JP2002244535A - Photosensitive composition and recording medium for hologram recording, hologram, and method for recording hologram, method for forming and method for reproducing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition for hologram recording which has good workability and handling property in a bright room, which can be processed in a dry state and which forms holograms with high sensitivity, and to provide a hologram recording medium, a method for recording a hologram, a method for forming a hologram, a hologram and a method for reproducing a hologram by using the above composition. SOLUTION: In the photosensitive composition for hologram recording to be used for the purpose of recording interference fringes produced by the interference of UV laser light or light with excellent coherency, the composition contains at least (a) a photopolymerization initiator having 300 to 450 nm maximum absorption wavelength and (b) a compound having addition polymerizable ethylenic unsaturated bonds. The composition is used for the hologram recording medium, the method for recording a hologram, the method for forming a hologram, the hologram and the method for reproducing a hologram.

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 hologram recording which can be dry-processed and has high sensitivity, a hologram recording medium using the same, a hologram recording method, a hologram forming method, a hologram, and a hologram. Related to the reproduction method.

[0002]

2. Description of the Related Art In general, in holographic recording in which information is recorded on a recording medium using holography, light having image information and reference light are overlapped inside the recording medium, and interference fringes formed at that time are formed. Is written on a recording medium. To reproduce the recorded information, the recording medium is irradiated with reference light, and the image information is reproduced by diffraction of the interference fringes.

In recent years, volume holography, especially digital volume holography, for ultra-high-density optical recording has been developed for practical use and has been receiving attention. Volume holography is a method of writing interference fringes three-dimensionally by actively utilizing the thickness direction of the recording medium. Increasing the thickness increases the diffraction efficiency, and increasing the recording capacity by using multiplex recording. There is a feature that can be achieved. And with digital volume holography,
While using the same recording medium and recording method as volume holography, the image information to be recorded is a so-called computer-oriented holographic recording method limited to a binary digital pattern. In this digital volume holography, for example, image information such as an analog picture is once digitized, developed into two-dimensional digital pattern information, and recorded as image information. At the time of reproduction, this digital pattern information is read out and decoded to return to the original image information for display. Thereby, even if the SN ratio (signal-to-noise ratio) is somewhat poor at the time of reproduction, differential detection is performed, the binary data is coded, and error correction processing is performed to reproduce the original information extremely faithfully. It becomes possible.

As a photosensitive material for recording such a 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 industrial production of holograms because they require wet development and complicated development and fixing treatments, and have problems such as loss of images due to moisture absorption even after recording. I was Also, JP-A-8-2
No. 49897, Ce-doped SBN (Sr _x B
_{a 1-x Nb y O z} ) and it is also possible to use photorefractive crystals of LiNbO ₃ or the like, but had the disadvantage of poor workability. In order to overcome the above-mentioned problems of the prior art, it is known that a hologram can be produced by using a photopolymer with good workability and a simple dry process, as disclosed in U.S. Pat. Nos. 3,658,526 and 3,658,526. 3,993,48
5, No. 4,942,102, and No. 4,942,112. Although these photopolymer materials have improved workability and made it possible to produce holograms by dry processing, they have low sensitivity and require exposure time with laser light or coherence light for information recording. There was a problem. When used with conventional photopolymer photosensitive materials,
Since it was a dark room, the handling was poor, which was a problem.

In particular, in the field of digital information recording, not only ultra-high density recording but also shortening of information recording / reproducing time is required, and a highly sensitive recording medium capable of recording / reproducing information in a short time is desired. Was rare.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a hologram recording photosensitive composition which has good workability, can be dry-processed, and provides a hologram with high sensitivity and good handleability in a bright room. It is an object of the present invention to provide a hologram recording medium, a hologram recording method, a hologram forming method, a hologram, and a hologram reproducing method.

[0007]

The above object of the present invention has been attained by the following constitutions.

[0008] 1. In a photosensitive composition for hologram recording used for recording interference fringes generated by interference of laser light or light having excellent coherence, the photosensitive composition is made of an ultraviolet ray curable resin, and at least 300 nm to 450 nm. A hologram recording photosensitive composition comprising a photopolymerization initiator having a maximum wavelength of: and a compound having an ethylenically unsaturated bond capable of addition polymerization.

[0009] 2. On the support, at least 300 nm
It has a recording layer consisting of a photopolymerization initiator having a maximum wavelength of 450 nm and an ultraviolet ray curable resin containing a compound having an ethylenically unsaturated bond capable of addition polymerization, and has excellent ultraviolet laser light or coherence. A hologram recording medium characterized in that it is used for recording interference fringes generated by interference of reflected light.

[0010] 3. A hologram recording photosensitive composition containing a photopolymerization initiator having at least a maximum wavelength of 300 nm to 450 nm and an addition-polymerizable compound having an ethylenically unsaturated bond, or the hologram recording photosensitive composition on a support. Recording medium having a recording layer made of
A hologram recording method, which comprises exposing an interference pattern generated by interference of an ultraviolet laser beam having a wavelength of from 00 nm to 450 nm or light having excellent coherence.

4. A hologram recording photosensitive composition containing a photopolymerization initiator having at least a maximum wavelength of 300 nm to 450 nm and an addition-polymerizable compound having an ethylenically unsaturated bond, or the hologram recording photosensitive composition on a support. A hologram recording method comprising exposing a recording medium having a recording layer made of an object to interference fringes formed by a binary digital information beam generated from ultraviolet laser light or light having excellent coherence and a recording reference beam. .

5. A hologram recording photosensitive composition containing a photopolymerization initiator having at least a maximum wavelength of 300 nm to 450 nm and an addition-polymerizable compound having an ethylenically unsaturated bond, or the hologram recording photosensitive composition on a support. Recording medium having a recording layer made of
A method for forming a hologram, comprising: exposing an interference fringe generated by interference of an ultraviolet laser beam having a wavelength of from 00 nm to 450 nm or light having excellent coherence, followed by heat treatment.

6. A hologram recording photosensitive composition containing a photopolymerization initiator having at least a maximum wavelength of 300 nm to 450 nm and an addition-polymerizable compound having an ethylenically unsaturated bond, or the hologram recording photosensitive composition on a support. A recording medium having a recording layer made of a material is exposed to an interference fringe formed by an ultraviolet laser beam or binarized digital information beam generated from light having excellent coherence and a recording reference beam, and then heat-treated. A method for forming a hologram.

7. A hologram recording photosensitive composition containing a photopolymerization initiator having at least a maximum wavelength of 300 nm to 450 nm and an addition-polymerizable compound having an ethylenically unsaturated bond, or the hologram recording photosensitive composition on a support. Recording medium having a recording layer made of
A hologram characterized by being exposed and recorded with interference fringes generated by interference of ultraviolet laser light having a wavelength of from 00 nm to 450 nm or light having excellent coherence.

