JP2001183527A - Polyimide-based resin for optical parts, and phase contrast plate and wavelength plate each using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-cost polyimide resin for optical parts having transparency to light of 400-1,000 nm wavelength and giving a high phase contrast, and a phase contrast plate and a wavelength plate each using the resin and having good light transmittance in a relatively short wavelength range of 400-1,000 nm and high birefringence. SOLUTION: The polyimide resin for optical parts used under a light source having the wavelength range of 400-1,000 nm contains repeating units of formula 1a or 1b. In the formulae 1a and 1b, R is a divalent organic group; R' and R" are each a monovalent organic group or H; R1 and R2 are each a monovalent organic group or H; and R', R", R1 and R2 may be mutually the same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin for an optical component used for a retardation plate, a wave plate and the like, and a retardation plate and a wave plate using the same.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable development of technology using light for transmitting and storing information using light as a medium, such as optical wiring, optical communication, optical storage devices and optical disk media. The use of light is compared with the case of transmitting information over a relatively long distance using light of a relatively long wavelength of 1300 nm or more, such as optical communication, and the use of light of a relatively short wavelength of 900 nm or less, such as an optical storage device. When information is transmitted over a short distance, it can be broadly divided.

Devices using relatively short wavelength light of 900 nm or less, such as optical storage media, include compact disks (CD), mini disks (MD), and CD-ROMs.
R (CDR), CD-RW (CDR rewritable), DVD (DVI), DVD
-There are RAM (Did-idrum), DVD-R (Dedd-R), and other optical disks. These media irradiate a certain coherent light to a recording medium such as an azo compound or a cyanine compound to write information, or irradiate light weaker than the writing to pick up reflected light and perform reading. There is a problem that a phase difference occurs at the time of irradiation and reflection, and reading accuracy and writing accuracy are remarkably reduced. Therefore, a quarter-wave plate or the like is used to remove a noise component having a phase difference, and a crystal or the like has been used so far.

A quartz wave plate can be obtained by cutting a crystal, which is a uniaxial crystal, in a plane parallel to the crystal axis. However, since the wave plate itself is expensive and relatively heavy, the cost of peripheral parts is high. is there. Further, there is a problem that it is difficult to stably supply a quartz wave plate, and there is a high possibility that it will not be possible to follow explosive optical information transmission and optical information storage devices expected in the future. Furthermore, quartz is fragile and may be broken during the manufacturing process of a part, resulting in a problem of lowering the yield.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to
An object of the present invention is to provide an inexpensive polyimide resin for an optical component, which is transparent to light having a wavelength of 0 to 1000 nm and can obtain a high phase difference.

[0006] Another object of the present invention is to provide a light source having a wavelength of 400 nm to 100 nm.
An object of the present invention is to provide a retardation plate having a good light transmittance in a relatively short wavelength region of 0 nm and a large birefringence.

[0007] Another object of the present invention is to provide a light source device having a wavelength of 400 nm
Good light transmission in the relatively short wavelength region of 0 nm, light weight,
It is to provide a thin film and an inexpensive wave plate.

[0008]

As a result of various studies on the polyimide resin, the present inventors have found that a polyimide resin containing a repeating unit having a specific structure is particularly 400 to 1000.
It has been found that the light transmittance is high in a relatively short wavelength region of nm and a high phase difference can be obtained, and the present invention has been completed based on this finding.

The present invention relates to a compound of the general formula 1a or 1b

[0010]

Embedded image (Wherein, R represents a divalent organic group, R ′ and R ″ represent a monovalent organic group or a hydrogen atom, R ¹ and R ² represent a monovalent organic group or a hydrogen atom, , R ″, R ¹ and R ² may be the same or different from each other.)
The present invention relates to a polyimide resin for an optical component used in a light source in a wavelength range of 0 to 1000 nm.

[0011] The present invention also relates to the polyimide resin for an optical component used in a light source in a wavelength region of 400 to 800 nm.

[0012] The present invention also relates to a retardation plate comprising the above-mentioned polyimide resin and used for light in a wavelength region of 400 to 1000 nm.

