JP4589008B2 - Volume hologram photosensitive composition - Google Patents

Description

Field of Invention

  The present invention relates to a volume hologram photosensitive composition and a volume hologram recording photosensitive medium using the composition.

Volume holograms are widely used for design, security, and optical element applications because they can represent objects in three dimensions, have high diffraction efficiency, wavelength selectivity, and require advanced manufacturing technology. Yes. Volume holograms have high coherence (coherence), make object light and reference light of the same wavelength interfere with each other, enter volume hologram recording material, and three-dimensional information about the object as interference fringes inside the material It is produced by recording.

This interference fringe is recorded as a refractive index modulation corresponding to the bright and dark part of the interference light. One feature of the volume hologram is that it has excellent wavelength selectivity, and only light having a specific angle or wavelength can be diffracted and reproduced with respect to a light source (input light) having a specific wavelength.

  In recent years, a photosensitive composition for volume type hologram recording that can be mass-produced and does not require a wet development process in the production of a volume hologram has been attracting attention. As such a dry type photosensitive composition, a photo-radically polymerizable monomer, a binder resin, a photo-radical polymerization initiator, and a sensitizing dye are the main components, and the difference in refractive index between the photo-polymerizable monomer and the binder resin is determined. (For example, Patent No. 2664234: Patent Document 1). That is, when the photosensitive composition formed into a film is subjected to interference exposure, photoradical polymerization is initiated at a portion where the light is strong, and a diffusion movement of the photoradically polymerizable monomer occurs accordingly. As a result, according to the intensity of the interference light, the photo-radical polymerizable monomer can be made dense and dense, and it appears as a difference in refractive index, so that a hologram appears. Such a dry-type photosensitive composition is required to have a large refractive index difference between the photopolymerizable monomer and the binder resin and to have excellent storage stability after the hologram is formed.

In response to the above requirements, there has been disclosed a volume hologram recording material that can realize a hologram having high brightness by increasing the diffusion movement of the photo-radical polymerizable monomer by using a thermoplastic resin as the binder resin (for example, Japanese Patent Laid-Open No. Hei 9 (1994)). 6-43634 gazette: patent documents 2). Japanese Patent Laid-Open No. 2000-310932 (Patent Document 3) discloses a hologram recording material that can realize a hologram having excellent film strength and heat resistance by using a thermosetting resin as a binder resin.

However, when a thermoplastic resin is used as the binder resin, the luminance of the hologram is improved, but the heat resistance and mechanical strength of the hologram are inferior. Further, when a thermosetting resin is used as the binder resin, there is a limit to keeping the refractive index modulation amount high, and there is a problem that a hologram with high luminance cannot be obtained.

Accordingly, an object of the present invention is to provide a volume hologram photosensitive composition capable of realizing a hologram having excellent hologram brightness and excellent heat resistance and mechanical strength, and a volume hologram recording photosensitive using the composition. It is to provide a sex medium.
Japanese Patent No. 2664234 JP-A-6-43634 JP 2000-310932 A

Summary of the Invention

  The present inventors have used a binder resin in which a thermosetting resin and a thermoplastic resin are mixed at a predetermined ratio, so that excellent recording performance (monomer) can be obtained during hologram recording without impairing heat resistance and mechanical strength. We obtained knowledge that we could realize (moving medium ability). The present invention is based on this finding.

  That is, the volume hologram photosensitive composition according to the present invention is a volume hologram photosensitive composition comprising a photoreactive monomer, a photopolymerization initiator, a sensitizing dye for sensitizing the initiator, and a binder resin. The binder resin is composed of a thermosetting resin and a thermoplastic resin, and a mixing ratio of the thermosetting resin and the thermoplastic resin formed the photosensitive composition as a volume hologram. In this case, the hologram is adjusted so that the main glass transition temperature of the hologram is 50 ° C. or higher.

  As a preferred embodiment of the present invention, the thermosetting resin is contained in an amount of 5 to 99% by weight based on the binder resin.

Thus, by using a binder resin containing a thermosetting resin and a thermoplastic resin at a predetermined ratio, it is possible to realize a hologram that is excellent in hologram brightness, heat resistance, and mechanical strength.