[8] A hologram recording photosensitive composition containing a photopolymerization initiator having at least a maximum wavelength of 300 nm to 450 nm and an addition-polymerizable compound having an ethylenically unsaturated bond, or the hologram recording photosensitive composition on a support. A recording medium having a recording layer made of an object is exposed to and recorded with an interference fringe formed by a binary digital information light generated from ultraviolet laser light or light having excellent coherence and a recording reference light. hologram.

9. A hologram recording photosensitive composition containing a photopolymerization initiator having at least a maximum wavelength of 300 nm to 450 nm and an addition-polymerizable compound having an ethylenically unsaturated bond, or the hologram recording photosensitive composition on a support. Recording medium having a recording layer made of
A hologram formed by exposing an interference fringe generated by interference of an ultraviolet laser beam having a wavelength of 00 nm to 450 nm or light having excellent coherence and then performing a heat treatment.

10. At least 300 nm to 450 nm
A hologram recording photosensitive composition containing a photopolymerization initiator having a maximum wavelength of and a compound having an addition-polymerizable ethylenically unsaturated bond, or recording of the hologram recording photosensitive composition on a support. A recording medium having a layer,
A hologram formed by exposing an interference fringe formed by an ultraviolet laser beam or a binarized digital information beam generated from light having excellent coherence and a recording reference beam, followed by heat development.

11. 11. Irradiating the hologram according to any one of the items 7 to 10 with an ultraviolet laser beam having a wavelength of 300 nm to 450 nm or a reference beam having excellent coherence, and generating reproduction light by diffraction by interference fringes in the hologram. A hologram reproducing method characterized by the above-mentioned.

The present invention will be described in more detail. Here, the photosensitive composition for hologram recording of the present invention includes: a) a photopolymerization initiator having a maximum wavelength of 300 nm to 450 nm; b) a hologram recording containing a compound having an addition-polymerizable ethylenically unsaturated bond. Is a photosensitive composition for
A composition containing a radical polymerizable compound that undergoes radical polymerization by radicals generated by irradiating active light, or a cation polymerizable compound that cation polymerizes with a cation of an acid generated by irradiating the specific compound with active light. The composition containing is used.

The radically polymerizable composition for producing the photosensitive composition for hologram recording or the acid-crosslinkable composition or the acid-decomposable composition for producing the cationically polymerizable composition includes: And other materials such as a binder resin, a colorant, and a surfactant described below.

(Photosensitive composition for hologram recording) Radical polymerizable composition The radical polymerizable compound contained in the radical polymerizable composition includes ordinary photopolymerizable compounds and thermopolymerizable compounds. The radically polymerizable compound is a compound having an addition-polymerizable ethylenically unsaturated bond, and may be any compound as long as it has at least one radically polymerizable ethylenically unsaturated bond in the molecule. , Oligomers, polymers and the like having a chemical form. Only one radical polymerizable compound may be used, or two or more radical polymerizable compounds may be used in an optional ratio in order to improve desired properties.

Radical Polymerization Examples of compounds having an ethylenically unsaturated bond capable of addition polymerization include acrylic acid, methacrylic acid, itaconic acid,
Unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, and maleic acid, and salts, esters, urethanes, amides and anhydrides thereof, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated polyamides Radical polymerizable compounds such as urethane are exemplified. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Litol tetraacrylate, trimethylolpropane triacrylate, tetramethylol methanetetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, acrylic acid derivatives such as epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxy polyethoxy phenyl) methacrylamide derivatives such as propane, other, allyl glycidyl ether, diallyl phthalate,
Derivatives of allyl compounds such as triallyl trimellitate are mentioned. More specifically, Shinzo Yamashita, "Crosslinking Agent Handbook", (1981 Taiseisha);
"UV / EB Curing Handbook (Raw Materials)" (1985)
Year, Society of Polymer Publications); edited by Radtech Study Group, “UV / E
Applications and Markets of B Curing Technology ", p. 79, (CMC, 1989); Eiichiro Takiyama," Polyester Resin Handbook ", (1988, Nikkan Kogyo Shimbun), etc., or known in the industry. Addition-polymerizable or crosslinkable monomers, oligomers and polymers can be used. The amount of the radical polymerizable compound added in the radical polymerizable composition is preferably 1 to 80% by mass, more preferably 10 to 70% by mass.

The radical polymerizable composition containing the above radical polymerizable compound is used in combination with the specific compound of the present invention, as described above, together with another compound which generates a radical upon irradiation with actinic rays or radiation. It is possible,
Further, the composition may contain a polymerization inhibitor, a chain transfer agent, a polymerization accelerator and the like described below.

Cationic Polymerization Examples of compounds having an ethylenically unsaturated bond capable of addition polymerization include cationic polymerizable compounds in addition to radical polymerizable compounds. Examples of the cationically polymerizable compound contained in the cationically polymerizable composition include the following (1) styrene derivatives, (2) vinylnaphthalene derivatives, (3) vinyl ethers, and (4) N-vinyl compounds. Can be.

(1) Styrene derivatives For example, styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-
(2) vinyl naphthalene derivatives, for example, 1-vinyl naphthalene, α-methyl-1-vinyl naphthalene, β-methyl-1-vinyl naphthalene,
-Methyl-1-vinylnaphthalene, 4-methoxy-1-
(3) vinyl ethers, for example, isobutyl vinyl ether, ethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-methoxyphenyl vinyl ether,
(4) N-vinyl compounds such as N-vinyl carbazole, N-vinyl pyrrolidone, N-vinyl indole, N-vinyl pyrrole, N-vinyl phenyl vinyl ether, β-methyl isobutyl vinyl ether, β-chloro isobutyl vinyl ether, etc.
Vinylphenothiazine, N-vinylacetanilide, N
-Vinylethylacetamide, N-vinylsuccinimide, N-vinylphthalimide, N-vinylcaprolactam, N-vinylimidazole and the like.

The content of the cationically polymerizable compound in the cationically polymerizable composition is preferably from 1 to 80% by mass, more preferably from 10 to 70% by mass.

