JP3532621B2 - Photosensitive composition for volume hologram recording, recording medium using the same, and method for forming volume hologram - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a photosensitive composition for volume hologram recording that provides a hologram excellent in heat resistance and the like, a hologram recording medium using the same, a volume hologram recording method, and a recorded hologram.

[0002]

2. Description of the Related Art A hologram is a hologram in which two light beams (object light and reference light) having the same wavelength interfere with each other and the wavefront of the object light is recorded as interference fringes on a photosensitive material. When light is applied, a diffraction phenomenon occurs due to interference fringes, and the same wavefront as the original object light can be reproduced. Holograms are classified into several types according to the recording form of interference fringes. In recent years, so-called volume holograms that record interference fringes with a difference in the refractive index inside the recording layer have been used due to their high diffraction efficiency and excellent wavelength selectivity. It is being applied to uses such as three-dimensional displays and optical elements.

As a photosensitive material for recording such a volume hologram, a material using silver halide or gelatin dichromate conventionally used in the art field is generally used. However, these methods are not suitable for industrially producing holograms because they require wet development and complicated development and fixing treatments, and have problems such as loss of an image due to moisture absorption even after recording. Was.

In order to overcome the above-mentioned problems of the prior art, it is disclosed in US Pat. No. 3,658,5 to produce a volume hologram by a simple dry process using a photopolymer.
No. 26, No. 3,993,485, and the like. In addition, regarding the estimated formation mechanism of the hologram by the photopolymer, “Applied optics (APPLIED OPTICS)” (B.
L. Booth, Vol. 14, No. 3, pp. 593-601 (1975) and WJ Tomlinson, E.A.
EA Chandross et al., Vol. 15, No. 2
No. 534-541 (1976)). However, these techniques at the beginning did not have the refractive index modulation, which is the most important performance of the hologram, inferior to the above-mentioned prior art.

In recent years, photopolymer materials having excellent refractive index modulation include, for example, binder polymers described in US Pat. Nos. 4,942,102 and 4,942,112. Materials utilizing the refractive index difference of radical polymerizable compounds, or JP-A-3-24968
No. 5 discloses a material utilizing the difference between the refractive index and reactivity of two specific radically polymerizable compounds, or a radical polymerizable compound having a different refractive index described in Japanese Patent Application No. 5-107999. Materials using a compound and a cationically polymerizable compound have been proposed. These photopolymer materials have made it possible to produce volume holograms with a relatively large refractive index modulation by dry processing, but they are not yet satisfactory, and they also have light resistance and heat resistance enough to withstand outdoor use. The appearance of volume holograms has been desired.

[0006]

The present invention relates to a photosensitive composition for a volume hologram having a high refractive index modulation and providing a volume hologram excellent in light resistance and heat resistance, and production of a volume hologram using the same. The purpose is to provide the law.

[0007]

SUMMARY OF THE INVENTION The present invention provides a photosensitive composition for volume hologram recording which is used for recording interference fringes generated by interference of laser light or light having excellent coherence as fringes having different refractive indices. Wherein the composition comprises: (a) a polymer binder having a siloxane bond (b) a radical polymerizable compound (c) a cationic polymerizable compound (d) a radical polymerization initiator system (e) a cationic polymerization initiator system The present invention relates to a photosensitive composition for volume hologram recording, which comprises the following components as essential components. Furthermore, the present invention provides the same or different
The present invention relates to a volume hologram recording medium having a recording layer composed of the above composition between two transparent supports. Further, the present invention exposes the recording medium to interference fringes generated by interference of laser light or light having excellent coherence, and subsequently irradiates the recording medium with ultraviolet and / or visible light over the entire surface and heat treatment. , Or a method of recording a volume hologram in which both are performed simultaneously or sequentially. Furthermore, the present invention relates to a volume hologram recorded by the above method.