DETAILED DESCRIPTION OF THE INVENTION

  Hereinafter, the volume hologram photosensitive composition of the present invention and the volume hologram recording photosensitive medium using the composition will be described.

1. Volume hologram photosensitive composition The volume hologram photosensitive composition according to the present invention comprises a photoreactive monomer, a photopolymerization initiator, a sensitizing dye for sensitizing the initiator, and a binder resin. Is. Hereinafter, each component will be described.

(1) Binder resin The binder resin used in the present invention is a mixture of a thermosetting resin and a thermoplastic resin, and the mixing ratio is obtained when the photosensitive composition is formed as a volume hologram. The hologram is adjusted so that the main glass transition temperature thereof is 50 ° C. or higher. By adjusting the mixing ratio of the resin mixture so as to have such a glass transition temperature, a hologram having a high refractive index modulation amount and excellent mechanical properties can be obtained. Here, the “main glass transition temperature” is a dynamic viscoelastic analysis of the light and / or thermoset of a volume hologram photosensitive composition in which two or more kinds of resins are mixed and used as a binder resin. The loss tangent (tan δ) is calculated by the apparatus (DMA), and the temperature of the maximum peak value derived from the binder resin among the peaks of the loss tangent curve is meant.

  The mixing ratio of the thermosetting resin and the thermoplastic resin in the binder resin depends on the glass transition temperature and compatibility of each resin used, but the thermosetting resin is 5 to 99 with respect to the binder resin. It is preferably contained by weight%, more preferably 30 to 99%.

  When a mixture containing a thermosetting resin at such a ratio is used as the binder resin, it is an advantage of the thermoplastic resin without impairing the properties of excellent heat resistance and mechanical strength, which is an advantage of using the thermosetting resin. The diffusion transfer ability of the reactive monomer species can be increased. The reason for this is not clear, but is considered as follows. That is, for the hologram, the photosensitive layer is exposed and the hologram is recorded, and then the resin is fixed by heating or ultraviolet irradiation. At the time of exposure, the higher the diffusivity of the photoreactive monomer, the higher the refractive index modulation amount, and a bright hologram can be obtained. At this time, when the thermoplastic resin is contained in the binder resin at a predetermined ratio, the diffusion transfer ability of the monomer species is increased. Further, when the hologram is fixed by heating / ultraviolet irradiation after hologram recording, the thermosetting resin and the unreacted monomer are three-dimensionally crosslinked and cured. Since the thermosetting resin is fixed to a network of polymer chains formed when these thermosetting resins are cured, it is considered that the apparent glass transition temperature of the thermoplastic resin is increased.

If the content of the thermoplastic resin is 1 to 50% by weight, preferably 1 to 30% by weight, based on the entire photosensitive composition, the thermoplastic resin hardly contributes to the physical properties and the mechanical properties of the hologram. Are mainly governed by a thermosetting resin or a polymer of photoreactive monomer species.

  As such a thermoplastic resin, the glass transition temperature is 200 ° C. or lower, preferably 170 ° C. or lower. When the glass transition temperature exceeds 200 ° C., the diffusion transfer ability of the reactive monomer species is poor, so that the refractive index modulation amount of the hologram is likely to be less than 0.04.

The thermoplastic resin having the above physical properties is not particularly limited, and specifically, poly (meth) acrylic acid ester or a partial hydrolyzate thereof, polyvinyl acetate or a partial hydrolyzate thereof, polyvinyl Alcohol or partial acetalized product thereof, triacetyl cellulose, polyisoprene, polybutadiene, polychloroprene, polyvinyl chloride, polyarylate, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinylcarbazole or a derivative thereof, poly-N-vinylpyrrolidone Or a derivative thereof, a copolymer of styrene and maleic anhydride or a half ester thereof, or a copolymer such as acrylic acid, acrylic ester, acrylamide, acrylonitrile, ethylene, propylene, vinyl chloride, or vinyl acetate. Copolymers of at least one polymerizable component of a monomer group may be used. Moreover, you may mix 2 or more types of those thermoplastic resins. In addition, it cannot be overemphasized that these thermoplastic resins need to be compatible with the thermosetting resin mentioned later.

