JPH06195014A - Holographic recording material and volume phase hologram manufacturing method using the same - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide a hologram recording material having excellent sensitivity and a method for producing a volume phase hologram using the hologram recording material. [Structure] Polymer compound (A), which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers, compound (B) having at least one polymerizable ethylenic unsaturated bond, and tetrabenzo A hologram material comprising a combination of a porphyrin derivative (C) and a sulfonium organic boron complex (D), and a method for producing a volume phase hologram in which light and / or heat is applied after hologram exposure of the hologram recording material. [Effect] According to the present invention, with high sensitivity over a long wavelength region,
It is possible to easily manufacture a volume phase hologram that is chemically stable, has high resolution, high diffraction efficiency, and high transparency.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent chemical stability and environmental resistance, and has high sensitivity in the long wavelength region.
The present invention also relates to a hologram recording material having excellent resolution, diffraction efficiency and transparency, and a simple method for producing a volume phase hologram using the hologram recording material.

[0002]

2. Description of the Related Art Conventionally, bleached silver salt and dichromated gelatin type photosensitive materials have been generally used as hologram recording materials. However, the hologram material using this material has a problem that it requires complicated wet development processing and is inferior in resolution or environment resistance characteristics such as humidity resistance and weather resistance.

In order to solve such a problem, a hologram recording material using a photopolymer has been proposed. For example, Japanese Patent Publication No. 62-22152 discloses a hologram recording material characterized by a combination of a polyfunctional monomer having two or more ethylenically unsaturated bonds, a non-crosslinkable polymer and an initiator. ing. According to the known technique, it is possible to manufacture a hologram that is excellent in terms of diffraction efficiency, resolution, environment resistance, etc., but it is inferior in sensitivity characteristics in the long wavelength region, or a wet treatment process is adopted in hologram manufacturing. However, there are drawbacks such as complications in production such as the occurrence of defects, uneven development caused by voids and cracks generated during the solvent immersion operation, and deterioration of transparency due to whitening. Further, since the polymer used is non-crosslinkable, the strength of the cured film is inferior.

In order to improve the sensitivity characteristics in the long wavelength region, a photopolymerization initiator comprising a combination of tetrabenzoporphyrins and their metal complexes with an electron-accepting radical generator, poly-N-vinylcarbazole and polymerization. A photosensitive material for hologram recording comprising a compound having at least one possible ethylenically unsaturated bond is disclosed in JP-A-3-278082. According to the material, it is possible to manufacture a volume phase hologram having excellent environment resistance properties, high resolution, and high diffraction efficiency, but it is desired to suppress deterioration of transparency due to whitening. .

On the other hand, a hologram recording material using a photopolymer (and a hologram recording material using a photopolymer capable of manufacturing a hologram only by interference exposure as the only processing step, which does not require a complicated or complicated wet processing step in the hologram manufacturing step (and ) Or its manufacturing method is disclosed. For example, JP-A-2-3081 or JP-A-2-30
No. 82, for hologram recording comprising a thermoplastic polymer characterized in that either the polymer or the monomer has a substituent containing an aromatic ring or a halogen atom, a liquid ethylenic monomer, and a photoinitiator. Photopolymerizable compositions and refractive index imaging elements are disclosed. According to this known technique, high diffraction efficiency,
The fact that holograms with high resolution, environmental resistance, and transparency are manufactured is characterized by the fact that SPIE “Practical H
volography IV, 1212, 30 (1990) and "Journal of Image".
ing Science ", Volume 35, pages 19 and 25.
Page (1991). However,
The sensitivity characteristic of the hologram recording material in the long wavelength region is on the order of several hundred mJ / cm ² , and it has been desired to further improve the sensitivity characteristic in order to shorten the exposure time in hologram replication.

