WO2003081344A1 - Photopolymer composition for holographic recording material, holographic recording medium, and process for producing the same - Google Patents

Abstract

A composition for holographic recording materials which comprises a binder polymer (A) soluble in organic solvents, a polymerizable compound (B) having an ethylenically unsaturated double bond, a photopolymerization initiator (C), and a photosensitizer dye (D). It is excellent in sensitivity, transparency, and diffraction efficiency, which are properties required for holography. The photopolymer composition for holography, which is for use in a volume-phase holographic recording material in which the intensity distribution concerning lightness/darkness of a light interference pattern is to be recorded based on changes in refractive index, comprises a binder polymer (A) soluble in organic solvents, a polymerizable compound (B) having an ethylenically unsaturated double bond, a photopolymerization initiator (C), a photosensitizer dye (D), and a supersensitizer (E).

Description

 Description Photopolymer composition for hologram recording material, hologram recording medium and method for producing the same

 The present invention relates to a novel photopolymer composition for a volume phase hologram recording material used for recording the intensity distribution of light and dark of a light interference pattern as a change in refractive index, and particularly the basic characteristics required for a hologram. The present invention relates to a photopolymer composition for a hologram recording material capable of producing a recording medium having excellent sensitivity, transparency, and diffraction efficiency, and further relates to a hologram recording medium obtained therefrom and a method for producing the same. Background art

 A hologram is a pattern in which the interference pattern of coherent light from a laser is recorded on a light-sensitive material or the like by means of refractive index modulation. Since it has multiple functions, it has an optical element, a stereoscopic image display, interference measurement, It is used for a wide variety of purposes such as processing.

 As typical conventional hologram recording material compositions, photosensitive materials such as silver halide emulsions and gelatin dichromate have been generally used. (For example, “Display-Holography-Handbook”, pp. 66-67, Dawn Stamp Library (1980), “Optical Engineering Handbook”, pp. 351-353, Asakura Shoten (1980) 6))).

 However, while dichromated gelatin has high diffraction efficiency and low noise characteristics, it has a short storage life and poor weather resistance of the manufactured hologram.Although silver halide emulsions have high sensitivity, There is a drawback that the material and the processing for producing the hologram are complicated.

In response to such problems, hologram recording materials that have the characteristics required of hologram recording materials, such as high weather resistance, high storage stability, high resolution, and high diffraction efficiency, without complicated processing, include, for example, Photopolymer resin composition for hologram recording consisting of cyclohexyl methacrylate, N-vinyl canolepazole and benzoin methyl ether, or butyl methacrylate and ethylene glycol dimethacrylate as photopolymerizable monomers 1-phenylnaphtha as an inert component that does not Photopolymerizable recording materials based on ren and photoinitiator (US Patent

3993485 and U.S. Pat. No. 3,658,526). These methods record a volume phase hologram by photopolymerizing a photopolymerizable monomer in a portion of the interference pattern where the amount of light is large, thereby causing a refractive index modulation in that portion.

 However, since these materials are inferior to silver halide emulsions in sensitivity characteristics, they are likely to be affected by vibration during recording and are not suitable for recording over a wide area. It was also disadvantageous in terms of hologram productivity, especially mass production. Therefore, a highly sensitive hologram recording material that does not require complicated processing, has excellent weather resistance and storage stability, and can perform recording with high resolution and high diffraction efficiency has been desired. An object of the present invention is to provide a photopolymer composition for a volume phase type photogram recording material used for recording a light-dark intensity distribution of an optical interference pattern as a change in a refractive index. An object of the present invention is to provide a photopolymer composition for a hologram recording material, which has high transparency in addition to excellent diffraction efficiency and high sensitivity. Disclosure of the invention

 As a result of repeated studies to solve the above problems, the present inventors have found the following novel photopolymer composition for hologram recording materials, and have completed the present invention. That is, the present invention relates to a photopolymer composition for a volume phase type photogram recording material used for recording a bright intensity distribution of an interference pattern obtained by interfering light as a change in refractive index. A binder polymer soluble in an organic solvent (A), a polymerizable compound having an ethylenically unsaturated double bond (B), a photopolymerization initiator (C), and a photosensitizing dye (D) And a supersensitizer (E), and optionally a plasticizer (F).

A preferred example of the photopolymer composition for a hologram recording material according to the present invention is that the refractive index of the polymerizable compound (B) is larger than that of the pinda-polymer (A) by 0.01 or more so that hologram recording is possible. , Or small. When a plasticizer (F.) is included, the refractive index of the polymerizable compound (B) is larger than the weighted average of the refractive index of the binder polymer (A) and that of the plasticizer (F) by 0.01 or more. Or small. The binder polymer (A) used in the present invention has good compatibility with the polymerizable compound (B). When a plasticizer (F) is added, the binder polymer (A) also has good compatibility with the plasticizer (F), and the organic polymer Any material that does not contain an insoluble portion in the medium and can be completely dissolved may be used. Typical examples include a homopolymer or copolymer obtained by polymerizing a monomer having an ethylenically unsaturated double bond, a condensation polymer of a diphenol compound and a dicarboxylic acid compound, and a carbonic ester group in the molecule. And a polymer having a —SO ₂ — group in the molecule, a cell opening derivative, and a combination of two or more of these.

 The binder polymer (A) used in the present invention may be a thermoplastic resin or a thermosetting resin, but the former is preferred.

The thermoplastic resin as the inner polymer (A) has good compatibility with the polymerizable compound (B) and the plasticizer (F) and can be completely dissolved in an organic solvent without containing an insoluble portion. I just need. Representative examples are a homopolymer or copolymer obtained by polymerizing a monomer having an ethylenically unsaturated double bond, a condensation polymer of a diphenol conjugate and a dicarbone conjugate, and carbonic acid in the molecule. It is selected from the group consisting of a polymer having an ester group, a polymer having one SO ₂ group in the molecule, a cellulose derivative, and a combination of two or more of these.

Specific examples of the thermoplastic resin include polyvinyl acetate, polyvinyl butyrate, polyvinyl formal, polyvinyl carbazole, polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, and polybutyl acrylate. , Polymethacrylonitrile, polyethyl methacrylate, polybutyl methacrylate, polyacrylonitrile, poly-1,2-dichloroethylene, ethylene-vinyl acetate copolymer, syndiotactic polymethyl methacrylate, poly (vinyl vinyl naphthalate), poly power One-port, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, polystyrene, poly-α-methylstyrene, poly-0-methylstyrene Ren, poly-ρ-methylstyrene, poly-p-phenylstyrene, poly-1,5-dichlorostyrene, poly-p-chlorostyrene, poly-2,5-dichlorostyrene, polyarylate, polysulfone, polyether Sulfone, styrene-acrylonitrile copolymer, styrene-divinylbenzene copolymer, styrene-butyl Even copolymer, styrene-maleic anhydride copolymer, ABS resin, polyethylene, polyvinyl chloride, polypropylene, polyethylene terephthalate, polyvinylpyrrolidone, polyvinylidene chloride, hydrogenated styrene-butadiene-styrene copolymer Coalesce, transparent polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, a copolymer of (meth) acrylic acid cyclic aliphatic ester and methyl (meth) acrylate, and the like.

