JPH06175553A - Hologram recording medium and production of volume phase type hologram by using this medium - Google Patents

Abstract

PURPOSE:To provide a hologram recording medium which is excellent in chemical stability and environmental resistant characteristic and excellent in wide photosensitive wavelength region characteristics, high sensitivity, high diffraction efficiency, high transparency and sensitivity characteristic and a process for production of a volume phase type hologram using this recording medium. CONSTITUTION:A photosensitive material for hologram recording consisting of a high-polymer compd. (A) which is a homo-polymer or copolymer of (meth) acrylate, a compd. (B) contg. at least >=1 pieces of polymerizable ethylenic unsatd. bonds, a merocyanine deriv. (C) and diaryl iodonium org. boron complex (D) is held by an optically transparent base material and an optically transparent protective film to form a photosensitive film to constitute this hologram recording medium. This process for production of the volume phase type hologram consists in using this recording medium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram recording medium which is excellent in chemical stability and environment resistance and has a wide photosensitive wavelength region characteristic, high resolution, high diffraction efficiency, high transparency and sensitivity characteristics. The present invention relates to a method for manufacturing a volume phase hologram using a hologram recording medium.

[0002]

2. Description of the Related Art Conventionally, bleached silver salt and dichromated gelatin type photosensitive materials have been generally used as hologram recording media. However, in the production of holograms using these hologram recording media, the method for producing the photosensitive plate and the process for producing the holograms are complicated, and the produced holograms are inferior in environmental resistance characteristics such as moisture resistance and weather resistance. Moreover, there is a problem that the resolution is limited.

In order to solve such a problem, an example of using a photopolymer as a method for producing a volume phase hologram having excellent environment resistance properties and high hologram characteristics such as high resolution and high diffraction efficiency. It has been known.
For example, in JP-B-62-22152, a light-sensitive material prepared by dispersing a polyfunctional monomer having two or more ethylenically unsaturated bonds, which is a photopolymerizable substance, in a polymer to be a carrier is radiated. First step of exposing to a line interference pattern, second step of treating the sensitive material with a first solvent to swell the sensitive material, and treatment with a second solvent having a poor swelling action to shrink the sensitive material There is disclosed a hologram manufacturing method comprising a third step of denying. However, this method requires 50 m in order to produce a hologram with sufficient diffraction efficiency.
Exposure energy of J / cm ² or more is required, and further improvement in sensitivity characteristics has been desired.

On the other hand, JP-A-3-704 discloses a photopolymerization initiator comprising a combination of a diaryliodonium organic boron complex and a merocyanine derivative. However, the specific structure of effective merocyanine derivatives is not specified. Further, there is no description about a concrete example or a production method for hologram recording, and a volume phase hologram could not be produced by simply using a photopolymerization initiator.

In the hologram recording photosensitive material containing a compound having a compound having at least one ethylenically unsaturated bond capable of polymerizing with the high molecular compound as a constituent and a method for producing a hologram using the same, a high molecular compound is used. Examples using vinylcarbazole and its derivatives have been disclosed so far. For example, Japanese Patent Laid-Open No. 2-216180 discloses
A hologram recording composition comprising polyvinyl carbazole or a derivative thereof, a polyfunctional monomer, a coumarin derivative and an organic peroxide is disclosed in JP-A-3-278082, in which polyvinyl carbazole and at least one polymerizable ethylenically unsaturated bond are contained. A hologram recording composition comprising a compound having one or more of them, a tetrabenzoporphyrin derivative and an electron-accepting radical generator is disclosed in Japanese Patent Application Laid-Open No. 4-141
Japanese Patent No. 3172 discloses a hologram recording composition comprising a polyvinylcarbazole, a methacrylate compound, a ketocoumarin dye and an iron arene complex. Since these photosensitive materials for hologram recording are mainly composed of polyvinylcarbazole or a derivative thereof, they are chemically stable and have high resolution, moisture resistance, heat resistance, and weather resistance. It has a problem that it is easily crystallized and whitened during the process, the reproducibility of transparency is poor, and the sensitivity characteristic is poor due to the rigidity of polyvinylcarbazole. Further, as an example of using a polymer compound other than polyvinylcarbazole, JP-A-1-33104 contains a gelatin polymer compound, a water-soluble non-volatile ethylene monomer, and at least one tertiary amino group. A hologram recording composition comprising a compound and a dye sensitizer,
JP-A-2-216181 discloses a hologram recording composition comprising polyvinylpyrrolidone, a polyfunctional monomer, a coumarin dye and an organic peroxide. However, these known materials have the drawback of being inferior in environmental resistance characteristics such as moisture resistance and water resistance because the polymer compound is water-swellable or water-soluble.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a hologram recording medium which is excellent in chemical stability and environmental resistance, and also has wide photosensitive wavelength region characteristics, high resolution, high diffraction efficiency, high transparency and sensitivity characteristics. And a method for manufacturing a volume phase hologram using the recording medium.