Further, Japanese Patent Application Laid-Open No. 2-51188 discloses a hologram composition comprising a plurality of compounds having at least one polymerizable carbon-carbon double bond in a molecule having different refractive indexes. It's According to this known technique, a hologram with high resolution and high diffraction efficiency which does not require complicated processing steps can be produced, but one of the compounds having one or more polymerizable carbon-carbon double bonds in the molecule is produced. As a result, since urethane acrylate having a low glass transition temperature is used, it has a drawback that the heat resistance of the hologram is inferior.

Further, Japanese Patent Laid-Open Nos. 3-36582 and 3-249785 disclose hologram recording materials which are characterized by combining an allyl monomer and an acrylic monomer having different refractive indices and polymerizability. There is. According to this known technique, it is possible to manufacture a volume phase hologram with high diffraction efficiency, "Holographic Display Research Group Bulletin", Vol. 10, No. 1.
Issue, page 3 (1990). However, in the known technique, since a monomer having fluidity is used as a main component, it is necessary to previously perform a treatment for suppressing fluidity of the photosensitive film such as heat treatment before hologram exposure. However, it has drawbacks such as complicated operation and difficulty in controlling the film thickness.

[0008]

DISCLOSURE OF THE INVENTION The present invention has excellent environment resistance characteristics, high sensitivity in a long wavelength region, and high resolution.
It is intended to provide a hologram recording material having excellent properties in diffraction efficiency and transparency and a simple method for producing a volume phase hologram using the hologram recording material.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides a hologram recording material having excellent environmental resistance, resolution, diffraction efficiency, transparency and sensitivity, and a simple method for producing a volume phase hologram using the hologram recording material. provide.

[0010]

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 is a polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers, and at least one polymerizable ethylenic unsaturated bond. A compound (B) having
A hologram recording material containing a combination of a tetrabenzoporphyrin derivative (C) and a sulfonium organic boron complex (D). A second invention is a hologram recording characterized in that the polymer compound (A), which is a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components, has a crosslinkable (meth) acryloyl group. It is a material. A third invention has a refractive index of a polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components, and at least one polymerizable ethylenic unsaturated bond. The hologram recording material according to the first invention is characterized in that the refractive index difference from the refractive index of the compound (B) is 0.005 or more. A fourth invention is a polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers, and a compound (B) having at least one polymerizable ethylenic unsaturated bond. In producing a hologram using a hologram recording material comprising a combination of a tetrabenzoporphyrin derivative (C) and a sulfonium organoboron complex (D), the hologram recording material is exposed to light and ( Or) A method for manufacturing a volume phase hologram characterized by applying heat.

The present invention will be described in detail below.

First, a polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of two or more components of vinyl monomers used in the present invention is exemplified. Polymers of such vinyl monomers include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t
ert-butyl, pentyl, neopentyl, hexyl,
Heptyl, octyl, nonyl, dodecyl, 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl, 1,3-
Dimethylbutyl, 2-ethylhexyl, 2-methylpentyl, cyclohexyl, adamantyl, isobornyl,
Polymers of chain, branched and cyclic alkyl (meth) acrylic acid ester monomers such as dicyclopentanyl and tetrahydrofurfuryl, 2-hydroxyethyl, 2-
Hydroxypropyl, 4-hydroxybutyl, glycerol, 2-hydroxy-3-phenoxypropyl, 2-
Polymers of (meth) acrylic acid ester monomer having a hydroxyl group such as (meth) acryloyloxyethyl-2′-hydroxypropyl phthalate, phenyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 4-butoxycarbonylphenyl, 4 -Tert
-Butylphenyl, benzyl, 4-phenylethyl, 4
-Polymer of (meth) acrylic acid ester monomer containing aromatic ring such as phenoxydiethylene glycol, 4-phenoxytetraethylene glycol, 4-phenoxyhexaethylene glycol, 4-biphenylyl, epoxy group such as glycidyl (meth) acrylate A polymer of a (meth) acrylic acid ester monomer containing, a polymer of a (meth) acrylic acid ester monomer containing an iron atom such as ferrocenylmethyl and ferrocenylethyl,
Trifluoroethyl, tetrafluoropropyl, heptadecafluorodecyl, octafluoropentyl, 2,3
-A polymer of a (meth) acrylic acid ester containing a halogen atom such as dibromopropyl, or an alkoxysilane group such as trimethoxysilylpropyl (meth)
Polymer of acrylic acid ester, polymer of (meth) acrylic acid ester monomer containing amino group such as N, N-dimethylaminoethyl, N, N-diethylaminoethyl, t-butylaminoethyl, (meth) acrylic acid , Itaconic acid, maleic acid, p-vinylbenzoic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth)
Vinyl monomers containing a carboxyl group such as acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid Polymer of a phosphoric acid group-containing (meth) acrylic acid ester monomer such as ethylene oxide-modified phosphoric acid (meth) acrylate, acrylamide, N-butylacrylamide, N, N-dimethylacrylamide, acrylonitrile, styrene, 4- Hydroxystyrene, 4-hydroxymethylstyrene, 4-bromostyrene, chloromethylstyrene, perfluorostyrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, N-bi Rupiroridon, N- vinyl carbazole, vinyl pyridine, vinyl pyrrolidine, vinyl butyral, polymers of vinyl monomers such as vinyl acetal and the like, also two or more components of the copolymer thereof.

