JPH08160842A - Photosensitive composition for three-dimensional hologram recording, recording medium using that and forming method of three-dimensional hologram - Google Patents

Abstract

PURPOSE: To provide a photosensitive compsn. with which a three-dimensional hologram having high refractive index modulation property and excellent light resistance and heat resistance is obtd. CONSTITUTION: This compsn. contains components (A)-(C) as the essential components: (A) cationic polymerizable compd. and radical polymerizable compd., (B) cationic polymn. initiator, and (C) radical polymn. initiator. At least one of the cationic polymerizable compd. and the radical polymerizable compd. has siloxane bonds. The difference of the refractive index between the cationic polymerizable compd. component and the radical polymerizable compd. component is >=0.01.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive composition for volume hologram recording which gives a hologram excellent in refractive index modulation, light resistance and heat resistance, a hologram recording medium using the same, and a volume hologram recording method. , And even recorded holograms.

[0002]

2. Description of the Related Art A hologram is one in which two light beams having the same wavelength (object light and reference light) are made to interfere with each other and the wavefront of the object light is recorded as an interference fringe on a photosensitive material. When this light is applied, a diffraction phenomenon due to interference fringes occurs, 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, but in recent years, so-called volume holograms that record interference fringes by the difference in refractive index inside the recording layer, due to their high diffraction efficiency and excellent wavelength selectivity, It is being applied to applications such as three-dimensional displays and optical elements.

As a light-sensitive material for recording such a volume hologram, a material using silver halide or dichromated gelatin which has been conventionally used in the art field is generally used. However, these are not suitable for industrial production of holograms because they require wet development and complicated development and fixing processing, and have a problem that the image disappears due to moisture absorption after recording. It was

In order to overcome the above-mentioned problems of the prior art, it is possible to prepare a volume hologram by using a photopolymer only by a simple dry process, US Pat. No. 3,658,5.
No. 26, No. 3,993,485, and the like. Also, regarding the presumed formation mechanism of the hologram by the photopolymer, "Applied OPTICS" (B.
BL Booth, Volume 14, Issue 3, Pages 593-601 (1975) and WJ Tomlinson, E.A.
Chandross et al., Volume 15, Volume 2
No., pp. 534-541 (1976)) and the like. However, in these original techniques, the most important performance of the hologram, that is, the refractive index modulation, did not reach the above-mentioned conventional techniques.

In recent years, binder polymers such as those described in US Pat. Nos. 4,942,102 and 4,942,112 are used as photopolymer materials having excellent refractive index modulation. Materials utilizing the difference in refractive index of radically polymerizable compounds, or JP-A-3-24968
A material utilizing the difference in refractive index and reactivity between two specific radically polymerizable compounds described in Japanese Patent No. 5 or a radical polymerizable compound having different refractive indexes described in Japanese Patent Application No. 5-107999. Materials using a compound and a cationically polymerizable compound have been proposed. Although these photopolymer materials have made it possible to create volume holograms with a relatively large refractive index modulation by dry processing, they are still insufficient, and they also have light resistance and heat resistance that can withstand outdoor use. The advent of volume holograms was desired.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides 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 a volume hologram using the same. The purpose is to provide the law.

[0007]

The present invention provides a photosensitive composition for volume hologram recording used for recording interference fringes produced by interference of laser light or light having excellent coherence as fringes having different refractive indexes. In the above, the composition comprises: Cationically polymerizable compound and radically polymerizable B. A cationic polymerization initiator system, and C.I. The present invention relates to a photosensitive composition for volume hologram recording, which contains each component of a radical polymerization initiator system as an essential component, and at least one of a cationically polymerizable compound and a radically polymerizable compound has a siloxane bond. Further, the present invention relates to a volume hologram recording medium having a recording layer made of the above composition between two transparent supports which are the same or different. Further, the present invention exposes the recording medium with interference fringes generated by the interference of laser light or light having excellent coherence, and then subjecting the recording medium to overall irradiation with light in the ultraviolet and / or visible range and heat treatment. , Or a method for recording a volume hologram in which both are performed simultaneously or sequentially. The invention further relates to a volume hologram recorded by the above method.

