JPH06175561A - Hologram recording medium and production of volume phase type hologram by using the recording medium - Google Patents

Abstract

PURPOSE:To provide a process for production of a hologram recording medium having excellent chemical stability and environmental resistance characteristic and characteristics of high sensitivity, high diffraction efficiency, high transparency and high resolution over a wide wavelength region and a volume phase type hologram by using the recording medium. CONSTITUTION:This hologram recording medium is constituted by containing a photosensitive material for hologram recording including a combination of a high-polymer compd. which is a single polymer of acrylate or methacrylate or a copolymer of >=2 components of the acrylate or methacrylate and vinyl monomer (A), a compd. having at least >=1 pieces of polymerizable ethylenic unsatd. bonds (B), pyrilium salt or thiopyrilium salt deriv. (C) and sulfonium org. boron complex (D) by an optically transparent base material and an optically transparent protective film to form a photosensitive film. This process for production of the volume phase type hologram consists using the hologram recording material.

Description

Detailed Description of the Invention

INDUSTRIAL APPLICABILITY The present invention has excellent chemical stability and environment resistance, high sensitivity characteristics over a wide wavelength range, and particularly excellent hologram characteristics such as resolution, diffraction efficiency and transparency. The present invention also relates to a hologram recording medium and a method of manufacturing a volume phase hologram using the hologram recording medium.

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 characteristics and having characteristics that a hologram should have, 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 A hologram manufacturing method is disclosed, which comprises a third step. However, in order to produce a hologram having a sufficient diffraction efficiency, the method of the known document requires 50 mJ / cm 2.
More than ^two exposure energies are required, and it has been desired to further improve the sensitivity characteristics, which are important characteristics in mass replication of holograms, that is, in shortening the exposure time.

[0002]

DISCLOSURE OF THE INVENTION The present invention is a hologram having excellent chemical stability and environmental resistance, high sensitivity over a wide wavelength range, and particularly excellent resolution, diffraction efficiency and transparency. The present invention provides a recording medium and a volume phase hologram manufacturing method using the same.

[0003]

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 achieved. That is, the first invention of the present 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. ), A compound having at least one polymerizable ethylenically unsaturated bond (B), a pyrylium salt or thiopyrylium salt derivative (C) and a sulfonium organoboron complex (D) in combination, for hologram recording. A second aspect of the present invention is a hologram recording medium, characterized in that a photosensitive material is formed by sandwiching an optically transparent base material and an optically transparent protective film to form a photosensitive film. A first step of exposing the recording medium to a radiation interference pattern,
A second treatment for removing the unpolymerized radiation-polymerizable substance from the recording medium and also treating with a solvent capable of swelling the recording medium;
And a third step of bringing the recording medium into contact with a solvent having poor solubility and swelling property with respect to the recording medium. In the invention, before or after exposing the hologram recording medium to an interference pattern due to radiation, exposure treatment to actinic rays such as ultraviolet rays, visible rays, electron rays, and / or heat treatment is performed. It is a method of manufacturing a volume phase hologram.

The present invention will be described in detail below.

The polymer compound (A) used in the hologram recording medium of the present invention comprises 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 and dodecyl. , 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl, 1,3-dimethylbutyl, 2-ethylhexyl, 2-methylpentyl, cyclohexyl, adamantyl, isobornyl, dicyclopentanyl, tetrahydrofurfuryl, etc. Polymers of branched and cyclic alkyl acrylic or methacrylic acid ester monomers, phenyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 4-
Acrylics containing aromatic rings such as butoxycarbonylphenyl, 4-tert-butylphenyl, benzyl, 4-phenylethyl, 4-phenoxydiethylene glycol, 4-phenoxytetraethylene glycol, 4-phenoxyhexaethylene glycol, 4-biphenylyl Polymers of acid or methacrylic acid ester monomers, ferrocenylmethyl, polymers of acrylic acid or methacrylic acid ester monomers containing iron atoms such as ferrocenylethyl, trifluoroethyl, tetrafluoropropyl, heptadecafluorodecyl, Polymers of acrylic acid or methacrylic acid ester monomers containing halogen atoms such as octafluoropentyl and 2,3-dibromopropyl, acetic acid containing silicon atoms such as trimethoxysilylpropyl. Polymer Le acid or methacrylic acid esters, polymers of acrylic acid or methacrylic acid ester monomer containing an epoxy group such as glycidyl acrylate and glycidyl methacrylate, N, N-dimethylaminoethyl, N, N-diethylaminoethyl, t-
Examples thereof include polymers of acrylic acid or methacrylic acid ester monomers containing an amino group such as butylaminoethyl. These acrylic acid ester or methacrylic acid ester monomers can be used as a copolymer of two or more components, if necessary.