Next, the polymer compound having a (meth) acryloyl group capable of being cross-linked by a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components used in the present invention is It can be obtained by introducing a (meth) acryloyl group into a polymer compound containing, as a unit, a vinyl monomer having a functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group, a chloromethyl group or an epoxy group among the polymers. Such reactive polymers include, for example, functional polymer series "reactive polymer", Yoshio Iwakura, Keisuke Kurita, Kodansha Scientific (1977), or functional series "photosensitive polymer", It can be synthesized by the method described by Gentaro Nagasue and Hideo Inui, Kodansha Scientific (1977).

The compound (B) having at least one polymerizable ethylenic unsaturated bond used in the present invention is
It contains an oligomer in addition to a monofunctional or polyfunctional vinyl monomer, and may be a high molecular weight compound. Next, these compounds will be exemplified.

Unsaturated acid compounds such as (meth) acrylic acid, itaconic acid and maleic acid, (meth) acryl such as methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate. Acid alkyl ester compound, tetrahydrofuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate,
Vinyl monomers such as dimethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-vinylcarbazole, and aliphatic poly Hydroxy 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, Di- or poly (meth) acryl such as 1,10-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, neopentyl glycol, sorbitol, mannitol, etc. Fluorine atom-containing (meta) such as esters, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate ) Acrylate compounds,
Bromine atom such as 2,3-dibromopropyl (meth) acrylate, tribromophenoltriethylene oxide (meth) acrylate, p-bromophenoxyethyl (meth) acrylate, tetrabromobisphenol A ethi (propyrene) oxide-modified di (meth) acrylate Containing (meth) acrylate compound, phenyl (meth) acrylate, 4-methoxycarbonylphenyl (meth) acrylate, 4-ethoxycarbonylphenyl (meth)
Acrylate, 4-butoxycarbonylphenyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, benzyl (meth) acrylate, 4
-Phenoxyethyl (meth) acrylate, 4-phenylethyl (meth) acrylate, 4-phenoxydiethylene glycol (meth) acrylate, 4-phenoxytetraethylene glycol (meth) acrylate, 4-
Aromatic ring-containing (meth) acrylate compounds such as phenoxyhexaethylene glycol (meth) acrylate, 4-biphenylyl (meth) acrylate, epichlorohydrin phthalate-modified di (meth) acrylate, aromatic polyhydroxy compounds such as hydroquinone, resorcin , Catechol, pyrogallol, and other di- or poly (meth) acrylate compounds, isocyanuric acid eth (propylene) oxide-modified (meth) acrylate, bisphenol A eth (propylene) oxide-modified di (meth) acrylate, (meth) acrylated epoxy resin ,
Examples thereof include heavy metal atom-containing (meth) acrylate compounds such as ferrocenylmethyl (meth) acrylate, ferrocenylethyl (meth) acrylate, and zinc di (meth) acrylate.