The cationically polymerizable compound used in the present invention has good compatibility with other components such as a radically polymerizable compound having a siloxane bond and is polymerized by a Bronsted acid or a Lewis acid generated from a cationic polymerization initiator. Anything will do. This cationically polymerizable compound may have a siloxane bond. Specific examples of the cationically polymerizable compound include diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl. Ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, paratertiary butyl phenyl glycidyl ether, adipic acid diglycidyl ester, orthophthalic acid diglycidyl ester, dibromophenyl glycidyl Ether, dibromoneopentyl glycol diglycidyl ether, 1,2,7,8-diepoxyoctane, , 6-dimethylol perfluorohexane diglycidyl ether, 4,4'-bis (2,3-epoxypropoxy perfluoro isopropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl -
3 ', 4'-epoxycyclohexanecarboxylate,
3,4-epoxycyclohexyloxirane, 1,2,5,
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-epoxy Cyclohexylmethyl) adipate, di-2,3-epoxycyclopentyl ether, vinyl-2-chloroethyl ether, vinyl-
n-butyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, trimethylolethane trivinyl ether, vinyl glycidyl ether, and formula

[0009]

Embedded image The compounds represented by are listed, and one or more of them may be used.

The cationically polymerizable compound having a siloxane bond used in the present invention is represented by the following general formula (I):

Embedded image In formula (I), at least one terminal of X _{1 to} X ₆ has a cationically polymerizable group. X _{1 to} X ₆ may be the same or different and each is 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, a hydroxyl group. Etc. n is an integer of 1 or more, preferably up to 7. Further, 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 cationically polymerizable group include a glycidyl group, a cyclic ether such as 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.

The radically polymerizable compound used in the present invention is
Any compound having a good compatibility with the cationically polymerizable compound having a siloxane bond and capable of being polymerized by the active radical species generated from the radical polymerization initiator may be used. This radically polymerizable compound may have a siloxane bond. A radically polymerizable group having at least one ethylenically unsaturated double bond is preferable. Specific examples of the radically polymerizable compound include, for example, acrylamide, methacrylamide, styrene, 2-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 [5,2,1
0 ^2.6] dibromo decyl thio) ethyl acrylate, S-
(1-naphthylmethyl) thioacrylate, dicyclopentanyl acrylate, methylenebisacrylamide, polyethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, diphenic acid (2-acryloxyethyl)
(3-acryloxypropyl-2-hydroxy) diester, 2,3-naphthalene dicarboxylic acid (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy)
Diester, 4,5-phenanthrenecarboxylic 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-acryloxy) Ethoxyphenyl) sulfone, bis (4-acryloxydiethoxyphenyl) sulfone, bis (4-acryloxypropoxyphenyl) sulfone, bis (4-acryloxyethoxy-3,5-dibromophenyl) sulfone, and the acrylates described above. Compounds changed to methacrylate, and further JP-A 2-24
7205 and JP-A-2-261808 include ethylenically unsaturated double bond-containing compounds containing at least two S atoms in the molecule, and at least one of them is used. You can do it.

The radically polymerizable compound having a siloxane bond used in the present invention is represented by the following general formula (II):

Embedded image In formula (II), at least one terminal of X _{1 to} X ₆ has a radical polymerizable group. X _{1 to} X ₆ may be the same or different and each is a hydrogen atom or a carbon atom number 1.
An alkyl group of 4 to 4, an alkoxy group having 1 to 4 carbon atoms,
It represents a dialkylamino group, a phenyl group, a hydroxyl group and the like. n
Is an integer of 1 or more, preferably 7 or less. The radical 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. The radically polymerizable group corresponds to a group having an ethylenically unsaturated double bond, and specific examples thereof include an acryloyl group, a methacryloyl group and a vinyl group.