The ultraviolet ray curable resin of the present invention has a
at least a photopolymerization initiator having a maximum wavelength of from 450 nm to 450 nm. Other compounds that generate radicals or acids as photopolymerization initiators include radical polymerization initiators. The specific compound of the present invention generates a radical (for example, Cl) by light or heat, and the radical extracts a proton in the layer to generate an acid (for example, HCl) to perform polymerization. Similarly, the following polymerization initiator generates a radical or an acid by light or heat to perform polymerization. Examples of the radical polymerization initiator include JP-B-59-12.
No. 81, JP-B-61-9621, and JP-A-60-6
No. 0104, etc., triazine derivatives described in JP-A Nos. 59-1504 and 61-243807, and organic peroxides described in JP-A Nos. 61-243807, and JP-B-43-23684.
Diazonium compounds described in JP-B-44-6413, JP-B-44-6413 and JP-B-47-1604, and U.S. Pat. No. 3,567,453; U.S. Pat. , 328, 2,85
Organic azide compounds described in JP-A-2,379 and JP-A-2,940,853, JP-B-36-22062, JP-B-37-13109, JP-B-38-18015,
Ortho-quinonediazides described in JP-B-45-9610 and the like; JP-B-55-39162;
Nos. 9-14023 and "Macromolecules, Vol. 10, No. 13.
Various onium compounds described on page 07 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109,
851, EP 126,712, etc., "Journal of Imaging Science" (J. Imag. Sci.), Vol. 30, No. 17,
Metal allene complex described on page 4 (1986);
(Oxo) sulfonium organoboron complexes described in JP-A-213861 and JP-A-5-255347, titanocenes described in JP-A-61-151197, "Coordination chemistry review (Coordination Chemistry Review)"
Review), Vol. 84, pages 85-277 (1988) and JP-A-2-182701, a transition metal complex containing a transition metal such as ruthenium;
The 2,4,5-triarylimidazole dimer, carbon tetrabromide described in JP-A-3-209777 and
And organic halogen compounds described in JP-A-9-107344. In the present invention, as a photopolymerization initiation system that absorbs ultraviolet light having a wavelength of less than 450 nm to generate radicals, dialkyl acetophenone, benzyl dialkyl ketal, benzoin, benzoin alkyl ether, thioxanthone derivatives, acylphosphine oxide, It is preferable to use hexaarylbiimidazoles, s-trihalomethyltriazines, titanocenes, and the like. These polymerization initiators are preferably contained in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the radically polymerizable compound having an ethylenically unsaturated bond. In the present invention, an initiator having a maximum absorption wavelength at 300 nm to 450 nm is preferable among the photopolymerization initiators from the viewpoint of handling in a bright room.

In the present invention, if necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added for the purpose of increasing the sensitivity.

Preferred examples of the photopolymerization initiation system sensitive to light having a wavelength of 300 nm or more and 450 nm or less include wavelengths of 300 to 450 nm.
A sensitizing dye having an absorption at 450 nm; 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-tetra (p-carbethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-bromophenyl) bi Hexaarylbiimidazole such as imidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, and 2-mercaptobenzthiazole; -Mercaptobenzoxazole,
A composite photopolymerization initiator comprising an organic thiol compound such as 2-mercaptobenzimidazole, or a wavelength of 350 to
Sensitizing dyes having absorption at 450 nm and dicyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyrrol-1-yl) -phenyl-1-yl, dicyclopentadienyl-Ti-bis -2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-
Initiation of composite photopolymerization consisting of titanocene compounds such as Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl and dialkylaminophenyl compounds such as ethyl p-diethylaminobenzoate and Michler's ketone Agents.

The dyes for sensitizing hexabiimidazole include, for example, JP-A-2-69, JP-A-57-168088, and JP-A-5-107761.
And sensitizing dyes described in JP-A-5-210240. Further, among the photopolymerization initiation systems sensitive to these visible light regions, wavelengths of 300 nm or more and 45
Those exhibiting absorption in the ultraviolet region of 0 nm or less and exhibiting high sensitivity may be used as a photopolymerization initiation system for a light source in the ultraviolet region.

Specifically, a system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-373)
No. 77), hexaarylbiimidazole and (p-
Dialkylaminobenzylidene) ketone system
No. 7-2528, JP-A-54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), and a system of a substituted triazine and a merocyanine dye (JP-A-48-18383). No. 54-151024), a system of ketocoumarin and an activator (JP-A-52-112).
681, JP-A-58-15503, JP-A-60-8
8005), a system of a substituted triazine and a sensitizer (JP-A-58-29803 and JP-A-58-40302), a system of biimidazole, a styrene derivative, and a thiol (JP-A-59-56403). Sensitizer containing a dialkylaminophenyl group and biimidazole (JP-A-2-69, JP-A-57-168088, JP-A-5-16888).
-107761, JP-A-5-210240 and JP-A-4-288818), a system of an organic peroxide and a dye (JP-A-59-140203, JP-A-59-1893)
No. 40) and titanocene (JP-A-59-1523).
No. 96, JP-A-61-151197, JP-A-63-1
0602, JP-A-63-41484, JP-A-2-2
No. 91, JP-A-3-12403, JP-A-3-2029
No. 3, JP-A-3-27393, JP-A-3-52050
JP-A-4-221), a combination of titanocene, a xanthene dye, and an addition-polymerizable ethylenically saturated double bond-containing compound having an amino group or a urethane group.
958, JP-A-4-219756).

Other Additives Thermal Polymerization Initiator The photosensitive composition containing a radically polymerizable compound may be used as a thermal polymerization initiator for a radically polymerizable monomer. The polymerization initiator can be contained without any particular limitation. Here, the thermal polymerization initiator is a compound capable of generating a polymerizable radical by giving thermal energy.

Such compounds include, for example, 2,
Azobisnitrile compounds such as 2'-azobisisobutyronitrile and 2,2'-azobispropionitrile, benzoyl peroxide, lauroyl peroxide, acetyl peroxide,
T-butyl perbenzoate, α-cumyl hydroperoxide, di-t-butyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, peracids, alkyl peroxycarbamates, nitrosoaryl acylamines Organic peroxides, such as organic peroxides, inorganic peroxides such as potassium persulfate, ammonium persulfate, potassium perchlorate, diazoaminobenzene, p-nitrobenzenediazonium, azobis-substituted alkanes, diazothioethers, arylazosulfones, etc. Azo or diazo compounds, nitrosophenyl urea, tetramethyl thiuram disulfide, diaryl disulfides, dibenzoyl disulfide, tetraalkyl thiuram disulfides, dialkyl xanthate disulfides Aryl sulfinic acids, arylalkyl sulfonic acids, it may be mentioned 1-alkanoic sulfinic acids and the like. Particularly preferred among these are compounds which are excellent in stability at normal temperature, have a high decomposition rate upon heating, and become colorless upon decomposition. Examples of such compounds include benzoyl peroxide, 2,2 '. -Azobisisobutyronitrile and the like. In the present invention, these thermal polymerization initiators can be used alone or in combination of two or more. Further, the thermopolymerization initiator is usually preferably 0.1 to 30% by mass in the thermopolymerizable composition,
The range is more preferably from 0.5 to 20% by mass.

