μm, it is difficult to wind in a roll shape, and the wavelength plate of the present invention aiming at high transmittance of light such as laser light is not preferable because the transmittance decreases.

  The thickness distribution of the cyclic olefin resin film used in the present invention is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3% relative to the average value. is there. The thickness variation per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.5% or less. By carrying out such thickness control, it is possible to prevent retardation unevenness when stretched and oriented.

  As the retardation film composed of the cyclic olefin resin film used for the wave plate of the present invention, a film obtained by stretching the cyclic olefin resin film obtained by the above method is preferably used. Specifically, it can be produced by a known uniaxial stretching method or biaxial stretching method. That is, a horizontal uniaxial stretching method by a tenter method, a compression stretching method between rolls, a longitudinal uniaxial stretching method using rolls with different circumferences, a biaxial stretching method in which horizontal uniaxial and longitudinal uniaxial are combined, a stretching method by an inflation method, etc. Can be used.

In the case of the uniaxial stretching method, the stretching speed is usually 1 to 5,000% / min, preferably 50
It is -1,000% / min, More preferably, it is 100-1,000% / min, Especially preferably, it is 100-500% / min.

In the case of the biaxial stretching method, stretching may be performed in two directions at the same time, or the stretching may be performed in a direction different from the first stretching direction after uniaxial stretching. In these cases, the intersection angle of the two stretching axes is usually in the range of 120 to 60 degrees. The stretching speed may be the same or different in each stretching direction, and is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, and more preferably Is 100 to 1,000% / min, particularly preferably 100 to 5%.
00% / min.

  The stretching temperature is not particularly limited, but is usually Tg ± 30 ° C., preferably Tg ± 10 ° C., more preferably Tg based on the glass transition temperature (Tg) of the cyclic olefin resin of the present invention. It is in the range of −5 to Tg + 10 ° C. Within the above range, it is possible to suppress the occurrence of phase difference unevenness, and control of the refractive index ellipsoid is facilitated, which is preferable.

  The draw ratio is not particularly limited because it is determined by desired properties, but is usually 1.01 to 10 times, preferably 1.1 to 5 times, and more preferably 1.1 to 3.5 times. When the draw ratio exceeds 10 times, it may be difficult to control the phase difference.

  The stretched film may be cooled as it is, but it is allowed to stand in a temperature atmosphere of Tg-20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes. Is preferred. Thereby, the retardation film which consists of a stable cyclic olefin resin film with little change with time of retardation characteristics is obtained.

Moreover, the linear expansion coefficient of the cyclic olefin resin film used in the present invention is preferably 1 × 10 ⁻⁴ (1 / ° C.) or less, more preferably 9 × 10, in the temperature range of 20 ° C. to 100 ° C. ⁻⁵ (1 / ° C.) or less, particularly preferably 8 × 10 ⁻⁵ (1 / ° C.) or less, and most preferably 7 × 10 ⁻⁵ (1 / ° C.) or less. In the case of a retardation film, the difference in linear expansion coefficient between the stretching direction and the direction perpendicular thereto is preferably 5 × 10 ⁻⁵ (1 / ° C.) or less, more preferably 3 × 10 ⁻⁵ (1 / ° C.). ) Or less, particularly preferably 1 × 10 ⁻⁵ (1 / ° C.) or less. By setting the linear expansion coefficient within the above range, when the retardation film composed of the above cyclic olefin resin film is used as the wave plate of the present invention, the stress change due to the influence of temperature and humidity during use is affected. A change in phase difference is suppressed, and long-term stability can be obtained when used as the wave plate of the present invention.

  The film stretched as described above is oriented with molecules by stretching and gives a phase difference to transmitted light. This phase difference is the retardation value of the film before stretching, the stretching ratio, the stretching temperature, the stretching orientation. It can be controlled by the thickness of the later film. Here, the phase difference is defined by the product (Δnd) of the refractive index difference (Δn) of birefringent light and the thickness (d).

  When the film before stretching has a certain thickness, the larger the stretching ratio, the larger the absolute value of the retardation. Therefore, the retardation film having a desired retardation value can be obtained by changing the stretching ratio. Can do.

  In the present invention, at least two retardation films are used. In order to obtain desired optical characteristics as a wave plate, the retardation values of the respective retardation films may be the same or different. Also good. Although the retardation value per sheet depends on the desired optical characteristics of the wave plate, it is generally preferably 2000 nm or less, more preferably 1500 nm or less, and even more preferably 1000 nm or less. When the retardation value per sheet is larger than 2000 nm, the stretch ratio is too large, and the film thickness unevenness and the retardation value unevenness are undesirably increased. In order to obtain a retardation film having a retardation value larger than 2000 nm, the above problem can be solved by bonding and fixing the optical axes of the retardation films in parallel.

The optical characteristics of the wave plate are determined as desired and are not particularly limited. For example, the wave plate functions as a “¼ wave plate” in the range of 400 to 800 nm or “1/2 wave plate”. And the like that function as "." In order to obtain a wave plate that expresses a specific function in such a wide band, for example, the optical axes of two retardation films may be bonded together, and the accuracy of the angle of the crossed optical axes is theoretically The value is preferably within ± 5 °, more preferably within ± 3 °, and still more preferably within ± 1 °. If the deviation from the theoretical value of the optical axis angle is larger than 5 °, desired optical characteristics may not be obtained.

Using two retardation films and functioning as a “¼ wavelength plate” in a wide band, one retardation film is used for light having a wavelength λ (nm) defined by the following equation (1). A phase difference of λ / 2 is given, and the other phase difference film gives a phase difference of λ / 4 to light having a wavelength λ (nm) defined by the following formula (1). Those laminated so that their optical axes cross each other are preferably used.
[(Λ _S + λ _L ) / 2] −200 ≦ λ ≦ [(λ _S + λ _L ) / 2] +200 (1)
λ _S : wavelength of monochromatic light on the shortest wavelength side (nm)
λ _L : wavelength of monochromatic light on the longest wavelength side (nm)
The angles formed by the optical axes of the two retardation films at this time are, for example, “R1” for the first film and “R2” for the second film from the direction of incidence of light such as laser light. The phase difference of R1 is 315 to 345 nm, preferably 320 to 340 nm, more preferably 325 to 335 nm, and the phase difference of R2 is 150 to 180 nm, preferably 155 to 175 nm, more preferably 160 to 170 nm. In such a combination, it is usually 46 to 70 degrees, preferably 52 to 64 degrees, more preferably 56 to 60 degrees. At this time, when incident light such as laser light is linearly polarized light, the polarization plane of the linearly polarized light of this incident light (hereinafter also referred to as “incident linearly polarized polarization plane”) and the optical axis of R1 Is normally +70 to +82 degrees, preferably +72 to +80 degrees, more preferably +74 to +78 degrees, and the angle formed with the optical axis of R2 is usually +12 to +24 degrees, preferably +14 to +22. Degrees, more preferably +16 to +20 degrees. By setting it as the range mentioned above, it can be set as the wideband "1/4 wavelength plate" with a favorable polarization conversion function. In addition, the sign of the angle was defined as a counterclockwise angle being positive and a clockwise angle being negative when the film was viewed from the light incident side (the same applies hereinafter).