[0007]

Means for Solving the Problems In consideration of the above points, the present inventors have made earnest studies to achieve the above object, and as a result,
The present invention has been reached. That is, the first invention is a polymer compound (A) which is a homopolymer of an acrylic ester or a methacrylic ester, or a copolymer of two or more components of an acrylic ester or a methacrylic ester and a vinyl monomer, Compound (B) having at least one polymerizable ethylenically unsaturated bond, general formulas (1) to (11), general formula (1)

[Chemical 13] General formula (2)

[Chemical 14] General formula (3)

[Chemical 15] General formula (4)

[Chemical 16] General formula (5)

[Chemical 17] General formula (6)

[Chemical 18] General formula (7)

[Chemical 19] General formula (8)

[Chemical 20] General formula (9)

[Chemical 21] General formula (10)

[Chemical formula 22] General formula (11)

[Chemical formula 23] (In the formula, n represents 1 or 2, X is a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group which may have a substituent, an aryloxy group, an aralkyl group or a halogen. Represents an atom, Ph represents a phenyl group, and R ¹ , R ² and R ³ each independently represent an alkyl group, an alkenyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group. Of at least one merocyanine derivative (C) selected from the group consisting of compounds

[Chemical formula 24] (In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, a lower alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, A cyano group or a nitro group, R ⁶ , R ⁷ , R ⁸ and R ⁹
Are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, A group selected from an alicyclic group which may have a substituent is shown, and R ⁶ , R ⁷ , R ⁸ and R ⁹ are not all aryl groups which may have a substituent at the same time. ) A photosensitive material for hologram recording comprising a diaryl iodonium organoboron complex (D) represented by (4) is sandwiched between an optically transparent base material and an optically transparent protective film to form a photosensitive film. Is a hologram recording medium.

In a second aspect of the present invention, the first step of exposing the hologram recording medium to a radiation interference pattern to polymerize and cure the hologram recording photosensitive material, and from the recording medium to the hologram recording photosensitive material, Second step of treating with a solvent that removes unpolymerized substances and swells the polymer compound (A) in the recording medium, and further the solubility and swelling property with respect to the polymer compound (A) in the recording medium And a third step of bringing the recording medium into contact with a poor solvent to produce a volume phase hologram.

A third aspect of the present invention is for hologram recording by exposing the hologram recording medium to actinic rays such as ultraviolet rays, visible rays and electron beams and / or heat treatment before exposing the hologram recording medium to radiation interference patterns. The method for producing a volume phase hologram comprises pre-curing a photosensitive material.

The polymer compound (A) used in the hologram recording medium of the present invention is a homopolymer of acrylic acid ester or methacrylic acid ester, or an acrylic acid ester or methacrylic acid ester and another vinyl monomer. It is a copolymer of more than one component. Specific homopolymers of acrylic acid ester or methacrylic acid ester include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,
Pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl, 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl, 1,3-dimethylbutyl,
Polymers of chain, branched and cyclic alkyl acrylic or methacrylic acid ester monomers such as 2-ethylhexyl, 2-methylpentyl, cyclohexyl, adamantyl, isobornyl, dicyclopentanyl, tetrahydrofurfuryl, phenyl, 4 -Methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 4-butoxycarbonylphenyl, 4-tert-butylphenyl, benzyl, 4-phenylethyl, 4-phenoxydiethylene glycol, 4-phenoxytetraethylene glycol, 4-phenoxyhexaethylene. Glycol,
Polymer of acrylic acid or methacrylic acid ester monomer containing aromatic ring such as 4-biphenylyl, polymer of acrylic acid or methacrylic acid ester monomer containing iron atom such as ferrocenylmethyl, ferrocenylethyl, trifluoro Ethyl, tetrafluoropropyl,
Heptadecafluorodecyl, octafluoropentyl,
Polymers of acrylic acid or methacrylic acid ester monomers containing halogen atoms such as 2,3-dibromopropyl, polymers of acrylic acid or methacrylic acid esters containing silicon atoms such as trimethoxysilylpropyl, glycidyl acrylate and glycidyl methacrylate. Polymers of acrylic acid or methacrylic acid ester monomers containing epoxy groups such as, acrylic acid or methacrylic acid containing amino groups such as N, N-dimethylaminoethyl, N, N-diethylaminoethyl, t-butylaminoethyl Examples thereof include polymers of ester monomers. These acrylic acid ester or methacrylic acid ester monomers may be used as a copolymer of two or more components, if necessary.