 The above examples of the thermoplastic resin may be used alone or in combination of two or more. '

 In order to obtain good film forming properties and optical properties such as diffraction efficiency, polyvinyl acetate, polyvinyl butyrate, cellulose acetate butyrate, ethylene-vinyl acetate copolymer, polymethyl methacrylate, polystyrene, Marl or the like is preferably used.

 In order to obtain better optical properties such as heat resistance, film formability and diffraction efficiency, a copolymer of (meth) acrylic acid cyclic aliphatic ester and methyl (meth) acrylate is preferably used.

 Copolymerization of (meth) acrylic acid cyclic aliphatic ester and methyl (meth) acrylate constituting the copolymer of (meth) acrylic acid cyclic aliphatic ester and methyl (meth) acrylate used in the present invention The composition ratio is preferably from 5 to 95:95 to 5, more preferably from 10 to 90:90 to: L0 in terms of molar ratio (same ester: same acrylate).

The (meth) acrylic acid cycloaliphatic ester constituting the copolymer of (meth) acrylic acid cycloaliphatic ester and methyl (meth) acrylate is represented by the following general formula [I]. Good.

m [I]

[Wherein, R ₅ represents a hydrogen atom or a methyl group. And R ₂ are the same or different and represent a hydrogen atom or a lower alkyl group. k is an integer of 0 to 6, m is an integer of 2 to 6, and n is an integer of 1 to 5 where m> n. Alkylene chain (CH ₂ )

Any hydrogen atom in k, (CH ₂ ) _m and (CH ₂ ) _n may be substituted with a lower alkyl group. Two hydrogens bonded to different carbons in the alkylene chain (C) _m may be substituted at both ends of another alkylene chain having 1 to 8 carbon atoms to form another cycloalkane ring. Any hydrogen in this other cycloalkane ring may be further substituted with a lower alkyl group. One of the carbons in the alkylene chain (C¾) _n has a hydroxyl group, and (meth) acrylic acid is ester-bonded to this hydroxyl group. Indicates an ester bond thus formed. ]

 The cycloaliphatic portion of the (meth) acrylic acid cyclic aliphatic ester constituting the copolymer of (meth) acrylic acid cyclic aliphatic ester and methyl (meth) acrylate has a bornyl skeleton, isopolnyl skeleton, or norpolnyl skeleton May be

Examples of (meth) acrylic cycloaliphatic esters that constitute a copolymer of (meth) acrylic acid cycloaliphatic ester and methyl (meth) acrylate are porunyl (meth) acrylate, isobornyl (meth) acrylate, norpolnil (Meth) acrylate.

The (meth) acrylic acid cyclic aliphatic ester may be one kind or two or more kinds. In the latter case, the copolymer is a terpolymer or more of two or more kinds of (meth) acrylic acid cycloaliphatic esters and methyl (meth) acrylate. The copolymer of (meth) acrylic acid cyclic aliphatic ester and methyl (meth) acrylate may be used alone or in a combination of two or more. The polymerizable compound (B) having an ethylenically unsaturated double bond used in the present invention is preferably a radical polymerizable compound. The polymerizable compound (B) may be a monomer or an oligomer of a dimer or trimer thereof.

 The polymerizable compound (B) may be any compound having good compatibility with the binder polymer (A) and the plasticizer (F), and may be a (meth) acrylate monomer and its oligomer, a vinyl monomer and its oligomer, And may be selected from the group consisting of a combination of two or more of these.

Specific examples of (meth) acrylate monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, and n-stearyl. Methacrylate, methoxydiethylene glycol methacrylate, cycle hexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, phenoxyshetyl methacrylate, isopolnyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Propyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, dimethylaminoethyl methacrylate Acrylate, getylaminoethyl methacrylate, glycidyl methacrylate, tert-butyl methacrylate, isostearyl methacrylate, n-butoxy methacrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxy acrylate, Ethoxyethylene glycol acrylate, methoxytriethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-acrylate 3-phenoxypropyl acrylate, 2-acrylic oxicetyl succinic acid, 2-acrylic oxicetyl phthalic acid, isooctyl acrylate, Isomyristyl acrylate, isostearyl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene dalicol Dimethyl acrylate, nonaethylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerin dimethacrylate, 2-hydro Xyl-3-acryloyloxypropyl methacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,10-decanediol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, Triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate Relay, glycerin 2,3-hydroxy-1-acryloyloxypropyl acrylate, neopentyldiolicyl diacrylate, 1,3-butanediol diacrylate, 1,10-decanediol diacrylate, trimethylol propane trimester, Pentaerythritol trimethacrylate, trimethylolpropane triacrylate, Penyu erythritol triacrylate, Penyu erythritol tetramethacrylate, Pentaerythri! Examples include rutetraacrylate, ditrimethylolpropanetetramethacrylate, ditrimethylol-propanetetraacrylate, tetramethylolmethanetetraacrylate, dipentaerythritolhexamethacrylate, and dipentaerythritolhexaacrylate.

 The radical polymerizable compound may be a dimer or trimer oligomer of the above (meth) acrylate monomer.

 These may be used alone or in combination of two or more.

Specific examples of the vinyl monomer include vinyl acetate, 4-vinylaniline, 9-vinylanthracene, 4-vinylanisole, vinylbenzaldehyde, vinylbenzoate, vinylbenzyl chloride, 4-vinylbiphenyl, vinyl bromide, N-vinylcaprolactam, and vinyl chloride. Mouth formate, vinyl crotonate, vinyl cyclohexane, 4-bier-1-cyclohexene gepooxide, vinyl cyclopentane, vinyl decanoate, 4-vinyl-1,3-dioxolan 1-2-one, vinyl carbonate, vinyl trithiocarbo Nato, vinyl 2-ethylhexanoate, vinyl phenol, vinylidene ride, vinyl 1-vinyl imidazole, 2-vinyl naphthylene, vinyl neodecanoate, 5-vinyl-2-norpolene, 4- (vinyloxy) butyl benzoate, 2- (pinyloxy) ethanol, .4-vinyl phenyl Examples include acetate, vinyl pivalate, vinyl propionate, 2-vinylpyridine, 1-vinyl-12-pyrrolidinone, vinylsulfone, and vinyltrimethylsilane. The radical polymerizable compound may be a dimer or a trimer of the above-mentioned vinyl compound monomer.

 These may be used alone or in combination of two or more.

 The polymerizable compound (B) preferably has a refractive index of 1.55 or more.

 The polymerizable compound (B) may also have a bis (thiophenyl) sulfide skeleton, a halogenated phenyl skeleton, a phenolazole skeleton, or a fluorene skeleton. As a specific example of a monomer having a bis (thiophenyl) sulfide skeleton, Is bis (4-acryloylthiophenyl) sulfide, bis (4-acryloylthio-12-cyclohexene-1-yl) sulfide, bis (2-acryloylthioenyl) sulfide, bis (3-acrylyl) Ruthiopyridyl) sulfide, bis (5-acryloylthioviranyl) sulfide, bis (5- (meth) acryloylthio 1,4-dithianyl) sulfide, etc. Further, an oligomer of about a dimer or a trimer of the above compound may be used. These may be used alone or in combination of two or more.