The tetrabenzoporphyrin derivative (C) used in the present invention has the general formula (1)

General formula (1)

[Chemical 1]

(In the formula (1), R ¹ to R ⁴ are each independently a hydrogen atom, an alkyl group, or an aromatic residue having or not having a substituent, and A 1 to A 4
The benzene ring of 4 may or may not independently have a substituent, and may have another condensed benzene ring. ) And a tetrabenzoporphyrin derivative (C).

Next, the substituent in the general formula (1) will be explained. The alkyl group is a methyl group, an ethyl group or a propyl group, and the aromatic residue is a phenyl group, a naphthyl group or a pyridyl group. And so on. This aromatic residue may or may not have a substituent, and as the substituent, a halogen atom, a lower alkyl group having 1 to 5 carbon atoms, a lower alkoxy group or Examples thereof include lower alkoxycarbonyl group, carboxy group, nitro group, amino group and sulfone group. One or two or more of these substituents may be introduced into each benzene ring. Further, each benzene ring of A1 to A4 may be condensed with another benzene ring to form a naphthalene ring.

Specific examples of such a tetrabenzoporphyrin derivative include unsubstituted tetrabenzoporphyrin, meso-phenyltetrabenzoporphyrin in which at least one of the meso positions is substituted with a phenyl group,
Meso-naphthyltetrabenzoporphyrin having at least one meso position substituted with a naphthyl group, meso-pyridyltetrabenzoporphyrin having at least one meso position substituted with a pyridyl group, 5,5 ′, 5 ″, 5 ″ '-
Tetra-tert-butyltetrabenzoporphyrin,
4,6,4 ', 6', 4 ", 6", 4 '",
6 '''-octamethyltetrabenzoporphyrin,
5,5 ′, 5 ″, 5 ′ ″-tetraethoxytetrabenzoporphyrin, meso-methyltetrabenzoporphyrin in which at least one of the meso positions is substituted with a methyl group,
Meso-benzyltetrabenzoporphyrin in which at least one of meso positions is substituted with a benzyl group, meso-p-tolyltetrabenzoporphyrin in which at least one of meso positions is substituted with a p-tolyl group, and a benzene ring as a condensed ring is further bonded. Examples thereof include tetranaphthoporphyrin, meso-phenyltetranaphthoporphyrin in which at least one of meso positions is substituted with a phenyl group.

Such a tetrabenzoporphyrin derivative represented by the general formula (1) can be prepared by the method described in JP-A-63-83087, more specifically, K. Ichimura
17th "Inorg. Chim. Acta."
Volume 6, page 31 (1990), volume 182, volume 83 (1991) and volume 186, volume 95 (1991).
Year) You can obtain it by the method described.

As the central metal (M) of the tetrabenzoporphyrins, for example, the above-mentioned tetrabenzoporphyrins and Mg, Zn, Cd, Pd, Co, Cu, P
Al, In, Ga, F in which a complex with a divalent metal atom such as b, a hydroxyl group or a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is vertically coordinated.
Examples thereof include a complex with a trivalent metal atom such as e and Cr, or a tetravalent metal atom such as Si and Sn. Further, as the other organic residue axially coordinated in the vertical direction, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylthio group which may have a substituent, Examples thereof include an arylthio group which may have a substituent, a substituted sulfonyl group, a sulfonate group, a heterocyclic group which may have a substituent and a phosphate group which may have a substituent. In this case, M Examples of the atom in the organic residue directly bonded to include an oxygen atom, a nitrogen atom, a sulfur atom and the like.

Compounds (a) to (h) are shown below as typical examples of the tetrabenzoporphyrin derivative represented by the general formula (1) used in the present invention.