The cationic polymerization initiator system (B) used in the present invention is an initiator system capable of initiating the polymerization of the cationically polymerizable compound by the action of light or heat. Examples of the cationic photopolymerization initiator system (B) include “UV Curing; Science and Technology (UV Curing: Science an
d Technology, "pages 23-76, S. Peter Pappa.
s) Editing, A Technology Marketing Publication (A Technology Marke)
Ting Publication and "Comments I Organic Chemistry (Comments I
Chem.), B. Klingert, M. Reediker and A. Rolov (B. Klin)
gert, M. Riedicker and A. Rol
off), Vol. 7, No. 3, pp. 109-138 (19)
1988) and the like, and one or more of them may be used.

Particularly preferred cationic photopolymerization initiator system (B) used in the present invention includes diaryl iodonium salts, triaryl sulfonium salts, iron allene complexes and the like.

As the diaryl iodonium salts as the photocationic polymerization initiator system (B), preferred are iodonium tetrafluoroborate, hexafluorophosphate, and hexafluoroarce shown in the photoradical polymerization initiator system (C) described later. Nate and hexafluoroantimonate, trifluoromethanesulfonate,
Examples include 9,10-dimethoxyanthracene sulfonate. Preferred triarylsulfonium salts are triphenylsulfonium, 4-tert-butyltriphenylsulfonium and tris (4-
Methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, sulfonium tetrafluoroborate such as 4-thiophenyltriphenylsulfonium, hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate, trifluoromethanesulfonate, 9 , 10-dimethoxyanthracene-2-sulfonate and the like.

When interference fringes are recorded by a polymerization reaction of a cationically polymerizable compound, a Bronsted acid or a Lewis acid is generated by irradiating a laser beam having a specific wavelength or a light having excellent coherence with the cation. A cationic polymerization initiator system capable of polymerizing the polymerizable compound is used. Examples of such a cationic polymerization initiator system include acridine-based dyes such as acridine orange and acridine yellow, or setoflavin (Setofl).
Examples thereof include a combination of a benzothiazolium dye such as avin) T and a diaryliodonium salt or a triarylsulfonium salt.

The radical polymerization initiator system (C) used in the present invention is an initiator system capable of initiating the polymerization of the radically polymerizable compound by the action of light or heat. When recording interference fringes by the polymerization reaction of a radically polymerizable compound, an active radical species is generated by irradiating a laser beam or light having excellent coherence, and the active radical species polymerizes the radically polymerizable compound. Such a radical polymerization initiator system is used. Examples of such a radical polymerization initiator system include, for example, U.S. Pat. Nos. 4,766,055, 4,868,092, and 4,96.
5,171, JP-A-54-151024, JP-A-58-15,503, and JP-A-58-29,803.
No. 59-189,340 and No. 60-76.
No. 735, Japanese Patent Application Laid-Open No. 1-287715, Japanese Patent Application No. 3
-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 known initiator systems can be used.

In the present specification, the term "initiator system" means that a sensitizer, which is a component that generally absorbs light, and an active radical generating compound or an acid generating compound can be used in combination. As the sensitizer in the radical polymerization initiator system, a colored compound such as a dye is often used in order to absorb visible laser light, but when the final hologram is required to be colorless and transparent (for example, an automobile, etc. (When used as a head-up display of JP-A-58-29803, JP-A-1-28803)
It is preferable to use a cyanine dye as described in Japanese Patent No. 7105 and Japanese Patent Application No. 3-5569. Since the cyanine dye is generally easily decomposed by light, the dye in the hologram is decomposed to have absorption in the visible region by being exposed to the light after exposure in the present invention or under room light or sunlight for several hours to several days. Disappears and a colorless and transparent hologram is obtained. Specific examples of the cyanine dye 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
-Henzothiazolilidene) -ethylidene-2-thiazolinylidene] methyl] 3-ethyl-4,5-diphenylthiazolinium iodide 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 salt are mentioned. More than one seed may be used.