[0013] The present invention also relates to the above retardation plate used for light in the wavelength region of 400 to 800 nm.

The present invention also relates to a wave plate made of the above-mentioned polyimide resin and used in a wavelength region of 400 to 1000 nm.

The present invention also relates to the above-mentioned wave plate used in the wavelength region of 400 to 800 nm.

The polyimide resin for optical parts of the present invention comprises:
When the orientation is advanced, the birefringence phase difference per unit becomes very large. When the polyimide resin for optical parts of the present invention is used, a phase difference of 1000 nm or more per 10 μm can be easily obtained.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION A polyimide resin containing a repeating unit represented by the general formula 1a or 1b is relatively easy to have a planar structure, and is easily oriented. Therefore, when formed into a film or a structure, birefringence occurs due to strong refractive index anisotropy. In particular, when the composition is applied and cured on the substrate, it is easily oriented with respect to the surface of the substrate, so that a large birefringence can be obtained when a laser beam or the like is passed through the application surface in a guided mode. Furthermore, this polyimide resin is 400 to 1000 n
The light transmittance is high in the wavelength region of light m.

When the film formed on the substrate is peeled off from the substrate or when the entire substrate is stretched, the molecules in the film tend to be oriented in the stretching direction. In the case where light is transmitted therethrough, it functions as a phase difference plate. At this time, various wavelength plates can be obtained by adjusting the thickness and the stretching ratio of the film.

Further, the wavelength plate made of a polyimide resin can increase the phase difference per the same film thickness as compared with that of a quartz crystal, so that the parts can be made thin. In addition, since the polyimide resin itself is light, the burden on peripheral parts and operating parts is increased. Is also greatly reduced. The fact that the burden on peripheral components and the operating section can be greatly reduced also has the advantage that cost reduction can be expected for them, and that not only the wave plate itself but also components and devices can be manufactured at low cost.

The retardation plate of the present invention can be obtained by obtaining a polyimide resin film for an optical component of the present invention.

As a method for obtaining a film, one of the methods of the present invention is used.
a method of applying a polyimide resin solution containing a repeating unit represented by a or 1b by applying, drying, curing if necessary, and stretching, and applying, drying, stretching, and optionally There is a method to obtain by curing.

As a method of coating, inorganic materials such as glass and quartz, semiconductors and metal materials such as silicon, gallium-arsenide, aluminum, titanium, copper, silver and stainless steel, and organic materials such as polyester, polypropylene, polyimide and polyamideimide are used. There are methods such as spin coating, cast coating and roll coating on a base material.

As a method for drying, the solvent is volatilized by heating to a temperature in the range of room temperature to 200 ° C. while holding the substrate, but when the film is stretched after drying, the film cannot be stretched if the amount of solvent in the film becomes extremely small. Therefore, the drying temperature is preferably not too high.

Examples of the stretching method include uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and uniaxial fixed uniaxial stretching.
Uniaxial fixing and uniaxial stretching are preferred because more uniform surfaces can be obtained more efficiently. In this case, the film may be stretched by heating.

Curing is usually performed at a temperature of 250 to 400 ° C. to obtain a polyimide resin.

The polyimide resin film made of a polyimide precursor containing a repeating unit represented by the general formula 1b which has been dried only has no problem depending on the conditions of use.

In order to use the obtained film as a phase plate or a wave plate, the thickness is preferably 0.1 to 100 μm.

The polyimide resin for optical parts containing a repeating unit represented by the general formula 1a or 1b according to the present invention comprises:
It is obtained by copolymerization of a tetracarboxylic dianhydride containing 3 ', 4,4'-biphenyltetracarboxylic dianhydride with a diamine.

R is preferably a divalent organic group having 1 to 30 carbon atoms, and more preferably a divalent organic group having an aromatic ring having 6 to 30 carbon atoms. R ', R ", R ¹ and R ²
Is preferably a monovalent organic group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is used in tetracarboxylic dianhydride.
0% is most preferred, but below that the desired properties of the present invention can be obtained. Therefore, other acid dianhydrides may be used as a mixture, but the proportion of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride used is at least 50 mol% in the tetracarboxylic dianhydride. It is preferred that

The polyimide resin used in the present invention includes a polyimide resin (including a polyimide resin precursor),
Examples thereof include polyimide / isoindoloquinazolinedione imide resin, polyether imide resin, and polyamide imide resin.