  The thermosetting resin used for the binder resin is not particularly limited as long as it is compatible with the thermoplastic resin, and a reactive monomer or oligomer having a curable group is preferably used. it can. Further, a curable group may be introduced into a copolymer of a monomer having a curable group and another type of monomer or a monomer or polymer having a functional group. Specific examples include glycidyl group-containing polymers and oxetanyl group-containing polymers such as polyacrylate esters (CP series manufactured by Nippon Oil & Fats Co., Ltd.). It is also possible to use an oligomer type curable resin. For example, bisphenol A, bisphenol S, novolak, o-cresol novolak, and epoxy compounds produced by the condensation reaction of various phenolic compounds such as p-alkylphenol novolak and epichlorohydrin can be mentioned. Is not to be done.

  Moreover, as a binder resin used for this invention, the organic-inorganic hybrid polymer using a sol-gel reaction can also be used conveniently. An example of the organic-inorganic hybrid polymer includes a copolymer of an organometallic compound having a polymerizable group represented by the following formula (I) and a vinyl monomer.

R _m M (OR ′) _n (I)
(In the above formula, M represents a metal such as Si, Ti, Zr, Zn, In, Sn, Al, or Sn, R represents a vinyl group having 1 to 10 carbon atoms or a (meth) acryloyl group, and R ′ Represents an alkyl group having 1 to 10 carbon atoms, and m + n represents a valence of metal M.)
Examples of compounds when the metal atom M is Si include vinyltriethoxysilane, vinylmethoxysilane, vinyltributoxysilane, vinyltriallyloxysilane, vinyltetraethoxysilane, vinyltetramethoxysilane, or (meth) acryloxy. And propyltrimethoxysilane. Examples of the vinyl monomer used in the organic-inorganic hybrid polymer include (meth) acrylic acid and (meth) acrylic acid esters, but are not limited thereto.

(2) Photopolymerizable compound Examples of the photopolymerizable compound constituting the photosensitive composition for volume hologram recording of the present invention include a photo radical polymerizable compound, a photo cationic polymerizable compound, and a photo dimerizable compound. It is done. As content of these photopolymerizable compounds, it is 10-1000 weight part with respect to 100 weight part of binder resin, Preferably it is 10-200 weight part.

  Examples of the photo-radical polymerizable compound include compounds having at least one addition-polymerizable ethylenically unsaturated double bond, such as unsaturated carboxylic acids and salts thereof, unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds. And an amide bond of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Specific examples include monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids. As acrylic acid esters, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylol Propanetri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Dipentaerythritol diacrylate, dipipe Intererythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, 2-phenoxyethyl Acrylate, 2-phenoxyethyl acrylate, phenol ethoxylate monoacrylate, 2- (p-chlorophenoxy) ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenylethyl acrylate, (2-acryloxyethyl) ether of bisphenol A Ethoxylated bisphenol A dia Acrylate, 2- (1-naphthyloxy) ethyl acrylate, o-biphenyl acrylate, o-biphenyl acrylate, 9,9-bis (4-acryloxydiethoxyphenyl) fluorene, 9,9-bis (4-acryloxytri) Ethoxyphenyl) fluorene, 9,9-bis (4-acryloxydipropoxyphenyl) fluorene, 9,9-bis (4-acryloxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4-acryloxy) Examples include ethoxy-3-ethylphenyl) fluorene and 9,9-bis (4-acryloxyethoxy-3,5-dimethyl) fluorene.

  In addition, a sulfur-containing acrylic compound disclosed in JP-A-61-72748 can also be used. For example, 4,4′-bis (β-acryloyloxyethylthio) diphenylsulfone, 4,4 ′ -Bis (β-acryloyloxyethylthio) diphenyl ketone, 4,4′-bis (β-acryloyloxyethylthio) -3,3 ′, 5,5′-tetrabromodiphenyl ketone, 2,4-bis (β -Acryloyloxyethylthio) diphenyl ketone, but is not limited thereto.