Compound (a)

[Chemical 2]

Compound (b)

[Chemical 3]

Compound (c)

[Chemical 4]

Compound (d)

[Chemical 5]

Compound (e)

[Chemical 6]

Compound (f)

[Chemical 7]

Compound (g)

[Chemical 8]

Compound (h)

[Chemical 9]

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

General formula (2)

[Chemical 10](R in the formula^Five, R⁶And R⁷Are each independently a substituent
An alkyl group which may have a substituent and an ant which may have a substituent
Group, an alkenyl group which may have a substituent, a substituent
Alkylene group that may have and alicyclic ring that may have substituent
Group, an alkoxy group which may have a substituent, a substituent
Optionally an aryloxy group, optionally substituted aryl
A thio group, an arylthio group which may have a substituent,
A group selected from an amino group which may have a substituent is represented by R⁸Is
R is an oxygen atom or lone pair of electrons ⁹, R^Ten, R¹¹And
And R¹²Are each independently an optionally substituted alkyl group.
Group, an aryl group which may have a substituent, and a substituent
Optionally alkenyl group, optionally substituted alkynyl group
R is a group selected from^Five, R⁶And R⁷Haso
It may be a cyclic structure in which two or more groups of
R^Five, R⁶And R ⁷Two or more of
R does not become an aryl group which may have⁹,
R^Ten, R¹¹And R¹²All may have substituents at the same time
It does not become an aryl group. ) Sulfoni
Organoboron complex or oxosulfonium organoboro
Showing sulfonium organoboron complexes selected from elementary complexes
You Sulfonium organoboron complex represented by general formula (2)
The body is made according to the method described in Japanese Patent Application No. 4-56831.
Can be made.

In the substituents R ⁵ , R ⁶ and R ⁷ 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.
The aryl group which may have a substituent includes 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, etc., and R ⁵ , R ⁶ and R ⁷ 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 ⁹ , R ¹⁰ , R ¹¹ and R ¹² 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, Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, allyl group, benzyl group, etc. Examples of the aryl group which may have a 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-chlorophenyl group, p-bromophenyl group and the like, the alkenyl group which may have a substituent is a vinyl group or 1-propenyl group. Examples of the alkynyl group that may have a substituent include a 1-butenyl group and the like, but include an ethenyl group, a 2-tert-butylethenyl group, a 2-phenylethenyl group, and the like, but the present invention is not limited thereto. Not a thing.

Particularly preferred structures in the general formula (2)
Then R^Five, R⁶And R⁷At least one of
Is an allyl group which may have a substituent, or a substituent which may have a substituent.
Good benzyl group, optionally substituted vinyl group, if
Or any of the phenacyl groups which may have a substituent.
R⁹Is an alkyl group which may have a substituent, R
^Ten, R¹¹And R¹²Is an aryl group which may have a substituent
Is the structure.

[0038] The reason, sulfonium organic boron complex represented by the general formula (2) is, although the tetrabenzoporphyrin derivative (C) can effectively be decomposed photosensitizer is required, R ^5, R ⁶ And at least one of R ⁷ has an allyl 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 an optional phenacyl group, 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 a sulfonium or oxosulfonium cation. This is because the efficiency of generating free radicals is considered to be increased by adding the charge, and as a result, the sensitivity can be improved.

Specific compounds (i) to (o)
Is shown below.

Compound (i)

[Chemical 11]

Compound (j)

[Chemical 12]

Compound (k)

[Chemical 13]

Compound (l)

[Chemical 14]

Compound (m)

[Chemical 15]

Compound (n)

[Chemical 16]

Compound (o)

[Chemical 17]

The hologram recording light-sensitive material used in the present invention comprises a polymer compound (A) which is a homopolymer of a vinyl monomer or a copolymer of two or more vinyl monomers, and a polymerizable ethylenic unsaturated bond. A solution obtained by dissolving a compound (B) having at least one or more and a photopolymerization initiator comprising a tetrabenzoporphyrin derivative (C) and a sulfonium organic boron complex (D) in a suitable solvent at an arbitrary concentration Can be obtained by coating in the form of a film on a substrate such as a glass plate. The refractive index of the polymer compound (A), which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers, The refractive index difference from the refractive index of the compound (B) having at least one polymerizable ethylenic unsaturated bond is preferably 0.005 or more, and further the refractive index And more preferably but 0.01 or more. 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 tetrabenzoporphyrin 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, a chain transfer agent, an antioxidant, a thermal polymerization inhibitor, a leveling agent, etc. may be added.