The polymer binder having a siloxane bond (a) used in the present invention may be, for example, a chlorosilane compound such as methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane or diphenyldichlorosilane, alone or in combination of several kinds. And pure silicone resin synthesized by condensation reaction by hydrolysis, low molecular weight polysiloxane having hydroxyl group or alkoxy group on silicon atom, alkyd resin having alcoholic hydroxyl group, polyester, acrylic resin, epoxy resin, phenol resin Varnish synthesized by reacting siloxane, polyurethane, melamine resin, etc., a polymer of a radical polymerizable compound having a siloxane bond or a copolymer of the compound and another radical polymerizable compound, a reactive siloxane oligomer. The organic polymer obtained by introducing a siloxane chain graft type by Ma, there like incorporating an organic polymer siloxane chain in blocks is by reaction of the siloxane oligomer. Among these, a polymer of a radical polymerizable compound having a siloxane bond or a copolymer of the compound and another radical polymerizable compound is preferable in terms of refractive index modulation.

The radical polymerizable compound having a siloxane bond is represented by the following general formula (I):

Embedded image In the formula (I), any one of X _{1 to} X ₆ has a radical polymerizable group at the terminal. The radical polymerizable group and the silicon atom are an alkyl chain, an oxyethylene chain,
The bond may be formed via an oxypropylene chain, a urethane bond, an amide bond, or the like. The radical polymerizable group corresponds to a group having an ethylenically unsaturated double bond, and specifically includes an acryloyl group, a methacryloyl group, and a vinyl group. These can be made homopolymers by performing radical polymerization by a conventional method alone. Further, it can be copolymerized with another compound having an ethylenically unsaturated double bond according to a conventional method.

Examples of the compound having an ethylenically unsaturated double bond include (meth) acrylic acid, methyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. ) Acrylic esters, vinyl monomers such as styrene, α-methylstyrene, and vinyl acetate are exemplified. One or more polymer binders having a silicone bond used in the present invention may be used.

The radical polymerizable compound (b) used in the present invention has good compatibility with other components such as a polymer binder having a siloxane bond, and is polymerized by an active radical species generated from a radical polymerization initiator. Anything should do. This radical polymerizable compound may have a siloxane bond. Those having at least one ethylenically unsaturated double bond as a radical polymerizable group are preferred. Specific examples of the radical polymerizable compound include, for example, acrylamide, methacrylamide, styrene,
Bromostyrene, phenyl acrylate, 2-phenoxyethyl acrylate, 2,3-naphthalenedicarboxylic acid (acryloxyethyl) monoester, methylphenoxyethyl acrylate, nonylphenoxyethyl acrylate, β-acryloxyethyl hydrogen phthalate, phenoxy polyethylene glycol acrylate,
2,4,6-tribromophenyl acrylate, diphenic acid (2-methacryloxyethyl) monoester, benzyl acrylate, 2,3-dibromopropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-naphthyl acrylate, N-vinylcarbazole, 2- (9-carbazolyl) ethyl acrylate, triphenylmethylthioacrylate, 2- (tricyclo
[5,2,10 ² · ⁶ ] dibromodecylthio) ethyl acrylate, S- (1-naphthylmethyl) thioacrylate, dicyclopentanyl acrylate, methylenebisacrylamide, polyethylene glycol diacrylate, trimethylolpropane triacrylate, penta Erythritol triacrylate, (2-acryloxyethyl) diphenate (3-acryloxypropyl-2-hydroxy)
Diester, 2,3-naphthalenedicarboxylic acid (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) diester, 4,5-phenanthylenedicarboxylic acid (2-acryloxyethyl) (3-acryloxypropyl- 2-hydroxy) diester, dibromoneopentyl glycol diacrylate, dipentaerythritol hexaacrylate, 1,3-bis [2-acryloxy-
3- (2,4,6-tribromophenoxy) propoxy] benzene, diethylenedithioglycol diacrylate,
2,2-bis (4-acryloxyethoxyphenyl) propane, bis (4-acryloxydiethoxyphenyl) methane, bis (4-acryloxyethoxy-3,5-dibromophenyl) methane, 2,2-bis ( 4-acryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxyethoxy-3,5-dibromophenyl) propane, bis (4- (Acryloxyethoxyphenyl) sulfone, bis (4-acryloxydiethoxyphenyl) sulfone, bis (4-acryloxypropoxyphenyl) sulfone, bis (4-acryloxyethoxy-3,5-dibromophenyl) sulfone, and Compounds in which acrylate is changed to methacrylate,
JP-A-7205 and JP-A-2-261808 include ethylenically unsaturated double bond-containing compounds containing at least two S atoms in a molecule, and one or more of these compounds may be used. You may. Specific examples of the resilient polymerizable compound having a siloxane bond are as described above.