As the active radical generating compound which may be used in combination with the cyanine dye, the above-mentioned JP-A-58 is used.
-29803, JP-A-1-287105,
Diaryl iodonium salts as described in Japanese Patent Application No. 3-5569, or 2,4,6-substituted-1,3,
Examples include 5-triazines. The use of diaryliodonium salts is particularly preferred when high photosensitivity is required. Specific examples of the diaryliodonium salts include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-ditert-butyldiphenyliodonium and 3,3′-dinitrodiphenyliodonium. Chloride, bromide, tetrafluoroborate, etc.
Hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate and the like are exemplified. Further, 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 etc. are illustrated.

In the combination of the respective components in the photosensitive composition for volume hologram recording of the present invention, the cationic polymerizable compound (A) has a siloxane bond of 2 to 70 wt% (more preferably 35 to 65 wt%). The cationically polymerizable compound has 2 to 70 wt% (more preferably 10 to
45 wt%), the radical polymerizable compound is 20 to 90 wt
% (More preferably 40 to 80 wt%), the radical polymerizable compound having a siloxane bond is 20 to 90 wt%.
(More preferably 35 to 65 wt%), the cationic polymerization initiator system (B) is 0.3 to 8 wt% (more preferably 1
~ 5 wt%), the radical polymerization initiator system of (C) is 0.3
-8 wt% (more preferably 1-5 wt%).
It is necessary that the difference in refractive index between the cationically polymerizable compound component (A) and the radically polymerizable compound component is 0.01 or more, and if the difference is 0.01 or less, the refractive index modulation value of the recorded hologram is small and the hologram is bright. Can't get

If necessary, the photosensitive composition for volume hologram recording of the present invention contains a polymer binder, a thermal polymerization inhibitor, and
An additive such as a silane coupling agent, a leveling agent, an antifoaming agent, or a coloring agent may be used in combination.

The polymeric binder must be compatible with the component (A) used in the present invention. Examples thereof include: chlorinated polyethylene, polystyrene, acrylic resin (acrylic acid ester homopolymer or copolymer), methacrylic resin (methacrylic acid ester homopolymer or copolymer). , Polyvinyl acetate, polyvinyl formal, polyvinyl butyral,
Polyvinylpyrrolidone, polyester, ethyl cellulose, acetyl cellulose. The polymer binder may have a reactive group such as a cationically polymerizable group in its side chain or main chain.

The photosensitive composition of the present invention may be prepared by a conventional method. For example, the above-mentioned essential components (A) to (C) and optional components may be used as they are or as required in a solvent (for example, a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone, ethyl acetate, butyl acetate, ethylene glycol diacetate). Such as an ester solvent, an aromatic solvent such as toluene and xylene, a cellosolve solvent such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, an alcohol solvent such as methanol, ethanol, propanol and n-butanol, an ether such as tetrahydrofuran and dioxane. It can be prepared by mixing a system solvent, a halogen solvent such as dichloromethane, dichloroethane, and chloroform) and mixing them in a cool dark place using, for example, a high-speed stirrer.

In the production of the hologram of the present invention, the recording layer is coated with the above-mentioned photosensitive composition on a transparent support such as a glass plate, a polyethylene terephthalate film, a polyethylene film, a triacetyl cellulose film or an acrylic plate by a conventional method. Then, 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 for use. As another method for producing a three-layer body in which the intermediate layer is the recording layer 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 treatment for easy peeling. A layer may be formed in advance, and one film may be peeled off at the time of use and the surface thereof may be laminated on an appropriate support. Further, for example, the composition of the present invention can be injected between two glass plates.

The recording layer thus prepared has a laser beam or light having excellent coherence (for example, a wavelength of 300 to 1).
Interference fringes are recorded in the inside by interference fringe exposure with a normal holographic exposure device at 200 nm). In the case of the composition of the present invention, diffracted light due to the recorded interference fringes can be obtained at this stage to form a hologram.
However, at this stage, the film strength of the hologram may not be obtained because the unreacted polymerizable compound remains in the photosensitive layer. In order to polymerize the unreacted components remaining in these photosensitive layers, as a post-exposure, xenon lamp, high-pressure mercury lamp, low-pressure mercury lamp, metal halide lamp, light from a light source such as a halogen lamp is entirely exposed to the hologram, By the heat treatment, the hologram of the present invention having excellent film strength can be obtained. An organic peroxide such as benzoyl peroxide may be used in combination to accelerate the polymerization of the unreacted monomer by the heat treatment.