Specific examples of the monomer having a halogenated phenyl skeleton include 2,4-dibromophenyl (meth) acrylate, 2,6-dibromophenyl (meth) acrylate, 4,6-dichloro-1-vinylbenzene, and 2,6-dibromophenyl (meth) acrylate. 6-dibromo-3-hydroxyphenyl acrylate, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6-trichloro-1-vinylbenzene, 2,4,6- Tribromophenoxyshetyl (meth) acrylate, 2,4-di-butadi 1,3-di (meth) acryloyloxybenzene, 2,4-di-dibutadi, 6-methyl-1,3,5-tri (meta) Acryloyloxybenzene; 2,4,6-trichloro-1,3-, 5-tri (meth) acryloyloxybenne. The oligomer may be a dimer or trimer of the above compound. These can be used alone You may use in combination of the above.

 Specific examples of the monomer having a carpazole skeleton include: 1-vinylcarbazole, 2-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 9-vinylcarbazole, 1- (meth) acryloyloxycarbazoline 2- (meth) acryloyloxycarbazole, 3- (meth) acryloyloxycarbazole, 4- (meth) acryloyloxycarbazole, 9- (meta) ) Acryloyloxycarbazole, 1,9-divinylcarbazole, 1,5,9-trivinylcarbazole, 2,7-di (meth) acryloyloxycarbazole, 2-methyl-1 , 9-divinylcarbazole, 1,9-di (meth) acryloyloxycarbazole and the like. In addition, oligomers such as dimers or trimers of the above compounds may be used. These may be used alone or in combination of two or more.

 The monomer having a fluorene skeleton may be represented by the following general formula [II].

General formula

[Wherein, R ₃ and R ₄ represent the same or different monovalent organic groups, and at least one of them has a (meth) acryloyl group or a (meth) acryloyloxy group at a terminal. Ιν ^ and M ₂ are the same or different from each other and are represented by one (OR ₆ ) _n — (R ₆ is a lower alkylene group which may have a hydroxyl group, n is 0, 1 or 2) ′ It means an organic group or a single bond. And X ₂ are the same or different from each other, and represent a hydrogen atom or a lower alkyl group. ]

Among R ₃ and R _4, the organic group having no (meth) acryloyl group has 1 carbon atom. It may be up to 3 lower alkyl groups.

In — (OR ₆ ) _n — of Mi and M ₂ , when n is 1 or 2, the number of carbon atoms of the lower alkylene group R ₆ is preferably 1-3, more preferably 1-2. Examples of R ₆ include oxymethylene, oxyethylene, oxypropylene, oxybutylene and the like, and examples of 1 (OR ₆ ) _n — include dioxymethylene and dioxethylene. When the lower alkylene group R ₆ has a hydroxyl group, the hydroxyl group may be located at any position of the alkylene group, and the alkylene having a hydroxyl group is, for example, (2-hydroxy) propylene. one

The organic group and X ₂ may be an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl and propyl.

 Specific examples of the monomer having a fluorene skeleton of the polymerizable compound (B) include 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene and 9,9-bis (4- (meta) Acryloyloxymethoxyphenyl) fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (meth) acryloyl 1-Methoxyphenyl] fluorene, 9,9-bis [4- (meth) acryloyloxymethoxy-3- 3-methylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyl 1-3-Methylphenyl] fluorene, 9,9_bis (4- (meth) acryloyloxy-3-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxymethoxy) 3—Ethylphenyl) fluorene, 9, 9— Bis [4- (2- (meth) acryloyloxyethoxy) -31-ethylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) 1-3- Ethylphenyl] fluorene, 9,9-bis [4- (3- (meth) acryloyloxy-2-hydroxy) propoxyphenyl] fluorene, 9,9-bis [4-1 (3- (meth) acryloyloxy — 2-hydroxy) propoxy-3-methylphenyl] fluorene, 9,9-bis {4- [2- (3-acryloyloxy-1-hydroxy-propoxy) —ethoxy] phenyl} fluorene, etc. Is mentioned. The oligomer may be a dimer or a trimer of the above-mentioned conjugate. These may be used alone or in combination of two or more.

In order to obtain good film forming properties and optical properties such as diffraction efficiency, an organic group R is required. and R ₄ is an acryloyl group and an acryloyloxy group, and n is 0, 1 or 2 and n is 1 or 2 in — (〇R ₆ ) n— of M ₂ Is preferably a lower alkylene group R having 1 to 2 carbon atoms, and and X ₂ is preferably a hydrogen atom.

 Among the compounds satisfying the above conditions, preferred compounds include the following:

 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene (manufactured by Nippon Steel Chemical Co., Ltd., “9,9-bis (4-hydroxyphenyl) fluorene glycidyl ether of fluorene Acrylic acid adduct, ASF400J), 9, 9-bis (4-methacryloyloxyphenyl) fluorene (manufactured by Nippon Steel Chemical Co., Ltd., "bisphenol full orange methyl acrylate"), 9, 9-bis (4-acrylic acid mouth) (Yloxyphenyl) fluorene, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Co., Ltd., “bisphenoxyethanol fluorene orange acrylate, BPEF-AJ), 9 , 9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Co., Ltd.) BPEF-MA "), 9,9-bis [4- [2- (3-acryloyloxy-2-hydroxy-propoxy) -ethoxy] phenyl] fluorene (Osaka Gas Co., Ltd., Bisphenoki Ciethanol full orange epoxy acrylate, BPEF-GAJ), 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxy-1-methylphenyl] fluorene (Osaka Gas Co., Ltd. One fluorene epoxy epoxy resin, BCF-GA ”).

 Further preferred compounds include the following:

 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene,

 9,9-bis (4-methacryloyloxyphenyl) fluorene,

 9, 9-bis (4-acryloyloxyphenyl) fluorene,

9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 9,9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluore N.

 The plasticizer (F) used as an optional component in the present invention is a compound that is non-reactive with the binder polymer (A) and the polymerizable compound (B). Examples of the plasticizer (F) include phthalic esters represented by dimethyl phthalate, getyl phthalate and octyl phthalate; dimethyl adipate, dibutyl adipate, dimethyl sebacate, getyl sebacate, dibutyl sebacate, getyl succinate Aliphatic dibasic acid esters such as triacetate; orthophosphates such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate; glyceryl triacetate and 2-ethylhexyl acetate Inactive compounds such as acetic acid esters represented by phosphites represented by triphenyl phosphite and dibutyl hydrogen phosphite. Further, an alkylene glycol alkyl ether represented by the following general formula [III] can also be used.

(Wherein, and R ₁₂ are the same or different and represent an alkyl group having 1 to 5 carbon atoms, a hydroxyl group or an acetyl group, and n represents an integer of 1 to 5.) Representative alkylene glycol alkyl ether Typical examples are ethylene dimethyl dimethyl ether, ethylene glycol dimethyl ether, ethylene glycol dipropyl ether, ethylene diol glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and diethylene diol. Recol dimethyl ether, diethylene diol alcohol, diethylene glycol dipropyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether , Triethylene glycol one dimethyl ether, triethylene glycol Jefferies chill E one ether, triethylene glycol dipropyl ether, collected by Li ethylene glycol one monomethyl ether, triethylene glycol monomethyl E Chill Ether, triethylene glycol monopropyl ether, cellosolve acetate, ethylene glycol diacetyl ether, ethylene glycol monoacetyl ether, diethylene glycol diacetyl ether, diethylene glycol monoacetyl ether, triethylene glycol diacetyl Examples thereof include ether and triethylene diol monoacetyl ether.