  Further, in a combination in which the phase difference of R1 is 230 to 260 nm, preferably 235 to 255 nm, more preferably 240 to 250 nm, and the phase difference of R2 is 110 to 140 nm, preferably 115 to 135 nm, more preferably 120 to 130 nm. In general, it may be 45 to 69 degrees, preferably 51 to 63 degrees, and more preferably 55 to 59 degrees. At this time, when incident light such as laser light is linearly polarized light, the angle formed between the incident linearly polarized light polarization plane and the optical axis of R1 is usually +68 to +80 degrees, preferably +70 to +78 degrees. More preferably, it is +72 to +76 degrees, and the angle formed by the optical axis of R2 is usually +11 to +23 degrees, preferably +13 to +21 degrees, and more preferably +15 to +19 degrees. By setting it as the range mentioned above, it can be set as the wideband "1/4 wavelength plate" with a favorable polarization conversion function.

  In addition, as one that uses two retardation films and functions as a “¼ wavelength plate” in a wide band, one retardation film can emit light having a wavelength λ (nm) defined by the above formula (1). A phase difference of λ is given to the other, and the other phase difference film gives a phase difference of λ / 4 or (3λ) / 4 to the light of the wavelength λ (nm) defined by the above formula (1). Those laminated so that the optical axes of two retardation films intersect each other are also preferably used.

The angles formed by the optical axes of the two retardation films at this time are such that the retardation of R1 is 690 to 750 nm, preferably 700 to 740 nm, more preferably 710 to 730 nm, and the retardation of R2 is 165 to 195 nm. In a combination of 170 to 190 nm, more preferably 175 to 185 nm, the angle is usually 39 to 63 degrees, preferably 45 to 57 degrees, and more preferably 49 to 53 degrees. At this time, when incident light such as laser light is linearly polarized light, the angle formed between the incident linearly polarized light angle and the optical axis of R1 is usually −1 to −13 degrees, preferably −3 to −. The angle formed by the optical axis of R2 is usually +38 to +50 degrees, preferably +40 to +48 degrees, and more preferably +42 to +46 degrees. By setting it as the range mentioned above, it can be set as the wideband "1/4 wavelength plate" with a favorable polarization conversion function.

  Using two retardation films and functioning as a “½ wavelength plate” in a wide band, both retardation films are for light of wavelength λ (nm) defined by the above formula (1). A film having a retardation of λ / 2 and laminated so that the optical axes of these two retardation films intersect is preferably used.

  The angle formed by the optical axes of the two retardation films at this time is usually 33 to in a combination in which the retardation of R1 and R2 is 260 to 290 nm, preferably 265 to 285 nm, more preferably 270 to 280 nm. It is 57 degrees, preferably 39 to 51 degrees, and more preferably 43 to 47 degrees. At this time, when incident light such as laser light is linearly polarized light, the angle formed by the incident linearly polarized light polarization plane and the optical axis of R1 is usually +15 to +27 degrees, preferably +17 to +25 degrees, Preferably, it is +19 to +23 degrees, and the angle formed by the optical axis of R2 is usually +59 to +71 degrees, preferably +61 to +69 degrees, and more preferably +63 to +67 degrees. By setting it as the range mentioned above, it can be set as the wideband "1/2 wavelength plate" with a favorable polarization conversion function.

  Further, in a combination in which the phase difference between R1 and R2 is 235 to 265 nm, preferably 240 to 260 nm, more preferably 245 to 255 nm, it is usually 33 to 57 degrees, preferably 39 to 51 degrees, more preferably 43 to 47 degrees. It is good. At this time, when the incident light such as laser light is linearly polarized light, the angle formed between the incident linearly polarized light polarization plane and the optical axis of R1 is usually +19 to +31 degrees, preferably +21 to +29 degrees, More preferably, it is +23 to +27 degrees, and the angle formed by the optical axis of R2 is usually +63 to +75 degrees, preferably +65 to +73 degrees, and more preferably +67 to +71 degrees. By setting it as the range mentioned above, it can be set as the wideband "1/2 wavelength plate" with a favorable polarization conversion function.

  Furthermore, as one that uses two retardation films and functions as a “½ wavelength plate” in a wide band, one retardation film is used for light having a wavelength λ (nm) defined by the above formula (1). A phase difference of λ is given to the other, and the other phase difference film gives a phase difference of λ / 2 to the light of the wavelength λ (nm) defined by the above formula (1). Those laminated so that their optical axes intersect each other are also preferably used.

  The angles formed by the optical axes of the two retardation films at this time are such that the retardation of R1 is 690 to 750 nm, preferably 700 to 740 nm, more preferably 710 to 730 nm, and the retardation of R2 is 345 to 375 nm. In a combination of 350 to 370 nm, more preferably 355 to 365 nm, the angle is usually 50 to 73 degrees, preferably 54 to 67 degrees, more preferably 59 to 63 degrees. At this time, when incident light such as laser light is linearly polarized light, the angle formed between the incident linearly polarized light polarization plane and the optical axis of R1 is usually +67 to +79 degrees, preferably +69 to +77 degrees, Preferably, it is +71 to +75 degrees, and the angle formed by the optical axis of R2 is usually −40 to −52 degrees, preferably −42 to −50 degrees, and more preferably −44 to −48 degrees. By setting it as the range mentioned above, it can be set as the wideband "1/2 wavelength plate" with a favorable polarization conversion function.