A larger refractive index modulation value can be obtained by performing radical polymerization during the exposure of the interference fringes of the hologram and then performing cationic polymerization during the subsequent exposure. for that purpose,
"The radical polymerization initiator system (C) is a radical polymerization initiator system having photosensitivity to laser light or light having excellent coherence, and the cationic polymerization initiator system (B) has excellent laser light or coherence. The combination of both initiators may be selected such that it is a cationic polymerization initiator system having low photosensitivity to light and photosensitivity to light of another wavelength. It is also possible to change the diffraction efficiency, the peak wavelength of the diffracted light, the half-value width, etc. by treating the recording layer with heat or infrared rays 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, optical polarizers for facsimiles, memory materials such as ID cards, architectural window glass, advertising media, etc.

The reason why the refractive index modulation is improved by using the cation- or radical-polymerizable compound having a siloxane bond has not been clarified so far, but it is presumed that it is due to the weak intermolecular interaction of the siloxane bond.
Considering the case where the radical polymerizable compound is polymerized in the bright portion of the interference fringe during the exposure of the interference fringe, the interaction between the molecules of the cation having the siloxane bond or the radical polymerizable compound is weak. The cationically polymerizable compound easily moves from the dark part to the bright part of the interference fringes, and the degree of separation between the two increases. As a result, it is considered that the refractive index modulation is improved.

[0029]

EFFECTS OF THE INVENTION The volume hologram recording photosensitive composition of the present invention can easily produce a volume hologram having excellent diffraction efficiency, wavelength selectivity, refractive index modulation, light resistance, and heat resistance.

[0030]

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

Preparation of Test Plate A predetermined amount of the photoradical polymerization initiator system component and the photocationic polymerization initiator system component were dissolved or dispersed in a mixed solvent of n-butyl alcohol and methyl isobutyl ketone, and then the remaining components were added. In addition, the mixture was stirred and filtered to obtain a photosensitive liquid. 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, an 80 μm thick polyethylene film (Tonen Kagaku)
LUPIC LI Co., Ltd. was laminated using a laminating roller, and this plate was divided into 3 to 4 cm squares to give test plates.

[0032] of all the exposure the first exposure is an argon ion laser 514.5
nm light was used. FIG. 1 shows a schematic diagram of a recording method of a reflection type hologram, and FIG. 2 shows a case of a transmission type hologram. In each case, the light intensity of one light flux on the surface of the test plate was 1.0 mw / cm ² , and the exposure was performed for 30 seconds. After the first exposure, as a post-exposure, a high pressure mercury lamp (manufactured by Nippon Battery Co., Ltd., an experimental ultraviolet irradiation device FL-1001)
The light of -2) was irradiated from the polyethylene film side for 1 minute.

The diffraction efficiency of the evaluation reflective hologram is calculated by Shimadzu's own spectrophotometer U.
V-2100 (manufactured by Shimadzu Corporation) and the integral sphere reflecting device ISR-260 were attached to measure the reflectance of the hologram. The diffraction efficiency of the transmission hologram was determined by measuring the transmittance of the hologram with the spectrophotometer. In addition, the film thickness of the diffraction efficiency measurement portion was measured using a film thickness measuring instrument Betascope 850 manufactured by Fisher. From the values of diffraction efficiency and film thickness thus obtained, the refractive index modulation
The value (half the change in the refractive index of the interference fringes) was calculated. The calculation formula is "Coupled Wave Theory for Thick Hologram Gratings" (Coupled Wa
ve Theory for ThickHologram Gratings (H. Kogelnik), Bell System
Technical Journal (Bell Syst. Tech.
J. ), 48, 2909-2947 (1969)
Year)) was used. The refractive index modulation value does not depend on the film thickness, and the refractive index modulation ability of the composition can be compared by this value.