Examples of vinyl monomers which can be used as a copolymer of two or more components with the above-mentioned acrylic acid ester or methacrylic acid ester monomers include butadiene, isoprene, acrylamide, N-butylacrylamide, N, N-dimethylacrylamide, Examples thereof include acrylonitrile, styrene, 4-bromostyrene, perfluorostyrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine and vinylpyrrolidine.

The compound (B) having at least one polymerizable ethylenic unsaturated bond to be used in the hologram recording medium of the present invention includes an oligomer in addition to a monofunctional vinyl monomer, Further, it may be a high molecular weight compound or a mixture thereof. Examples of such a compound include high boiling point vinyl monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamide, methacrylamide, diacetone acrylamide, 2-hydroxyethyl (meth) acrylate, N-vinylcarbazole, and the like. , Aliphatic polyhydroxy compounds such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,3
-Propanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 1,
Di- or poly (meth) acrylic esters such as 10-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, and mannitol; aromatic polyhydroxy compounds such as hydroquinone, resorcin, catechol, and pyrogallol. Poly (meth) acrylic ester, ethylene oxide-modified (meth) acrylate of isocyanuric acid, and further a polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in the side chain and acrylic acid, methacrylic acid, croton A polymer obtained by a polymer reaction with an unsaturated carboxylic acid such as an acid can also be suitably used. Examples of such polymer compounds include polyvinyl alcohol, copolymers of vinyl alcohol and vinyl acetate, polyepichlorohydrin, phenoxy resin, polychloromethylstyrene, copolymers of 2-hydroxy (meth) acrylate with various acrylate monomers. , Phenolic resins and the like. Furthermore, (meth) acrylated epoxy resin, polyester acrylate oligomer, (meth) acrylated urethane oligomer, acroleinized polyvinyl alcohol, etc. can be mentioned.

In the merocyanine derivative (C), X represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group which may have a substituent, an aryloxy group or a substituent. Represents a good aralkyl group or a halogen atom. Examples of the alkyl group include linear or branched alkyl groups having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the substituent of the substituted alkyl group include halogen atoms such as fluorine, chlorine, bromine and iodine, hydroxyl group, carboxyl group, cyano group, alkoxy group, alkoxycarbonyl group, dialkylamino group, tetrahydrofuryl group, oxanyl group (or tetrahydropyranyl group). Group) or a dioxanyl group. A substituted alkyl group is a substituted alkyl group in which only one of these substituents or two of these substituents are bonded to the alkyl group. Specific examples of the substituted alkyl group include carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, cyanomethyl group, 2-cyanomethyl group, 3-cyanopropyl group, methoxyethyl group, 2-methoxyethyl group, 3 -Methoxypropyl group, ethoxymethyl group, dimethoxymethyl group,
2,2-dimethoxyethyl group, 2,2-diethoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, 2- (methoxycarbonyl) ethyl group, 2- (ethoxycarbonyl) ethyl group, Dimethylamino group, diethylamino group,
Examples thereof include a dipropylamino group, a methylethylamino group, a 2-tetrahydrofuryl group, a 2-oxanyl group, a 4-oxanyl group and a dioxanyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and a benzyloxy group.

Examples of the aryl group which may have a substituent include a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group and a phenanthryl group. Examples of the aryloxy group include a phenoxy group, a p-fluorophenoxy group, a p-cyanophenoxy group and the like. Examples of the aralkyl group which may have a substituent include a benzyl group, a p-chlorobenzyl group, a p-bromobenzyl group, a p-cyanobenzyl group, a p-nitrobenzyl group, a p-methylbenzyl group and a p-tert-group. A butylbenzyl group and the like are exemplified.

The substituents R ¹ , R ² and R ³ of the merocyanine derivative (C) represented by the general formulas (1) to (11) are each independently an alkyl group or an alkenyl group which may have a substituent. Represents an aryl group which may have a substituent or an aralkyl group which may have a substituent. When R ¹ , R ² and R ³ are an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, X is substituted. It has the same meaning as in the case of an alkyl group which may have a group, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

The alkenyl group has 2 to 4 carbon atoms.
Up to the linear or branched alkenyl group, and specific examples thereof include a vinyl group, an allyl group, a 1-propenyl group, a 2-butenyl group, a 3-butenyl group and an isopropenyl group.

The merocyanine derivatives represented by the general formulas (1) to (11) are "Journal of Amer".
ican Chemical Society, Vol. 73, pages 5326-5332 (1951) and L.S. G. S. Brooker et al., "Studies i
n the Cyanine Dye SeriesX
I, The Merocyanines ”, and can be obtained from Japan Photosensitive Dye Research Institute.