Polymerization Inhibitor In the radically polymerizable composition containing a radically polymerizable compound, a thermal polymerization inhibitor can be contained for the purpose of preventing polymerization during storage of the image forming layer. Specific examples of the thermal polymerization inhibitor that can be added to the radical polymerizable composition include p-
Methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butyl catechol, phenothiazine and the like, and these thermal polymerization inhibitors, based on 100 parts by mass of a radically polymerizable compound having an ethylenically unsaturated bond It is preferably added in the range of 0.001 to 5 parts by mass.

Chain Transfer Agent and Polymerization Accelerator The radical polymerizable composition containing the radical polymerizable compound of the present invention may further contain a polymerization accelerator represented by amine, thiol, disulfide, etc. A transfer catalyst or the like can be contained. Specific examples of polymerization accelerators and chain transfer catalysts that can be contained,
For example, amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, U.S. Pat. No. 4,414,312 and JP-A-64-1314.
No. 4; disulfides described in JP-A-2-29161; U.S. Pat. No. 3,558,32.
And thiones described in JP-A-2-17048 and o-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

Binder Suitable binders for the photosensitive composition for hologram recording of the present invention are transparent or translucent and generally colorless, and include natural polymers, synthetic polymers and copolymers, and other film-forming media such as binder resins. Examples thereof include polyester resin, polyvinyl acetal resin, polyvinyl butyral resin, polyurethane resin, polyamide resin, cellulose resin, olefin resin, vinyl chloride resin, styrene resin, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, and polysulfone. , Polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, rubber resin and the like. Further, a resin having an unsaturated bond in the resin, for example, diallyl phthalate resin and its derivative, chlorinated polypropylene and the like can be polymerized with the above-mentioned compound having an ethylenically unsaturated bond, so that it is suitably used depending on the application. be able to. In addition, as polyacrylic resin, JP-A-10-97067 and JP-A-200
Resins and the like described in 0-258903 and the like can be used. Optionally, it may be a hydrophilic resin, and these are
It may be used as a solution together with a solvent to be dissolved, or in the form of an aqueous dispersion such as latex.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound can be contained for controlling the formation of interference fringes and improving the storage stability of interference fringes. When a mercapto compound is used in the present invention, any structure may be used, but Ar-SM, Ar-SM
Those represented by -SS-Ar are preferred. Where M
Is a hydrogen atom or an alkali metal atom, and Ar represents an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms, preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, Benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms) and alkoxy (eg, For example, it may have one selected from a substituent group consisting of one or more carbon atoms, preferably one having 1 to 4 carbon atoms. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole and 2-mercaptobenzimidazole.
Mercapto-5-methylbenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole, 2-
Mercaptoquinoline, 8-mercaptopurine, 2,3
Examples include 5,6-tetrachloro-4-pyridinethiol, 4-hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole, and the like, but the invention is not limited thereto.

Various dyes and pigments can be used in the photosensitive composition for hologram recording of the present invention from the viewpoint of improving the recording density. Dyes and pigments used in the photosensitive composition for hologram recording of the present invention are not particularly limited, and include, for example, pigments and dyes described in Color Index, and specifically include pyrazoloazole dyes, anthraquinone dyes, azo dyes, and azomethine. Organic dyes such as dyes, oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes, and indophenol dyes, azo pigments, polycyclic pigments (phthalocyanine pigments,
Organic pigments such as anthraquinone-based pigments), dye lake pigments, azine pigments, and inorganic pigments. Preferred dyes used in the present invention include anthraquinone dyes (for example, compounds 1 to 9 described in JP-A-5-341441, compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147). Azomethine dye (compound 17 described in JP-A-5-341441)
To 47, etc.), indoaniline dyes (for example,
Compounds 11 to 19 described in JP-A-289227;
Compound 47 described in No. 341441, JP-A-5-1651
47 and the azo dyes (compounds 10 to 1 described in JP-A-5-341441).
6). Among them, specific examples of preferable pigments include anthraquinone-based indanthrone pigments (C.I.
I. Pigment Blue 60) and phthalocyanine pigments (CI Pigment Blue 15).
Copper phthalocyanine such as C.I. I. Pigment Bl
metal-free phthalocyanine such as ue 16), triarylcarbonyl pigments based on dyed lake pigments, indigo,
Inorganic pigments (ultramarine, cobalt blue, etc.) can be mentioned. Solutions for adding these dyes and pigments include solutions,
Any method such as an emulsion, a solid fine particle dispersion, and a state in which it is mordanted with a polymer mordant may be used. The amount of these compounds to be used is determined depending on the desired amount of absorption, but is generally 1%.
It is preferable to use 1 μg or more and 1 g or less per m ² . Further, a dioxane pigment, a quinacridone pigment, a diketopyrrolopyrrole pigment, or the like may be used.

By providing the photosensitive composition for hologram recording of the present invention as a recording layer on a support, a hologram recording medium can be produced.

The support used in the present invention is not particularly limited as long as the photosensitive composition for hologram recording can be applied thereto. Examples thereof include paper, plastic, glass, and metals such as aluminum and stainless steel. Can be Examples of plastics include polyethylene terephthalate,
Polyester such as polyethylene naphthalate, polystyrene, polycarbonate, polyether sulfone, polyimide, polycyclopentadiene, polynorbornene, nylon, cellulose triacetate and the like are preferable. Preferred supports are polyethylene terephthalate (hereinafter abbreviated as PET) and A plastic (hereinafter abbreviated as SPS) support containing a styrenic polymer having an tactic structure may be used.

PET is composed of polyethylene terephthalate in which all polyester components are used. In addition to polyethylene terephthalate, terephthalic acid, naphthalene-2,6-dicarboxylic acid, isophthalic acid, butylene dicarboxylic acid, and 5-sodium are used as acid components. A polyester containing a modified polyester component of sulfoisophthalic acid, adipic acid, or the like and a glycol component of ethylene glycol, propylene glycol, butanediol, cyclohexane dimethanol, or the like in an amount of 10 mol% or less of the entire polyester may be used.

SPS is a polystyrene having steric regularity unlike ordinary polystyrene (atactic polystyrene). The regular stereoregular structure part of SPS is called a racemo chain, and it is preferable that there are more regular parts such as two, three, five or more. In the present invention, the racemo chain is 2 85% in chain
It is preferable that the ratio is 75% or more for three chains, 50% or more for five chains, and 30% or more for more chains. SPS
Can be carried out according to the method described in JP-A-3-131843.