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

Examples 1 and 2 Here, a compound TS having an epoxy group as a cationic group in a cationically polymerizable compound having a siloxane bond is used.
L9906 or compound XC96-B0370 (both structural formulas are shown later) is used, and AEPM (the structural formula is given later) as a radically polymerizable compound having a higher refractive index than this compound and having no siloxane bond.
An example in which a reflection hologram is created by using is shown. As the photocationic polymerization initiator system, TPS · SbF ₆ (details will be described later) was used. DYE- as a photo-radical polymerization initiator system
1 and DPI / TF (details are given later) were used. Table 1 shows the composition of the photosensitive composition for hologram recording used in Examples 1 and 2 and the evaluation results of holograms. In each of the examples, a colorless and transparent reflection hologram within the practical range was obtained.

[0036]

[Table 1]

Examples 3 and 4 Here, A-BPHE (the structural formula is shown later) is used as a cationically polymerizable compound having a higher refractive index than the cationically polymerizable compound having a siloxane bond and having no siloxane bond. The same experiment as in Examples 1 and 2 was carried out except that the reflection hologram was prepared. Table 1 shows the composition of the photosensitive composition for hologram recording used in Examples 3 and 4, and the evaluation results of holograms. In each of the examples, a colorless and transparent reflection hologram within the practical range was obtained.

Examples 5 and 6 The same experiments as in Examples 1 and 2 were carried out except that the polymer binder P-1 was not used.
A reflection hologram was created. Table 1 shows the compositions of the hologram recording photosensitive compositions used in Examples 5 and 6, and the hologram evaluation results. In each of the examples, a colorless and transparent reflection hologram within the practical range was obtained.

Comparative Examples 1 to 4 These are comparative examples to Examples 1 to 4, and when a cationically polymerizable compound having no siloxane bond was used in place of the cationically polymerizable compound having a siloxane bond, reflection type holograms were obtained. Is inferior to Examples 1 to 4 in performance. Table 2 shows the composition of the photosensitive compositions for hologram recording used in Comparative Examples 1 to 4 and the evaluation results of holograms.

[0040]

[Table 2]

Examples 7 and 8 The same experiments as in Examples 1 and 2 were carried out except that the polymer binder P-1 was not used.
A transmission hologram was created. Table 3 shows the compositions of the hologram recording photosensitive compositions used in Examples 7 and 8 and the hologram evaluation results. In each of the examples, a transparent and colorless transparent hologram within the practical range was obtained.

[0042]

[Table 3]

Examples 9 and 10 In this example, the light resistance test and the heat resistance test of the reflection hologram test plates prepared in Examples 3 and 4 were performed. The results are shown in Table 4.

[0044]

[Table 4]

Comparative Examples 5 and 6 In these examples, the light resistance and weather resistance of the reflection hologram test plate prepared by using the cationically polymerizable compound having no siloxane bond are inferior to those in Examples 9 and 10. It is an example shown. The results are shown in Table 5.

[0046]

[Table 5]

Examples 11 to 13 In this example , a compound PS2A having an acryloyl group as a radical polymerizable group in a radical polymerizable compound having a siloxane bond (a structural formula is given later) or a compound TSL9706 or TSL9 having a methacryloyl group is used.
705 (both of which structural formulas will be described later) are used, and P is used as a cationically polymerizable compound having no siloxane bond.
CAT-3 or TSL9 with lower refractive index than S2A
706, which has a higher refractive index than TSL9705
An example in which a reflection hologram is created by using it in combination with No. 4 will be shown. Photocationic polymerization initiator system is TPS / SbF ₆
Was used. A combination of DYE-1 and DPI.TF was used as the photoradical polymerization initiator system. Example 6 in Table 6
13 to 13 show the composition of the photosensitive composition for hologram recording used and the evaluation results of holograms. In each of the examples, a colorless and transparent reflection hologram within the practical range was obtained.