Vinyl monomers that 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, acrylonitrile, Examples thereof include 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.

The pyrylium salt or thiopyrylium salt derivative (C) used in the present invention has the general formula (1)

General formula (1)

[Chemical 1]

(In the formula, R ^{1 to} R ⁵ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a haloalkyl group which may have a substituent, or a substituent. Alkenyl group, optionally substituted styryl group, optionally substituted alkoxy group, optionally substituted aryl group, nitro group, optionally substituted group A group selected from an amino group, a hydroxy group, and a heterocyclic group which may have a substituent, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ are respectively Together, they may form an aromatic ring or a heterocyclic ring, Y represents an oxygen atom or a sulfur atom, X represents a halogen, BF.
₄ , PF ₆ , AsF ₆ , ClO ₄ , SbF ₆ , CF ₃ S
Indicates O ₃ , CH ₃ SO ₃ , or CH ₃ C ₆ H ₄ SO ₃ . ).

The halogen atom includes fluorine, chlorine, bromine and iodine atoms, and the alkyl group which may have a substituent includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group,
Examples thereof include linear or branched alkyl groups such as octyl group, decyl group, dodecyl group and octadecyl group, and examples of the substituent of the haloalkyl group which may have a substituent include fluorine, chlorine, bromine and iodine. Examples of the alkenyl group that may have a substituent include a vinyl group, a 1-propenyl group, a 1-butenyl group, and the like, and as the styryl group that may have a substituent, Examples include styryl group, p-methylstyryl group, p-methoxystyryl group, p-ethoxystyryl group, p-tert-butylstyryl group, p-chlorostyryl group, p-dimethylaminostyryl group, p-nitrostyryl group and the like. Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and a butoxy group. Examples of the aryl group that may have a substituent include a phenyl group, a p-tolyl group, a p-tert-butylphenyl group, and an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a benzyloxy group. A p-chlorophenyl group, a p-methoxyphenyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like can be mentioned. Examples of the amino group which may have a substituent include a dimethylamino group and a diethylamino group. Is mentioned.