The thickness of the support used in the present invention is about 50 to 2000 μm, preferably 70 to 150 μm.
0 μm. A heat-treated plastic support can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support is
After forming these supports, before the recording layer is coated, at a temperature 30 ° C. or more higher than the glass transition point of the supports,
Preferably at a temperature higher than 35 ° C., more preferably 40 ° C.
It is preferable to heat at a temperature higher than ℃.

The support coated with the photosensitive composition of the present invention may be further bonded to a support of the same or different type, or the coated support may be bonded together.
The support used in the present invention may be subjected to easy contact treatment for the purpose of improving the adhesion between the support and the photosensitive composition for hologram recording. Specifically, silane coupling agents, titanium coupling agents, aluminum coupling agents, JP-A-2-4258, JP-A-4-161957
And a coupling agent having a vinyl group, a glycidyl group, an amino group, and a (meth) acryloyl group in order to improve the adhesion to the hologram recording photosensitive composition. It is preferred to use agents.

In order to protect the surface of the hologram recording medium and prevent scratches, a protective layer may be provided outside the recording layer. The binder used for these protective layers may be the same as or different from the binder used for the recording layer.

For the protective layer provided on the photosensitive composition for hologram recording, for example, a coating solution obtained by dissolving a polymer compound usable as a protective layer in a solvent may be applied on the photosensitive layer.
Alternatively, a film that can be used as a protective layer can be formed by lamination using a method such as lamination. The protective layer can also be provided by forming a protective layer by applying a coating solution obtained by dissolving a polymer compound in a solvent on another support, and transferring the obtained protective layer onto the photosensitive layer.

Examples of the protective layer include a water-soluble polymer soluble in water or a mixed solvent of water and a water-miscible organic solvent;
Specifically, a water-soluble organic polymer is preferable. Specific examples of such an organic polymer include hydrolyzed polyvinyl acetate and polyacrylic acid, and poly (meth) acrylic acid. Sodium, poly (meth) acrylic acid amide, poly (meth) acrylic acid derivatives such as partially saponified poly (meth) acrylate, or aqueous solutions of methylcellulose, hydroxycellulose, hydroxypropylcellulose, carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, etc. Functional cellulose derivatives, or polyvinyl alcohol and partial esters of polyvinyl alcohol containing unsubstituted vinyl alcohol units required for it to be solvent-soluble as described above, ethers and acetals, other starches,
Gum arabic, gelatin, methyl vinyl ether / maleic anhydride copolymer, saccharose octaacetate, ammonium alginate, sodium alginate, polyvinylamine polyethylene oxide, polystyrene sulfonic acid, and the like. These may be used alone or as a mixture. Of these compounds, polyvinyl alcohol is preferably used.

Additives such as surfactants can be added to the coating solution for the protective layer, if necessary, for the purpose of improving coatability.

When the protective layer is formed by coating, the protective layer preferably has a thickness of 0.2 to 10 μm.
More preferably, it is 1.0 to 2.0 μm.

The film used as the protective layer includes polypropylene, polyethylene, polybutadiene,
Examples thereof include eval, polyvinylpyrrolidone, vinylidene chloride, and polycarbonate, but are not limited thereto, and the film thickness is preferably about 2 to 100 μm.

In the present invention, the recording layer or the recording layer-side protective layer includes US Pat. No. 3,253,921 and US Pat.
Light absorbing materials and filter dyes as described in 274,782, 2,527,583 and 2,956,879 can be included. Also,
Dyes can be mordant, for example, as described in U.S. Pat. No. 3,282,699. The amount of the filter dye used is preferably such that the absorbance at the exposure wavelength is 0.1 to 3.0, particularly preferably 0.2 to 1.5.

In the present invention, the antihalation layer can be provided on the side farther from the light source than the recording layer. The antihalation layer preferably has a maximum absorption in a desired wavelength range of 0.3 or more and 2 or less, more preferably an absorption of an exposure wavelength of 0.5 or more and 2 or less,
Further, the absorption in the visible region after the treatment is preferably 0.001 or more and less than 0.5, and more preferably a layer having an optical density of 0.001 or more and less than 0.3.

When an antihalation dye is used in the present invention, the dye has a desired absorption in the wavelength range, has a sufficiently low absorption in the reading light after processing, and has a desirable absorbance spectrum shape of the antihalation layer. Any compound may be used, if possible. For example, the following are disclosed, but the present invention is not limited thereto. A single dye is disclosed in JP-A-59-564.
No. 58, JP-A-2-216140 and JP-A-7-13295
No. 7,114,432, US Pat. No. 5,380,63.
No. 5, JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9, 3-24539
JP-A Nos. 52-139136, 53-132334, and 5 include compounds described in page 14, lower left column to page 16, lower right column of the same.
Nos. 6-501480, 57-60060, 57-
No. 68831, No. 57-101835, No. 59-18
2436, JP-A-7-36145 and 7-1994
09, JP-B-48-33692, 50-1664
No. 8, JP-B-2-41734, U.S. Pat.
No. 8,497, No. 4,283,487, No. 4,5
48,896 and 5,187,049.

The hologram recording medium of the present invention may contain a matting agent on the recording layer side or on the opposite side, if necessary. The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, Belgian Patent No. 625,451 and British Patent No. 981,198.
Derivatives, polyvinyl alcohol described in JP-B-44-3643 and the like, Swiss Patent No. 33
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,16.
An organic matting agent such as polycarbonate described in No. 9 or the like can be used.

In the present invention, the matting agent can be contained in any constituent layer. However, in order to achieve the object of the present invention, the matting agent is preferably a constituent layer other than the recording layer, and more preferably from the support. The outermost layer to look at. In the present invention, the method for adding the matting agent may be a method in which the matting agent is dispersed in a coating solution in advance, or a method in which the matting agent is sprayed before the drying is completed after applying the coating solution. You may. When a plurality of types of matting agents are added, both methods may be used in combination.

In the present invention, a conductive compound such as a metal oxide or a conductive polymer can be contained in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the recording layer and the undercoat, and the like. In the present invention, US Pat. No. 5,244,773 column 1
The conductive compounds described in 4 to 20 are preferably used.