The amount of the polymer compound (A), which is a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components, in the entire photosensitive material is required to perform hologram recording having high diffraction efficiency. 10 to 90% by weight, preferably 30 to 70% by weight. The amount of the compound (B) having at least one polymerizable ethylenic unsaturated bond used is a polymer compound which is a homopolymer of a vinyl monomer as a support or a copolymer of two or more vinyl monomers ( A) 10-2 for 100 parts by weight
00 parts by weight, preferably 40 to 150 parts by weight. 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 tetrabenzoporphyrin derivative (C) of the general formula (1) is
0.1 to 30 parts by weight, preferably 0.5 to 100 parts by weight of the polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers.
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) is a homopolymer of a vinyl monomer or a copolymer of two or more vinyl monomers.
It is used in the range of 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight.

By using a spin coater, a roll coater, a knife coater, a bar coater or the like, a photosensitive solution prepared by dissolving the hologram recording photosensitive material having the above composition ratio in an appropriate solvent is directly applied to a glass plate, a plastic film or the like. A photosensitive film is formed on the base material. Further, a protective layer for blocking oxygen may be formed thereon. The protective layer may be formed by laminating a film or plate made of a plastic such as polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol or polyethylene terephthalate, or applying a solution of the polymer. Alternatively, a glass plate may be attached. Further, an adhesive or a liquid substance may be present between the protective layer and the photosensitive film (and / or) or between the substrate and the photosensitive film in order to enhance airtightness.

The photosensitive plate or film formed of the hologram recording photosensitive material obtained as described above is
After fixing to the holder so that it is not affected by vibration, H
Volume phase hologram recording is performed by irradiating a visible light laser such as an e-Ne laser, a Kr ion laser, or a ruby laser. FIG. 1 shows an example of the optical system.

The hologram-recorded photosensitive plate or film requires application of light and / or heat for fixing an unexposed portion or an exposed portion.
In addition to visible light laser, light is visible light such as carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp and / or
Use ultraviolet light. The heat is preferably between 40 ° C and 160 ° C. Light and heat may be applied simultaneously to the hologram-recorded photosensitive plate or film, or light and heat may be applied separately. Further, an operation of peeling the protective film may be performed before and after applying light and / or heat.

[0053]

The hologram recording material used in the present invention comprises a polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers, and at least one polymerizable ethylenic unsaturated bond. It is characterized in that it contains a combination of a compound (B) having an individual compound, a tetrabenzoporphyrin derivative (C) and a sulfonium organic boron complex (D).

In the hologram recording, when the photopolymerizable hologram recording material is irradiated with a laser beam, a compound having at least one polymerizable ethylenically unsaturated bond is present in a site having a strong interference action in the laser irradiation site. The polymerization reaction of (B) occurs, and at that time, the compound (B) having at least one polymerizable ethylenic unsaturated bond at a site having a weak interference action is transferred to a site having a strong interference action of the laser beam. Diffuses and polymerizes. Therefore, in the portion where the interference effect of the laser light is strong, the density is improved as compared with the portion where the interference effect is weak, and as a result, a difference in refractive index occurs between the two portions and a hologram is recorded. At this time, the refractive index of the polymer compound (A), which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers, and a compound having at least one polymerizable ethylenic unsaturated bond (B When the refractive index difference with the refractive index of (1) is 0.005 or more, the refractive index difference between the site where the laser light has a strong interference action and the site where the laser light has a strong interference action becomes large, and a volume phase hologram with high diffraction efficiency was manufactured. Conjectured to be. Further, after the hologram recording, a post-treatment step with light and / or heat is added to accelerate the polymerization of the unreacted compound (B) having at least one polymerizable ethylenically unsaturated bond, and to chemically react. A hologram that is stable and does not change with time is manufactured. At this time, when the polymer compound (A), which is a homopolymer of vinyl monomers or a copolymer of two or more components of vinyl monomers, has a crosslinkable (meth) acryloyl group, (A) and (B 2), a cross-linking reaction takes place between the above-mentioned) and a chemically stable hologram that does not change with time. Also, this post-treatment step,
In particular, the tetrabenzoporphyrin derivative (C) remaining as a coloring component is effectively decolorized by light irradiation, and the transparency of the hologram is improved.