The cationically polymerizable compound (c) used in the present invention has good compatibility with other components such as a high molecular weight binder having a siloxane bond, and is a Bronsted acid or Lewis acid generated from a cationic polymerization initiator. What is necessary is just to polymerize with an acid. This cationically polymerizable compound may have a siloxane bond. The cationically polymerizable compound having a siloxane bond is represented by the following general formula (I
Indicated by I):

Embedded image In the formula (II), at least one terminal among X _{1 to} X ₆ has a cationically polymerizable group. X _{1 to} X ₆ may be the same or different, and include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group, a phenyl group, and a hydroxyl group. And so on. n is an integer of 1 or more, preferably up to 7. The cationically polymerizable group and the silicon atom may be bonded via an alkyl chain, an oxyethylene chain, an oxypropylene chain, a urethane bond, an amide bond, or the like. Examples of the cationic polymerizable group include a cyclic ether such as a glycidyl group and an alicyclic epoxy group, a cyclic sulfide, a cyclic imine, a cyclic disulfide, a lactone, a lactam, a cyclic formal, a cyclic imino ether, and a vinyl ether. Specific examples of the cationically polymerizable compound include diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, and trimethylolpropane polyglycidyl. Ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether,
Phenyl glycidyl ether, para-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ester, orthophthalic acid diglycidyl ester, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,2,7,8-diepoxyoctane, 1 , 6-Dimethylol perfluorohexane diglycidyl ether, 4,4'-bis (2,3-
Epoxypropoxyperfluoroisopropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane,
2,5,6-diepoxy-4,7-methanoperhydroindene, 2- (3,4-epoxycyclohexyl) -3 ′, 4 ′
-Epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy-bis (3,4-epoxycyclohexylmethane), 4 ', 5'-epoxy-2'
-Methylcyclohexylmethyl-4,5-epoxy-2
-Methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate), bis- (3,4-epoxycyclohexylmethyl) adipate, di-2,3-epoxycyclopentyl ether, vinyl-2-chloroethyl Ether, vinyl-n-butyl ether, triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, trimethylolethane trivinyl ether, vinyl glycidyl ether, and the formula

[0013]

Embedded image And one or more of these may be used.

The radical polymerization initiator system (d) used in the present invention is an initiator system capable of initiating polymerization of a radical polymerizable compound by the action of light or heat. When recording interference fringes by a polymerization reaction of a radical polymerizable compound, an active radical species is generated by irradiating laser light or light having excellent coherence, and the active radical species causes the radical polymerizable compound to polymerize. Such a radical polymerization initiator system is used. Examples of such radical polymerization initiator systems include, for example, U.S. Pat. Nos. 4,766,055, 4,868,092 and 4,964.
5,171, JP-A-54-151024, JP-A-58-15,503 and JP-A-58-29,803.
JP-A-59-189,340 and JP-A-60-76
735, JP-A-1-28715, and Japanese Patent Application No. 3
No.-5569 and "Proceedings of Conference on Radiation Curing Asia" (PROCEEDINGS OF CONFER
ENCE ON RADIATION CURING
ASIA) "(pp. 461-477, 1988) and the like, but not limited thereto.