Specific examples of the merocyanine dyes represented by the general formulas (1) to (11) include (1a) to (1).
Examples thereof include compounds represented by l). That is, (1a):
5-[(1'-ethyl-2'-pyridylidene) ethylidene] -3-ethylrhodanine, (1b): 5-[(3 '
-Ethyl-4 ', 5'-diphenyl-2'-thiazolilidene) ethylidene] -3-ethylrhodanine, (1
c): 5-[(3'-ethyl-2'-benzothiazolilidene) ethylidene] -3-ethyl-4-oxo-2-thioxosazolidine, (1d): 5-[(3'-ethyl −
2'-Benzothiazolilidene) ethylidene] -2-phenyl-5 (4) oxazolone, (1e): 5-[(3 '
-Ethyl-2'-benzothiazolilidene) ethylidene]
-1-Phenyl-3-methyl-pyrazolone, (1f):
5-[(3'-ethyl-2'-benzoxazolidene)
Ethylidene] -3-ethyl-4-oxo-2-thioxooxazolidine, (1 g): 5-[(3'-ethyl-
2'-benzoxazolilidene) ethylidene] -3-ethylrhodonine, (1h): 5-[(3 ', 3'-dimethyl-2'-indolinylidene) ethylidene] -3-ethyl-4-oxo -2-thioxooxazazolidine,
(1i): 5-[(1'-ethyl-2'-quinolilidene) ethylidene] -3-ethylrhodanine, (1j):
5-[(1'-ethyl-2'-quinolilidene) ethylidene] -3-ethylrhodanine, (1k): 5-[(3 '
-Ethyl-2'-benzothiazolilidene) ethylidene]
-3-Ethyl Rhodanine, (1l): 5-[(3'-Ethyl-2'-benzothiazolilidene) butenylidene]-
Examples thereof include 3-ethyl rhodanine.

Next, in the diaryliodonium organoboron complex (D) represented by the general formula (12), R ⁶ ,
The alkyl group which may have a substituent represented by R ⁷ , R ⁸ and R ⁹ may be the alkyl group which may have a substituent as exemplified in the case of X. The aryl group which may have a substituent includes a phenyl group, a p-tolyl group, a xylyl group, a mesicle group, a cumenyl group, a p-methoxyphenyl group, a naphthyl group, and a 2,4-bis (trifluoromethyl) phenyl group. Group, p-fluorophenyl group, p-chlorophenyl group, p-bromophenyl group, p-tert-butylphenyl group and the like. As an alkenyl group,
Examples thereof include a vinyl group, a 2-propenyl group, an isopropenyl group and a butenyl group. Examples of the alkynyl group which may have a substituent include an ethenyl group, a 2-tert-butylethenyl group, a 2-phenylethenyl group and the like. Examples of the alicyclic group which may have a substituent include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a bornyl group and a 1-cyclohexenyl group.

Diaryl iodonium organic boron (D)
As specific examples of, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis (pt-butylphenyl) iodonium, bis (p-
N-butyltriphenylborate complex such as cyanophenyl) iodonium, sec-butyltriphenylborate complex, tert-butyltriphenylborate complex,
Examples thereof include n-butyltris (p-methoxyphenyl) borate complex, methyltriphenylborate complex, n-butyltris (p-fluorophenyl) borate complex and the like. As a typical compound, a compound of the formula (13), a compound of the formula (1
Examples include the compound of 4) and the compound of formula (15).
Formula (14)

[Chemical 25] Formula (15)

[Chemical formula 26] Formula (16)

[Chemical 27]

The hologram recording medium of the present invention is a homopolymer of acrylic acid ester or methacrylic acid ester,
Alternatively, a polymer compound (A) which is a copolymer of two or more components of an acrylic acid ester or a methacrylic acid ester and a vinyl monomer, a compound (B) having at least one polymerizable ethylenic unsaturated bond, a general formula ( The merocyanine derivative (C) represented by 1) to (11) and the diaryl iodonium organoboron complex (D) represented by the general formula (12) are dissolved in a suitable solvent, and the resulting solution is optically transparent. It is formed by coating in a film form on a transparent base material or on an optically transparent protective film. The applied thickness is preferably 1 μm to 20 μm as a film thickness after drying, and more preferably 4 μm to 10 μm. There is no particular limitation on the compounding ratio of each of the above components, but it is preferable to adjust the concentration of the merocyanine derivative (C) so that the transmittance of the laser light for irradiation is 1% or more. Further, if necessary, various additives such as a plasticizer, an antioxidant and a thermal polymerization inhibitor may be added.