In the present invention, it is preferable to use a surfactant in order to apply the photosensitive composition for hologram recording to a support without unevenness. Examples of surfactants include:
Any materials such as nonionic, anionic, cationic, and fluorine can be used as appropriate. Specifically, Japanese Patent Application Laid-Open No. Sho 62
-170950, U.S. Pat. No. 5,380,644, and the like.
No. 44945, No. 63-188135, No. 60-24
Nos. 4945 and 63-306437, JP-A-7-23
No. 3268, No. 7-173225, etc., fluorine surfactants described in U.S. Pat. No. 3,885,965, etc., polysiloxane acid surfactants described in U.S. Pat.
Polyalkylene oxide and anionic surfactant described in No. 40 and the like. Among them, a (meth) acrylate polymer having a fluorinated alkyl group in a side chain, which is a fluorine-based surfactant, can be mentioned as a preferable example. In this case, preferably, the number average molecular weight is 30,000 in terms of standard polystyrene. 000 or less, more preferably in the range of 2,000 to 10,000.

Examples of the solvent used in the present invention include the solvents described in New Edition Solvent Pocket Book (Ohm Co., 1994) and the like, but the present invention is not limited thereto. Further, the boiling point of the solvent used in the present invention is preferably from 40 ° C to 180 ° C. Examples of the solvent of the present invention, hexane, cyclohexane, toluene, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate,
1,1,1-trichloroethane, tetrahydrofuran,
Triethylamine, thiophene, trifluoroethanol, perfluoropentane, xylene, n-butanol, phenol, methyl isobutyl ketone, cyclohexanone, butyl acetate, diethyl carbonate, chlorobenzene,
Examples include dibutyl ether, anisole, ethylene glycol diethyl ether, N, N-dimethylformamide, morpholine, propane sultone, perfluorotributylamine, water and the like.

The application of the photosensitive composition for hologram recording of the present invention includes a sequential multi-layer coating method in which coating and drying of each layer are repeated, roll coating methods such as reverse roll coating and gravure roll coating, blade coating, and wire coating. Bar coating, die coating and the like are used. In addition, before drying the already applied layer using a plurality of coaters, or applying the next layer and simultaneously drying a plurality of layers, using a slide coating, curtain coating or an extrusion die coater having a plurality of slits, A simultaneous multilayer coating method in which a plurality of coating liquids are laminated and applied is also used. As a drying method, a hot air drying method, an infrared drying method, or the like is used, and a hot air drying method is particularly preferable. The drying temperature at that time is 30 to 10
0 ° C. is preferred.

The hologram recording medium of the present invention may be cut into a desired size immediately after coating and drying, and then wrapped, or may be wound into a roll, temporarily stored before being cut and wrapped. The winding system is not particularly limited, but winding by tension control is generally used.

The hologram recording photosensitive composition of the present invention,
Alternatively, the dry thickness of the recording layer of the hologram recording medium is 10
It is preferably at least μm. For ultrahigh-density optical recording, the thickness is more preferably larger and more preferably 50 μm or more. Thereby, recording in the thickness direction becomes possible, and a volume hologram can be manufactured.

The photosensitive composition for hologram recording or the hologram recording medium of the present invention has interference fringes recorded therein by interference fringe exposure using a laser beam or light having excellent coherence by a normal holographic exposure apparatus. As the hologram, either a reflection hologram or a transmission hologram can be obtained. The reflection hologram can be recorded by, for example, the exposure apparatus shown in FIG. 1, and the transmission hologram can be recorded by, for example,
Recording can be performed by the exposure apparatus shown in FIG. When an object image is to be obtained, the object may be placed at the position of each mirror 10 in FIG. 1 or FIG. When recording digital information, the recording medium of the present invention is processed into a disc shape,
For example, exposure can be performed using an exposure apparatus described in JP-A-11-31936.

The wavelength of laser light or light having excellent coherence is preferably from 350 nm to 450 nm in view of the recording density and the resolution of the photosensitive composition. Further, for ultrahigh-density optical recording, the wavelength is short. Preferably, 350
More preferably, it is ４430 nm. As the laser light according to the present invention, a blue-violet semiconductor laser, a purple semiconductor laser, or the like is preferably an ultraviolet laser from the viewpoint of handling in a bright room. Specifically, NL manufactured by Nichia Corporation
HV-500C, NLHV3000M, NLHV300
0E.

Further, a semiconductor laser and a second harmonic generation element can be used. Further, it is desirable to perform chemical sensitization or color sensitization so that the sensitivity becomes the highest at the exposure wavelength. The exposure energy for recording is 0.
It may be a 0001μJ / cm ² ~300mJ / cm ^{2 but, 0.001μJ / cm 2 ~200mJ / cm} 2 is preferred. The exposure time is preferably as short as possible, and is preferably 10 seconds or less, and more preferably 5 seconds or less. In the case of the composition of the present invention, diffracted light due to interference fringes may be directly obtained by exposure for recording, or diffracted light due to interference fringes may be obtained by heat development processing after exposure for recording. . After recording and exposing the recording medium of the present invention, a method of uniformly irradiating a high-energy laser beam for heating, etc. may be used.

As the heat treatment method, the method of passing the recording medium of the present invention through a heat treatment apparatus for a necessary time, and when performing heat treatment, are preferably carried out at 60 to 200 ° C. for 5 seconds to 5 minutes. . The heating temperature is preferably 80 ° C. or higher, and the heating time is preferably 30 seconds or less, depending on the heating temperature. As a heating method, various conventionally known methods can be used. For example, a method using a panel heater or a ceramic heater, a method using a lamp, and the like can be given. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

The hologram obtained as described above has 3
The recorded information can be read by irradiating a laser beam having a wavelength of 50 nm to 450 nm or a reference beam having excellent coherence and generating reproduction light by diffraction by interference fringes in the hologram. When the reproduced light is a visible light image, the image can be directly seen by the naked eye. When the reproduced light is a digital pattern, the image can be read by a light receiving element such as a CCD and decoded by a CPU to obtain information. In order to suppress the deterioration of the recorded interference fringes,
The energy of the reproduction reference light is preferably smaller than the exposure energy used for recording. It is also preferable to use a laser having a wavelength lower in sensitivity than the wavelength used for recording as reference light.

[0067]

EXAMPLES Hereinafter, the effects of the present invention will be described in detail with reference to examples, but the embodiments of the present invention are not limited thereto.