 Further, polyethylene glycol or silicone oil having a weight average molecular weight of 1000 or less can also be used.

 As the plasticizer (F), the above examples may be used alone or in combination of two or more. The amount of the plasticizer (F) added is preferably about 0.1 to 50 parts by weight in 100 parts by weight of the total of the binder polymer (A), the polymerizable compound (B) and the plasticizer (F). It is. In a preferred embodiment of the present invention, the binder polymer (A) soluble in an organic solvent is a thermoplastic resin, and the polymerizable compound (B) having an ethylenically unsaturated double bond is a radical polymerizable compound; It also contains a plasticizer (F).

 Examples of the photopolymerization initiator (C) used in the present invention include carbonyl compounds, organotin compounds, alkylaryl boron salts, ionic salts, iron-allene complexes, trihalogenomethyl-substituted triazine compounds, and organic peroxides. Oxides, bisimidazole derivatives, titanocene compounds and the like are preferably used.

 Examples of the carbonyl compound include benzyl, benzoinethyl ether, benzophenone, and ethoxyacetophenone.

 Examples of the organotin compound include tributylbenzyltin.

 Examples of the alkylaryl boron salt include tetrabutylammonium triphenylbutylporate and triphenyl-n-butylporate.

 Diphenyl salt may be mentioned as an example of the salt.

 7-5-Cyclopentageneru as iron arene complex? 7 6—Cumenyl monoiron (1 +) — Hexafluorophosphate (11) can be exemplified.

 Examples of trioctogenomethyl-substituted triazine compounds include tris (trimethyl) methyl triazine.

3,3 ', 4,4'-tetra (tert-butylperoxyl-propionyl) benzophenone, di-tert-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylpara Oxy) hexane, tert-butyl Poxy benzoate can be exemplified.

 Examples of bisimidazole derivatives include 2,2,1-bis (0-chlorophenyl) 1.4,4 ', 5,5,1-tetraphenyl-1,1, -biimidazole and bis (2,4,5-triphenyl) imidazolyl. .

 As a titanocene compound, bis (7-5-2,4-cyclopentene-1-1-fur) -bis (2,6-difluoro-3-(1H-pyrrol-1--1-yl) -phenyl) titanium is Can be illustrated.

 These may be used alone or in combination of two or more.

 The photosensitizing dye (D) used in the present invention includes lasers used for recording holograms: He-Ne (wavelength 633 nm), Ar (wavelengths 515, 488 nm). ), YAG (wavelength 532 nm), He-Cd (wavelength 442 nm), etc., which absorbs laser light are good, and show spectral sensitization to photopolymerization initiator (C) Those are preferred. As such a photosensitizing dye, for example, mihirageton, acridine yellow, merocyanine, methylene blue, camphorquinone, eosin, weakened lipoxylated rose bengal and the like are preferably used. The photosensitizing dye may be any as long as it absorbs light in the visible region.In addition to the above, for example, a cyanine derivative, a melocyanin derivative, a phthalocyanine derivative, a xanthene derivative, a thioxanthene derivative, an acridine derivative, a porphyrin derivative, Coumarin derivatives, ketocoumarin derivatives, quinolone derivatives, stilbene derivatives, oxazine derivatives, thiazine dyes, etc. can also be used, and furthermore, “Dye Handbook” (edited by Shin Okawara et al., Kodansha, 1986,) Mitsumitsu described in “Dye Chemistry” (Nobuo Ogawara et al., Eds., 1983) and “Special Functional Materials” (Chadasaburo Ikemori et al., Eds., 1986) Sensitizing dyes can also be used. These may be used alone or in combination of two or more.

 The following can be exemplified as the coumarin derivative;

 3-(2-benzothiazolyl) 1-7-Jethylamino) coumarin,

3- (2-benzothiazolyl) -7-dibutylamino coumarin,

 3- (2-benzothiazolyl) -7-dioctylamino) coumarin,

 3-(2-benzimidazolyl)-7-getylamino) coumarin.

Examples of ketocoumarin derivatives include the following: 3, 3'-Carponylbis (7-Jetylaminocoumarin),

3, 3'-Carbonylbis-7-getylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin,

 3,3'-carbonylbis (7-dibutylaminocoumarin).

 Examples of the merocyanine derivative include the following:

 3—Ethyl-5 — [(3-Ethyl-2 (3H) —benzothiazolylidene) ethylidene] —2-Toxo—4—oxazolidinone,

 1,3-Jetyl-5- [2- (3-Ethyl-2 (3H) —benzothiazolylidene) ethylidene] —2-thiothiodantoin,

 3-Ethyl-5- [2- (3-Ethyl-2 (3H) -benzothiazolylidene) e-Tilidene] —2-Toki, / —4-Thiazolidone,

 3—Ethyl—5—2— (3-Ethyl—2 (3H) 1-benzothiazolylidene) ethylidene] 1—2-Toxo—4—oxazolidinone,

 5- [(1,3-dihydro-1,3,3-trimethyl-2H-indole-1-ylidene) ethylidene]-3-ethyl-2-thioxo-4-oxazolidinone Organic peroxy acid-light Specific examples of the combination of sensitizing dyes include 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, and NKX 653, a photosensitizing dye manufactured by Nippon Kogaku Dyestuff Research Institute. NKX3883, NKX 1880, NKX 1595, NKX 1695, M79, NK85, NK 1046, NK4 256, NK1886, NK1473, NK1474, NK4795, NK42 76, NK4278, NK91, NK1046, NK1237, NK1420, NK590, etc. Are preferred.

 Specific examples of the combination of the carbonyl compound and the photosensitizing dye include benzyl monomethyl ketone and benzyl acridine yellow. As a photosensitizing dye to be combined with the amine compound, weakened lipoxylated rose bengal is preferable. As the photosensitizing dye to be used in combination with the porate compound, a cyanine dye such as cyanines, isocyanines, and pseudocynins is preferable.

As a bisimidazole derivative, B-CIM manufactured by Hodogaya Chemical Co., Ltd., and a chain transfer agent such as 2-mercaptobenzoxazole and 21-mercaptobenzthiazole, and the above photosensitizer Combinations with sensitizing dyes can also be suitably used.

 The addition amount of the photopolymerization initiator (C) in the composition of the present invention is usually 1 to 20% by weight, preferably 100% by weight of the total of the binder polymer (A) and the polymerizable compound (B). Is about 0.3 to 15% by weight. When the composition of the present invention contains a plasticizer (F), the photopolymerization initiator (B) is added to a total of 100 parts by weight of the binder polymer (A), the polymerizable compound (B) and the plasticizer (F). The addition amount of C) is usually about 0.1 to 15% by weight, preferably about 0.3 to 10% by weight.

