JPH06202543A - Production of volume phase type hologram - Google Patents

Abstract

PURPOSE:To provide the simple process for production of the volume phase type hologram having excellent chemical stability and environmental resistance characteristic and a particularly excellent photo-sensitivity characteristic, resolution, diffraction efficiency and transparency. CONSTITUTION:This process for production of the volume phase type hologram consists in subjecting a hologram recording medium to hologram exposing, then applying light and (or) heat thereto at the time of forming a hologram by using the hologram recording medium formed with a photosensitive film by holding a polymerizable compsn. contg. a high-polymer compd. (A) which is a single polymer of a vinyl monomer or a copolymer of vinyl monomers of >=2 components, a compd. (B) contg. at least >=1 pieces of polymerizable ethylenic unsatd. bonds, cyanine dyestuff (C) and diaryl iodonium-org. boron complex (D) between an optically transparent base material and an optically transparent protective film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a volume phase type having excellent chemical stability and environmental resistance, high sensitivity over a wide wavelength range, and particularly excellent in resolution, diffraction efficiency and transparency. The present invention relates to a hologram manufacturing method.

[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 materials using this both have the problems that they require complicated wet development processing and that they are inferior in resolution or environmental 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.

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.

On the other hand, a photopolymerizable composition containing a photopolymerization initiator comprising a combination of a cyanine dye and a diaryliodonium organoboron complex is disclosed in Japanese Patent Laid-Open No. 3-704. Does not describe a specific example for hologram recording or a specific method for producing a hologram, and a volume phase hologram can be obtained by simply using the photopolymerizable composition described in the known document. It could not be manufactured.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a simple volume phase hologram which is excellent in chemical stability and environmental resistance, and which is particularly excellent in high sensitivity characteristics, resolution, diffraction efficiency and transparency in a wide wavelength range. A manufacturing method is provided.

[0009]

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 polymerizable composition comprising a combination of a cyanine dye (C) and a diaryliodonium organic boron complex (D) is sandwiched between an optically transparent base material and an optically transparent protective film to form a photosensitive film. In producing a hologram using the hologram recording medium, the hologram recording medium is subjected to hologram exposure, and then light and / or heat is applied to the hologram recording medium. Is a volume phase hologram, wherein the polymer compound (A) which is a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers has a crosslinkable (meth) acryloyl group. The third invention is a method for polymerizing a homopolymer of vinyl monomers or a copolymer of vinyl monomers of two or more components. Volume phase type having a refractive index difference of 0.005 or more between the refractive index of the compound (A) and the refractive index of the compound (B) having at least one polymerizable ethylenic unsaturated bond. It is a method of manufacturing a 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 vinyl monomers used in the present invention will be 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, the polymer compound having a (meth) acryloyl group which can be crosslinked 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).

As the compound (B) having at least one polymerizable ethylenic unsaturated bond used in the present invention,
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 cyanine dye (C) used in the present invention has the general formula (1)

General formula (1)

[Chemical 1]

(In the formula (1), Y and Y'are independent of each other.
By the way, oxygen atom, sulfur atom, selenium atom, NH group, CH
= CH group, or C (CH₃)₂Represents a group, n is 0, 1
Or an integer such as 2 and R¹And R²Is a substituent
Alkyl group which may have and aryl which may have a substituent
Group, aralkyl group or alkenyl group,
They may be the same or different, X is halogen, NO
₃, BF_Four, PF₆, AsF₆, ClO_Four, SbF₆,
CF₃SO₃, CH₃SO₃Or CH₃C₆H _FourSO
₃Indicates. ) The cyanine dye (C) represented by
It

Next, the substituent in the general formula (1) will be described. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, an n-butyl group and a sec- group.
Butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, stearyl group, cyclohexyl group, menthyl group, bornyl group, benzyl group, acetonyl group, phenacyl group,
Salicyl group, anisyl group, cyanomethyl group, chloromethyl group, bromomethyl group, methoxycarbonylmethyl group,
An ethoxycarbonylmethyl group, chloromethyl group, bromomethyl group, trifluoromethyl group, trichloromethyl group, methoxymethyl group, carboxymethyl group, hydroxymethyl group, menthyl group, pinanyl group, etc., which may have a substituent As the group, 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-
Examples of the alkenyl group include a dimethylaminophenyl group and a p-phenylthiophenyl group, and the alkenyl group represents a linear or branched alkenyl group having 2 to 4 carbon atoms, such as a vinyl group, an allyl group, and a 1-propenyl group. , 2-butenyl group, 3-butenyl group, isopropenyl group and the like.

The cyanine dye represented by the general formula (1) as described above is described in G. E. Ficken, K .; Venkatar
aman ed "The Chemistry of Sy"
nthetic Dyes ”, Vol. 4, pages 211-340 (1971), or it can be obtained from Japan Photosensitive Dye Research Institute.