The amount of the polymer compound (A) occupied in the hologram recording material is 10 to 9 in order to produce a volume phase hologram having high diffraction efficiency, high resolution and high transparency.
It is 0% by weight, preferably 30 to 70% by weight. The amount of the compound (B) used is 10 to 200 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the polymer compound (A). If it deviates from the above range, it becomes difficult to maintain high diffraction efficiency and improve sensitivity characteristics, which is not preferable.
Among the photopolymerization initiators used in the present invention, the merocyanine derivative (C) is 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the polymer compound (A). Used in the range. The amount used is limited by the film thickness of the photosensitive layer and the optical density of the film thickness. That is, it is preferably used in a range where the optical density does not exceed 2. The diaryliodonium organic boron complex salt (D) is used in an amount of 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the polymer compound (A).

The photosensitive material for hologram recording in the present invention is formed on a recording medium sandwiched between an optically transparent base material and an optically transparent protective film before being exposed to a radiation interference pattern. Examples of the optically transparent substrate include a glass plate, a polycarbonate plate, a polymethylmethacrylate plate and a polyester film. Examples of the optically transparent protective film include polyvinyl alcohol, polyethylene terephthalate, polyolefin, polyvinyl chloride, polyvinylidene chloride, and cellophane film. When the photosensitive material for hologram recording is formed on the above-mentioned transparent base material, the above-mentioned optically transparent protective film is applied in a solution state, electrostatically adhered, or using an extruder. It can be laminated on the photosensitive material by laminating or laminating a film in which an adhesive is applied to the protective film in advance. On the other hand, when the photosensitive material for hologram recording is formed on the above-mentioned transparent protective film, it can be attached by a method of bringing the photosensitive material surface side into close contact with an optically transparent substrate.

As described above, before the hologram recording photosensitive material of the present invention is exposed to the radiation interference pattern,
By forming it in the form of a recording medium sandwiched between an optically transparent base material and an optically transparent protective film, the photosensitive material for hologram recording is protected from various external effects, and radiation interference It is possible to suppress the inhibitory effect of oxygen on radical polymerization that occurs in the recording light-sensitive material during exposure.

Next, a method of manufacturing the volume phase hologram of the present invention will be described. That is, the hologram recording medium described above is converted into radiation, particularly He-Cd, Ar ions,
1st exposed to interference pattern of visible laser beam emitted from He-Ne, Kr ion, ruby laser, etc.
Subject to the process. Then, after removing the protective film covering the recording medium from the recording medium, the substance in the unpolymerized hologram recording photosensitive material is removed from the recording medium, and then the polymer in the recording medium is removed. It is subjected to a second step of soaking the compound (A) in a solvent having an action of swelling, a so-called swelling step. As the solvent preferably used in the step, aromatic organic solvents such as benzene, toluene and xylene, acetic ester organic solvents such as ethyl acetate and butyl acetate, ketone organic solvents such as acetone, methyl ethyl ketone and cyclohexanone, and methanol. , Commonly used organic solvents such as alcohol-based organic solvents such as ethanol and isopropanol, cyclic ether-based organic solvents such as dioxane and tetrahydrofuran, chlorine-based organic solvents such as dichloromethane, chloroform and tetrachloroethane, or mixed solvents thereof can do. In that case, the organic solvent needs to have a function of swelling the polymer compound (A) in the hologram recording medium without completely dissolving it, and is appropriately selected depending on the type of the polymer compound (A) used. There is a need to. The immersion time required to complete the swelling step depends on the swelling efficiency of the solvent used and the immersion temperature, but at room temperature,
It is completed in about 30 seconds to 5 minutes.

Subsequent to the swelling treatment step, the recording medium was brought into contact with a solvent having poor solubility and swelling property with respect to the polymer compound (A) in the recording medium, and swelled in the swelling treatment step. A third step of shrinking the recording medium, a so-called shrinking step, is performed. Specific examples of the solvent preferably used in the step include n-alkane organic solvents such as pentane, hexane, heptane, and petroleum ether, but any solvent having an action of shrinking the recording medium can be used. However, the solvent is not limited to the above-mentioned solvents.

Furthermore, in the production of a volume phase hologram using the hologram recording medium of the present invention, the recording medium is exposed to ultraviolet rays, visible rays, or electron beams before being exposed to a radiation interference pattern. It is possible to manufacture a volume phase hologram having particularly improved transparency by exposing it to actinic radiation such as and / or precuring it by heat treatment.

