JPH06175563A - Hologram recording material and production of volume phase type hologram by using the recording material - Google Patents

Abstract

PURPOSE:To provide a process for production of a hologram recording material exhibiting excellent photosensitivity and a volume phase type hologram formed by using the recording material. CONSTITUTION:This hologram material consists of a combination of a high- polymer compd. which is a single polymer of a vinyl monomer or a copolymer of 2 components of vinyl monomers (A), a compd. having at least 1 pieces of polymerizable ethylenic unsatd. bonds (B), a pyrilium salt or thiopyrilium salt deriv. (C) and sulfonium org. boron complex (D). This process for production of the volume phase type hologram consists in subjecting this hologram masterial and the hologram recording material to hologram exposing, then applying light and (or) heat thereto. As a result, the volume phase type hologram having a high sensitivity and chemical stability and having a high resolution, high diffraction efficiency and high transparency is easily produced.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a hologram recording material having excellent chemical stability and environmental resistance, high sensitivity over a wide wavelength range, and excellent resolution, diffraction efficiency and transparency. The present invention relates to a simple method for producing a volume phase hologram using a.

[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 and photosensitive wavelength region characteristics, 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.

On the other hand, a hologram recording material using a photopolymer (and a hologram recording material using a photopolymer capable of producing 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 production 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
olography IV ", Vol. 1212, p. 30 (1
990) and "Journal of Image
gScience, "Vol. 35, pp. 19 and 25 (1
991). However, the sensitivity characteristic of the hologram recording material to Ar ion laser is on the order of several tens of mJ / cm ² , and it is 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 one or more 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 indexes and polymerizable properties. 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.

[0007]

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

[0008]

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 comprising a combination of a pyrylium salt or thiopyrylium salt derivative (C) and a sulfonium organic boron complex (D). The second invention is a polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components.
Is a cross-linkable (meth) acryloyl group, which is the hologram recording material according to the first invention.
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 ethylenically 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, the hologram recording material is exposed to light, and the hologram recording material is exposed to light. And / or heat is applied to the volume phase hologram.

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 ester, polymer of (meth) acrylic 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, as the polymer compound having a (meth) acryloyl group which is crosslinkable with a homopolymer of vinyl monomers or a copolymer of two or more components of vinyl monomers used in the present invention, the above-mentioned vinyl monomers can be used. 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) acrylic compounds 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 pyrylium salt or thiopyrylium salt derivative (C) used in the present invention has the general formula (1)

General formula (1)

[Chemical 1]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R
⁵ independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a haloalkyl group which may have a substituent, an ethylenyl group which may have a substituent, or a substituent. A styryl group, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a nitro group, an amino group which may have a substituent, a hydroxy group, which has a substituent A group selected from the most suitable heterocyclic groups is shown.
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ are
They may be combined together to form an aromatic ring or a heterocycle. Y represents an oxygen atom or a sulfur atom, and X
Is halogen, BF ₄ , PF ₆ , AsF ₆ , ClO ₄ ,
SbF ₆ , CF ₃ SO ₃ , CH ₃ SO ₃ , or CH ₃
Shows the C ₆ H ₄ SO _3. ).

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 , R ⁷ and R ⁸ 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, a substituent An alkylene group which may have a group, an alicyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, and a substituent A group selected from an optionally substituted alkylthio group, an optionally substituted arylthio group, and an optionally substituted amino group, R ⁹ is an oxygen atom or a lone electron pair, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ 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, or a substituent which may have a substituent. It represents a group selected from an alkynyl group, R ^6, R ⁷ and R ⁸ are two or more groups of binding To well be a cyclic structure, it never becomes also an aryl group having two or more simultaneously substituents R ^6, R ⁷ and R ^8, R ^10,
Not all R ¹¹ , R ¹² and R ¹³ are aryl groups 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 , R ¹¹ , R ¹² and 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, 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.

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.