Specific compounds represented by the general formula (1) include 2,4,6-triphenylpyrylium, 2,
4,6-tris (4-methoxyphenyl) pyrylium,
2,4,6-Tris (4-butoxyphenyl) pyrylium, 2,4,6-tris (4-dimethylaminophenyl) pyrylium, 2,6-diphenyl-4- (4-methoxyphenyl) pyrylium, 4- ( 4-butoxyphenyl) -2,6-diphenylpyrylium, 2,6-bis (4-methoxyphenyl) -4-phenylpyrylium,
4- (4-dimethylaminophenyl) -2,6-diphenylpyrylium, 4- (2,4-dichlorophenyl)-
2,6-diphenylpyrylium, 2,6-diphenyl-
4- (4-ethylphenyl) pyrylium, 2,6-bis (4-butoxyphenyl) -4- (4-methoxyphenyl) pyrylium, 2- (4-ethoxyphenyl) -4,
6-diphenylpyrylium, 2- (β, β-bis (4-
Dimethylaminophenyl) vinylene) -4,6-diphenylpyrylium, 2- (4-dimethylaminostyryl)
-4,6-diphenylpyrylium, 2- (3,4-diethoxystyryl) -4,6-diphenylpyrylium, 2
-(4-dimethylamino-β-ethylstyryl) -4,
6-diphenylpyrylium, 4,6-bis (4-butylphenyl) -2- (4-nitrophenyl) pyrylium,
2,6-bis (4-methoxyphenyl) -4-methylpyrylium, 4,6-bis (4-dimethylaminophenyl-β-methoxystyryl) -2-hydroxypyrylium, 4- (4-methoxyphenyl) -2-Nitro-6-
Phenylpyrylium, 4,6-bis (4-dimethylaminostyryl) -2-nitropyrylium, 4,6-bis (4-butoxystyryl) -2-aminopyrylium, 2
-Methoxy-4-naphthyl-6-styrylpyrylium,
2,4,6-triphenylthiopyrylium, 2,4,6
-Tris (4-methoxyphenyl) thiopyrylium,
2,4,6-Tris (4-butoxyphenyl) thiopyrylium, 2,4,6-tris (4-dimethylaminophenyl) thiopyrylium, 2,6-diphenyl-4- (4
-Methoxyphenyl) thiopyrylium, 4- (4-butoxyphenyl) -2,6-diphenylthiopyrylium,
2,6-bis (4-methoxyphenyl) -4-phenylthiopyrylium, 4- (4-dimethylaminophenyl)
-2,6-diphenylthiopyrylium, 4- (2,4-
Dichlorophenyl) -2,6-diphenylthiopyrylium, 2,6-diphenyl-4- (4-ethylphenyl)
Thiopyrylium, 2,6-bis (4-butoxyphenyl) -4- (4-methoxyphenyl) thiopyrylium,
2- (4-ethoxyphenyl) -4,6-diphenylthiopyrylium, 2- (β, β-bis (4-dimethylaminophenyl) vinylene) -4,6-diphenylthiopyrylium, 2- (4- Dimethylaminostyryl) -4,6
-Diphenylthiopyrylium, 2- (3,4-diethoxystyryl) -4,6-diphenylthiopyrylium, 2
-(4-dimethylamino-β-ethylstyryl) -4,
6-diphenylthiopyrylium, 4,6-bis (4-butylphenyl) -2- (4-nitrophenyl) thiopyrylium, 2,6-bis (4-methoxyphenyl) -4-
Methylthiopyrylium, 4,6-bis (4-dimethylaminophenyl-β-methoxystyryl) -2-hydroxythiopyrylium, 4- (4-methoxyphenyl) -2
-Nitro-6-phenylthiopyrylium, 4,6-bis (4-dimethylaminostyryl) -2-nitrothiopyrylium, 4,6-bis (4-butoxystyryl) -2-
Aminothiopyrylium, 2-methoxy-4-naphthyl-
In addition to chlorine salts such as 6-styrylthiopyrylium, bromine salts, iodine salts, tetrafluoroborate salts, perchlorates, hexafluoroantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, etc. Chem. Ber. ”, No. 23
09 to 2320 (1959), or
"Journal of Organic Chemistry", Vol. 36, page 600-
The compounds described on page 602 (1971) can be exemplified.

Next, the sulfonium organic boron complex (D) used in the present invention is represented by the general formula (2)

General formula (2)

[Chemical 2] (In the formula, R ^{6 to} R ⁸ each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent which may have a substituent. Alkylene group which may be substituted, alicyclic group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, and which may have a substituent A group selected from an alkylthio group, an arylthio group which may have a substituent, and an amino group which may have a substituent, R ⁹ is an oxygen atom or a lone electron pair, R ¹⁰ , R ¹¹ , R ¹² and R ^13's each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, or an alkynyl group which may have a substituent. A group selected from the group consisting of two or more groups represented by R ⁶ , R ⁷ and R ⁸ It may have a cyclic structure, and R ⁶ ,
Two or more of R ⁷ and R ⁸ do not become an aryl group which may have a substituent at the same time, and all R ^{10 to} R ¹³ do not become an aryl group which may have a substituent at the same time. . ) Represents a sulfonium organoboron complex selected from a sulfonium organoboron complex or an oxosulfonium organoboron complex. The sulfonium organic boron complex represented by the general formula (2) can be synthesized according to the method described in Japanese Patent Application No. 4-56831.