The term "initiator system" as used herein means that a sensitizer, which is a component that absorbs light, can be used in combination with an active radical-generating compound or an acid-generating compound. As a sensitizer in the radical polymerization initiator system, a colored compound such as a dye is often used to absorb visible laser light, but when the final hologram is required to be colorless and transparent (for example, an automobile, etc. Examples of sensitizers include those described in JP-A-58-29803 and JP-A-1-228.
It is preferable to use a cyanine dye as described in JP-A-7105 and Japanese Patent Application No. 3-5569. Since cyanine dyes are generally easily decomposed by light, the dye in the hologram is decomposed by post-exposure in the present invention, or left for several hours to several days under room light or sunlight, and has absorption in the visible region. And a colorless and transparent hologram is obtained. Specific examples of cyanine dyes include anhydro-
3,3′-dicarboxymethyl-9-ethyl-2,2′thiacarbocyanine betaine, anhydro-3-carboxymethyl-3 ′, 9′-diethyl-2,2′thiacarbocyanine betaine, 3,3 ′ , 9-Triethyl-2,2'-thiacarbocyanine iodine salt, 3,9-diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine iodine salt, 3,3 ', 9-triethyl- 2,2 '-(4,5,4', 5 '
-Dibenzo) thiacarbocyanine iodine salt, 2- [3
-(3-Ethyl-2-benzothiazolidene) -1-propenyl] -6- [2- (3-ethyl-2-benzothiazolidene) ethylideneimino] -3-ethyl-1,3,5- Thiadiazolium iodine salt, 2-[[3-allyl-4-
Oxo-5- (3-n-propyl-5,6-dimethyl-2
-Henzothiazolylidene) -ethylidene-2-thiazolinylidene] methyl] 3-ethyl-4,5-diphenylthiazolinium iodine salt, 1,1 ', 3,3,3', 3'-hexamethyl-2, 2′-Indotricarbocyanine iodine salt, 3,3′-diethyl-2,2′-thiatricarbocyanine perchlorate, anhydro-1-ethyl-4-methoxy-3′-carboxymethyl-5 '-Chloro-2,2'-quinothiacyanine betaine; anhydro-5,5'-diphenyl-9-ethyl-3,3'-disulfopropyloxacarbocyanine hydroxide triethylamine; More than one species may be used.

The active radical-generating compound which may be used in combination with a cyanine dye is described in the above-mentioned JP-A-58
-29803, JP-A-1-287105,
Diaryliodonium salts as described in Japanese Patent Application No. 3-5569, or 2,4,6-substituted-1,3,
5-triazines. When high photosensitivity is required, the use of diaryliodonium salts is particularly preferred. Specific examples of the above diaryliodonium salts include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-ditertiarybutyldiphenyliodonium, and 3,3′-dinitrodiphenyliodonium. Such as chloride, bromide, tetrafluoroborate,
Hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate and the like are exemplified. Specific examples of 2,4,6-substituted-1,3,5-triazines include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6 -Tris (trichloromethyl) -1,
3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis
(Trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine, 2- (4′-methoxy-1 ′
-Naphthyl) -4,6-bis (trichloromethyl) -1,3,
5-triazine is exemplified.

The cationic polymerization initiator system (e) used in the present invention is an initiator system capable of initiating polymerization of a cationically polymerizable compound by the action of light or heat. As a specific example, for example, “UV curing; science and technology (UV Cur)
ing: Science and Technology
y) ", pp. 23-76, edited by S. Peter Pappas, A Technology Marketing Publication (AT)
technology Marketing Publi
) and “Comments in Organic.
Chemistry (Comments Inorg. Che
m.) ", B. Klingert, M. Reedyker and A. Rolov (B. Klingert, M. Ri.
editor and A. Rolloff), Volume 7,
No. 3, pages 109 to 138 (1988) and the like, and one or more of these may be used.