The actinic radiation source used for the above-mentioned pretreatment is not particularly limited, but as the ultraviolet ray source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide is used. lamp,
Fluorescent lamps, tungsten lamps, and the like, and visible light sources include He-Cd, Ar ions, and
A visible light laser light source such as He-Ne, Kr ion, ruby, a light emitting diode, a white light, a fluorescent light, or the like can be used. In this case, the active rays emitted from the active light source used must be effectively absorbed by the merocyanine derivative (C) and / or the diaryl iodonium salt (D) used in the hologram recording photosensitive material of the present invention. There is. The time and amount of exposure to these actinic rays differ depending on the actinic ray source, but when curing the hologram recording photosensitive material using the actinic ray source, exposure to the minimum amount of energy at which gelation can be initiated. Is desirable. As a heat source for the heat treatment, a heat circulation type oven is generally preferably used, but the heat source is not limited to this. Heat treatment temperature range is 50 ℃ to 12
0 ° C is preferred, more preferably 60 ° C to 90 ° C
Is in between.

[0030]

The hologram recording photosensitive material of the present invention is characterized by comprising a polymer compound (A), a compound (B), a merocyanine derivative (C) and a diaryliodonium organoboron complex (D). The merocyanine derivative (C) used in the light-sensitive material is arbitrarily selected from the ultraviolet light wavelength region to the near-infrared wavelength region in the light-sensitive wavelength region of the hologram recording light-sensitive material by appropriately selecting the molecular structure. The exposure of the selected radiation makes it possible to efficiently decompose the diaryl iodonium organoboron complex (D) and effectively induce radical polymerization by the resulting free radicals. In particular, the diaryliodonium organoboron complex used in the present invention is considered to have effectively generated free radicals and contributed to the improvement of sensitivity characteristics because it had two free radical generation sources in its molecule.
Further, it is presumed that the use of the polymer compound (A) makes it possible to manufacture a volume phase hologram having excellent chemical stability and environment resistance characteristics, as well as excellent transparency and sensitivity characteristics. .

On the other hand, in the volume phase hologram recording using the hologram recording medium, when an interference pattern of radiation is exposed on the recording medium, the compound is detected in the radiation-exposed portion at a portion having a strong interference action. The polymerization reaction of (B) occurs, forms a network structure together with the polymer compound (A) as a support, and becomes insoluble in the solvent used in the next swelling treatment step. On the other hand, in the radiation-exposed region, the compound (B) is not polymerized at the site having a weak interference action, or the compound (B) is dissolved by the swelling solvent because the polymerization degree is low. While being removed from the recording medium, the recording medium swells. It is presumed that this causes a difference in density between the two parts, resulting in a difference in refractive index and hologram recording. This effect is remarkably amplified by bringing it into contact with the second solvent having poor solubility and swelling property for the recording medium, and is also combined with the effect of returning the film thickness of the recording medium to the film thickness before the swelling treatment. It is considered that the present invention has provided a volume phase hologram excellent in high diffraction efficiency and playback wavelength reproducibility.

[0032]

The present invention will be described in more detail based on the following examples. In the following examples, parts represent parts by weight unless otherwise specified.

Example 1 100 parts of polymethyl methacrylate (manufactured by Aldrich, weight average molecular weight: 710,000), isocyanuric acid ethylene oxide-modified triacrylate (trade name Aronix M
-315, Toa Gosei Chemical Industry Co., Ltd. 70 parts, merocyanine derivative (1a) 2.5 parts, diphenyliodonium-n-butyltriphenylborate (compound of formula (13)) 5 parts, dioxane 900. Part of the photosensitive solution was applied onto a 100 × 125 × 3 mm glass plate using a 3 mil applicator so that the film thickness after drying the photosensitive solution would be 6 μm, and dried in a 60 ° C. oven for 20 minutes. . Further, an aqueous solution of polyvinyl alcohol (manufactured by Aldrich, saponification degree of 99% or more) was applied onto the hologram recording photosensitive film to prepare a volume phase hologram recording medium.

In this medium, an optical system for producing a volume phase hologram shown in FIG.
After the volume phase hologram recording was performed using light, the photosensitive layer was developed and swollen by immersing it in xylene for 1 minute, and was immersed in heptane for 30 seconds and contracted to produce a volume phase hologram. Diffraction efficiency is JASCO Corporation
It was measured with an ART 25C spectrophotometer manufactured by KK. In this device, a photomultimeter having a slit with a width of 3 mm can be installed on the circumference of a 20 cm radius centered on 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 diffraction efficiency was defined as the ratio between the maximum value other than the specular reflection light and the value when the incident light was received directly without placing the sample. With an exposure dose of 10 mJ / cm ² ,
Playback wavelength 480nm, diffraction efficiency 70%, 6
A volume phase hologram having a transmittance at 00 nm of 92% was produced. This volume phase hologram is
No decrease in diffraction efficiency was observed even when left for 180 days in an environment of 60% RH.