In the substituents R ⁶ , R ⁷ and R ⁸ on the sulfonium or oxosulfonium cation in the general formula (2), the alkyl group which may have a substituent is a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, isobutyl group, sec-butyl group, te
rt-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, allyl group, benzyl group, acetonyl group, phenacyl group, salicyl group, anisyl group, cyanomethyl group, chloromethyl group,
Bromomethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, menthyl group, pinanyl group, etc.
Examples of the aryl group which may have a substituent include a phenyl group, p-tolyl group, xylyl group, mesityl group, cumenyl group, p-methoxyphenyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, p- Cyanophenyl group, 2,4-bis (trifluoromethyl) phenyl group, p-fluorophenyl group, p-chlorophenyl group, p-dimethylaminophenyl group, p-phenylthiophenyl group, etc. have a substituent As the alkenyl group which may also be a vinyl group, a 1-propenyl group, a 1-butenyl group, a 3,3-dicyano-1-propenyl group, or the like, an alicyclic group which may have a substituent is a cyclopentyl group, A cyclohexyl group, a norbornyl group, a bornyl group, a 1-cyclohexenyl group and the like are methoxy as an alkoxyl group which may have a substituent. , Tert- butoxy group, a benzyloxy group, the aryloxy group which may have a substituent, a phenoxy group, p- tolyloxy group,
P-fluorophenoxy group, p-nitrophenoxy group and the like are alkylthio groups which may have a substituent, methylthio group, ethylthio group, butylthio group and the like are arylthio groups which may have a substituent. , Phenylthio group, p-tolylthio group, p-cyanophenylthio group and the like, the amino group which may have a substituent is, for example, amino group, methylamino group, dimethylamino group, cyclohexylamino group, anilino group, piperidino group. Group, morpholino group and the like, and R ⁶ , R ⁷ and R ⁸ may have a cyclic structure in which two or more groups are bonded, and examples thereof include a tetramethylene group, a pentamethylene group, 1, Alkylene group which may have a substituent such as 4-dichlorotetramethylene group, ethylenedioxy group, diethylenedioxy group, adipoyl group and ethyle The present invention is not limited to these.

In the substituents R ^{10 to} R ¹³ on the organic boron anion in the general formula (2), the alkyl group which may have a substituent is a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, isobutyl group, s
An ec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an allyl group, a benzyl group and the like, an aryl group which may have a substituent is phenyl. Group, p-tolyl group, xylyl group, mesityl group, cumenyl group, p-methoxyphenyl group, naphthyl group, 2,4-bis (trifluoromethyl) phenyl group, p-fluorophenyl group, p-
Examples of the alkenyl group which may have a substituent include a chlorophenyl group and a p-bromophenyl group, and a vinyl group, 1-
Examples of the alkynyl group which may have a substituent include a propenyl group and a 1-butenyl group, and an ethenyl group and 2-tert.
Examples thereof include -butylethenyl group and 2-phenylethenyl group, but the present invention is not limited thereto.

In the general formula (2), as a particularly preferred structure, at least one of R ⁶ , R ⁷ and R ⁸ is an allyl group which may have a substituent or a benzyl group which may have a substituent. , A vinyl group which may have a substituent, or a phenacyl group which may have a substituent, and R ¹⁰ is an alkyl group which may have a substituent;
^{A structure in which 11} , R ¹² and R ¹³ are aryl groups which may have a substituent.

[0018] For this reason, a sulfonium organic boron complex represented by the general formula (2) is, but effectively is required to be degraded photosensitized by pyrylium salt or thiopyrylium salt derivatives (C), R ^6, At least one of R ⁷ and R ⁸ is an aryl group which may have a substituent, a benzyl group which may have a substituent, a vinyl group which may have a substituent, or a substituent. By introducing the phenacyl group which may be contained, the electron accepting property of the polymerization initiator represented by the general formula (2) is enhanced, and these groups are preferentially and efficiently decomposed from the sulfonium or oxosulfonium cation. This is because it is considered that the efficiency of generating free radicals is increased by imparting such a property, and as a result, the sensitivity can be improved.

Specific compounds (a) to (g) are shown below.

Compound (a)

[Chemical 3]

Compound (b)

[Chemical 4]

Compound (c)

[Chemical 5]

Compound (d)

[Chemical 6]

Compound (e)

[Chemical 7]

Compound (f)

[Chemical 8]

Compound (g)

[Chemical 9]

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 ester or methacrylic ester and a vinyl monomer, a compound (B) having at least one polymerizable ethylenic unsaturated bond, a pyrylium salt, or The thiopyrylium salt derivative (C) and the sulfonium organoboron complex (D) are dissolved in a suitable solvent, and the resulting solution is formed into a film on an optically transparent substrate or an optically transparent protective film. It is formed by coating. 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 pyrylium salt or thiopyrylium salt derivative (C) so that the transmittance of the irradiation laser light is 1% or more. Further, if necessary, various additives such as a plasticizer, an antioxidant and a thermal polymerization inhibitor may be added.