[0024] The reason, 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 light-sensitive 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 a polymerizable ethylenically unsaturated bond. A compound (B) having at least one compound, and a photopolymerization initiator comprising a pyrylium salt or thiopyrylium salt derivative (C) and a sulfonium organic boron complex (D) are dissolved in a suitable solvent at an arbitrary concentration to obtain a Can be obtained by coating the above solution on a substrate such as a glass plate in a film form, and the refractive index of the polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components. And the refractive index difference between the compound (B) having at least one polymerizable ethylenic unsaturated bond and the refractive index is 0.005 or more, Refractive index difference is more preferably at least 0.02. There is no particular limitation on the blending ratio 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 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 light-sensitive 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 pyrylium salt or thiopyrylium salt derivative (C) of the general formula (1) is a homopolymer of a vinyl monomer or a copolymer of two or more vinyl monomers. It is used in an amount of 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). 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. In addition, sulfonium organic boron complex (D)
Is a high molecular compound (A) 10 which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers.
0.1 to 20 parts by weight, preferably 1 to 0 parts by weight
Used in the range of 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-Cd laser, an Ar ion laser, a He-Ne laser, a Kr ion laser, and a ruby laser. FIG. 1 shows an example of the optical system.

A 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.

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), a pyrylium salt or a thiopyrylium salt derivative (C) and an sulfonium organoboron complex (D) each having an individual compound.

In the hologram recording, when the photopolymerizable hologram recording material is irradiated with laser light, 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 light irradiation effectively erases the color of the pyrylium salt or thiopyrylium salt derivative (C) remaining as a coloring component, and improves the transparency of the hologram.

[0040]

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 10 100 parts by weight of polymethylmethacrylate (PMMA),
90 parts of phenoxyethyl acrylate (POEA),
A 100 × 125 × 3 mm glass plate containing a photosensitive solution containing 2 parts of a pyrylium salt or thiopyrylium salt derivative represented by the general formula (1), 5 parts of a sulfonium organoboron complex (compound (a)) and 900 parts of dioxane. A 3 mil applicator was applied on the top of the photosensitive solution so that the film thickness after drying the photosensitive solution would be 7 μm to prepare a hologram recording photosensitive plate. Further, a 5 wt% aqueous solution of polyvinyl alcohol was applied with a 3 mil applicator. On this photosensitive plate,
Holographic exposure was performed by two-beam interference using the hologram creating optical system shown in FIG. At that time, Examples 1 to 5
488 nm light of Ar ion laser is used in Examples, 514 nm light of Ar ion laser is used in Examples 6 and 7, and 63 of He-Ne laser is used in Examples 8 to 10.
3 nm light was used. After performing the hologram exposure, one of the two light fluxes was further blocked and the hologram was exposed to the same exposure time as the hologram exposure, and then placed in an oven at 120 ° C. for 1 hour.

Diffraction efficiency is measured by 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 the exposure energy amount that gives the maximum diffraction efficiency, the diffraction efficiency, the playback wavelength, and the storage stability test results.

Examples 11 to 16 Example 1 except that the sulfonium organoboron complex (compound (a)) in Example 1 was replaced with a sulfonium organoboron complex (compound (b)) to (compound (g)). Sensitivity characteristics, diffraction efficiency,
Table 2 shows the playback wavelength and the storage stability test results.

Example 17 Sensitivity characteristics, diffraction efficiency, and play when operating in the same manner as in Example 1 except that the polymerizable monomer in Example 1 was replaced with tetrabromobisphenol A ethylene oxide-modified dimethacrylate. The back wavelength and the storage stability test results are shown in Table 3.

Example 18 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage when operating in the same manner as in Example 1 except that the polymerizable monomer in Example 1 was replaced with N-vinylcarbazole. The stability test results are shown in Table 3.