Particularly preferred cationic photopolymerization initiator systems (e) used in the present invention include diaryliodonium salts, triarylsulfonium salts and iron-allene complexes. Preferred diaryl iodonium salts as the cationic photopolymerization initiator system (e) are the tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate and hexafluoroiodonium of iodonium shown in the aforementioned photoradical polymerization initiator system (d). Fluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracenesulfonate and the like can be mentioned. Preferred triarylsulfonium salts include triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium,
Examples thereof include tetrafluoroborate of sulfonium such as thiophenyltriphenylsulfonium, hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate, trifluoromethanesulfonate, and 9,10-dimethoxyanthracene-2-sulfonate.

In the case of recording interference fringes by a polymerization reaction of a cationic polymerizable compound, a laser beam having a specific wavelength or light having excellent coherence is irradiated to generate a Bronsted acid or a Lewis acid, and the cation is thereby formed. A cationic polymerization initiator system that can polymerize the polymerizable compound is used. Examples of such a cationic polymerization initiator system include acridine dyes such as acridine orange and acridine yellow and setoflavin (Setofl).
avin) A combination of a benzothiazolium-based dye such as T with a diaryliodonium salt or a triarylsulfonium salt.

The combination of the components in the photosensitive composition for volume hologram recording of the present invention is as follows: (a) 10 to 50 wt% of a polymer binder having a siloxane bond.
(More preferably 15 to 25 wt%), and (b) the radical polymerizable compound is 20 to 90 (more preferably 35 to 65 wt%).
wt.), (c) 2 to 70 wt.
% (More preferably 10 to 45 wt%), and (d) the radical polymerization initiator system is 0.3 to 8 wt% (more preferably 1 to 45 wt%).
(E) cationic polymerization initiator system is from 0.3 to
8 wt% (more preferably 1 to 5 wt%).
It is necessary that the difference between the refractive indices of (b) and (c) is not less than 0.01. If the difference is not more than 0.01, a bright hologram cannot be obtained because the recorded hologram has a small refractive index modulation value.

The photosensitive composition for volume hologram recording of the present invention may optionally contain additives such as a thermal polymerization inhibitor, a silane coupling agent, a leveling agent, an antifoaming agent, or a coloring agent. You may.

The photosensitive composition of the present invention may be prepared by a usual method. For example, the above-mentioned essential components (a) to (e) and optional components may be used as they are or as needed (for example, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol diacetate). Ester solvents such as toluene, aromatic solvents such as toluene and xylene, cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, alcohol solvents such as methanol, ethanol, propanol and n-butanol, and ethers such as tetrahydrofuran and dioxane. System solvent, a halogen-based solvent such as dichloromethane, dichloroethane, chloroform, etc.) and mixing in a cool and dark place using, for example, a high-speed stirrer.

In the production of the hologram of the present invention, the above-mentioned photosensitive composition is coated on a transparent support such as a glass plate, a polyethene terephthalate film, a polyethylene film, a triacetyl cellulose film, an acrylic plate, etc. by a usual method. It can be formed by drying if necessary. The amount applied is selected appropriately, for example, dry coating amount may be ^{1g / m 2 ~50g / m 2} . Further, usually, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a triacetyl cellulose film or the like is provided as a protective layer on the recording layer. As another method for producing a three-layer body in which the intermediate layer is a recording layer made of the composition of the present invention, for example, recording is performed between two polyethylene terephthalate films each of which has been subjected to a process of easily peeling. After forming a layer, one of the films may be peeled off at the time of use, and the surface thereof may be laminated on a suitable support. Further, for example, the composition of the present invention can be injected between two glass plates.