Amount of polymer compound (A), which is a homopolymer of acrylic acid ester or methacrylic acid ester, or a copolymer of two or more components of acrylic acid ester or methacrylic acid ester and vinyl monomer, in the hologram recording material. Is required to produce a volume phase hologram having high diffraction efficiency, high resolution and high transparency.
˜90 wt%, preferably 30-70 wt%.
The amount of the compound (B) having at least one polymerizable ethylenic unsaturated bond used is a homopolymer of acrylic acid ester or methacrylic acid ester, or two components of acrylic acid ester or methacrylic acid ester and vinyl monomer. The amount 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) which is the above copolymer. 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 hologram recording medium of the present invention, the pyrylium salt or thiopyrylium salt derivative (C) is a homopolymer of acrylic acid ester or methacrylic acid ester, or acrylic acid ester or methacrylic acid ester. 2 of ester and vinyl monomer
0.1 to 30 parts by weight, preferably 0.5 to 100 parts by weight of the polymer compound (A) which is a copolymer of at least one component.
Used in the range of up to 15 parts by weight. 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 sulfonium organoboron complex (D) which is the other component of the photopolymerization initiator is a homopolymer of acrylic acid ester or methacrylic acid ester, or two or more components of acrylic acid ester or methacrylic acid ester and a vinyl monomer. It 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) which is a copolymer.

The photosensitive material for hologram recording in the present invention is used as a recording medium which is 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. Also,
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 hologram recording photosensitive material is formed on the above-mentioned transparent protective film, it can be bonded by a method of bringing the photosensitive material surface side into close contact with an optically transparent substrate.

As described above, before exposing the hologram recording photosensitive material of the present invention to the radiation interference pattern,
By using it in the form of a recording medium sandwiched between an optically transparent base material and an optically transparent protective film, the hologram recording photosensitive material 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 laser, Ar.
The first step of exposing to an interference pattern of a visible laser beam emitted from an ion laser, a He-Ne laser, a Kr ion laser, a ruby laser, or the like is performed. Then, the protective film coating the recording medium is peeled off from the recording medium, the unpolymerized radiation-polymerizable substance is removed from the recording medium, and the acrylate ester or Second step of immersing the polymer compound (A), which is a homopolymer of methacrylic acid ester or a copolymer of two or more components of acrylic acid ester or methacrylic acid ester and vinyl monomer, in a solvent having an action of swelling , So-called swelling process. As the solvent preferably used in the step, benzene, toluene, an aromatic organic solvent such as xylene,
Ethyl acetate, acetate organic solvents such as butyl acetate, acetone, methyl ethyl ketone, ketone organic solvents such as cyclohexanone, alcohol organic solvents such as methanol, ethanol and isopropanol, dioxane, cyclic ether organic solvents such as tetrahydrofuran, dichloromethane, A commonly used organic solvent such as a chlorine-based organic solvent such as chloroform or tetrachloroethane, or a mixed solvent thereof can be applied. In that case, a homopolymer of acrylic acid ester or methacrylic acid ester in the hologram recording medium,
Alternatively, it is necessary that the 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, does not completely dissolve but has a function of swelling. It is necessary to select it appropriately depending on the type of the molecular compound (A). The dipping time required to complete the swelling step varies depending on the swelling efficiency of the solvent used and the dipping temperature, but at room temperature, the dipping time is generally completed within 30 seconds to 5 minutes.

Next to the swelling treatment step, the recording medium is brought into contact with a solvent having poor solubility and swelling property with respect to the recording medium, and the recording medium swollen in the swelling treatment step is contracted. Process, so-called shrinking process. 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.