Compounds a to k are typical examples of the cyanine dye 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]

Compound i

[Chemical 10]

Compound j

[Chemical 11]

Compound k

[Chemical 12]

Next, the diaryliodonium organoboron complex (D) used in the present invention has the general formula (2)

General formula (2)

[Chemical 13] (In the formula, R ³ and R ⁴ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a cyano group, a nitro group or a halogen atom, and R ^{5 to} R ⁸ each independently have a substituent. Selected from a good alkyl group, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and an alicyclic group which may have a substituent. And R ^{5 to} R ⁸ are not all aryl groups which may have a substituent at the same time.) Represents a diaryliodonium organoboron complex (D) represented by the substituent R ³ And R ⁴ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a lower alkyl group such as a tert-butyl group, a methoxy group, an ethoxy group, a propoxy group, An isopropoxy group, Butoxy group, isobutoxy group,
It represents a lower alkoxy group such as a sec-butoxy group and a tert-butoxy group, a cyano group, a nitro group, and a halogen atom such as fluorine, chlorine, bromine and iodine. Then R
^{5 to} R ⁸ 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 a substituent which may have a substituent. A group selected from a good alkynyl group and an alicyclic group which may have a substituent is shown, and R ^{5 to} R ⁸ are not all aryl groups which may have a substituent at the same time. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a 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 and the like are aryl groups which may have a substituent. Is a phenyl group, a p-tolyl group, a xylyl group, a mesityl group, a cumenyl group, or the like, and as the alkenyl group which may have a substituent, a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group. Etc., the alkynyl group which may have a substituent includes an ethynyl group, 1-hexynyl group, 1-
Examples of the alicyclic group which may have a substituent, such as a propynyl group, include a cyclohexyl group, a cyclopentyl group, a cyclohexenyl group, a norbornyl group, a bornyl group, a menthyl group, a pinanyl group and an adamantyl group. The group may be substituted with a hydrogen atom, and further with another substituent, and examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a methoxy group and an ethoxy group. , An alkoxy group such as butoxy group, a phenyl group, a p-tolyl group, an aryl group such as p-methoxyphenyl group, a mesyl group, a p-toluenesulfonyl group,
A trifluoromethyl group is mentioned.

Specific examples of such a diaryliodonium organic boron complex include diphenyliodonium, ditolyliodonium, phenyl (p-methoxyphenyl) iodonium, bis (m-nitrophenyl) iodonium and bis (pt-butylphenyl). ) Iodonium, bis (p-cyanophenyl) iodonium, and other n-
Butyltriphenylborate complex, sec-butyltriphenylborate complex, tert-butyltriphenylborate complex, n-butyltris (p-methoxyphenyl) borate complex, methyltriphenylborate complex,
Examples thereof include n-butyl tris (p-fluorophenyl) borate complex. Compounds 1 to o are shown as typical compounds.

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 compound and a photopolymerization initiator comprising a cyanine dye (C) and a diaryliodonium organoboron 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 with 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 difference is 0.0 That it is more preferably 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 cyanine dye (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 cyanine dye (C) represented by the general formula (1) or (2) 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 diaryl iodonium organoboron complex (D) is 0.1 to 20 parts by weight with respect 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. It is preferably used in the range of 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 material having the above composition ratio in a suitable solvent is directly used as a base material such as a glass plate or a plastic film. A photosensitive film is formed on the 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 hologram recording medium obtained as described above is fixed to a holder so as not to be affected by vibration, and then a He--Cd laser, Ar ion laser, He--
Hologram recording is performed by irradiating a visible light laser such as a Ne laser, a Kr ion laser, or a ruby laser. FIG. 1 shows an example of the optical system.

The photosensitive plate or film on which the hologram is recorded requires the application of light and / or heat for fixing the unexposed portion or the portion having a small exposure amount.
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) having an individual compound, a cyanine dye (C) and a diaryliodonium organic boron complex (D).

In 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 at 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. In addition, the cyanine dye (C) remaining as the coloring component is effectively decolored by this post-treatment step, and the transparency of the hologram is improved.

[0047]

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 11 100 parts by weight of polymethylmethacrylate (PMMA),
90 parts of phenoxyethyl acrylate (POEA),
A cyanine dye (compound a to compound k) represented by the general formula (1) (5 parts), a diaryl iodonium organic boron complex (compound 1) (5 parts) and dioxane (900 parts) were added to a photosensitive solution of 100 × 125 × 3 mm. The hologram plate was coated on a glass plate with a 3 mil applicator so that the film thickness after drying the photosensitive solution would be 10 μm to prepare a hologram recording plate. Further, a 5% 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 the figure. At that time, 488 nm light of Ar ion laser was used in Examples 1 and 3, and 514 nm light of Ar ion laser was used in Examples 2, 4 and 5, and Example 6, Example 8 and Example were carried out. In Example 11, 633 nm light of He-Ne laser was used, in Example 7 and Example 9, 647 nm light of Kr ion laser was used, and in Example 10, 676 nm light of Kr ion laser 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. Tables 1 and 2 show the amount of exposure energy that gives the maximum diffraction efficiency, the diffraction efficiency, the playback wavelength, and the storage stability test results.