The glass substrate used in the present invention preferably has substantially no birefringence. It is not preferable that the transparent support has birefringence because it affects the properties as a wave plate. The shape of the glass substrate is not particularly limited, and may be a flat plate shape or a shape having an optical function such as a lattice shape or a prism shape. Moreover, thickness is 0.01-5 mm normally, Preferably it is 0.05-3 mm, More preferably, it is 0.05-1 mm. When the thickness is less than 0.01 mm, the rigidity is insufficient and the handling property is inferior. On the other hand, when the thickness exceeds 5 mm, the size of the wave plate increases and it is difficult to reduce the size of the optical system device.

In the present invention, an antireflection film can be laminated on one side or both sides of the glass substrate.
As a method for forming the antireflection film, for example, a fluorine-based copolymer is dissolved in an organic solvent, and the solution is used on a film, a sheet material, a retardation plate, or the like by a cast method using a bar coater or the like. Examples of the method include coating, forming, heating using a press, and curing. The heating temperature is usually 80 to 165 ° C, preferably 100 to 150 ° C, and the heating time is usually 10 minutes to 3 hours, preferably 30 minutes to 2 hours.

The thickness of the antireflection film is usually 5 to 2,000 nm, preferably 10 to 1,000 nm, and more preferably 50 to 200 nm. When the thickness is less than 5 nm, the antireflection effect cannot be exhibited. On the other hand, when the thickness exceeds 2,000 nm, unevenness is likely to occur in the thickness of the coating film, and the appearance is deteriorated.

Further, an antireflection film can be formed by providing a coating layer of a transparent inorganic oxide such as aluminum, magnesium, or silicon by using a vapor deposition method or a sputtering method.
In the case of such an inorganic antireflection film, the thickness of the transparent inorganic oxide coating layer is ¼ of the specific light wavelength. Furthermore, it is said that the antireflection performance can be further improved by laminating such transparent inorganic oxide coating layers.

  Examples of the adhesive (A) used in the present invention include natural rubber, synthetic rubber, vinyl acetate / vinyl chloride copolymer, silicon, polyvinyl ether, acrylic, modified polyolefin, epoxy, and urethane. Selected from those having the characteristics described below. Of these, acrylic adhesives are preferably used because they have excellent adhesion to an adherend.

  In order to obtain a wave plate that has excellent initial characteristics and is not easily affected by the use environment or manufacturing environment, and has excellent long-term reliability, the glass transition temperature of the adhesive (A), that is, the adhesive in a dried or cured state. The peak temperature of tan δ (loss tangent) in the dynamic viscoelasticity measurement (measurement frequency 1 Hz) of (A) needs to be 0 ° C. or less, preferably −20 ° C. or less, more preferably −40 ° C. or less. It is desirable to be.

  About the glass transition temperature of an adhesive agent, for example, in the case of an acrylic adhesive agent, it controls by selecting suitably the acrylic polymer or acrylic monomer to contain. In other words, acrylic monomers are classified as monofunctional, bifunctional, or polyfunctional depending on the number of double bonds in the molecule, but generally use many monofunctional acrylic monomers. Has a low glass transition temperature, and those using many polyfunctional acrylic monomers tend to have a high glass transition temperature, so acrylics used for polymerizing acrylic polymers to be blended in adhesives By adjusting the type and amount of the monomer or adjusting the type and amount of the acrylic monomer to be blended in the adhesive, an adhesive having a target glass transition temperature can be obtained.

The adhesive (A) has a Young's modulus (value when JIS Z1702, No. 3 dumbbell, pulling speed 10 mm / min) at room temperature (23 ° C.) in a dried or cured state is 10M.
It is necessary to be Pa or less, preferably 5 MPa or less, more preferably 2 MPa or less.

  In addition, in laminating and fixing, a surface treatment such as corona treatment, plasma treatment, coupling agent treatment or anchor coat treatment may be applied to the surface of each retardation film.

  Examples of the adhesive (B) used in the present invention include natural rubber, synthetic rubber, vinyl acetate / vinyl chloride copolymer, silicon, polyvinyl ether, acrylic, modified polyolefin, epoxy, and urethane. Selected from those having the characteristics described below. Of these, acrylic adhesives are preferably used because they have excellent adhesion to an adherend.

  In order to obtain a wave plate that has excellent initial characteristics and is not easily influenced by the use environment or manufacturing environment, and has excellent long-term reliability, the glass transition temperature of the adhesive (B), that is, the adhesive in a dried or cured state The peak temperature (glass transition temperature) of tan δ (loss tangent) in the dynamic viscoelasticity measurement (measurement frequency 1 Hz) of (B) needs to be 40 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 It is desirable that the temperature is not lower than ° C. Here, when there are two or more peak temperatures of the adhesive (B), the peak temperature on the high temperature side is adopted. At this time, the peak area of tan δ on the high temperature side is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more with respect to the peak area of all tan δ.

  The adhesive (B) has a Young's modulus (JIS Z1702, No. 3 dumbbell, value at a pulling speed of 10 mm / min) of the adhesive (B) in a dried or cured state at a room temperature (23 ° C.) of 30 MPa. It is necessary to be larger, preferably 50 MPa or more, more preferably 70 MPa or more.

The glass transition temperature difference between the adhesive (B) and the adhesive (A) is 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher.
Furthermore, the difference in Young's modulus between the adhesive (B) and the adhesive (A) at 23 ° C. is 40 MPa or more, preferably 50 MPa or more, more preferably 60 MPa or more.

  In the adhesion fixation, the surface of the retardation film or glass substrate may be subjected to a ground treatment such as corona treatment, plasma treatment, coupling agent treatment or anchor coat treatment.

  The wave plate according to the present invention is a wave plate in which at least two retardation films are laminated, and a glass substrate is laminated on at least one surface of the laminated retardation film. The phase difference film and the glass substrate are selected from the adhesives (A) and (B), and are laminated and fixed with different adhesives. In the present invention, a glass substrate is laminated on both surfaces of the laminated retardation film (a structure in which the laminated retardation film is sandwiched between two glass substrates), and the retardation films are laminated with an adhesive (A). It is preferable that the retardation film and the glass substrate are fixed with an adhesive (B).

  By using the above-mentioned adhesive (A) and adhesive (B) in combination for laminating the retardation films and laminating the retardation film and glass, the amount of change in the in-plane aberration of the wave plate is reduced. Therefore, the wave plate is less affected by the use environment and the manufacturing environment and has excellent long-term reliability.

The reason for this is not clearly clarified, but deformation due to external stress to the wave plate can be prevented by using a hard adhesive (B), and the distortion generated when the temperature changes is soft. It is presumed that the use of a large adhesive (A) would ease both in a balanced manner.