Further, in the production of a volume phase hologram using the hologram recording medium of the present invention, before or after exposing the recording medium to the radiation interference pattern,
By exposing the recording medium to actinic rays such as ultraviolet rays, visible rays, or electron rays, and / or by subjecting it to heat treatment, the production of the volume phase hologram of the present invention can be made more effective. It is possible.

The actinic radiation source used for the above treatment is not particularly limited, but as the ultraviolet ray source, a low pressure mercury lamp,
Medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, and the like, and visible light sources other than the above light source, such as He-Cd and Ar ions. It is possible to use a visible light laser light source, a white light, a fluorescent light, or the like. In this case, the actinic ray emitted from the actinic light source used is effectively provided by the pyrylium salt or thiopyrylium salt derivative (C) and / or the sulfonium organoboron complex (D) used in the hologram recording medium of the present invention. Need to be absorbed. Since the exposure time and the exposure amount of these actinic rays differ depending on the actinic ray source, it is necessary to appropriately determine the optimum value.

As the heat source for the heat treatment, a heat circulation type oven or a heating roll is generally preferably used, but the heat source is not limited to this. The heat treatment temperature range is preferably between 50 ° C and 120 ° C, more preferably between 60 ° C and 90 ° C.

The hologram recording medium of the present invention is a high molecular 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. ), A compound (B) having at least one polymerizable ethylenic unsaturated bond, a pyrylium salt or thiopyrylium salt derivative (C) and a sulfonium organoboron complex (D) in combination. The pyrylium salt or thiopyrylium salt derivative (C) used in the present invention is an Ar ion laser, He-C.
Visible light emitted from a visible laser light source such as a d laser, a He-Ne laser, or a Kr ion laser is efficiently absorbed, and the sulfonium organoboron complex (D) is efficiently decomposed by its spectral sensitizing action. As a result, free radicals are generated, and radical polymerization is effectively induced. In particular, the sulfonium organoboron complex used in the present invention has two free radical generation sources in its molecule, and therefore, it is possible to effectively generate free radicals and significantly improve the sensitivity characteristics. It is presumed that it was Further, by using a polymer compound (A) which is a homopolymer of acrylic acid ester or methacrylic acid ester or a copolymer of two or more components of methacrylic acid ester and vinyl monomer, chemical stability and resistance can be improved. It is presumed that it has become possible to manufacture a volume phase hologram having excellent environmental characteristics and 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, polymerization occurs at a portion having a strong interference action in the exposed portion of the radiation. Polymerization reaction of the compound (B) having at least one possible ethylenically unsaturated bond occurs, and a homopolymer of acrylic acid ester or methacrylic acid ester as a support, or acrylic acid ester or methacrylic acid ester and vinyl monomer A network structure is formed together with the polymer compound (A) which is a copolymer of two or more components with and becomes insoluble in the solvent used in the next swelling treatment step. On the other hand, in the radiation-exposed portion, in the portion having a weak interference action, the polymerization reaction of the compound (B) having at least one polymerizable ethylenic unsaturated bond does not occur, or the polymerization degree is low, The recording medium swells with the swelling treatment solvent. This creates a density difference between the two parts,
As a result, a difference in refractive index is generated, and it is estimated that hologram recording is performed. 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.

[0038]

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.

Examples 1 to 10 Polymethyl methacrylate (manufactured by Aldrich, weight average molecular weight: 710,000) 100 parts, pentaerythritol triacrylate (PETA) 70 parts, represented by the general formula (1) shown in Table 1. 5 parts of pyrylium salt or thiopyrylium salt derivative, dimethylphenacylsulfonium-n
-Butyltriphenylborate (compound (a))
Part, 900 parts of methyl ethyl ketone
A 3 mil applicator was applied onto a glass plate of 00 × 125 × 3 mm so that the film thickness after drying the photosensitive solution was 7 μm, and dried in an oven at 60 ° C. 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. Then, the recording medium was exposed to a 60 W fluorescent lamp for 60 seconds to perform a pre-exposure treatment.