 The amount of the photosensitizing dye (D) ′ added to the composition of the present invention is usually 0.01% based on 100 parts by weight of the total of the binder polymer (A) and the polymerizable compound (B). It is about 2% by weight, preferably about 0.03 to 0.15% by weight. When the composition of the present invention contains the plasticizer (F), the photosensitizing dye (100 parts by weight in total) of the binder polymer (A), the polymerizable compound (B) and the plasticizer (F) is used. The amount of D) added is usually about 0.01 to 1% by weight, preferably about 0.03 to 0.8% by weight.

 It is preferable that the supersensitizer (E) used in the present invention does not absorb the light of the wavelength oscillated by the laser used for hologram recording, and when the photosensitizing dye (D) is not added, Preference is given to those which do not themselves exhibit a spectral sensitizing effect on the photopolymerization initiator (C). Examples of such supersensitizers include basestyryl derivatives, amine compounds and the like. These may be used alone or in combination of two or more. Examples of the base styryl derivative include the following:

2-[p- (dimethylamino) styryl] benzothiazol,

2— [p— (dimethylamino) styryl] benzoxazole,

2- [p- (dimethylamino) styryl] -3,3-dimethyl-3H-indole, 2- [p- (dimethylamino) styryl] naphtho [1,2-d] thiazole, 2- [p- (dimethylamino) styryl ] Quinoline,

4— [p— (dimethylamino) styryl] quinoline,

 2-[(m-hydroxy-p-methoxy) styryl] benzothiazol.

 Examples of the amine compound include the following:

Triethylamine, pyridine, 2-aminopyridine, 1-aminopiperidine, N-aminophthalimide, 2-aminomethylviridine, 5-amino-2-methoxypyridine. Specific examples of the combination of the photosensitizing dye and the supersensitizer include cyanine dyes, styryl dyes, merocyanine dyes, styryl dyes, coumarin dyes, base styryl dyes, and ketocoumarin dyes. — Amine compounds and the like.

 In the composition of the present invention, the supersensitizer (E) is usually added in an amount of 0.01 to 1.0 with respect to 100 parts by weight of the total of the binder polymer (A) and the polymerizable compound (B). It is about 3% by weight, preferably about 0.02 to 1% by weight. When the composition of the present invention contains a plasticizer (F), the photosensitizing dye is used in a total of 100 parts by weight of the binder polymer (A), the polymerizable compound (B) and the plasticizer (F). The amount of (D) added is usually about 0.01 to 1% by weight, preferably about 0.02 to 0.7% by weight.

 The molar ratio of the photosensitizing dye (D) and the supersensitizer (E) in the hologram recording material composition according to the present invention is (E): (F) = 10 to 90: 90 to 10. When, the sensitivity is excellent. The molar ratio is preferably (E) :( F) = 30 to 70:70 to 30 When an amine compound is used as the supersensitizer (E), the photosensitizing dye (D A) styryl derivative can be used.

 The hologram recording material composition according to the present invention can contain additives such as a thickener, a thermal polymerization inhibitor, a chain transfer agent, etc., and a solvent, if necessary.

As a thickener, inorganic fine particles, for example, Daiso Ichi Gel SP Series manufactured by Daiso Co., Ltd., Silica and Fuji Silica Gel manufactured by Fuji Silica Chemical Co., Ltd., and Shionogi Pharmaceutical Co., Ltd. You can use "Raiichi Plex", "Aerosil" manufactured by Nippon Aerosil, "Leo mouth seal", "Tokuseal", "Fine seal" manufactured by Tokuyama. Alternatively, organic fine particles, for example, diaryl phthalate-based polymers which can be prepared by the methods described in JP-A-10-72510 and JP-A-10-310684, or "New material series" Ultrafine particles "PB, 200 Series" manufactured by Kao Corporation, "Bellpar Series" manufactured by Kanebo Co., Ltd. You can use "Tech Polymer Series" manufactured by Seishin Co., Ltd., "Micropal Series" manufactured by Sekisui Fine Chemical Co., Ltd., "MR Series" and "MP Series" manufactured by Soken Chemical Company. The particle size of these fine particles may be smaller than the thickness of the hologram, and is usually in the range of 0.1 to 20 m. Is preferred. The amount of the thickener is preferably about 0.5 to 30 parts by weight based on 100 parts by weight of the total of the thermoplastic polymer (A), the polymerizable compound (B) and the plasticizer (F). It is.

 Examples of the thermal polymerization inhibitor include those having a function of eliminating generated radicals, such as hydroquinone, p-methoxyphenol, tert-butylcatechol, naphthylamine, diphenylpicrylhydrazine, diphenylamine, and the like. . Examples of chain transfer agents include α-methylstyrene dimer, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, tert-butyl alcohol, n-butanol, isobutanol, isopropylbenzene, ethylbenzene, chloroform, methyle Tilketone, propylene, vinyl chloride, and the like. Organic solvents are effective for improving viscosity and compatibility, as well as improving film forming properties.Examples include acetone, xylene, toluene, methyl ethyl ketone, tetrahydrofuran, benzene, methylene chloride, dichloromethane, and chloroform. Mouth form, methanol, etc. are often used. However, water cannot be used because it hinders viscosity adjustment, compatibility adjustment, film forming properties, and the like. Water cannot be used as a solvent, even in emulsion form.

 The amount of the solvent used is about 1 to 150 parts by weight based on 100 parts by weight of the total of the binder polymer (A) and the polymerizable compound (B). When the composition of the present invention contains a plasticizer (F), the amount of the solvent used is 100 parts by weight in total of the binder polymer (A), the polymerizable compound (B) and the plasticizer (F). Usually, it is about 0.5 to 100 parts by weight.

 To prepare the hologram recording material composition, for example, a binder polymer (A), a polymerizable compound CB), a photopolymerization initiator (C), a photosensitizing dye (D) and a supersensitizer (E), If necessary, the above-mentioned optional components including the plasticizer (F) are placed in an organic solvent-resistant container such as a glass beaker, and the whole is stirred. In this case, in order to promote the dissolution of the solid component, the composition may be heated to, for example, about 40 to 90 as long as the composition is not denatured.

In order to prepare a holo-hola recording medium using the photopolymer composition for a hologram recording material according to the present invention, the recording material composition is applied to one surface of a substrate, and the resulting coating film, that is, a recording layer and a substrate is formed. A recording medium having a layer structure is obtained. Also, if necessary Then, a three-layer structure is obtained by covering the recording layer on the substrate with a film-like, sheet-like, or plate-like protective material. It is preferable to use an organic solvent in the step of preparing the composition. In this case, the binder polymer (A), polymerizable compound (B), photopolymerization initiator (C), photosensitizing dye (D), supersensitizer (E), and optionally plasticizer ( F) is dissolved in a solvent, and the obtained solution is applied on a substrate. Thereafter, the solvent is volatilized to form a recording layer. When the recording layer is covered with a protective material, the solvent is preferably removed by air drying or evaporation under reduced pressure before coating the protective material.