FIG. 1 is a block diagram of a two-beam laser exposure apparatus for manufacturing a volume phase hologram. In the figure, 1 is a laser light source, 2 is a mirror, 3 is a lens, 4 is a spatial filter, 5 is a substrate (glass plate), 6 is a hologram photosensitive film, and 7 is a protective film (polyvinyl alcohol film).

Examples 2 to 12 Sensitivity characteristics, diffraction efficiency and playback were performed in the same manner as in Example 1 except that the merocyanine derivative (1a) in Example 1 was changed from the merocyanine derivative (1b) to (1l). The wavelength was measured. The test results are shown in Table 1. In addition, in Examples 5 to 8, 514 nm light of Ar ion laser was used, and in Examples 9 and 10, 63 of He-Ne laser was used.
In the twelfth embodiment, a 3 nm light is emitted from the Kr ion laser of 64 nm.
7 nm light was used.

Example 13 Diphenyliodonium-n-butyltriphenylborate (compound of formula (13)) obtained in Example 1 was mixed with bis (p-tert-butylphenyl) iodonium-n-.
Table 1 shows the results of the hologram characteristics measured by operating in the same manner as in Example 1 except that butyltriphenylborate (compound of formula (14)) was used.

Example 14 The diphenyliodonium-n-butyltriphenylborate (compound of formula (13)) obtained in Example 1 was converted into bis (p-cyanophenyl) iodonium-sec-butyltriphenylborate (formula (15)). Table 1 shows the results of the hologram characteristics measured by operating in the same manner as in Example 1 except that the compound was changed.

Example 15 Table 1 shows the results of the hologram characteristics measured in the same manner as in Example 1 except that polymethyl methacrylate in Example 1 was changed to polyisobornyl methacrylate.

Example 16 Table 1 shows the results of the hologram characteristics measured in the same manner as in Example 1 except that polymethyl methacrylate in Example 1 was changed to polyferrocenylmethyl methacrylate. In addition, poly ferrocenyl methyl methacrylate is
C. U. Pittman et al., "Macromoleculecu
Les ”, Vol. 3, page 746 (1970).

Example 17 Table 1 shows the results of hologram characteristics measured in the same manner as in Example 1 except that polymethyl methacrylate in Example 1 was changed to polybenzyl methacrylate.

Example 18 Table 1 shows the results of hologram characteristics measured by the same operation as in Example 1 except that polymethyl methacrylate in Example 1 was changed to trimethoxysilylpropyl polyacrylate.

Example 19 The polymethylmethacrylate in Example 1 was replaced by a copolymer of polymethylmethacrylate and styrene (7: molar ratio).
Table 1 shows the results of the hologram characteristics measured by operating in the same manner as in Example 1 except for changing to 3).

Example 20 In Example 1, the recording medium was heated to 100 ° C. before performing the volume phase hologram recording with the Ar ion laser beam.
Of the volume phase hologram produced by the pre-curing treatment for 1 hour in the hot air dryer of No. 1 and then the same operation as in Example 1 had a transmittance at 600 nm of 96%.
Then, the transparency was further improved. Other hologram characteristics are shown in Table 1.

Example 21 In Example 20, as a pre-curing treatment method, the recording medium was pre-cured by exposing it to white light emitted from a Xe lamp for 3 seconds, and then, in the same manner as in Example 1. 600n volume phase hologram produced by operation
The transparency at m was 98%, further improving the transparency. The results of other hologram characteristics are shown in Table 1.

Comparative Example 1 In Example 1, the volume phase hologram could not be produced only by exposing the recording medium to the interference pattern of the Ar ion laser.

Comparative Example 2 Volume phase type obtained by the same operation as in Example 1 except that diphenyliodonium-n-butyltriphenylborate complex (2a) was changed to diphenyliodonium hexafluorophosphate. The hologram has a diffraction efficiency of 70%, a playback wavelength of 480 nm, and 6
92% transmittance at 00 nm and 25% at 60 ° R
The volume phase hologram was excellent in hologram characteristics with a storage stability in H of 180 days or more, but the sensitivity characteristics were 30 mJ / cm ² , which was about 1/3 inferior to that of Example 1.

Comparative Example 3 The same as Example 1 except that methyl methacrylate was changed to poly-N-vinylcarbazole and the developing swelling solvent was changed to a mixed solvent having a volume ratio of toluene and xylene of 1: 1. The hologram recording was performed by operating the. Although it was possible to manufacture a volume phase hologram with an exposure amount of 60 mJ / cm ² , its diffraction efficiency was 10%, and its transmittance was 70% in the entire visible light region, indicating poor transparency.