The precursor solution of the polyimide resin includes N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
It is obtained by reacting a tetracarboxylic dianhydride with a diamine in a polar solvent such as γ-butyl lactone dimethyl sulfoxide.

Examples of tetracarboxylic dianhydride used together with 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride include pyromellitic dianhydride, 2,3,3
3 ', 4'-biphenyltetracarboxylic dianhydride,
2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic acid Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride Anhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis ( 2-methyl-
3,4-dicarboxyphenyl) ether dianhydride, bis (2,5-dimethyl-3,4-dicarboxyphenyl) ether dianhydride, bis (2,5-diethyl-3,
4-dicarboxyphenyl) ether dianhydride, bis (2,5-diethoxy-3,4-dicarboxyphenyl) ether dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, , 2-bis (4- (4
-Carboxyphenoxy) phenyl) propane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6 -Pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, p-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-diphthalic dianhydride,
(Trifluoromethyl) pyromellitic dianhydride, di (trifluoromethyl) pyromellitic dianhydride, di (heptafluoropropyl) pyromellitic dianhydride, pentafluoroethyl pyromellitic dianhydride object,
Bis {3,5-di (trifluoromethyl) phenoxy}
Pyromellitic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride,
5,5'-bis (trifluoromethyl) -3,3 ',
4,4'-tetracarboxybiphenyl dianhydride, 2,
2 ', 5,5'-tetrakis (trifluoromethyl)-
3,3 ', 4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis (trifluoromethyl) -3,
3 ', 4,4'-tetracarboxybiphenyl ether dianhydride, 5,5'-bis (trifluoromethyl)-
3,3 ', 4,4'-tetracarboxybenzophenone dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} benzene dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} (trifluoromethyl) benzene Dianhydride, bis (dicarboxyphenoxy) (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene Dianhydride, 2,2-bis {(4- (3,4-dicarboxyphenyl) phenyl} hexafluoropropane dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy}
Biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} diphenyl ether dianhydride, bis (dicarboxyphenoxy) bis Known tetracarboxylic dianhydrides such as (trifluoromethyl) biphenyl dianhydride may be used in combination of two or more.

When obtaining a polyamideimide resin, trimellitic anhydride chloride or the like is used.