  Examples of the acrylic adhesive include, for example, a polymer containing a monomer composition containing at least one acrylic monomer (acrylate compound) and a solvent, and a composition containing at least one acrylate compound and a curing agent. A composition containing the above polymer, a composition containing at least one acrylate compound and a curing agent, and the like, but the present invention is not limited thereto. Here, the acrylate compound has at least one (meth) acryloyl group in the molecule, and examples thereof include a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound.

Specific examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert -Butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate , Alkyl (meth) acrylates such as lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like Of phenoxyalkyl (meth) acrylates;
Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate;
Polyethylene glycol (meth) acrylates such as polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate;
Polypropylene glycol (meth) acrylates such as polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate;
Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl ( Cycloalkyl (meth) acrylates such as (meth) acrylate and tricyclodecanyl (meth) acrylate;
Examples include benzyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate and the like.

These monofunctional (meth) acrylate compounds can be used individually by 1 type or in mixture of 2 or more types.
Specific examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 1.4. -Alkylene glycol di (meth) acrylates such as butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate;
Trimethylolpropane tri (meth) acrylate, trimethylolpropane trihydroxyethyl tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa Poly (meth) acrylates of polyhydric alcohols such as (meth) acrylate and hydroxypivalate neopentyl glycol di (meth) acrylate;
Isocyanurate poly (meth) acrylates such as isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate;
Poly (meth) acrylates of cycloalkanes such as tricyclodecanediyldimethyldi (meth) acrylate;
Di (meth) acrylate of bisphenol A ethylene oxide adduct, di (meth) acrylate of propylene oxide adduct of bisphenol A, di (meth) acrylate of alkylene oxide adduct of bisphenol A, ethylene oxide addition of hydrogenated bisphenol A Di (meth) acrylate, di (meth) acrylate of propylene oxide adduct of hydrogenated bisphenol A, di (meth) acrylate of alkylene oxide adduct of hydrogenated bisphenol A, bisphenol A diglycidyl ether and (meth) acrylic (Meth) acrylate derivatives of bisphenol A such as (meth) acrylate obtained from acids;
3,3,4,4,5,5,6,6-octafluorooctanedi (meth) acrylate, 3- (
2-perfluorohexyl) ethoxy-1,2-di (meth) acryloylpropane, N-
Examples thereof include fluorine-containing (meth) acrylates such as n-propyl-N-2,3-di (meth) acryloylpropyl perfluorooctylsulfonamide.

These polyfunctional (meth) acrylate compounds can be used individually by 1 type or in mixture of 2 or more types.
The adhesive strength of the adhesive (A) or adhesive (B) needs to be such that it cannot be easily peeled off during handling. As a specific value of the adhesive strength, in the adhesive (A), the 90-degree peeling force when two retardation films are bonded to each other is preferably 0.5 N / cm ² or more, more preferably 1 N / cm ^2. As described above, most preferably 3 N / cm ² or more, and in the adhesive (B), the 90-degree peeling force when the retardation film and the glass substrate are bonded is preferably 0.5 N / cm ² or more. Preferably it is 1 N / cm ² or more, most preferably 3 N / cm ² or more. If the adhesive strength is less than 0.5 N / cm ² , it is not preferable because it may be peeled off due to an impact during handling or the bonded layers may be displaced.

  The thickness of the adhesive (A) or the adhesive (B) is not particularly limited as long as the above adhesive strength can be ensured, but is usually 1 μm to 100 μm, preferably 2 μm to 70 μm, more preferably 3 μm to 50 μm, Most preferably, it is 4 micrometers-30 micrometers. If the thickness of the adhesive (A) or the adhesive (B) is greater than 100 μm, the thickness of the wave plate may increase, causing problems in optical characteristics such as light transmittance, and inconvenience in handling. is there. Moreover, when the thickness is less than 1 μm, the adhesive strength may not be ensured.

The difference between the refractive index of the retardation film and the refractive index of the adhesive that bonds the retardation films to each other is preferably within 0.20, more preferably within 0.15, particularly preferably within 0.10, and most preferably 0. The difference between the refractive index of the retardation film and the refractive index of the adhesive for bonding the glass substrate is preferably within 0.20, more preferably within 0.15, and particularly preferably 0.10. Within 0.05, and most preferably within 0.05. Further, the difference in refractive index between the retardation film and the glass substrate is preferably within 0.20, more preferably within 0.15, particularly preferably within 0.10, and most preferably within 0.05. The refractive index difference within this range is preferable because loss due to reflection of transmitted light can be minimized.

  Of course, the in-plane aberration of the wave plate of the present invention is preferably as small as possible, and is usually within 50 (mλ), preferably within 30 (mλ), and more preferably within 20 (mλ). By setting the in-plane aberration of the wave plate within the above range, it is preferable because an excellent S / N and an allowable jitter range are obtained. Here, λ represents the wavelength of transmitted light, and the wavelength of laser light that is generally used is used.

The number of foreign substances in the wave plate of the present invention is preferably as small as possible, and those having a particle size of 10 μm or more are usually 10 (pieces / mm ² ) or less, preferably 5 (pieces / mm ² ) or less, Preferably it is 1 (pieces / mm ² ) or less. It is not preferable that foreign matters having a size of 10 μm or more exist in the wave plate in a number exceeding 10 (pieces / mm ² ) because the noise signal increases and the S / N ratio becomes small. Here, the foreign matter in the wave plate includes those that reduce the transmission of the laser light and those that greatly change the traveling direction of the laser light due to the presence of the foreign matter. Examples of the former include dust, dust, resin burns, powders of metal powder, minerals, and the like, and examples of the latter include contamination of other resins and transparent substances having different refractive indexes.

  Note that the wave plate of the present invention has been colored using a known colorant or the like in order to block or reduce the transmission of light having a wavelength other than the desired wavelength as necessary for noise reduction or the like. May be.

  The wave plate of the present invention is conventionally known except that it is selected from adhesives (A) and (B) and uses different adhesives for laminating and fixing the retardation films and between the retardation film and the glass substrate. This method can be used for manufacturing.

  The wave plate of the present invention is a wave plate in which at least two retardation films are laminated with an adhesive, and a glass substrate is laminated on at least one surface of the laminated retardation film, and the retardation film Since each other and the retardation film and glass are selected from the adhesive (A) and the adhesive (B) and are laminated and fixed with different adhesives, the initial characteristics can be maintained over a long period of time. . In particular, a retardation film obtained by stretching and orientationing a cyclic olefin resin film is preferable. By using such a wave plate of the present invention, it is possible to manufacture a highly durable optical information recording / reproducing apparatus and liquid crystal projector apparatus that can maintain performance over a long period of time.