Example 19 Sensitivity characteristics, diffraction efficiency, and playback when operated in the same manner as in Example 1 except that the polymerizable monomer in Example 1 was replaced with tribromophenoltriethylene oxide modified acrylate. The wavelength and storage stability test results are shown in Table 3.

Example 20 Sensitivity characteristics, diffraction efficiency, playback wavelength, and playback wavelength when operated in the same manner as in Example 1 except that the polymerizable monomer in Example 1 was replaced with ferrocenylethyl methacrylate. The storage stability test results are shown in Table 3.

Example 21 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage when operated in the same manner as in Example 19 except that PMMA in Example 19 was replaced with poly (isobornyl methacrylate). The stability test results are shown in Table 3.

Example 22 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage stability when operated in the same manner as in Example 19 except that PMMA in Example 19 was changed to poly (vinyl butyral). The test results are shown in Table 3.

Example 23 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage stability when operated in the same manner as in Example 19 except that PMMA in Example 19 was changed to poly (vinyl acetate). The test results are shown in Table 3.

Example 24 The PMMA of Example 19 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. to give acrylolyl. Table 3 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in the same manner as in Example 19 except that the polymer compound (compound h) into which a group was introduced was used. It was

Compound (h)

[Chemical 10]

Example 25 The PMMA of Example 19 was added to a copolymer of methyl methacrylate and glycidyl methacrylate in a molar ratio of 8: 2, acrylic acid was added to toluene in the presence of oxygen at 60 ° C. using dimethylaniline as a catalyst. Sensitivity characteristics, diffraction efficiency, playback wavelength and storage stability test when operated in the same manner as in Example 19, except that the polymer compound (compound (i)) introduced with an acrylolyl group was reacted. The results are shown in Table 3.

Compound (i)

[Chemical 11]

Example 26 The PMMA obtained in Example 19 was used in a molar ratio of methyl methacrylate to 2-hydroxyethyl methacrylate of 8%.
Same as Example 19 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 (j)) into which an acryloyl group was introduced. Table 3 shows the sensitivity characteristics, the diffraction efficiency, the playback wavelength, and the storage stability test results when operated by the above method.

Compound (j)

[Chemical 12]

Example 27 The same procedure as in Example 19 was carried out except that PMMA in Example 19 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 28 Example 27 except that the poly (p-bromophenyl methacrylate) in Example 27 was replaced with poly (styrene).
Table 3 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in the same manner as in.

Example 29 The same operation as in Example 19 was carried out except that PMMA in Example 19 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 30 The poly (p-bromophenyl methacrylate) of Example 27 was added in a molar ratio of styrene to maleic anhydride of 9
Using 2-hydroxyethyl acrylate in toluene and dimethylaniline as a catalyst, the copolymer of Pair 1 was reacted in the presence of oxygen and at 60 ° C. to be a polymer compound (compound (k)) having an acryloyl group introduced. Other than Example 27,
Table 3 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in the same manner as in.

Compound (k)

[Chemical 13]

[0061]

[Table 1]

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

[0063]

[Table 2]

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

[0065]

[Table 3]

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

[0067]

According to the present invention, it is possible to easily manufacture a volume phase hologram which is highly sensitive, chemically stable, has high resolution, high diffraction efficiency and high transparency.

[0068]

[Brief description of drawings]

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

[0070]

[Explanation of symbols]

 1: Laser oscillator 2: Mirror 3: Lens 4: Spatial filter 5: Glass plate 6: Photosensitive film

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area G03F 7/038

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, A hologram recording material comprising a combination of a pyrylium salt or thiopyrylium salt derivative (C) and a sulfonium organic boron complex (D). 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, A hologram recording material for producing a hologram using the hologram recording material according to any one of claims 1 to 3, comprising a combination of a pyrylium salt or thiopyrylium salt derivative (C) and a sulfonium organoboron complex (D). A method for producing a volume phase hologram, which comprises subjecting a hologram to a hologram exposure and then applying light and / or heat.