  Specific examples of the methacrylic acid ester include compounds in which “acrylate” is “methacrylate”, “acryloxy” is “methacryloxy”, and “acryloyl” is “methacryloyl” among the above acrylic ester compound names. .

  Examples of the photocationically polymerizable compound include cyclic ethers represented by epoxy rings and oxetane rings, thioethers, and vinyl ethers. Specific examples include epoxy ring-containing compounds. Examples include polyalkylene glycol diglycidyl ether, bisphenol A diglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, diglycidyl hexahydrophthalate, trimethylolpropane diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, etc. However, it is not limited to these.

  Moreover, the compound which modified the metal fine particle surface with the reactive group can also be used, for example, Ti, Zr, Zn, In, Sn etc. with a high refractive index are illustrated as a metal fine particle. Examples of the photopolymerization include the above radical polymerization and cation polymerization. Examples of the radically polymerizable functional group include at least one addition-polymerizable ethylenically unsaturated double bond. For example, the metal surface is treated with an ethylenically unsaturated double bond-containing silane coupling agent. Can be introduced. As the ethylenically unsaturated double bond-containing silane coupling agent, the above-mentioned vinyl silane, (meth) acryloyl silane and the like can be used, but are not limited thereto.

  Examples of the functional group capable of photocationic polymerization include cyclic ethers represented by epoxy rings and oxetane rings, thioethers, and vinyl ethers. For example, they can be introduced by treating a metal surface with an epoxy ring-containing silane coupling agent. . Examples of the epoxy ring-containing silane coupling agent include, but are not limited to, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like.

(3) Photopolymerization initiator As the polymerization initiator constituting the photosensitive composition for volume hologram recording of the present invention, a radical photopolymerization initiator or a cationic photopolymerization initiator can be used. Content of these photoinitiators is 0.1-20 weight part with respect to 100 weight part of binder resin, Preferably it is 5-15 weight part.

  Examples of the photo radical polymerization initiator include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. More specifically, 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, 3-phenyl-5-isoxazolone 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name Irgacure 651, Ciba Specialty Chemicals Co., Ltd.) 1-hydroxy-cyclohexyl-phenyl-ke (Trade name Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name Irgacure 369, Ciba Specialty Chemicals) Chemicals Co., Ltd.), bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (trade name Irgacure) 784, manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like.

  Examples of the cationic photopolymerization initiator include sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, (η6-benzene) (η5-cyclopentadienyl). ) Iron (II) and the like are exemplified, and more specific examples include benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide, and the like, but are not limited thereto.

  Examples of photo radical polymerization initiators and photo cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, etc. More specifically, diphenyliodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium and the like iodonium chloride, bromide, borofluoride, hexafluorophosphate salt, Iodonium salts such as hexafluoroantimonate salt, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromide, borofluoride, hexa Sulfonium salts such as fluorophosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, 2,4,6-substituted-1,3,5-triazine compounds such as 3,5-triazine and 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine It is not limited to these.

  The photopolymerization initiator is preferably decomposed after hologram recording from the viewpoint of stabilization of the recorded hologram.

(4) Sensitizing dye The sensitizing dye constituting the photosensitive composition for volume hologram recording of the present invention plays a role of sensitizing the sensitivity of the photopolymerization initiator to recording light. Specifically, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salts Illustrative are dyes such as dyes, cyclopentanone dyes, and cyclohexanone dyes. Specific examples of cyanine and merocyanine dyes include 3,3′-dicarboxyethyl-2,2′-thiocyanine bromide, 1-carboxymethyl-1′-carboxyethyl-2,2′-quinocyanine bromide, 1 , 3′-diethyl-2,2′-quinothiocyanine iodide, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolylidene) ethylidene] -2-thioxo-4-oxazolidine, 3,9-diethyl-3′-carboxymethyl-2,2′-thiacarbocyanine / iodine salt, and the like. Specific examples of coumarin and ketocoumarin dyes include 3- (2′-benzimidazole) -7. -Diethylaminocoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), 3,3'-carbonylbiscoumarin, 3,3'-carbonylbis (5,7-di) Methoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin) and the like, but are not limited thereto.