The recording layer manufactured in this manner is applied to a laser beam or light having excellent coherence (for example, a wavelength of 300 to
The interference fringes are recorded therein by exposure to interference fringes using a conventional holographic exposure apparatus (1200 nm).
In the case of the composition of the present invention, at this stage, diffracted light due to the recorded interference fringes is obtained, and a hologram can be obtained. However, at this stage, since the unreacted polymerizable compound remains in the photosensitive layer, the film strength of the hologram may not be obtained. In order to polymerize unreacted components remaining in these photosensitive layers, a xenon lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp,
The hologram of the present invention having excellent film strength can be obtained by exposing the entire surface of the hologram to light from a light source such as a halogen lamp or by performing a heat treatment. An organic peroxide such as benzoyl peroxide may be used in combination to promote the polymerization of the unreacted monomer by the heat treatment.

A larger refractive index modulation value can be obtained by performing radical polymerization during exposure of the interference pattern of the hologram and then performing cationic polymerization during subsequent exposure. for that purpose,
"The radical polymerization initiator system (d) is a radical polymerization initiator system having photosensitivity to laser light or light having excellent coherence, and the cationic polymerization initiator system (e) is excellent in the laser light or coherence. The combination of the two initiators may be selected so as to be a cationic polymerization initiator system having low photosensitivity to light and photosensitivity to light of another wavelength. The diffraction efficiency, the peak wavelength of the diffracted light, the half-value width, and the like can be changed by treating the recording layer with heat or infrared light before or after the post-exposure.

The volume hologram is, for example, a lens,
It can be used for diffraction gratings, interference filters, head-up display devices, general three-dimensional displays, optical fiber couplers, facsimile optical polarizers, memory materials such as ID cards, architectural windows, advertising media, and the like.

Although the reason why the refractive index modulation is improved by using a resin having a siloxane bond is not clear at present, the radical polymerizable compound is polymerized in the bright portion of the interference fringe at the stage of exposure of the interference fringe. It is considered that since the interaction between the molecules of the resin having a siloxane bond is weak, the radically polymerizable compound easily moves from the dark part to the bright part of the interference fringes, and the refractive index modulation is improved.

[0028]

According to the photosensitive composition for recording a volume hologram of the present invention, a volume hologram excellent in diffraction efficiency, wavelength selectivity, refractive index modulation, light resistance and heat resistance can be easily produced.

[0029]

The present invention will be specifically described below with reference to examples.
Using the photosensitive compositions shown in each of the following Examples and Comparative Examples, test plates were prepared by the following methods and exposed to obtain holograms. The physical properties were evaluated by the following methods.

Preparation of Test Plate A predetermined amount of the cationic photopolymerization initiator system component and the photoradical polymerization initiator system component are dissolved or dispersed in a mixed solvent of n-butyl alcohol and methyl isobutyl ketone. The mixture was stirred and filtered to obtain a photosensitive solution. This photosensitive solution was applied on a 16 cm × 16 cm glass plate using an applicator, and dried at 90 ° C. for 5 minutes. Furthermore, a polyethylene film of 80 μm thickness (Tonen Kagaku
(LUPIC LI) was laminated using a laminating roller, and this plate was divided into 3 to 4 cm squares to obtain test plates.

[0031] of all the exposure the first exposure is an argon ion laser 514.5
This was performed using nm light. FIG. 1 shows a schematic diagram of a recording method of a reflection hologram. The light intensity of one light beam on the test plate surface was 1.0 mw / cm ² , and the exposure was performed for 30 seconds. After the end of the first exposure, a high-pressure mercury lamp (manufactured by Nihon Battery Co., Ltd., experimental ultraviolet irradiation apparatus FL-1001) is used as a post-exposure.
The light of -2) was irradiated for 1 minute from the polyethylene film side.

Evaluation The diffraction efficiency of the reflection hologram was measured using the Shimadzu self-recording spectrophotometer U.
It was determined by measuring the reflectance of a hologram using V-2100 (manufactured by Shimadzu Corporation) and an attached integrating sphere reflector ISR-260. Further, the film thickness of the diffraction efficiency measurement portion was measured using a film thickness measuring device Betascope 850 manufactured by Fischer. The refractive index modulation (half the change in the refractive index of the interference fringes) was calculated from the diffraction efficiency and film thickness values thus obtained. The calculation formula is "coupled wave theory for thick hologram gratings"
(Coupled Wave Theory for Thick Hologram
Gratings) (H. Kogelnik, Bell System Technical Journal (Bell Sys.)
t. Tech. J. ), Vol. 48, pp. 2909-2947
(1969)). The value of the refractive index modulation does not depend on the film thickness, and the refractive index modulating ability of the composition can be compared by this value.