The substrate is made of an optically transparent material, for example, a glass plate, a plastic plate such as a polyethylene terephthalate plate, a polymethyl methacrylate plate, a polymethyl methacrylate plate, or a film. The thickness of the substrate is preferably between 0.02 and 10 mm. The substrate does not need to be flat, but may be bent, curved, or have an uneven structure on the surface. The protective material is also made of an optically transparent material like the substrate. The thickness of the protective material is preferably from 0.02 to: L 0 mm. Coating methods include gravure coating, roll coating, bar coating, and spin coating. It is preferable to apply the recording layer so that the thickness of the recording layer after removing the solvent is preferably 1 to 100 m. To record a hologram on the hologram recording medium, a normal recording method can be adopted. That is, the laser beam is split into two light beams by a beam splitter or the like, and the two are combined again by using a mirror or the like to obtain an interference fringe. Alternatively, interference fringes are obtained by reflecting one laser beam with a mirror. The recording medium is placed at a position where this interference fringe can be captured. In this state, when laser light irradiation is normally performed for several seconds to several minutes, interference fringes serving as holograms are recorded on the recording medium. Amount of use are les one The first light is expressed by the product of the light intensity and the irradiation time is preferably 1~1 0, 0 0 O m J / cm 2 approximately. If the amount of light is less than this range, it is difficult to record, and if it exceeds this range, the diffraction efficiency of the hologram tends to decrease.

After the hologram is formed, post-processing such as development and fixing is not indispensable.However, in order to stabilize the formed image, the entire surface is irradiated with light or heated to remove the remaining unreacted monomer. It may be polymerized. The recording material composition of the present invention comprises a binder polymer (A) and a polymerizable compound before exposure. (B), photopolymerization initiator (C), photosensitizing dye (D), supersensitizer (E) and optionally plasticizer) are compatible with each other. The photopolymerization initiator (C) generates a polymerization active species by the spectral sensitization effect of (D) and the supersensitizer (E), and the polymerizable compound (B) is preferentially photopolymerized to polymerize. Eventually, it becomes a hologram recording layer.

 That is, when a two-layer structure obtained by applying the recording material composition according to the present invention on a substrate or a three-layer structure obtained by covering a protective material on the recording layer is exposed to an interference pattern, Photopolymerization initiator (C) generates polymerization active species by spectral sensitization by photosensitizing dye (D) and supersensitizer (E) in a large part, and polymerizable compound rich in photopolymerization reactivity (B) starts photopolymerization, and that portion undergoes volume shrinkage. As a result, the unpolymerized material flows from the portion having a small amount of light into the recess formed by this, and the binder polymer (A) is phase-separated from the polymerizable compound (B) and is removed to the portion having a small amount of light. The photopolymerization of the polymerizable compound (B) that has diffused and moved to the portion having a large amount of light proceeds further. As a result, a structure in which the polymer of the polymerizable compound (B) accumulates in the portion where the light amount is large, and conversely, a structure in which the binder-polymer (A) is accumulated in the portion where the light amount is small.

 Here, when the optional plasticizer (F) is present in the system, the plasticizer (F) is a component for adjusting the viscosity and compatibility of the system, and the binder polymer (A) and the polymerizable compound ( It functions as a component to promote the separation of B). When the binder polymer (A) is a thermoplastic resin, the plasticizer (F) uniformly present in the system at the beginning of the exposure is eventually removed to the portion where the amount of light is small, that is, to the thermoplastic resin side. . In this way, an interference pattern is formed as a hologram based on the composition distribution according to the amount of light, that is, the interference pattern based on the difference in refractive index between the portion containing a large amount of the thermoplastic resin and the plasticizer (F) and the portion containing a large amount of the polymerizable compound (B). You.

 Here, the photosensitizing dye (D) is a component for absorbing and spectrally sensitizing the laser beam, and functions as a catalyst for promoting radical generation of the photopolymerization initiator (C) by electron transfer or energy transfer. I do.

 The supersensitizer (E) is a component for increasing the efficiency of spectral sensitization by the photosensitizing dye (D).

To record an object to be recorded as a hologram on the hologram recording medium according to the present invention The normal recording method can be adopted. That is, light having a wavelength in the range of 200 to 80 O nm is divided into two light beams, one of which is referred to as a reference light and the other is irradiated with an object to be recorded. And the transmitted light (object light) from the master hologram obtained by irradiating the reflected light (object light) and (or the other light beam on the volume phase master hologram in which the information of the object is recorded in advance) The hologram recording material medium is arranged at a position where it is possible to catch the interference fringes obtained by causing the light to enter the recording object from the same plane or from the front and back surfaces to cause interference, and place the hologram recording material medium on the same medium. Record the object.

 More specifically, the laser beam is split into two light beams using a beam splitter or the like, and the two are combined again using a mirror or the like to obtain interference fringes (two-beam exposure method). Alternatively, one laser beam is reflected by a mirror, and both the incident light and the reflected light are recombined to obtain interference fringes (one-beam exposure method). When obtaining an interference pattern, a hologram created separately is placed on the optical path as a mass hologram.

The interference fringes may be obtained by one light beam and / or two light beam exposure methods. The recording medium is placed at a position where the light and dark intensity distribution of the interference pattern thus formed can be captured. In this state, when laser light irradiation is performed for several seconds to several minutes, interference fringes that become holo-lam are recorded on the recording medium. The amount of laser light used is expressed as a product of light intensity and irradiation time, and is preferably about 10,000 to 10,000 mJZ cm ² . If the amount of light is less than this range, recording is difficult, and if it exceeds this range, the diffraction efficiency of the hologram tends to decrease. The light source used in the present invention is a photopolymerization initiator (C) or a photopolymerization initiator (0 and a photosensitizing dye (D) or a photopolymerization initiator (C) and a photosensitizing dye (D). Any material may be used as long as the photopolymerization initiation system composed of the combination of the color sensitizers (E) is irradiated with light emitted from the light source and causes electron transfer to induce polymerization of the polymerizable compound (B). Examples of typical light sources include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, metal halide lamps, etc. These can be used when copying master hologram information to the recording medium. It can also be used as a light source for fixing a hologram recorded with interference fringes. A laser can be used as a preferred light source.The laser has a single wavelength and has coherence, so it can be used as a hologram. Record Oite a preferred light source. More preferred light source with excellent one Reference property Kohi, For example, an optical element such as an etalon is mounted on the laser, and the frequency of the single wavelength is changed to a single frequency. Typical lasers have an oscillation wavelength of 200 to 80 Onm, specifically Kr (wavelength 647 nm), He-Ne (wavelength 633 nm), Ar (wavelength 515, 488 ni), YAG (wavelength 532 nm), He-Cd (wavelength 442 nm) and the like. These light sources may be used alone or in combination of two or more. Further, the light source may be a continuous light, or may pulsate at a certain or arbitrary interval. The light obtained from the light source may be applied to the recording material before and after the recording in addition to when the recording is performed.

 After the hologram is formed, post-processing such as development and fixing is not essential. However, in order to stabilize the formed image, light irradiation or heat treatment is performed on the entire surface to remove the remaining unreacted monomer. It may be polymerized. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a schematic diagram showing an example of a transmission hologram.

 FIG. 2 is a schematic diagram showing an example of a reflection hologram. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be specifically described with reference to some examples of the present invention. However, these examples do not limit the present invention.