  The visible light sensitizing dye is preferably one that becomes colorless due to decomposition or the like in a post-process after hologram recording, heating, or ultraviolet irradiation when high transparency is required as in an optical element.

  Moreover, content of this sensitizing dye is 0.01-10 weight part with respect to 100 weight part of binder resin, Preferably it is 0.01-3 weight part.

  These photosensitive compositions for volume hologram recording are dissolved in a solvent and used as a coating solution. Solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4-dioxane, 1, Examples include, but are not limited to, 2-dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol, and the like.

2. Next, a photosensitive medium for volume hologram recording using the above-described composition for volume hologram recording will be described.

The photosensitive medium for volume hologram recording is applied to a substrate by applying a coating liquid comprising the above composition using a spin coater, gravure coater, comma coater, bar coater or the like, drying, and photosensitizing. It is obtained by forming a layer.

  The substrate used for the photosensitive medium for volume hologram recording may be a resin having transparency, such as a polyethylene film, a polypropylene film, a polyfluorinated ethylene film, a polyvinylidene fluoride film, a polyvinyl chloride film, a polychlorinated film. Polyester such as vinylidene film, ethylene-vinyl alcohol film, polyvinyl alcohol film, polymethyl methacrylate film, polyether sulfone film, polyether ether ketone film, polyamide film, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film, polyethylene terephthalate film Examples of the resin include a film and a polyimide film.

  The thickness of the substrate is 2 to 200 μm, preferably 10 to 50 μm. The coating amount of the composition is preferably such that the thickness of the coating film after coating and drying is 1 to 100 μm, particularly 10 to 40 μm. Moreover, when the coating film after drying has adhesiveness, the film illustrated as the said base material can be used as a protective film, and this film can be laminated on an application surface. In this case, the contact surface between the laminate film and the coated surface may be subjected to a release treatment so that it can be easily peeled off later.

3. Volume hologram recording method For hologram recording, visible laser light such as argon ion laser (458 nm, 488 nm, 514.5 nm), krypton ion laser (647.1 nm), helium-neon ion laser (633 nm), YAG laser is used. Using a laser beam such as (532 nm), recording can be performed on a photosensitive medium for volume hologram recording.

  As a method for recording a volume hologram on the photosensitive medium for volume hologram recording, any conventionally known method may be used.

  For example, by adhering the original plate to the hologram recording material layer of the photosensitive medium for volume hologram recording and performing interference exposure using ionizing radiation such as visible light, ultraviolet light or electron beam from the transparent substrate film side A volume hologram is recorded.

  Further, in order to promote the refractive index modulation and complete the polymerization reaction, after the interference exposure, a process such as full exposure with ultraviolet rays or heating can be appropriately performed.

Example 1
As the binder resin 1, a mixture of the following resins was used.

Thermosetting epoxy group-containing acrylate (CP-50M: manufactured by NOF Corporation) 40 parts by weight Polyvinyl acetate (manufactured by Sowa Kagaku) 40 parts by weight Volume hologram recording using the binder resin 1 and the material shown below. A photosensitive composition solution was prepared.

1,6-hexanediol diglycidyl ether (EX-212 manufactured by Nagase ChemteX) 70 parts by weight Diphenoxyethanol full orange acrylate (BPEFA made by Osaka Gas) 80 parts by weight Diaryliodonium salt (PI2074: manufactured by Rhodia) 5 parts by weight 3,9 -Diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine, iodine salt 1 part by weight 1-butanol 30 parts by weight Methyl ethyl ketone 30 parts by weight Using a bar coater on Lumirror (T-60), a volume hologram recording photosensitive medium was prepared by coating so as to have a dry film thickness of 20 μm.

The photosensitive layer side was laminated on a mirror, and 532 nm laser light was incident on the PET side at 60 mJ / cm ² to record a volume hologram. Next, the photosensitive layer was fixed by heating and ultraviolet irradiation, and a volume hologram was obtained.