Regarding the light fastness, a hologram test plate having a wavelength of 2 was used by using a super-accelerated weathering tester, i-Super UV tester W type, manufactured by Dainippon Plastics Co.
The change in the diffraction efficiency, the change in the diffraction peak wavelength, and the yellowing of the test plate of the hologram when continuously irradiated with ultraviolet rays of 95 nm to 450 nm for 60 hours were examined. Regarding the heat resistance, the change in the diffraction efficiency, the change in the diffraction peak wavelength, and the yellowing of the hologram test plate when the hologram was allowed to stand in an incubator at 100 ° C. for 1000 hours were examined. The photosensitive compositions of the following Examples and Comparative Examples were prepared, and each hologram was prepared by the above-mentioned method, and this evaluation was performed as described above.

Examples 1 to 5 In this example, the polymer binder having a siloxane bond was P-
1, CAT-1 or CAT-2 is used as the cationic polymerizable compound, and AE is used as the radical polymerizable compound.
An example in which a reflection hologram is created using PM, A-BPHE, or PS2A will be described. TPS · SbF ₆ was used as a photocationic polymerization initiator system. A combination of DYE-1 and DPI · TF was used as the photoradical polymerization initiator system. Table 1 shows the compositions of the photosensitive compositions for hologram recording used in Examples 1 to 5 and the evaluation results of the holograms. Table 2 shows the hologram evaluation results. In each case, a colorless and transparent reflection type hologram in a practical range was obtained.

[0035]

[Table 1]

[0036]

[Table 2]

Examples 6 to 10 Here, the light resistance test and the heat resistance test of the test plates of the reflection holograms produced in Examples 1 to 5 were performed. Table 3 shows the results.

[0038]

[Table 3]

Comparative Examples 1 and 2 These are comparative examples with respect to Examples 1 to 5.
This is an example showing that when a polymer binder P-2 having no siloxane bond is used instead of the polymer binder having a siloxane bond, the performance of the reflection hologram is inferior to those of Examples 1 to 5. Table 4 shows the compositions of the photosensitive compositions for hologram recording used in Comparative Examples 1 and 2, and the evaluation results of the holograms. Table 5 shows the hologram evaluation results.

[0040]

[Table 4]

[0041]

[Table 5]

Comparative Examples 3 and 4 These were polymer binders P- having no siloxane bond.
This is an example showing that the light resistance and the heat resistance of the test plates of the reflection holograms of Comparative Example 1 and Comparative Example 2 produced by using Sample No. 2 are inferior to those of Examples 6 to 10. Table 6 shows the results.

[0043]

[Table 6] The compounds used as abbreviations in the above Examples, Comparative Examples and Tables represent the following. Polymer binder having siloxane bond [P-1] Ethyl acrylate / siloxane-containing methacrylate (Toshiba Silicone TSL9705) copolymer (copolymerization ratio = 60:40) Trade name: Toshiba Silicone Co., Ltd. TSL9705 has the following structure Compound having

[0044]

Embedded image

Cationic polymerizable compound [CAT-1] Glycidyl ether obtained by adding 4 mol of propylene oxide to petaerythritol (the number of glycidyl groups per molecule is 3) [CAT-2] Compound having the following structure Trade name: Toshiba Silicone, TSL9906

[0046]

Embedded image

Radical polymerizable compound [AEPM] Trade name: R712 bis (4-acryloxydiethoxyphenyl) methane [A-BPHE] 9,9'-bis (3-ethyl-4-acrylic, manufactured by Nippon Kayaku Co., Ltd. Roxydiethoxyphenyl) fluorene [PS2A] Compound having the following structure