Example 1

1) As a thermoplastic resin, 2.5 g of vinyl acetate polymer (“Vinyl acetate polymer”, manufactured by Kishida Chemical Co., Ltd., polymerization degree 500, polymer refractive index: 1.43) was used as a viscous liquid at room temperature and pressure. As a polymerizable compound (B), bisphenoxyethanol full orange acrylate (manufactured by Osaka Gas Co., Ltd., “BPEFA”, refractive index of a single substance: 1.61) 2.2 g, plasticizer (F) Cyl acetate (manufactured by Wako Pure Chemical Industries, "ADE", refractive index: 1.42) 1.0 g, 3,3 ', 4,4'-tetra (tert-butylpropylcarbonyl) as initiator (C) 3.75 g of 3,3,4,4'-tetra (tert-butylperoxyl-propionyl) benzophenone solid obtained by distilling off the toluene solvent of benzophenone ("BTT B-25J" manufactured by NOF CORPORATION) under reduced pressure, photosensitized Cyanine dye (NK1538, manufactured by Nippon Kogaku Dyestuffs Co.) 0.008 g, strong color A base styryl dye having an equimolar number as the photosensitizing dye as a sensitizer

NK1819) and 0035 g of acetone as a solvent were mixed at room temperature to prepare a photopolymer composition for a hologram recording material.

 2) This composition is applied to one side of a 6 Omm x 6 Omm glass substrate by spin coating so that the thickness after drying is 10 to 15 m, and the solvent is removed from the coating layer by applying heat treatment. Then, a recording medium having a two-layer structure including a substrate and a recording layer was prepared.

 3) A 50-inch thick PET film was placed over the recording layer of this recording medium to prepare a hologram recording photosensitive plate having a three-layer structure.

 4) Next, the 515-nm Ar ion laser was split by a beam splitter, the angles of which were changed by a mirror, and the two were combined again to cause interference to obtain interference fringes. The photosensitive plate was set at a position where the interference fringes could be captured.

 5) Figures 1 and 2 show examples of transmission holograms and reflection holograms, respectively. In the figure, (Α) is a laser generator, (BS) is a beam splitter, (Μ) is a mirror, (S) is a photosensitive plate, (B1) is object light, and (Β2) is reference light.

 6) The photosensitive plate was exposed in this state, and interference fringes serving as holograms were recorded on the photosensitive plate.

Exposure of transmission hologram and the reflection hologram, one strongly light density at the photosensitive plate as 0. 5 mW / cm ^2, 40 seconds 5 seconds, 2. 5m J Zcm ² from 2 Om J as exposure Zcm ² went.

Example 2

In the composition of Example 1, NK-85 was used as the photosensitizing dye (D) in place of M-1538 at the ratio shown in Table 1. The exposure of the transmission hologram and the reflection-type Horodara beam has one light intensity on the photosensitive plate as 0. 5mWZcm ^2, 5 seconds or et 80 seconds, from 2. 5m J / cm ² as an exposure amount 4 OmJZcm ² went. Otherwise, the same operation as in Example 1 was performed.

Example 3

In the composition of Example 1, the initiator (C) was replaced by 2,2'-bis (0-chloro), instead of 3,3,4,4'-tetra (tert-butylvinyloxyl-propionyl) benzophenone. Phenyl) one, four, four, five, five, one tetraphenyl -Biimidazole (Hodogaya Logistics, B-CIM) was used in combination with 2-mercaptobenzothiazole (Tokyo Kasei Kogyo, 2-mercaptobenzothiazool) in the proportions shown in Table 1. Further, the transmission type exposure hologram and the reflection-type hologram is one of the light intensity on the photosensitive plate as 0. 5mWZcm ^2, 80 seconds 5 seconds, as the exposure amount 2. 5mJZcm ² from 4 OmJ / cm ² went. Otherwise, the same operation as in Example 1 was performed.

 Example 4

In the composition of Example 3, 2-mercaptobenzozoazole (manufactured by Kanto Chemical Co., Ltd., 2-benzoxazothiol) was used instead of 2-mercaptobenzozothiazole (manufactured by Tokyo Chemical Industry Co., Ltd., 2-mercaptobenzothiazool). Was used in the proportions shown in Table 1. Moreover, the exposure of the transmission hologram and the reflection hologram, one of the light intensity on the photosensitive plate as 0. 5 mW / cm ^2, 80 seconds 5 seconds, from 2. 5m J / cm ² as an exposure amount 4 Om J / cm ^{2 was} performed. Otherwise, the operation was the same as in Example 1.

 Example 5

In the composition of Example 1, instead of bisphenoxyethanol fluorenediacrylate and rate (“BPEFA” manufactured by Osaka Gas Co., Ltd.), an acrylic acid adduct of glycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene ( “ASF-400” manufactured by Nippon Steel Chemical Co., Ltd.) was used in the proportions shown in Table 1. Furthermore, transmission type Horodara exposure beam and the reflection hologram, one of the light intensity on the photosensitive plate as 0. 5mW / cm ^2, 80 seconds 5 seconds, 40 m from the 2. 5mJZcm ² as the exposure amount JZ cm 2 I went. Otherwise, the same operation as in Example 1 was performed.

 Example 6

In the composition of Example 3, bisphenoloxyethanol full orange acrylate (manufactured by Osaka Gas Co., Ltd., "BPEFA") was replaced by pentaerythritol triacrylate (Aldrich, pentaerythritol triacrylate) in the proportions shown in Table 1. Used in. Further, the transmission type exposure hologram and the reflection hologram, one of the light intensity on the photosensitive plate as 0. 5mWZcm ^2, 80 seconds 5 seconds, as the exposure amount 2. 5 m JZ cm ² from 40 m J / cm2. Otherwise, the same operation as in Example 1 was performed. Comparative Example 1

 A recording photopolymer composition was prepared in which the supersensitizer "NK1819" was removed from the composition of Example 1, that is, no NK1819 was added. Otherwise, the same operation as in Example 1 was performed.

Comparative Example 2

 A recording photopolymer composition was prepared by removing the supersensitizer "NK1819" from the composition of Example 2, that is, adding no NK1819. Otherwise, the same operation as in Example 2 was performed. '

Comparative Example 3

 A recording photopolymer composition was prepared by removing the supersensitizer "NK1819" from the composition of Example 3, that is, adding no NK1819. Otherwise, the same operation as in Example 3 was performed.

Comparative Example 4

 A recording photopolymer composition was prepared by removing the supersensitizer "NK1819" from the composition of Example 4, that is, adding no NK1819. Otherwise, the same operation as in Example 4 was performed.

 Comparative Example 5

 A recording photopolymer composition was prepared in which the supersensitizer "NK1819" was removed from the composition of Example 5, that is, no NK1819 was added. Otherwise, the same operation as in Example 5 was performed.

 Comparative Example 6

 A recording photopolymer composition was prepared by removing the supersensitizer "NK1819" from the composition of Example 6, that is, adding no NK1819. Otherwise, the same operation as in Example 6 was performed. This comparative example corresponds to that of U.S. Pat. No. 3,658,526 shown as prior art.