The optical system for producing a volume phase hologram shown in FIG. 1 is used for this medium, and 488 nm light of an Ar ion laser is used in Examples 1 to 5 and 514 nm of an Ar ion laser is used in Examples 6 and 7. the light,
In Examples 8 to 10, a He-Ne laser 6 was used.
Volume phase hologram recording was performed using 33 nm light. Then, after removing the polyvinyl alcohol layer, which is a protective layer, by peeling off, the recording medium is immersed in xylene for 1 minute to develop and swell the photosensitive layer, and then to a heptane.
A volume phase type hologram was manufactured by immersing it for 0 seconds and shrinking it. Diffraction efficiency is ART2 manufactured by JASCO Corporation
It was measured with a 5C type spectrophotometer. 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. Table 1 collectively shows the amount of exposure energy that gives the maximum diffraction efficiency, the diffraction efficiency, the playback wavelength, and the storage stability test results.

Examples 11 to 16 In Example 1, dimethylphenacylsulfonium-
n-butyltriphenylborate (compound (a)),
A volume phase hologram was prepared in the same manner as in Example 1 except that the sulfonium organoboron complex represented by the compound (b) to the compound (g) was used. The hologram properties obtained are summarized in Table 2.

Example 17 Table 3 shows the results of hologram characteristics when polymethylmethacrylate in Example 1 was replaced by polyisomethanylmethacrylate and the same operation as in Example 1 was carried out.

Example 18 The results of hologram characteristics are shown in Table 3 when polymethylmethacrylate in Example 1 was changed to ferrocenylmethylmethacrylate and the same procedure was followed as in Example 1. In addition, polyferrocenylmethyl methacrylate is
C. U. Pittman et al., "Macromoleculecu
It can be obtained by the method described in "Les" magazine, Vol. 3, page 746 (1970).

Example 19 Table 3 shows the results of hologram characteristics when polymethyl methacrylate in Example 1 was changed to polybenzyl methacrylate and the same operation as in Example 1 was carried out.

Example 20 Table 3 shows the results of hologram characteristics when polymethyl methacrylate in Example 1 was changed to polymethoxytrimethoxysilylpropyl and the same operation as in Example 1 was carried out.

Example 21 Polymethylmethacrylate in Example 1 was replaced by a copolymer of polymethylmethacrylate and styrene (molar ratio 7:
Table 3 shows the results of hologram characteristics when the same procedure as in Example 1 was performed except that the above method was used.

[0047]

[Table 1]

Storability 1 indicates durability under storage at 25 ° C. and 60% RH. Storability 2 indicates durability under storage at 90 ° C.

[0049]

[Table 2]

Storability 1 indicates durability under storage at 25 ° C. and 60% RH. Storability 2 indicates durability under storage at 90 ° C.

[0051]

[Table 3]

Storability 1 indicates durability under storage at 25 ° C. and 60% RH. Storability 2 indicates durability under storage at 90 ° C.

[0053]

Industrial Applicability By the use of the hologram recording medium of the present invention and the method for producing a hologram of the present invention using the recording medium, chemical stability can be achieved with a small exposure energy of 20 mJ / cm ² or less over a wide wavelength range. It becomes possible to manufacture a volume phase hologram having excellent environment resistance characteristics, high resolution, high diffraction efficiency, and high transparency.

[0054]

[Brief description of drawings]

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

[0056]

[Explanation of symbols]

 1: Laser light source 2: Mirror 3: Lens 4: Spatial filter 5: Substrate (glass plate) 6: Hologram photosensitive film 7: Protective film (polyvinyl alcohol film)

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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 photosensitive material for hologram recording, comprising a combination of a compound (B) having at least one or more unsaturated unsaturated bonds, a pyrylium salt or thiopyrylium salt derivative (C) and a sulfonium organic boron complex (D), A holographic recording medium characterized in that a photosensitive film is formed by being sandwiched between a transparent base material and an optically transparent protective film. 2. The hologram recording medium according to claim 1, wherein the hologram recording medium is exposed to a radiation interference pattern, a first step, a second step of treating the hologram recording medium with a solvent for swelling the medium, and a solubility in the recording medium. And a method for producing a volume phase hologram, comprising a third step of bringing the recording medium into contact with a solvent having a poor swelling property. 3. The exposure treatment (and / or) or heat treatment to active rays such as ultraviolet rays, visible rays, and electron beams before or after exposing the hologram recording medium according to claim 1 to an interference pattern by radiation. The method for producing a volume phase hologram according to claim 2, wherein the hologram is a volume phase hologram.