[0048]

[Table 6]

Examples 14 to 16 Here, the results of the light resistance test of the reflection hologram test plates prepared in Examples 11 to 13 are shown. The results are shown in Table 7.

[0050]

[Table 7]

Example 17 In this example , a compound PS2A having an acryloyl group as a radically polymerizable group was used as a radically polymerizable compound having a siloxane bond, and T having a lower refractive index than PS2A was used as a cationically polymerizable compound having a siloxane bond.
An example of creating a reflection hologram using SL9906 will be shown. As the photocationic polymerization initiator system, TPS · SbF ₆ was used. DYE-1 and D as photo-radical polymerization initiator system
A combination of PI and TF was used. Table 8 shows the composition of the photosensitive composition for hologram recording used in Example 17 and the evaluation results of holograms. In each of the examples, a colorless and transparent reflection hologram within the practical range was obtained.

[0052]

[Table 8]

Example 18 Here, the light resistance test and the heat resistance test of the test plate of the reflection hologram prepared in Example 17 were conducted. The results are shown in Table 9.

[0054]

[Table 9]

Example 19 Here, the same photosensitive composition as in Example 1 was used to perform the first exposure and the post-exposure in the same manner as in Example 1, and then the heat treatment was performed at 100 ° C. for 30 minutes to form a reflection hologram. An example of creating Table 10 shows the composition and the results.

[0056]

[Table 10]

The compounds used as abbreviations in the above examples, comparative examples and tables represent the following: Cationic polymerizable compound having siloxane bond [TSL9906] Refractive index 1.452 Product name: Toshiba Silicone Co., Ltd., TSL9906 Compound having the following structure

[Chemical 4]

[XC96-B0370] Refractive index 1.47
4 Trade name: Toshiba Silicone Co., Ltd., XC96-B0370 Compound having the following structure

Embedded image

Radical Polymerization Having No Siloxane Bond
Compound [AEPM] Refractive index 1.539 Trade name: Nippon Kayaku Co., Ltd., R712 Bis (4-acryloxydiethoxyphenyl) methane [A-BPHE] Refractive index 1.587 9,9'-Bis (3-ethyl) -4-acryloxydiethoxyphenyl) fluorene

Radical Polymerization Having Siloxane Bond
Compound [PS2A] Refractive index 1.490 Compound having the following structure

[Chemical 6]

[TSL9706] Refractive index 1.451 Trade name: Toshiba Silicone, TSL9706 Compound having the following structure

[Chemical 7]

[TSL9705] Refractive Index 1.427 Trade name: Toshiba Silicone, TSL9705 Compound having the following structure

Embedded image

Cationic polymerizable compound [CAT-1] Refractive index 1.462 Trade name: Denacol EX-211, neopentyl glycol diglycidyl ether [CAT-2] Refractive index 1.498, trade name, manufactured by Nagase Kasei Kogyo Co., Ltd. Trade name: Union Carbide, UVR6110 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate [CAT-3] Refractive index 1.469 Glycidyl ether obtained by adding 4 moles of propylene oxide to pentaerythritol (per molecule. There are three glycidyl groups) [CAT-4] Refractive index 1.601 Trade name: Denacol EX-147 dibromophenylglycidyl ether manufactured by Nagase Chemicals

Photocationic polymerization initiator system [TPS.SbF ₆ ] Trade name: UVI-6974 triarylsulfonium hexafluoroantimonate compound manufactured by Ciba Geigy

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

Polymer binder [P-1] Copolymer of methyl methacrylate / ethyl acrylate / acrylic acid (copolymerization ratio = 45/49/6) Other component solvent [BuOH] n-butyl alcohol [MIBK] methyl Isobutyl ketone

[Brief description of drawings]

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

FIG. 2 shows a schematic diagram of a recording method of a transmission hologram in the 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 lens

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[Procedure amendment]

[Submission date] December 19, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