Examples 12 to 14 The procedure of Example 3 was repeated, except that the diaryliodonium organoboron complex (l) in Example 3 was replaced with diaryliodonium organoboron complexes (m) to (o). Tables 3 and 4 show the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results at that time.

Example 15 Sensitivity characteristics, diffraction efficiency and play when operating in the same manner as in Example 3 except that the polymerizable monomer in Example 3 was replaced with tetrabromobisphenol A ethylene oxide-modified dimethacrylate. The back wavelength and the storage stability test results are shown in Tables 5 and 6.

Example 16 Sensitivity characteristics, diffraction efficiency, playback wavelength and storage when operated in the same manner as in Example 3 except that the polymerizable monomer in Example 3 was replaced with N-vinylcarbazole. The stability test results are shown in Tables 5 and 6.

Example 17 Sensitivity characteristics, diffraction efficiency and playback when operated in the same manner as in Example 3 except that the polymerizable monomer in Example 3 was replaced with tribromophenoltriethylene oxide modified acrylate. The wavelength and storage stability test results are shown in Tables 5 and 6.

Example 18 Sensitivity characteristics, diffraction efficiency, playback wavelength, and playback wavelength when operated in the same manner as in Example 3 except that the polymerizable monomer in Example 3 was replaced with ferrocenylethyl methacrylate. The storage stability test results are shown in Tables 5 and 6.

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 shown in Tables 5 and 6.

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 replaced with poly (vinyl butyral). The test results are shown in Tables 5 and 6.

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 shown in Tables 5 and 6.

Example 22 The PMMA of Example 17 was reacted with a copolymer of methylmethacrylate and chloromethylstyrene at a molar ratio of 8: 2 and potassium acrylate in dimethylformamide in the presence of oxygen at 60 ° C. to react with acryloyl. Table 5 shows 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) into which a group was introduced was used. 6 shows.

Compound p

[Chemical 18]

Example 23 PMMA was used as a copolymer of Example 17 in a copolymer of methylmethacrylate and glycidylmethacrylate 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. Except for reacting and changing to a polymer compound (compound q) having an acryloyl group introduced, the sensitivity characteristics, diffraction efficiency, playback wavelength and storage stability test results when operated in the same manner as in Example 17 are shown. The results are shown in Table 5 and Table 6.

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. Tables 5 and 6 show the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated at.

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. Tables 5 and 6 show the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated.

Example 26 Example 25 except that the poly (p-bromophenyl methacrylate) in Example 25 was replaced with poly (styrene).
Tables 5 and 6 show the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in the same manner as in.

Example 27 The procedure of Example 17 was repeated, except that PMMA was changed to poly (α-naphthylstyrene) and tribromophenoltriethylene oxide-modified diacrylate was replaced with pentaerythritol triacrylate. Tables 5 and 6 show the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results at the time.

Example 28 The poly (p-bromophenyl methacrylate) of Example 25 was added in a molar ratio of styrene to maleic anhydride of 9
2-hydroxyethyl acrylate in toluene was used for the copolymer of pair 1, dimethylaniline was used as a catalyst, and the reaction was carried out at 60 ° C. in the presence of oxygen to replace it with a polymer compound (compound s) having an acryloyl group introduced. Table 5 and Table 6 show the sensitivity characteristics, diffraction efficiency, playback wavelength, and storage stability test results when operated in the same manner as in Example 25.

Compound s

[Chemical 21]

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

[0073]

[Table 5]

[0074]

[Table 6]

[0075]

According to the present invention, a volume phase hologram which is highly sensitive and chemically stable over a wide wavelength range, and has high resolution, high diffraction efficiency and high transparency can be easily produced. .

[0076]

[Brief description of drawings]

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

[Explanation of symbols]

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

Claims (3)

[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 polymerizable composition comprising a combination of a cyanine dye (C) and a diaryliodonium organic boron complex (D) is sandwiched between an optically transparent base material and an optically transparent protective film to form a photosensitive film. In producing a hologram using the hologram recording medium, the hologram recording medium is subjected to hologram exposure, and then light and / or heat is applied to the hologram recording medium. 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. A method for producing the volume phase hologram 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 method for producing a volume phase hologram according to claim 1, wherein the refractive index difference from the refractive index of (B) is 0.005 or more.