Examples of the diamine include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone,
4,4'-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-amino Phenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether,
1,4-bis (4-aminophenoxy) benzene, 2,
2'-dimethyl-4,4'-diaminobiphenyl, 2,
2'-diethyl-4,4'-diaminobiphenyl, 3,
3'-dimethyl-4,4'-diaminobiphenyl, 3,
3'-diethyl-4,4'-diaminobiphenyl, 2,
2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetraethyl-4,
4'-diaminobiphenyl, 2,2'-dimethoxy-
4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'- Diaminobiphenyl, 2,2'-
Di (trifluoromethyl) -4,4'-diaminobiphenyl, 4- (1H, 1H, 11H-eicosafluoroundecyloxy) -1,3-diaminobenzene, 4-
(1H, 1H-perfluoro-1-butyloxy)-
1,3-diaminobenzene, 4- (1H, 1H-perfluoro-1-heptyloxy) -1,3-diaminobenzene, 4- (1H, 1H-perfluoro-1-octyloxy) -1,3- Diaminobenzene, 4-pentafluorophenoxy-1,3-diaminobenzene, 4-
(2,3,5,6-tetrafluorophenoxy) -1,
3-diaminobenzene, 4- (4-fluorophenoxy) -1,3-diaminobenzene, 4- (1H, 1H,
2H, 2H-perfluoro-1-hexanoxy) -1,
3-diaminobenzene, 4- (1H, 1H, 2H, 2H
-Perfluoro-1-dodecyloxy) -1,3-diaminobenzene, 2,5-diaminobenzotrifluorofluoride, bis (trifluoromethyl) phenylenediamine, diaminotetra (trifluoromethyl) benzene,
Diamino (pentafluoroethyl) benzene, 2,5-
Diamino (perfluorohexyl) benzene, 2,5-
Diamino (perfluorobutyl) benzene, 2,2'-
Bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,
4'-diaminobiphenyl, octafluorobenzidine, 4,4'-diaminodiphenyl ether, 2,2-
Bis (p-aminophenyl) hexafluoropropane,
1,3-bis (anilino) hexafluoropropane,
1,4-bis (anilino) octafluorobutane, 1,
5-bis (anilino) decafluoropentane, 1,7-
Bis (anilino) tetradecafluoroheptane, 2,
2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether,
3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,
3'-bis (trifluoromethyl) -4,4'-diaminobenzophenone, 4,4'-diamino-p-terphenyl, 1,4-bis (p-aminophenyl) benzene,
p-bis (p-amino-2-trifluoromethylphenoxy) benzene, bis (aminophenoxy) bis (trifluoromethyl) benzene, bis (aminophenoxy)
Tetrakis (trifluoromethyl) benzene, 2,2-
Bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (3-aminophenoxy) phenyl} hexafluoropropane, 2,2
-Bis {4- (2-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (4-aminophenoxy) -3,5-dimethylphenyl} hexafluoropropane, 4,4'-bis ( 4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy)
Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone,
4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis {4- (4
-Amino-3-trifluoromethylphenoxy) phenyl {hexafluoropropane, bis [{(trifluoromethyl) aminophenoxy} phenyl] hexafluoropropane, bis {(trifluoromethyl) aminophenoxy} biphenyl, bis [2-} (Aminophenix)
Aromatic diamine compounds such as [phenyl [hexafluoropropyl] benzene] are used alone or in combination of two or more. Among these, aromatic diamine compounds having at least one or more of an ether group, a methylene group and a carbonyl group among bonds between two or more aromatic rings are preferable, and aromatic diamine compounds having an ether group are more preferable. preferable. In addition, an aromatic diamine compound having at least one phenylene structure in which at least one alkyl group is present as a substituent is preferable, and the phenylene group in which the alkyl group is located ortho to the bond between the aromatic rings. Aromatic diamine compounds having a structure are more preferred.

[0036]

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 200 g of 4,4'-diaminodiphenyl ether was added to N,
After dissolving in 588 g of N-dimethylacetamide,
294.2 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added and stirred at room temperature for 20 hours to obtain a polyimide precursor solution. Si as substrate
Using a 6-inch silicon wafer coated with ₂ μm of O ₂ , the above-mentioned polyimide precursor solution was dropped on the silicon wafer and spin-coated (1400 rpm / 30 seconds), and then heated in an oven (100 ° C./30 minutes) ) To form a polyamic acid film. The film was peeled off and uniaxially fixed uniaxial stretching was performed with a biaxial stretching device manufactured by Toyo Seiki Seisaku-sho. The stretching ratio at this time was 20%. The stretched film was taken out, the stretching direction was fixed with a jig, and curing was performed at 200 ° C./1 hour + 350 ° C./1 hour using a clean oven manufactured by Toyo Seiki. The thickness of this film after curing was 17 μm.

The 50% transmission wavelength of this film is 440n.
m. Further, the retardation at the center of the film was measured with a birefringence measuring apparatus (XY100 type, manufactured by Oak Corporation) to be about 800 nm. This film is 633 nm
It was found to function as a 5 / 4λ wave plate at the wavelength of.

Example 2 200 g of 4,4'-diaminodiphenyl ether was added to N,
After dissolving in 588 g of N-dimethylacetamide,
294.2 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added and stirred at room temperature for 20 hours to obtain a polyimide precursor solution. Si as substrate
Using a 6-inch silicon wafer coated with ₂ μm of O ₂ , the above-mentioned polyimide precursor solution was dropped on the silicon wafer and spin-coated (1400 rpm / 30 seconds), and then heated in an oven (100 ° C./30 minutes) + 200 ° C / 30 minutes +
(350 ° C./1 hour) to form a polyimide film. This film was peeled off and stretched while heating to 250 ° C. with a tensile tester. The stretching ratio at this time was 5%. The stretched film was taken out and its film thickness was measured to be 19 μm.