Examples 1 and 2 In this example , TSL9906 or compound XC96-B03 is used as the cationically polymerizable compound having a siloxane bond.
70 (both structural formulas are shown later) is used, and AEPM (structural formulas are given later) is used as a radically polymerizable compound having a higher refractive index than this compound and having no siloxane bond. An example of creating a type hologram is shown. Photo-cationic polymerization initiator system is TPS / SbF
₆ (detailed later) was used. DYE-1 and DPI / TF as photo-radical polymerization initiator system (details are given later)
Was used. Table 1 shows the composition of the photosensitive composition for hologram recording used in Examples 1 and 2 and the evaluation results of holograms. In each of the examples, a colorless and transparent reflection hologram within the practical range was obtained.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

Examples 3 and 4 Here, A-BPHE (the structural formula is shown later) is used as a radically polymerizable compound having a higher refractive index than a cationically polymerizable compound having a siloxane bond and having no siloxane bond. The same experiment as in Examples 1 and 2 was carried out except that the reflection hologram was prepared. Table 1 shows the composition of the photosensitive composition for hologram recording used in Examples 3 and 4, and the evaluation results of holograms. In each of the examples, a colorless and transparent reflection hologram within the practical range was obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042]

[Table 3]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048]

[Table 6]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

Examples 14 to 16 Here, the results of the light resistance test and heat resistance test of the reflection hologram test plates prepared in Examples 11 to 13 are shown.
The results are shown in Table 7.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

Example 17 In this example , PS2A was used as the radically polymerizable compound having a siloxane bond, and T2 having a lower refractive index than PS2A was used as the cationically polymerizable compound having a siloxane bond.
An example of creating a reflection hologram using SL9906 will be shown. As the photocationic polymerization initiator system, TPS · SbF ₆ was used. DYE-1 and D as photo-radical polymerization initiator system
A combination of PI and TF was used. Table 8 shows the composition of the photosensitive composition for hologram recording used in Example 17 and the evaluation results of holograms. In each of the examples, a colorless and transparent reflection hologram within the practical range was obtained.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

[0052]

[Table 8]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

[0056]

[Table 10]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03F 7/029 7/075 511 G03H 1/04 1/28 (72) Inventor Sumiyoshi Iwao Osaka Prefecture Neyagawa 19-17 Ikedanaka-cho, Ichi, Japan Paint Co., Ltd.

Claims (11)

[Claims] 1. A photosensitive composition for volume hologram recording, which is used to record interference fringes produced by interference of laser light or light having excellent coherence as fringes having different refractive indexes, the composition comprising: A. A cationically polymerizable compound and a radically polymerizable compound, B. A cationic polymerization initiator system, and C.I. A photosensitive composition for volume hologram recording, which comprises each component of a radical polymerization initiator system as an essential component, and at least one of the cationically polymerizable compound of A and the radically polymerizable compound contains a siloxane bond. 2. The photosensitive composition for volume hologram recording according to claim 1, wherein both the cationically polymerizable compound and the radically polymerizable compound A have a siloxane bond. 3. The composition according to claim 1, wherein the difference in refractive index between the cationically polymerizable compound and the radically polymerizable compound is 0.01 or more. 4. The radical polymerization initiator system (C) is a radical polymerization initiator system having photosensitivity to the laser light or light having excellent coherence, and the cationic polymerization initiator system (B) is the laser light or 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 having another wavelength. 5. The composition according to claim 1, wherein a cyanine dye is used as a sensitizer in the radical polymerization initiator system (C) and a diaryl iodonium salt is used as an active radical generating compound. 6. The method according to claim 1, further comprising a polymeric binder.
The composition according to. 7. A volume hologram recording medium having a recording layer of the composition of 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 produced 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 over the entire surface. Hologram recording method. 9. A volume hologram recording method, wherein the recording medium of claim 7 is exposed to interference fringes generated by interference of laser light or light having excellent coherence, and then the recording medium is heat-treated. 10. The recording medium according to claim 7 is exposed to interference fringes produced by interference of laser light or light having excellent coherence, and then the recording medium is irradiated with UV light and / or visible light over the entire surface and heated. A volume hologram recording method in which processing is performed simultaneously or sequentially. 11. A volume hologram recorded by the method according to claim 8.