Performance evaluation

 For the holograms obtained in the above Examples and Comparative Examples, the sensitivity at the time of recording, the film thickness of the hologram after recording, and the diffraction efficiency were measured.

 a) Film thickness

The thickness of the hologram after recording was measured using a micrometer. b) Diffraction efficiency

 The diffraction efficiency of the transmission hologram is calculated by calculating the ratio of the incident light and the diffracted light using the optical power meter (OPTICAL POWER / ENERGY METER, MODEL 66XLA, manufactured by PH0T0DYNE).

It was calculated from:

 Diffraction efficiency (%) = (Diffraction light intensity / Incident light intensity) X 100 c) The diffraction efficiency of the reflection hologram is calculated using the UV-visible spectrophotometer (V-550, manufactured by JASCO Corporation). It was determined by measurement.

 The results obtained are summarized in Table 1.

 As is evident from Table 1, the transmission hologram and the reflection hologram obtained in the examples have extremely high sensitivity, their diffraction efficiency and transmittance are both high, and the hologram has no coloring and is not developed. It was bright even without fixing operation. Further, this hologram recording was performed only by refractive index modulation, not unevenness of the recording layer, and was highly transparent with almost no absorption in the visible part.

On the other hand, the diffraction efficiency and transmittance of the transmission hologram and the reflection type hologram obtained in Comparative Examples 1 to 6 are almost the same as those of Examples 1 to 6, respectively. It was inferior to the containing composition.

table"!

t

 Diffraction efficiency 80% or more: 〇

 Diffraction efficiency less than 70% 50% or more: Δ

Diffraction efficiency less than 50%: X

In the table, BPEFA: bisphenoxyethanol full orange acrylate (manufactured by Osaka Gas Co., Ltd.)

 B-CIM: 2,2'-bis (0-cloth ferrule) 1-4,4,, 5,5,1-tetraflu 1,2,1-biimidazole (Hodogaya Logistics)

BTTB: 3,3,, 4,4, -tetra (iert-butylpyroxycarbonyl) benzophenone (manufactured by NOF Corporation)

 ASF-400: 9,9-bis (4-hydroxyphenyl) fluorene adduct of dalicydyl ether with acrylic acid (manufactured by Nippon Steel Corporation)

Sensitivity: The minimum exposure energy (mJ / cm ² ) at which holograms began to be recorded Industrial applicability

 In the present invention, a binder polymer (A) soluble in an organic solvent, a polymerizable compound (B) having an ethylenically unsaturated double bond, a photopolymerization initiator (C), a photosensitizing dye (D ) Can contain a supersensitizer (E), whereby a hologram capable of recording an image with high transparency, high sensitivity and high diffraction efficiency can be produced.

 In addition, the photopolymer composition for hologram recording according to the present invention has excellent film-forming properties, and is close to a solid even after film formation, so that a heat treatment for solidifying a fluid composition like a conventional product is required. And not. Furthermore, the diffraction efficiency is sufficiently high without performing heat treatment for amplification of diffraction efficiency after hologram recording. Therefore, the film forming operation and post-processing in the production of the hologram recording medium can be simplified and the workability is excellent.

 Furthermore, the recording medium after hologram recording has high transparency, and the binder polymer (A) and the polymer of the polymerizable compound (B) both exist as a sufficiently high molecular weight after only one exposure. As a result, there is no disadvantage that both records are re-spread and the record becomes unclear. In addition, it has excellent long-term heat resistance, weather resistance, solvent resistance and the like. Therefore, development and fixing operations for stabilizing the recorded image are not essential, and holograms can be produced in real time.

Claims

The scope of the claims 1. In a photopolymer composition for a volume phase hologram recording material used for recording the intensity distribution of light and dark of an optical interference pattern as a change in refractive index, a binder polymer soluble in an organic solvent is used. A), a polymerizable compound having an ethylenically unsaturated double bond (B), a photopolymerization initiator (C), a photosensitizing dye (D), and a supersensitizer (E). A photopolymer composition for a hologram recording material comprising:  2. The photopolymer composition for a hologram recording material according to claim 1, further comprising a plasticizer (F).  3. The binder polymer (A) soluble in an organic solvent is a thermoplastic resin, and the polymerizable compound (B) having an ethylenically unsaturated double bond is a radical polymerizable compound. 2. The photopolymer composition for a hologram recording material according to 2.  4. The hologram recording material according to claim 1, wherein the polymerizable compound (B) having an ethylenically unsaturated double bond is an ethylenically unsaturated monomer having a refractive index of 1.55 or more. Photopolymer composition.  5. The polymerizable compound (B) having an ethylenically unsaturated double bond is a radically polymerizable ethylenically unsaturated monomer having a 9,9-diarylfluorene skeleton. The photopolymer composition for a hologram recording material according to any one of the above.  6. When the photopolymerization initiator (C) is a carbonyl compound, an organotin compound, an alkylaryl boron salt, an onium salt, an iron arene complex, a trihalogenomethyl-substituted triazine compound, an organic peroxide, a bisimidazole derivative, a titanocene compound and the like. The photopolymer composition for a hologram recording material according to any one of claims 1 to 5, which is selected from the group consisting of two or more of the following. 7. The photopolymerization initiator (C) is an organic peroxide, and the organic peroxide is 3,3,4,4,4-tetra (tert-butylperoxycarbonyl) benzophenone, g-tert-butylperoxyiso. Claims selected from the group consisting of phthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, tert-butylperoxybenzoate, and combinations of two or more of these. 6 The photopolymer composition for a hologram recording material according to the above.  8. The photopolymerization initiator (C) is a bisimidazole derivative, and the bisimidazole derivative is 2,2, -bis (0-chlorophenyl) -4,4,5,5,5-tetraphenyl 7. The photopolymer composition for a hologram recording material according to claim 6, wherein the photopolymer composition is selected from the group consisting of 1,1,1-biimidazole, bis (2,4,5-triphenyl) imidazolyl, and a combination of two or more thereof. .  9. Photosensitizing dye (D) is mihiraketone, acridine yellow, melocyanin, methylene blue, camphorquinone, eosin, decarboxylated rose bengal, cyanine derivative, merocyanine derivative, phthalocyanine derivative, xysanthene derivative, thioxanthen derivative 9. An acridine derivative, a porphyrin derivative, a coumarin derivative, a ketocoumarin derivative, a quinolone derivative, a stilbene derivative, an oxazine derivative, a thiazine dye, and a combination of two or more of these. Or a photopolymer composition for a hologram recording material.  10. The hologram recording material according to any one of claims 1 to 9, wherein the supersensitizer (E) is selected from the group consisting of a base styryl derivative, an amine compound, and a combination of two or more thereof. Photopolymer composition for use.  11. A hologram recording medium in which a recording layer comprising the photopolymer composition for hologram recording material according to any one of claims 1 to 10 is formed on a substrate.  1 2. In producing the hologram recording medium according to claim 11, a binder polymer (A), a polymerizable compound (B), a photopolymerization initiator (0, a photosensitizing dye (D), and supersensitization) Dissolving agent (E) in a solvent, adding a plasticizer (F) if necessary, applying the obtained solution on a substrate, and then volatilizing the solvent to form a hologram recording layer for forming a recording layer. Media manufacturing method.