  The optical information recording / reproducing apparatus using the wave plate of the present invention can be applied to any of a reproduction-only recording medium, a write-once recording medium, and a rewritable recording medium, and can be a CD-ROM, CD-R, or rewritable. It is used for a recording device such as a DVD and an OA device using them, an audio playback device such as a CD, an image playback device such as a DVD and an AV device using them, a game machine using the CD, DVD, etc. it can. The wave plate of the present invention can also be used for a liquid crystal projector device.

[Example]
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. In addition, unless otherwise indicated, the part and% in an Example are a weight part and weight%. In addition, various tests and measurement methods in the examples are as follows.

[Intrinsic viscosity ([η] _inh )]
Chloroform or cyclohexane was used as a solvent, and measurement was performed with an Ubbelohde viscometer at a polymer concentration of 0.5 g / dl at 30 ° C.

[Gel content]
At a temperature of 25 ° C., 50 g of a hydrogenated (co) polymer was dissolved in chloroform to a concentration of 1%, and this solution was previously weighed to a membrane filter having a pore diameter of 0.5 μm [Advantech Toyo Corp. The gel content was calculated from the increase in weight after drying the filter after filtration.

[Hydrogenation rate]
In the case of a hydrogenated homopolymer, 500 MHz, ¹ H-NMR is measured, the ratio of the absorption intensity of methyl hydrogen and olefinic hydrogen of the ester group, or the absorption intensity of paraffinic hydrogen and olefinic hydrogen, respectively. The hydrogenation rate was measured from the ratio of In the case of a hydrogenated copolymer, the calculation was made by comparing the ¹ H-NMR absorption of the copolymer after polymerization with that of the hydrogenated copolymer after hydrogenation.

[Glass transition temperature of resin]
The measurement was carried out with a scanning calorimeter (DSC) at a heating rate of 10 ° C./min in a nitrogen atmosphere.

[Membrane thickness]
Measurement was performed using a laser focus displacement meter, LT-8010, manufactured by Keyence Corporation.
[Glass transition temperature of adhesive (tan δ peak temperature)]
A strip-shaped test piece (5 mm × 7 cm) of an adhesive was prepared using Leo Vibron (Model DDV-01FP) manufactured by Orientec Co., Ltd., and measured at a temperature range of −100 to 150 ° C. and a frequency of 1 Hz. When two or more types of peaks exist, the value on the high temperature side is defined as the peak temperature (glass transition temperature).

  For glass transition temperatures of room temperature or lower, measurement was performed by applying a 1 mm thickness on a base material (ARTON manufactured by JSR Corporation, thickness 10 μm) whose tan δ peak temperature had been confirmed in advance. The tan δ peak temperature derived from the agent was confirmed.

[Young's modulus of adhesive]
Using a tensile tester manufactured by Instron Co., Ltd., No. 3 dumbbell was prepared and measured at 23 ° C. in accordance with JIS-Z1702. The pulling speed was 10 mm / min.

  For those with a glass transition temperature of room temperature or lower, a PET base material previously coated with an adhesive is formed into a No. 3 dumbbell shape, and the test part is exposed by removing the PET base material immediately before the measurement. A tensile test was conducted.

[In-plane aberration]
Using a small-diameter laser interferometer R10 manufactured by Fuji Photo Optical Co., Ltd., transmitted wavefront aberration was measured using a laser beam having a wavelength of 650 nm in a range of 5 mmφ.

[Phase difference value]
Measured at wavelengths of 480, 550, 590, 630, and 750 nm using KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd. Calculated using the dispersion formula.

[High temperature and high humidity test]
An ESPEC Co., Ltd. environmental tester was set at 95 ° C. and 95% RH. The sample was taken out after being placed in a bath for 1000 hours, and visually observed, measured for a retardation value, and measured for in-plane aberration.

<Synthesis Example 1>
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Charge 250 parts of dodecene (specific monomer), 18 parts of 1-hexene (molecular weight regulator) and 750 parts of toluene (solvent for ring-opening polymerization reaction) to a nitrogen-substituted reaction vessel, and heat the solution to 60 ° C. Heated. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst and tungsten hexachloride modified with t-butanol and methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. = 0.35 mol: 0
. (3 mol: 1 mol) of a toluene solution (concentration: 0.05 mol / l) 3.7 parts was added, and the system was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction. A solution was obtained. The polymerization conversion in this polymerization reaction was 97%, and the intrinsic viscosity (η _inh ) of the obtained ring-opened polymer measured in chloroform at 30 ° C. was 0.75 dl / g.

The autoclave was charged with 4,000 parts of the ring-opening polymer solution thus obtained, and 0.48 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C.

  After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter referred to as “resin A”).

The hydrogenation rate of the resin A thus obtained was measured using ¹ H-NMR and found to be 99.9%. Moreover, it was 165 degreeC when the glass transition temperature (Tg) was measured by DSC method about the said resin. Further, when the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were measured by GPC method (solvent: tetrahydrofuran) for the resin, Mn was 32,000, Mw was 137,000, and molecular weight distribution. (Mw / Mn) was 4.29. Further, the saturated water absorption rate at 23 ° C. of the resin was measured and found to be 0.3%. Moreover, it was 19 (MPa ^{/ 2} ) when SP value was measured. Further, the intrinsic viscosity (η _inh ) of the resin was measured in chloroform at 30 ° C. and found to be 0.78 dl / g. The gel content was 0.4%.

<Synthesis Example 2>
A specific monomer as a 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 215 parts, bicyclo [2.2.1] hept - 2-ene 35
A hydrogenated polymer was obtained in the same manner as in Synthesis Example 1 except that the amount of 1-hexene (molecular weight regulator) added was 18 parts. The hydrogenation rate of the obtained hydrogenated polymer (hereinafter referred to as “resin B”) was 99.9%. Moreover, it was 125 degreeC when the glass transition temperature (Tg) was measured by DSC method about the said resin. Moreover, when the number average molecular weight (Mn) and weight average molecular weight (Mw) of polystyrene conversion were measured by the GPC method (solvent: tetrahydrofuran) about the said resin, Mn was 46,000, Mw was 190,000, molecular weight distribution (Mw / Mn) was 4.15. Moreover, when the saturated water absorption rate at 23 ° C. was measured for the resin, it was 0.18%. Moreover, it was 19 (MPa ^{/ 2} ) when SP value was measured. Further, the intrinsic viscosity (η _inh ) of the resin was measured in chloroform at 30 ° C. and found to be 0.69 dl / g. The gel content was 0.2%.