[Preparation of PET-Drawn Substrate]
An undercoating coating solution a-1 shown below was applied as an undercoat layer on the coated surface of the photosensitive composition for hologram recording of a 100 μm-thick transparent PET film that had been axially stretched and heat-fixed so as to have a dry film thickness of 0.01 μm. After drying at 80 ° C. for 1 minute, undercoat layer A-1
And

<< Undercoating Coating Solution a-1 >> γ-methacryloxypropyltrimethoxysilane 0.1 part Methanol 10 parts MEK 90 parts Example 1 << Preparation of Coating Solution 1 for Photosensitive Composition for Hologram Recording >> Butyral resin; ESLEC BLS (manufactured by Sekisui Chemical Co., Ltd.) 66 parts Photopolymerization initiator having a maximum wavelength of 300 nm to 450 nm 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (Ciba Specialty Chemical) 2 parts (maximum absorption wavelength, 325 nm) ethyl p-dimethylaminobenzoate (EPA manufactured by Nippon Kayaku Co., Ltd.) 3 parts (maximum absorption wavelength, 307 nm) Compound having an ethylenically unsaturated bond capable of addition polymerization vinyl carbazole (Tokyo Kasei Co., Ltd.) 12 parts 2,2-bis (4- (methacryloxy-diethoxy) phenyl ) Propane (Shin-Nakamura Chemical Co., Ltd .: NK ester: BPE-200) 5 parts Bis type epoxy oligomer (Shin-Nakamura Chemical Co., Ltd .: NK oligo: EA-1020) 11 parts Phthalocyanine pigment (Mikuni Pigment Co., Ltd .: MHI454) 1 part Methyl ethyl ketone 60 parts Cyclohexanone 140 parts The above-mentioned photosensitive composition coating solution for hologram recording 1 was applied on an undercoat layer of the surface of the hologram recording photosensitive composition application surface with an applicator so as to have a dry film thickness of 100 μm, and was dried at 80 ° C. for 5 hours. After drying for a minute, the photosensitive composition for hologram recording 1 was obtained.

Further, an overcoat layer having the following composition was
The hologram recording medium 1 was coated on the photosensitive layer with an applicator so as to have a thickness of 2.0 μm, and was thermally dried at 80 ° C. for 3 minutes. Polyvinyl alcohol (GL-05, manufactured by Nippon Synthetic Chemical Co., Ltd.) 99 parts Surfactant (F-120: Dainippon Ink Co., Ltd.) 1 part Water 900 parts The hologram recording medium 1 is used for hologram photographing shown in FIG. Argon laser (51) as a light source by the two-beam optical system
(4.5 nm) to form a hologram image, and then heat-treated at 100 ° C. for 30 minutes.

The diffraction efficiency of the obtained hologram was measured with a spectrophotometer manufactured by JASCO Corporation. In this spectrophotometer, a photomultimeter having a slit having a width of 3 mm can be installed on a circumference having a radius of 20 cm around a sample. The measurement conditions were such that monochromatic light having a width of 0.3 mm was incident on the sample at an angle of 45 degrees, and diffracted light from the sample was detected. The ratio between the largest value other than the specular reflection light and the case where the incident light was directly received without placing the sample was defined as the diffraction efficiency.
The diffraction efficiency before heating was also measured in the same manner.

An optical system for manufacturing a volume phase type hologram shown in FIG.
After performing the volume phase hologram recording using light, the photosensitive layer was immersed in xylene for 1 minute to develop and swell the photosensitive layer, and then immersed in heptane for 30 seconds and shrunk to produce a volume phase hologram. Diffraction efficiency is measured by JASCO Corporation
It was measured with an ART25C type spectrophotometer manufactured by KK. In this apparatus, a photomultimeter having a slit having a width of 3 mm can be installed on a circumference having a radius of 20 cm around the sample. Monochromatic light having a width of 0.3 mm was incident on the sample at an angle of 45 degrees, and diffracted light from the sample was detected. The ratio between the largest value other than the specularly reflected light and the value when directly incident light was received without placing the sample was defined as the diffraction efficiency. At an exposure amount of ² mJ / cm ² , the playback wavelength is 480 nm, the diffraction efficiency is 70%,
A volume phase hologram having a transmittance of 92% at 0 nm was produced. This volume phase hologram was prepared at 25 ° C. for 6 hours.
No reduction in diffraction efficiency was observed even after being left for 180 days in an environment of 0% RH. FIG. 1 is a schematic view of a two-beam laser exposure apparatus for producing a volume phase hologram.
In the figure, 4 is a laser light source, 6 and 10 are mirrors, 8 is an objective lens, 9 is a condensing lens, 1 is a substrate (glass plate), 7
Indicates a beam splitter.

<< Evaluation of Sensitivity of Hologram Recording Medium 1 >> The hologram recording medium 1 produced as described above
At nm violet semiconductor laser (manufactured by Nichia Corporation) hologram manufacturing apparatus shown in FIG. 1 with a, placing a reflective liquid crystal display device at the position of 10, it displays the digital pattern, of 30 mJ / cm ² This digitally patterned hologram was exposed to energy and then heated at 90 ° C. for 10 minutes to obtain a hologram. The obtained hologram was visually observed using a laser beam of the same wavelength as reference light, and the generated reproduction light was visually observed. As a result, a very good hologram could be reproduced. The laser power of the reference light is
It was set to 1/10 of the laser power at the time of exposure.

Comparative Example 1 << Preparation of Coating Solution 2 for Photosensitive Composition for Hologram Recording >> Butyral resin; Esrec BLS (manufactured by Sekisui Chemical Co., Ltd.) 66 parts 3,3'-carbonylbis (diethylaminocoumarin) 1 part (maximum absorption) Wavelength 490 nm) 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone 4 parts (maximum absorption wavelength 340 nm) vinylcarbazole (manufactured by Tokyo Chemical Industry) 12 parts 2,2-bis (4- ( Methacryloxydiethoxy) phenyl) propane (NK ester: BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 parts Bis-type epoxy oligomer (NK oligo: EA-1020, manufactured by Shin-Nakamura Chemical Co., Ltd.) 11 parts Phthalocyanine pigment (Okuni Pigment Co., Ltd.) Manufactured by: MHI454) 1 part Methyl ethyl ketone 600 parts Cyclohexanone 1400 parts On the undercoat layer of the hologram recording photosensitive composition coating surface, the hologram recording photosensitive composition coating solution 2 was dried to a film thickness of 2
The composition was coated to a thickness of 0 μm and dried at 80 ° C. for 5 minutes to obtain a photosensitive composition 2 for hologram recording. Example 1
Similarly, it was used at a thickness of 200 μm, but the solubility of the initiator was poor and the above film thickness of 20 μm was the limit.

Further, an overcoat layer having the following composition was
The hologram recording medium 2 was coated on the photosensitive layer with an applicator so as to have a thickness of 2.0 μm, and was thermally dried at 80 ° C. for 3 minutes. Polyvinyl alcohol (GL-05, manufactured by Nippon Synthetic Chemical Co., Ltd.) 99 parts Surfactant (F-120: Dainippon Ink Co., Ltd.) 1 part Water 900 parts << Sensitivity evaluation of hologram recording medium 2 >> The hologram recording medium 2 produced by using the hologram production apparatus shown in FIG. 1 equipped with a 420 nm violet semiconductor laser (manufactured by Nichia Chemical Co., Ltd.) Display the pattern, 30m
The digitally patterned hologram was exposed with an energy of J / cm ² and then heated at 90 ° C. for 10 minutes to obtain a hologram. Using the obtained holograms as laser beams of the same wavelength as reference light, the generated reproduction light was visually observed.As a result, a satisfactory digital pattern could be obtained, but it could not be handled in a bright room. It took time to work in the darkroom.