Comparative Example 4 Hologram recording was carried out in the same manner as in Example 1 except that poly-N-vinylpyrrolidone was used as the methyl methacrylate in Example 1 and ethyl acetate was used as the developing swelling solvent. Diffraction efficiency of 60% at an exposure dose of 10 mJ / cm ^2.
Although it was possible to manufacture the volume phase hologram of No. 3, since the poly-N-vinylpyrrolidone was water-soluble, the hologram had a diffraction efficiency of 10% after being left for one day.

Comparative Example 5 The procedure of Example 1 was repeated except that the polymethylmethacrylate in Example 1 was changed to polystyrene and the developing and swelling solvent was changed to toluene, but the film was whitened and a volume phase hologram was obtained. It could not be manufactured.

Table 1 Examples Recording wavelength Exposure amount Diffraction efficiency (Nm) (mJ / cm ² ) (%) 1 488 10 70 2 488 12 65 3 488 8 70 4 4 488 8 70 5 5 514 10 70 70 6 514 10 75 7 514 10 60 60 8 514 8 65 9 9 633 35 65 10 5 75 11 488 10 60 12 12 647 15 70 13 488 12 12 70 14 488 8 70 15 15 488 18 70 16 488 20 80 80 17 488 12 75 8 18 488 10 70 19 19 488 21 70 70 20 488 8 8 8 65 21

Table 1 (continued) Example Playback Transmittance * Storability ** Wavelength (nm) (%) (days) 1 480 92> 180 2 480 92> 180 3 485 92> 180 4 475 92> 180 5 520 92> 180 6 505 92> 180 7 500 92> 180 8 515 92> 180 9 625 92> 180 10 630 92> 180 11 485 92> 180 12 650 92> 180 13 480 92> 180 14 480 92> 180 15 485 92> 180 16 490 92> 180 17 17 480 92> 180 18 180 485 19 490 92> 180 20 470 96> 180 21 475 98> 180 * Transmittance at 600 nm ** Durability under storage at 25 ° C and 60% RH

[0053]

According to the present invention, over a wide wavelength range,
A hologram recording medium having a high resolution, a high diffraction efficiency and a high transparency, and a volume phase using the same, with a small exposure energy of ² mJ / cm ² to 15 mJ / cm ² and having excellent chemical stability and environmental resistance. It becomes possible to manufacture type holograms.

[Brief description of drawings]

FIG. 1 shows a block diagram of a two-beam laser exposure apparatus for manufacturing a volume phase hologram.

[Explanation of symbols]

 1 laser light source 2 mirror 3 lens 4 spatial filter 5 glass plate 6 hologram photosensitive film 7 protective film

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03F 7/028 7/033 7/11 501 501 7/26 7124-2H

Claims (3)

[Claims] 1. A polymer compound (A), which is a homopolymer of an acrylic ester or a methacrylic ester, or a copolymer of two or more components of an acrylic ester or a methacrylic ester and a vinyl monomer, and a polymerizable ethylene. A compound (B) having at least one polyunsaturated bond, the general formulas (1) to (11), and the general formula (1): General formula (2) General formula (3) General formula (4) General formula (5) General formula (6) General formula (7) General formula (8) General formula (9) General formula (10) General formula (11) (In the formula, n represents 1 or 2, X represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group which may have a substituent, an aryloxy group, or a substituent. Represents an aralkyl group or a halogen atom which may be represented by P
h represents a phenyl group, R ¹ , R ² and R ³ are each independently an alkyl group, an alkenyl group, which may have a substituent,
It represents an aryl group or an aralkyl group which may have a substituent. ) At least one merocyanine derivative (C) selected from the group consisting of the compounds) and a compound represented by the general formula (12): (In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a cyano group or a nitro group, and R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently substituted. An alkyl group which may have a group, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent which may have a substituent. A group selected from good alicyclic groups, R ⁶ , R ⁷ , R ⁸ and R ⁹
Not all of them are aryl groups which may have a substituent at the same time. ) A photosensitive material for hologram recording comprising a diaryl iodonium organoboron complex (D) represented by (4) is sandwiched between an optically transparent base material and an optically transparent protective film to form a photosensitive film. A holographic recording medium characterized by. 2. A first step of exposing the hologram recording medium according to claim 1 to an interference pattern of radiation to polymerize and cure the photosensitive material for hologram recording. The second step of treating with a solvent that removes the polymerized substance and swells the polymer compound (A) in the recording medium, and further improves the solubility and swelling property with respect to the polymer compound (A) in the recording medium. And a third step of bringing the recording medium into contact with a poor solvent to produce a volume phase hologram. 3. A hologram recording photosensitive material for exposure to active rays such as ultraviolet rays, visible rays, and electron beams, and / or heat treatment before exposing the hologram recording medium according to claim 1 to an interference pattern of radiation. The method for producing a volume phase hologram according to claim 2, wherein the material is pre-cured.