The 50% transmission wavelength of this film is 440n.
m. In addition, the retardation at the center of the film was measured by using a birefringence measuring apparatus (Model XY100) manufactured by Oak Corporation and found to be about 320 nm. This film is 633 nm
It was found to function as a 1 / 2λ wavelength plate at the wavelength of.

Example 3 200 g of 4,4'-diaminodiphenyl ether was added to N,
After dissolving in 3000 g of N-dimethylacetamide,
147.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 109 g of pyromellitic dianhydride were added, and the mixture was stirred at room temperature for 20 hours to obtain a polyimide precursor solution.

The polyimide precursor solution obtained here was added to 188
It was applied to a μm polyester film using a comma coater. After drying the film, it was stretched 15% uniaxially. Thereafter, the composition was cured at 350 ° C., and the phase difference was measured to be about 790 nm. This film was found to function as a ／ wavelength plate at 633 nm wavelength light.
The transmittance of this film at a wavelength of 633 nm was as good as 85%.

Example 4 100 g of 4,4'-diaminodiphenyl ether, p-
After dissolving 53 g of phenylenediamine in 2000 g of N, N-dimethylacetamide, 3,3 ', 4,4'-
147.1 g of biphenyltetracarboxylic dianhydride and 109 g of pyromellitic dianhydride were added and stirred at room temperature for 20 hours to obtain a polyimide precursor solution.

The polyimide precursor solution obtained here was cast applied with a gap of 300 μm, and 100
The film was dried by heating at 150 ° C. for 15 minutes to obtain a film. This film is simultaneously stretched 3% uniaxially and 10% uniaxially,
While the temperature was increased from 5 ° C. to 350 ° C. at a rate of 5 ° C./min, the composition was heated and cured on a hot plate. When the retardation at the center of the film was measured with light having a wavelength of 633 nm, it was 200 nm.
Met. The transmittance of this film at a wavelength of 633 nm was as good as 90%.

[0045]

According to the present invention, 400 nm to 1000 n
m, a polyimide resin for optical parts having excellent light transmittance in a relatively short wavelength region of 400 m to 400 nm to 1000 nm.
A polymer retardation plate excellent in light transmittance in a relatively short wavelength light region can be obtained. Further, since the phase difference can be easily controlled by the film thickness and the degree of orientation, a light-weight, thin-film, and inexpensive wave plate can be easily obtained.

Continued on the front page F term (reference) 2H049 BA06 BA25 BC03 BC09 CA20 4J043 PA02 PC115 PC135 PC136 PC145 PC146 PC155 PC156 QB15 QB26 QB31 RA05 RA35 SA06 SA54 SA55 SA56 SA61 SA71 SA72 TA01 TA22 TA47 TA48 TA49 TA71 TB01 UA041 UA121 UA122 UA122 UA122 UA122 UA261 UA262 UB011 UB012 UB121 UB122 UB281 UB301 VA021 VA031 VA041 VA061 VA101 ZA51 ZA55 ZB21

Claims (6)

[Claims] 1. A compound of the general formula 1a or 1b (Wherein, R represents a divalent organic group, R ′ and R ″ represent a monovalent organic group or a hydrogen atom, R ¹ and R ² represent a monovalent organic group or a hydrogen atom, , R ″, R ¹ and R ² may be the same or different from each other.)
Polyimide resin for optical parts used in a light source in a wavelength range of 0 to 1000 nm. 2. The polyimide resin for an optical component according to claim 1, which is used in a light source in a wavelength range of 400 to 800 nm. 3. A retardation plate comprising the polyimide resin according to claim 1 and used for light in a wavelength region of 400 to 1000 nm. 4. The retardation plate according to claim 3, which is used for light in a wavelength range of 400 to 800 nm. 5. A wave plate comprising the polyimide resin according to claim 1 and used in a wavelength region of 400 to 1000 nm. 6. The wave plate according to claim 5, which is used in a wavelength range of 400 to 800 nm.