<Synthesis Example 3>
Identified as monomer 8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 225 parts Using the addition amount of 30 parts of 1-hexene (molecular weight modifier) A hydrogenated polymer was obtained in the same manner as in Synthesis Example 1 except that cyclohexane was used in place of toluene as a solvent for the ring-opening polymerization reaction. The hydrogenation rate of the obtained hydrogenated polymer (hereinafter referred to as “resin C”) was 99.9%. Moreover, it was 138 degreeC when the glass transition temperature (Tg) was measured by DSC method about the said resin. Moreover, when the number average molecular weight (Mn) and weight average molecular weight (Mw) of polystyrene conversion were measured by the GPC method (solvent: cyclohexane) about the said resin, Mn was 50,000, Mw was 190,000, molecular weight distribution (Mw / Mn) was 3.80. Further, the saturated water absorption rate at 23 ° C. of the resin was measured and found to be 0.01%. Moreover, it was 17 (MPa ^{/ 2} ) when SP value was measured. In addition, for the resin, the intrinsic viscosity (
η _inh ) was measured and found to be 0.72 dl / g. The gel content was 0.4%.

<Film Production Example 1>
Resin A is dissolved in toluene to a concentration of 30% (solution viscosity at room temperature is 30,000 mPa · S), and the surface is made hydrophilic (easy-adhesion) with acrylic acid using INVEX Lab Coater made by Inoue Metal Industry. It apply | coated so that the film thickness after drying might be set to 100 micrometers on the processed PET film (Toray, Lumirror U94) of 100 micrometers, and this was primary-dried at 50 degreeC, and then secondary-dried at 90 degreeC. . A resin film A peeled from the PET film was obtained. The amount of residual solvent in the obtained film was 0.5%.

The photoelastic coefficient (C _P ) and stress optical coefficient (C _R ) of this film were determined by the following method. Specifically, the photoelastic coefficient (C _P ) was calculated from a phase difference generated at the room temperature (25 ° C.) and a stress applied to the sample at that time by applying several kinds of constant loads to the strip-shaped film sample. For the stress optical coefficient (C _R ), the phase difference generated after the film sample was slowly cooled to room temperature after being stretched by several percent under several constant loads above Tg and returned to room temperature was measured. It was calculated from the applied stress. The results were C _P = 4 (× 10 ⁻¹² pa ⁻¹ ) and C _R = 1750 (× 10 ⁻¹² pa ⁻¹ ), respectively.

The characteristic values of the resin film A are shown in Table 1.
<Film Production Example 2>
Resin B was used and Resin Film B was obtained in the same manner as Film Production Example 1. The amount of residual solvent of the obtained resin film B is 0.5%, and the photoelastic coefficient (C _P ) and the stress optical coefficient (C _R ) are C _P = 9 (× 10 ⁻¹² pa ⁻¹ ) and C, respectively. _R = 2,350 (× 10 ⁻¹² pa ⁻¹ ).
The characteristic values of the resin film B are shown in Table 1.

<Film Production Example 3>
Resin C was obtained in the same manner as in Film Production Example 1 except that Resin C was used and the solvent was cyclohexane. The amount of residual solvent of the obtained resin film C is 0.4%, and the photoelastic coefficient (C _P ) and the stress optical coefficient (C _R ) are C _P = 4 (× 10 ⁻¹² pa ⁻¹ ) and C, respectively. _R
= 1,950 (× 10 ⁻¹² pa ⁻¹ ).
The characteristic values of the resin film C are shown in Table 1.

<Example 1>
The resin film A is heated to 175 ° C., which is Tg + 10 ° C. in a tenter, uniaxially stretched 1.4 times at a stretching rate of 400% / min, and this state is maintained for 1 minute in an atmosphere at 110 ° C. When cooled to room temperature and taken out, a retardation film A-1 having a thickness of 89 μm and a retardation at a wavelength of 655 nm of 160 nm could be obtained. The resin film A is heated in a tenter to 175 ° C. which is Tg + 10 ° C., uniaxially stretched 2.1 times at a stretching rate of 400% / min, and this state is maintained in an atmosphere at 110 ° C. for 1 minute. Then, when cooled and taken out to room temperature, a retardation film A-2 having a thickness of 81 μm and a retardation at a wavelength of 655 nm of 330 nm could be obtained.

  These retardation films A-1 and A-2 are bonded together using an acrylic adhesive having a thickness of 10 μm (manufactured by Sumitomo 3M Co., Ltd., 8142) so that each optical axis is 60 °. A glass plate having a thickness of 250 μm was laminated on both surfaces of the bonded film using an acrylic adhesive having a thickness of 10 μm (manufactured by Kyoritsu Chemical Industry Co., Ltd., XVL-90) to obtain a wave plate A. Here, 8142 manufactured by Sumitomo 3M Co., Ltd. used as the adhesive (A) has a tan δ peak temperature of −63 ° C. and Young's modulus of 0.6 Mpa, and Kyoritsu Chemical Industry Co., Ltd. used as the adhesive (B). The tan δ peak temperature of XVL-90 produced was 61 ° C., and the Young's modulus was 75 Mpa.

  When the phase difference of the wave plate A was measured, the phase difference at 655 nm was 161 nm, and the phase difference at 785 nm was 195 nm. Therefore, it was confirmed that the wave plate A functions as a “¼ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate A was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate A was confirmed, it was 18 mλ.

  When the high-temperature and high-humidity test was performed on the wave plate A, the change amount of the retardation value was within 3%, the change amount of the in-plane aberration was 5 mλ or less, and no change in appearance was observed, and good characteristics were maintained. I confirmed.

<Example 2>
A retardation film having a thickness of 89 μm and a retardation at a wavelength of 655 nm of 275 nm, except that the resin film B is used and the stretching conditions are 1.3 times and the heating temperature is 130 ° C. B-1 was obtained.