  About the obtained volume hologram, the transmittance | permeability measurement of the spectrophotometer (Shimadzu UVPC-3100) was performed, and the refractive index modulation amount ((DELTA) n) was calculated. Moreover, the tensile test was done using the universal material tester (made by Instron 5565), and the Young's modulus was computed.

Comparative Example 1
The following resins were used as the binder resin 2.

Vinyl acetate (manufactured by Sowa Kagaku) 80 parts by weight A photosensitive composition solution for volume hologram recording was prepared using the binder resin 2 described above and the materials shown below.

1,6-hexanediol diglycidyl ether (EX-212 manufactured by Nagase ChemteX) 70 parts by weight Diphenoxyethanol full orange acrylate (BPEFA made by Osaka Gas) 80 parts by weight Diaryliodonium salt (PI2074: manufactured by Rhodia) 5 parts by weight 3,9 -Diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine, iodine salt 1 part by weight 1-butanol 30 parts by weight Methyl ethyl ketone 30 parts by weight The above-prepared solution was obtained in the same manner as in Example 1 and 38 .mu.m polyethylene terephthalate. This was coated on a (PET) film (Lumirror T-60 manufactured by Toray Industries, Inc.) to produce a volume type hologram recording photosensitive medium. Next, a hologram was recorded in the same manner as in Example 1, and the photosensitive layer was fixed to obtain a volume hologram.

  About the obtained volume hologram, the refractive index modulation amount and Young's modulus were measured in the same manner as in Example 1.

Comparative Example 2
The following resins were used as the binder resin 3.

Thermosetting epoxy group-containing acrylate (CP-50M: manufactured by NOF Corporation) 80 parts by weight A photosensitive composition solution for volume hologram recording was prepared using the binder resin 3 and the material shown below.

1,6-hexanediol diglycidyl ether (EX-212 manufactured by Nagase ChemteX) 70 parts by weight Diphenoxyethanol full orange acrylate (BPEFA made by Osaka Gas) 80 parts by weight Diaryliodonium salt (PI2074: manufactured by Rhodia) 5 parts by weight 3,9 -Diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine, iodine salt 1 part by weight 1-butanol 30 parts by weight Methyl ethyl ketone 30 parts by weight This was coated on a (PET) film (Lumirror T-60 manufactured by Toray Industries, Inc.) to produce a volume type hologram recording photosensitive medium. Next, a hologram was recorded in the same manner as in Example 1, and the photosensitive layer was fixed to obtain a volume hologram.

  About the obtained volume hologram, the refractive index modulation amount and Young's modulus were measured in the same manner as in Example 1.

The results of Example 1, Comparative Example 1 and Comparative Example 2 are shown in Table 1.

Claims (6)

A volume hologram photosensitive composition comprising a photoreactive monomer, a photopolymerization initiator, a sensitizing dye for sensitizing the initiator, and a binder resin,
The binder resin consists of a thermosetting resin and a thermoplastic resin,
The mixing ratio of the thermosetting resin and the thermoplastic resin was adjusted so that the main glass transition temperature of the hologram was 50 ° C. or higher when the photosensitive composition was formed as a volume hologram. Is,
The thermosetting resin is composed of an epoxy group-containing polymer or oligomer ,
A volume hologram photosensitive composition, wherein the photoreactive monomer is composed of an epoxy ring-containing compound .   The volume hologram photosensitive composition according to claim 1, wherein the thermosetting resin is contained in an amount of 5 to 99% by weight based on the binder resin.   The volume hologram photosensitive composition according to claim 1 or 2, wherein the thermoplastic resin is contained in an amount of 1 to 50% by weight based on the entire photosensitive composition.   The volume hologram photosensitive composition of any one of Claims 1-3 whose glass transition temperature of the said thermoplastic resin is 200 degrees C or less.   The photosensitive medium for volume type hologram recording in which the photosensitive layer which consists of a volume type hologram photosensitive composition of any one of Claims 1-4 is provided on the transparent base material.   A volume hologram using the photosensitive medium for volume hologram recording according to claim 5, wherein the refractive index modulation amount Δn is 0.04 or more.