[0055]

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 8 100 parts by weight of polymethylmethacrylate (PMMA),
90 parts of phenoxyethyl acrylate (POEA),
Photosensitization comprising 2 parts of a tetrabenzoporphyrin derivative (compound (a) to compound (h)) represented by the general formula (1), 5 parts of a sulfonium organic boron complex (compound (i)), and 900 parts of tetrachloroethane. Liquid 100 × 12
The film thickness after drying the photosensitive solution is 20 on a 5 × 3 mm glass plate.
A hologram recording photosensitive plate was prepared by coating with a 4 mil applicator so as to have a thickness of μm. Further, a 5% aqueous solution of polyvinyl alcohol was applied with a 3 mil applicator. This photosensitive plate was subjected to hologram exposure by two-beam interference using the hologram-forming optical system shown in FIG. At that time, 647 nm light of Kr ion laser was used in Examples 1 and 6, 633 nm light of He—Ne laser was used in Examples 2 to 5 and 7, and 694 nm light of ruby laser was used in Example 9. I was there. After performing the hologram exposure, further blocking one of the two light fluxes and exposing it to the same exposure time as the hologram exposure,
Then, it was placed in a 120 ° C. oven for 1 hour.

Diffraction efficiency is ART manufactured by JASCO Corporation
It was measured with a 25C 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. Width 0.3 mm
The monochromatic light of was incident on the sample at an angle of 45 degrees, and the 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 shows hologram characteristics such as sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results.

Examples 9 to 14 Same as Example 2 except that the sulfonium organoboron complex (compound (i)) in Example 2 was replaced with a sulfonium organoboron complex (compound (j)) or compound (o). Table 2 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated by the above method.

Example 15 Sensitivity characteristics, diffraction efficiency and play when operating in the same manner as in Example 2 except that the polymerizable monomer in Example 2 was replaced with tetrabromobisphenol A ethylene oxide-modified dimethacrylate. The back wavelength and the storage stability test results are summarized in Table 3.

Example 16 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage when operated in the same manner as in Example 2 except that the polymerizable monomer in Example 2 was replaced with N-vinylcarbazole. The stability test results are summarized in Table 3.

Example 17 Sensitivity characteristics, diffraction efficiency, and playback when operated in the same manner as in Example 2 except that the polymerizable monomer in Example 2 was replaced with tribromophenoltriethylene oxide modified acrylate. The wavelength and storage stability test results are summarized in Table 3.

Example 18 Sensitivity characteristics, diffraction efficiency, playback wavelength, and playback wavelength when operated in the same manner as in Example 2, except that the polymerizable monomer in Example 2 was replaced with ferrocenylethyl methacrylate. The storage stability test results are summarized in Table 3.

Example 19 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage when operated in the same manner as in Example 17 except that PMMA in Example 17 was replaced with poly (isobornyl methacrylate). The stability test results are summarized in Table 3.

Example 20 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage stability when operated in the same manner as in Example 17 except that PMMA in Example 17 was changed to poly (vinyl butyral). The test results are summarized in Table 3.

Example 21 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage stability when operated in the same manner as in Example 17, except that PMMA in Example 17 was changed to poly (vinyl acetate). The test results are summarized in Table 3.