[0048]

Embedded image

The photo-cationic polymerization initiator system [TPS-SbF _6] Product name: Ciba-Geigy Ltd., UVI-6974 triarylsulfonium & hexafluoroantimonate compound

Photoradical polymerization initiator system [DYE-1] 3,9-diethyl-3'-carboxymethyl-2,2 '
-Thiacarbocyanine, iodine salt [DPI · TF] diphenyliodonium trifluoromethanesulfonate

Polymer binder having no siloxane bond [P-2] Methyl methacrylate / ethyl acrylate / acrylic acid copolymer (copolymerization ratio = 45/49/6)

Other components Solvent [BuOH] n-butyl alcohol [MIBK] methyl isobutyl ketone

[Brief description of the drawings]

FIG. 1 shows a schematic diagram of a recording system of a reflection hologram in a first exposure.

[Explanation of symbols]

1 glass plate 2 recording layer 3 Polyethylene film 4 Laser 5 Laser beam 6 Mirror 7 Beam splitter 8 Objective lens 9 lenses

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/075 511 G03F 7/075 511 G03H 1/04 G03H 1/04 (72) Inventor Iwao Sumiyoshi 19 Ikedanakamachi, Neyagawa-shi, Osaka No. 17 Nippon Paint Co., Ltd. (56) References JP-A-5-107999 (JP, A) JP-A-6-19040 (JP, A) JP-A-6-148880 (JP, A) JP-A-6 -202548 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03H 1/00-5/00 G03F 7/004-7/04 G03F 7/06 G03F 7/075-7 / 115

Claims (11)

(57) [Claims] 1. A volume hologram recording photosensitive composition used for recording interference fringes generated by interference of laser light or light having excellent coherence as fringes having different refractive indices. (A) a polymer binder having a siloxane bond; (b) a radical polymerizable compound; (c) a cationic polymerizable compound; (d) a radical polymerization initiator system; and (e) a cationic polymerization initiator system. Photosensitive composition for volume hologram recording. 2. The composition according to claim 1, wherein at least one of the radically polymerizable compound (b) and the cationically polymerizable compound (c) has a siloxane bond. 3. The difference in refractive index between the radically polymerizable compound component (b) and the cationically polymerizable compound component (c) is 0.03.
2. The composition of claim 1, wherein the composition is one or more. 4. The radical polymerization initiator system (d) is a radical polymerization initiator system having photosensitivity to the laser beam or light having excellent coherence, and the cationic polymerization initiator system (e) is the radical polymerization initiator system. The composition according to claim 1, which is a cationic polymerization initiator system having low photosensitivity to light having excellent coherence and photosensitivity to light of another wavelength. 5. The polymer binder (a) having a siloxane bond is a polymer of a radical polymerizable compound having a siloxane bond or a copolymer of the compound and another radical polymerizable compound. Composition. 6. The composition according to claim 1, wherein a cyanine dye is used as a sensitizer in the radical polymerization initiator system (d), and a diaryliodonium salt is used as an active radical generating compound. 7. A volume hologram recording medium having a recording layer comprising the composition according to claim 1 between two transparent supports which are the same or different. 8. A volume for exposing the recording medium according to claim 7 to interference fringes generated by interference of laser light or light having excellent coherence, and subsequently irradiating the recording medium with light in the ultraviolet and / or visible region. Hologram recording method. 9. A method for recording a volume hologram, comprising exposing a recording medium according to claim 7 to interference fringes generated by interference of laser light or light having excellent coherence, and subsequently heating the recording medium. 10. A recording medium according to claim 7, wherein the recording medium is exposed to interference fringes generated by interference of laser light or light having excellent coherence, and then the recording medium is entirely irradiated with ultraviolet and / or visible light and heated. A method of recording a volume hologram in which processing is performed simultaneously or sequentially. 11. A volume hologram recorded by the method according to claim 8, 9 or 10.