  Two retardation films B-1 were laminated using an acrylic adhesive having a thickness of 10 μm (manufactured by Sumitomo 3M Co., Ltd., 8142) so that each optical axis was 45 °, and further laminated. A glass plate having a thickness of 250 μm was laminated on both surfaces of the film using an acrylic adhesive having a thickness of 10 μm (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.) to obtain a wave plate B.

  When the phase difference of the wave plate B was measured, the phase difference at 500 nm was 246 nm and the phase difference at 785 nm was 395 nm. Therefore, it was confirmed that the wave plate B functions as a “½ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate B was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate B was confirmed, it was 15 mλ.

  When this wavelength plate B was subjected to a high-temperature and high-humidity test, the change amount of the retardation value was within 3%, the change amount of the in-plane aberration was 5 mλ or less, the appearance change was not observed, and good characteristics were maintained. I confirmed.

<Example 3>
A retardation film having a thickness of 96 μm and a retardation of 125 nm at a wavelength of 655 nm is the same as in Example 1 except that the resin film C is used and the stretching conditions are 1.08 times the stretching ratio and the heating temperature is 148 ° C. C-1 was obtained. Further, using the resin film C, the thickness was 91 μm and the phase difference at a wavelength of 655 nm was 250 nm, except that the stretching conditions were a stretching ratio of 1.18 times and a heating temperature of 148 ° C. A phase difference film C-2 was obtained.

  These retardation films C-1 and C-2 are bonded together using an acrylic adhesive having a thickness of 10 μm (manufactured by Sumitomo 3M Co., Ltd., 8142) so that each optical axis is 55 °. A glass plate having a thickness of 250 μm was laminated on both surfaces of the bonded film using a 10 μm-thick acrylic adhesive (manufactured by Kyoritsu Chemical Industry Co., Ltd., XVL-90) to obtain a wavelength plate C.

  When the retardation of the wave plate C was measured, the retardation at 405 nm was 102 nm and the retardation at 655 nm was 165 nm. Therefore, it was confirmed that the wave plate C functions as a “¼ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate C was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wavelength plate C was confirmed, it was 35 mλ.

  When the high-temperature and high-humidity test was performed on the wave plate C, the change amount of the retardation value was 3% or less, the change amount of the in-plane aberration was 5 mλ or less, and no change in appearance was observed, and good characteristics were maintained. I confirmed.

<Example 4>
Two retardation films C-2 were bonded together using an acrylic adhesive (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.) having a thickness of 10 μm so that each optical axis was 40 °. A glass plate having a thickness of 250 μm was laminated on one surface of the bonded film using an acrylic adhesive having a thickness of 20 μm (manufactured by Sumitomo 3M Co., Ltd., 8142) to obtain a wave plate D.
When the retardation of the wave plate D was measured, the retardation at 405 nm was 199 nm and the retardation at 655 nm was 325 nm. Therefore, it was confirmed that the wave plate D functions as a “½ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate D was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate D was confirmed, it was 17 mλ.

  When this high-temperature and high-humidity test was performed on this wave plate D, the amount of change in the retardation value was within 3%, the amount of change in in-plane aberration was 5 mλ or less, and no change in appearance was observed, and good characteristics were maintained. I confirmed.

<Example 5>
A retardation film having a thickness of 70 μm and a retardation at a wavelength of 655 nm of 710 nm, except that the resin film B was used and the stretching conditions were a stretching ratio of 1.92 times and a heating temperature of 148 ° C. B-2 was obtained. Further, a retardation film A-3 having a thickness of 90 μm and a retardation of 175 nm at a wavelength of 175 nm was obtained in the same manner as in Example 1 except that the stretching condition was 1.42 times using the resin film A. Got. Using these retardation films B-2 and A-3, an acrylic adhesive (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.) having a thickness of 10 μm so that each optical axis is 50 °. A glass plate having a thickness of 250 μm was laminated on one side of the laminated film and a laminated film using an acrylic adhesive having a thickness of 20 μm (manufactured by Sumitomo 3M Co., Ltd., 8142) to obtain a wave plate E.
When the retardation of the wave plate E was measured, the retardation at 655 nm was 164 nm and the retardation at 785 nm was 196 nm. Therefore, it was confirmed that the wave plate E functions as a “¼ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate E was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate E was confirmed, it was 32 mλ.

  When this wavelength plate E was subjected to a high-temperature and high-humidity test, the change amount of the retardation value was within 3%, the change amount of the in-plane aberration was 5 mλ or less, and no change in appearance was observed, and good characteristics were maintained. I confirmed.

<Example 6>
A retardation film having a thickness of 87 μm and a retardation at a wavelength of 655 nm of 355 nm, except that the resin film B is used and the stretching conditions are 1.58 and the heating temperature is 148 ° C. B-3 was obtained.

The retardation films B-2 and B-3 are bonded together using an acrylic adhesive (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.) having a thickness of 10 μm so that each optical axis is 60 °. Further, a glass plate having a thickness of 250 μm was laminated on one surface of the bonded film using a 20 μm-thick acrylic adhesive (manufactured by Sumitomo 3M Co., Ltd., 8142) to obtain a wave plate F.
When the retardation of the wave plate F was measured, the retardation at 655 nm was 320 nm and the retardation at 785 nm was 395 nm. Therefore, it was confirmed that the wave plate F functions as a “½ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate F was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate F was confirmed, it was 32 mλ.

  When the high-temperature and high-humidity test was performed on the wave plate F, the change amount of the retardation value was within 3%, the change amount of the in-plane aberration was 5 mλ or less, and no change in appearance was observed, and good characteristics were maintained. I confirmed.

<Example 7>
The retardation films A-1 and A-2 are bonded using an acrylic adhesive (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.) having a thickness of 10 μm so that each optical axis is 60 °. Further, a glass plate having a thickness of 250 μm was laminated on both surfaces of the bonded film by using an acrylic adhesive having a thickness of 20 μm (manufactured by Sumitomo 3M Co., Ltd., 8142) to obtain a wave plate G.
When the phase difference of the wave plate G was measured, the phase difference at 655 nm was 162 nm, and the phase difference at 785 nm was 195 nm. Therefore, it was confirmed that the wave plate G functions as a “¼ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate G was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate G was confirmed, it was 31 mλ.

  When the high-temperature and high-humidity test was performed on the wave plate G, the change amount of the retardation value was within 3%, the change amount of the in-plane aberration was 5 mλ or less, the appearance change was not observed, and good characteristics were maintained. I confirmed.