Example 22 The PMMA of Example 17 was reacted with a copolymer of methyl methacrylate and chloromethylstyrene in a molar ratio of 8: 2 and potassium acrylate in dimethylformamide in the presence of oxygen at 60 ° C. for acrylolyl. Table 3 summarizes the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in the same manner as in Example 17, except that the polymer compound (compound p) having a group introduced was used. Showed.

Compound (p)

[Chemical 18]

Example 23 PMMA was used as a copolymer of Example 17 in a copolymer of methyl methacrylate and glycidyl methacrylate in a molar ratio of 8: 2, and acrylic acid in toluene in the presence of oxygen with dimethylaniline as a catalyst at 60 ° C. Sensitivity characteristics, diffraction efficiency, playback wavelength and storage stability test when operated in the same manner as in Example 17 except that the polymer compound (compound (q)) introduced with an acryloyl group was reacted. The results are summarized in Table 3.

Compound (q)

[Chemical 19]

Example 24 The PMMA obtained in Example 17 was used in a molar ratio of methyl methacrylate to 2-hydroxyethyl methacrylate of 8%.
The same method as in Example 17 except that the copolymer of Pair 2 was reacted with acrylic acid chloride in dimethylformamide in the presence of oxygen and at room temperature to replace the polymer compound (compound r) having an acryloyl group introduced therein. Table 3 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in Table 3.

Compound (r)

[Chemical 20]

Example 25 In the same manner as in Example 17, except that PMMA in Example 17 was changed to poly (p-bromophenyl methacrylate) and tribromophenoltriethylene oxide-modified diacrylate was changed to trifluoroethyl acrylate. Table 3 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated.

Example 26 Example 25 except that poly (styrene) was used in place of poly (p-bromophenylmethacrylate) in Example 25.
Table 3 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in the same manner as in.

Example 27 The same procedure as in Example 17 was carried out except that PMMA in Example 17 was replaced with poly (α-naphthylstyrene) and tribromophenoltriethylene oxide-modified diacrylate was replaced with pentaerythritol triacrylate. Table 3 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results at the time.

Example 28 The poly (p-bromophenylmethacrylate) of Example 25 was added in a molar ratio of styrene to maleic anhydride of 9
2-hydroxyethyl acrylate in toluene, dimethylaniline was used as a catalyst for the copolymer of 1 and reacted in the presence of oxygen at 60 ° C. to replace it with a polymer compound (compound (s)) having an acryloyl group introduced. Example 25
Table 3 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in the same manner as in.

Compound (s)

[Chemical 21]

Table 1

[Table 1]

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

Table 2

[Table 2]

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

Table 3

[Table 3]

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

[0083]

According to the present invention, it is possible to easily manufacture a volume phase hologram having high sensitivity, chemical stability, high resolution, high diffraction efficiency, and high transparency over a long wavelength region. Is possible.

[0084]

[Brief description of drawings]

FIG. 1 shows a block diagram of a two-beam exposure apparatus for hologram production.

[Explanation of symbols]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03F 7/038 G03H 1/08 8106-2K

Claims (4)

[Claims] 1. A polymer compound (A) which is a homopolymer of a vinyl monomer or a copolymer of two or more vinyl monomers, a compound (B) having at least one polymerizable ethylenic unsaturated bond, Tetrabenzoporphyrin derivative (C) and sulfonium organic boron complex (D)
A hologram recording material comprising a combination of 2. The polymer compound (A), which is a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components, has a crosslinkable (meth) acryloyl group. The hologram recording material described. 3. A compound having a refractive index of a polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components, and at least one polymerizable ethylenic unsaturated bond. The hologram recording material according to claim 1, wherein the refractive index difference from the refractive index of (B) is 0.005 or more. 4. A polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components, a compound (B) having at least one polymerizable ethylenic unsaturated bond, Tetrabenzoporphyrin derivative (C) and sulfonium organic boron complex (D)
The method of producing a hologram using the hologram recording material according to claim 1, wherein the hologram recording material is subjected to hologram exposure, and then light and / or heat is applied. Type hologram manufacturing method.