Comparative Example 2 Photopolymer type Omnide manufactured by DuPont, USA
An x-705 holographic recording film was used.

<< Evaluation of Sensitivity of Omnidex-705 Holographic Recording Film >> The Omnidex-705 holographic recording film was placed on a hologram producing apparatus shown in FIG. A display device was arranged, a digital pattern was displayed on the display device, the digitally patterned hologram was exposed with energy of 30 mJ / cm ² , and the entire surface was heated with a high-output semiconductor laser having a wavelength of 780 nm to obtain a hologram. Using a 660 nm semiconductor laser as a reference beam, the obtained sample
A good digital pattern could be reproduced by reading on a CD. Although we were able to obtain a satisfactory digital pattern, we could not handle it in a bright room, so we had to work in a dark room.

[0078]

Industrial Applicability According to the present invention, a photosensitive composition for hologram recording which has good workability, can be dry-processed, and provides a hologram with high sensitivity and good handleability in a bright room, and a hologram recording medium using the same, A hologram recording method, a hologram forming method, a hologram, and a hologram reproducing method can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a reflection hologram recording method according to the present invention.

FIG. 2 is a schematic view showing an example of a transmission hologram recording method according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass plate 2 Recording layer 3 Polyethylene terephthalate film 4 Laser light source 5 Laser beam luminous flux 6,10 Mirror 7 Beam splitter 8 Objective lens 9 Condensing lens

Claims (11)

[Claims] 1. A hologram recording photosensitive composition used for recording interference fringes generated by interference of laser light or light having excellent coherence, wherein the photosensitive composition comprises an ultraviolet ray-curable resin, and A photosensitive composition for hologram recording, comprising: a photopolymerization initiator having at least a maximum wavelength of 300 nm to 450 nm; and a compound having an addition-polymerizable ethylenically unsaturated bond. 2. At least 300 nm to 4 nm on a support.
It has a recording layer made of a photopolymerization initiator having a maximum wavelength of 50 nm and an ultraviolet ray curable resin containing a compound having an ethylenically unsaturated bond capable of addition polymerization, and has excellent ultraviolet laser light or coherence. A hologram recording medium characterized in that it is used for recording interference fringes generated by interference of reflected light. 3. A hologram recording photosensitive composition containing a photopolymerization initiator having a maximum wavelength of at least 300 nm to 450 nm and a compound having an ethylenically unsaturated bond capable of addition polymerization, or the hologram on a support. A recording medium having a recording layer made of a photosensitive composition for recording may have 30
A hologram recording method, which comprises exposing an interference pattern generated by interference of ultraviolet laser light having a wavelength of 0 nm to 450 nm or light having excellent coherence. 4. A hologram recording photosensitive composition containing a photopolymerization initiator having a maximum wavelength of at least 300 nm to 450 nm and a compound having an ethylenically unsaturated bond capable of addition polymerization, or the hologram on a support. A recording medium having a recording layer composed of a photosensitive composition for recording is exposed to an interference fringe by a binary digital information light and a recording reference light generated from ultraviolet laser light or light having excellent coherence. Hologram recording method. 5. A hologram recording photosensitive composition containing a photopolymerization initiator having a maximum wavelength of at least 300 nm to 450 nm and a compound having an ethylenically unsaturated bond capable of addition polymerization, or the hologram on a support. A recording medium having a recording layer made of a photosensitive composition for recording may have 30
A method of forming a hologram, comprising: exposing an interference fringe generated by interference of ultraviolet laser light having a wavelength of 0 nm to 450 nm or light having excellent coherence, followed by heat treatment. 6. A hologram recording photosensitive composition comprising a photopolymerization initiator having a maximum wavelength of at least 300 nm to 450 nm and a compound having an ethylenically unsaturated bond capable of addition polymerization, or the hologram on a support. A recording medium having a recording layer made of a photosensitive composition for recording is exposed to an interference fringe formed by ultraviolet laser light or binarized digital information light generated from light having excellent coherence and a recording reference light, followed by heat treatment. A method for forming a hologram, comprising: 7. A hologram recording photosensitive composition comprising a photopolymerization initiator having a maximum wavelength of at least 300 nm to 450 nm and a compound having an ethylenically unsaturated bond capable of addition polymerization, or the hologram on a support. A recording medium having a recording layer made of a photosensitive composition for recording may have 30
A hologram characterized by being exposed and recorded with interference fringes generated by interference of ultraviolet laser light having a wavelength of 0 nm to 450 nm or light having excellent coherence. 8. A hologram recording photosensitive composition comprising a photopolymerization initiator having a maximum wavelength of at least 300 nm to 450 nm and a compound having an ethylenically unsaturated bond capable of addition polymerization, or the hologram on a support. A recording medium having a recording layer made of a photosensitive composition for recording was exposed to an interference fringe formed by a binary digital information light generated from ultraviolet laser light or light having excellent coherence and an interference fringe by a recording reference light, and was recorded. A hologram, characterized in that: 9. A hologram recording photosensitive composition containing a photopolymerization initiator having a maximum wavelength of at least 300 nm to 450 nm and an addition-polymerizable compound having an ethylenically unsaturated bond, or the hologram on a support. A recording medium having a recording layer made of a photosensitive composition for recording may have 30
A hologram formed by exposing an interference fringe generated by interference of an ultraviolet laser beam having a wavelength of 0 nm to 450 nm or light having excellent coherence and then performing a heat treatment. 10. A hologram recording photosensitive composition comprising a photopolymerization initiator having a maximum wavelength of at least 300 nm to 450 nm and a compound having an ethylenically unsaturated bond capable of addition polymerization, or the hologram on a support. After a recording medium having a recording layer made of a photosensitive composition for recording is exposed to an interference fringe caused by a binary digital information beam generated from an ultraviolet laser beam or light having excellent coherence and a recording reference beam, heat is applied. A hologram formed by being developed. 11. The hologram according to claim 7, which is irradiated with an ultraviolet laser beam having a wavelength of 300 nm to 450 nm or a reference beam having excellent coherence, and diffracted by interference fringes in the hologram. A method for reproducing a hologram, comprising generating reproduction light.