<Example 8>
Two retardation films C-2 are laminated using an acrylic adhesive having a thickness of 10 μm (manufactured by Sumitomo 3M Co., Ltd., 8142) so that each optical axis is 40 °, and further laminated. A glass plate having a thickness of 250 μm was laminated on one surface of the glass plate using an acrylic adhesive having a thickness of 10 μm (manufactured by Kyoritsu Chemical Industry Co., Ltd., XVL-90).
When the retardation of the wave plate H was measured, the retardation at 405 nm was 201 nm and the retardation at 655 nm was 326 nm. Therefore, it was confirmed that the wave plate H functions as a “½ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate H was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate H was confirmed, it was 31 mλ.

  When the high-temperature and high-humidity test was performed on the wave plate H, the change amount of the retardation value was within 3%, the change amount of the in-plane aberration was 5 mλ or less, and no change in appearance was observed, and good characteristics were maintained. I confirmed.

<Comparative Example 1>
The retardation films A-1 and A-2 are bonded using an acrylic adhesive (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.) having a thickness of 10 μm so that each optical axis is 60 °. Further, a glass plate with a thickness of 250 μm is laminated on both surfaces of the bonded film using a 10 μm-thick acrylic adhesive (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.) to obtain a wave plate I. It was.
When the phase difference of the wave plate I was measured, the phase difference at 655 nm was 160 nm, and the phase difference at 785 nm was 196 nm. Therefore, it was confirmed that the wave plate I functions as a “¼ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate I was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate I was confirmed, it was 20 mλ.
When this wavelength plate I was subjected to a high-temperature and high-humidity test, the amount of change in retardation value was within 3% and no change in appearance was observed, but it was confirmed that the amount of change in in-plane aberration was 10 mλ. .

<Comparative example 2>
Two retardation films B-1 are laminated using an acrylic adhesive (Sumitomo 3M, 8142) having a thickness of 10 μm so that each optical axis is 45 °, and further laminated. A glass plate having a thickness of 250 μm was laminated on both surfaces using an acrylic adhesive having a thickness of 10 μm (manufactured by Sumitomo 3M Limited, 8142) to obtain a wave plate J.

  When the retardation of the wave plate J was measured, the retardation at 655 nm was 328 nm and the retardation at 785 nm was 390 nm. Therefore, it was confirmed that the wave plate J functions as a “½ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle size of 10 μm or more in the wave plate J was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate J was confirmed, it was 18 mλ.

  When a high-temperature and high-humidity test was performed on this wave plate J, the amount of change in retardation value was within 3% and no change in appearance was observed, but it was confirmed that the amount of change in in-plane aberration was 15 mλ. .

<Comparative Example 3>
Two retardation films C-2 were bonded together using an acrylic adhesive (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.) having a thickness of 10 μm so that each optical axis was 40 °. A glass plate with a thickness of 250 μm was laminated on one surface of the bonded film using a 10 μm-thick acrylic adhesive (XVL-90, manufactured by Kyoritsu Chemical Industry Co., Ltd.), and a wave plate K was obtained.

  When the phase difference of the wave plate K was measured, the phase difference at 405 nm was 200 nm, and the phase difference at 655 nm was 323 nm. Therefore, it was confirmed that the wave plate K functions as a “½ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate K was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate K was confirmed, it was 24 mλ.

  When a high-temperature and high-humidity test was performed on this wave plate K, the amount of change in retardation value was within 3% and no change in appearance was observed, but it was confirmed that the amount of change in in-plane aberration was 18 mλ. .

<Comparative example 4>
The retardation films B-2 and A-3 are bonded together using an acrylic adhesive having a thickness of 10 μm (manufactured by Sumitomo 3M Co., Ltd., 8142) so that each optical axis is 50 °, and further bonded. A wave plate L was obtained by laminating a glass plate having a thickness of 250 μm on one side of the film using an acrylic adhesive having a thickness of 10 μm (manufactured by Sumitomo 3M Limited, 8142).
When the retardation of the wave plate L was measured, the retardation at 655 nm was 162 nm and the retardation at 785 nm was 198 nm. Therefore, it was confirmed that the wave plate L functions as a “¼ wave plate” in a wide band.

It was confirmed by a polarizing microscope that the number of foreign matters having a particle diameter of 10 μm or more in the wave plate L was 10 / mm ² or less.
Furthermore, when the in-plane aberration of the wave plate L was confirmed, it was 20 mλ.

  When a high-temperature and high-humidity test was performed on this wave plate L, the amount of change in the retardation value was within 3% and no change in appearance was observed, but it was confirmed that the amount of change in in-plane aberration was 16 mλ. .

Claims (4)

It is a wavelength plate in which at least two retardation films are laminated, and a glass substrate is laminated on at least one surface of the laminated retardation film, and the retardation films and the retardation film and the glass substrate, A wavelength plate selected from the following adhesives (A) and (B) and laminated and fixed with different adhesives;
Adhesive (A): Adhesive with a glass transition temperature of 0 ° C. or lower and a Young's modulus at 23 ° C. of 10 MPa or lower (B): A glass transition temperature of 40 ° C. or higher and a Young at 23 ° C. Adhesive having a rate of 30 MPa or more (however, the difference in glass transition temperature between the adhesive (A) and the adhesive (B) is 60 ° C. or more, and the adhesive (A) and the adhesive (B The difference in Young's modulus with that of 40) is 40 MPa or more.)   A glass substrate is laminated on both surfaces of the laminated retardation film, the retardation films are laminated and fixed with an adhesive (A), and the retardation film and the glass substrate are fixed with an adhesive (B). The wave plate according to claim 1, wherein:   The wave plate according to claim 1 or 2, wherein the retardation film is obtained by stretching and orienting a cyclic olefin resin film. It is a method for producing a wave plate by laminating at least two retardation films and laminating a glass substrate on at least one side of the laminated retardation film, and the retardation films and the retardation film and glass, A method for producing a wave plate, characterized in that it is selected from the following adhesives (A) and (B) and laminated and fixed with different adhesives;
Adhesive (A): Adhesive with a glass transition temperature of 0 ° C. or lower and a Young's modulus at 23 ° C. of 10 MPa or lower (B): A glass transition temperature of 40 ° C. or higher and a Young at 23 ° C. An adhesive having a rate of 30 MPa or more (however, the difference in glass transition temperature between the adhesive (A) and the adhesive (B) is 60 ° C. or more, and the adhesive (A) and the adhesive (B The difference in Young's modulus with that of 40) is 40 MPa or more.)