JPH05188843A - Formation of hologram - Google Patents

Abstract

PURPOSE:To form the bright hologram free from unequalness by immersing a recording carrier into a developer contg. a photo- or thermal polymn. initiator and subjecting this carrier to development processing, then curing the recording carrier by heat or light. CONSTITUTION:The recording carrier consisting of a binder polymer, a photopolymerizable compd. and the photopolymn. initaitor is exposed to interference patterns of a laser beam. The developing stage is then executed by immersing the carrier formed with the latent image of the hologram into the developer contg. the guest monomer or the photo- or thermal polymn. initiator. In this developing stage, the unpolymerized host monomer or the low-polymn. degree component of the host monomer is eluted in the developer according to the hologram pattern formed on this recording carrier and the developer contg. the guest monomer and the photo- or thermal polymn. initiator is penetrated into the recording carrier, by which the unpolymerized host monomer or the low-polymn. degree component of the host monomer is substd. with the guest monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram forming method, and more particularly to a volume phase hologram forming method.

[0002]

2. Description of the Related Art As a conventional hologram forming method, for example, there is one described below. As the binder polymer, for example, poly-N-vinylcarbazole is 1.0
g, a photopolymerizable compound (called a host monomer), for example, 0.5 g of tribromophenol methacrylate, and a photopolymerization initiator such as 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 0.08 g, 3,3'-carbonylbis (7-diethylaminocoumarin), 0.003 g, and a solvent capable of dissolving the above composition, for example, 10 g of 1,4-dioxane, and using an applicator on glass. A film is formed and dried to obtain a record carrier.

Argon ion laser on the record carrier
Exposing the interference pattern with light at a wavelength of 488 nm. afterwards,
A compound capable of photo- or heat-polymerization (called a guest monomer),
For example, the hologram is formed by immersing it in a developing solution composed of a solvent such as trimethylolpropane acrylate and acetone to elute the unpolymerized component of tribromophenol methacrylate in the record carrier and substituting it with trimethylolpropane acrylate. Further, the hologram is fixed by irradiating light rays from a xenon lamp to cure the substituted trimethylolpropane acrylate.

[0004]

However, in such a conventional hologram forming method, since the polymerization initiator is not contained in the developer, the guest monomer is not polymerized in the curing process of the guest monomer. Since it was not a system that can be performed efficiently, it takes a significantly long time to cure the guest monomer after the development is completed, or light irradiation with an extremely high energy density or heating at a high temperature is required, which leads to an increase in hologram efficiency. However, there are problems such as a decrease in wavelength and a shift in the diffraction wavelength.

[0005]

SUMMARY OF THE INVENTION The present invention has been made by paying attention to such conventional problems, and by incorporating a guest monomer and a photo or thermal polymerization initiator in a developing solution, the guest monomer This is based on the finding that the polymerization of light by heat or light can be efficiently performed.

That is, according to the hologram forming method of the present invention, after a record carrier comprising a binder polymer, a photopolymerizable compound and a photopolymerization initiator is exposed to an interference pattern of laser light, the record carrier can be photo- or heat-polymerized. It is characterized in that the recording medium is immersed in a developing solution containing a compound and light or a thermal polymerization initiator to carry out a developing treatment, and then the record carrier is cured by heat or light.

The present invention will be described below. First, the components constituting the record carrier will be described. The record carrier used in the present invention comprises a binder polymer, a photopolymerizable compound and a photopolymerization initiator.

As the binder polymer, polymethacrylic acid ester or its partial hydrolyzate, polyvinyl acetate or its hydrolyzate, polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, poly- N-vinylcarbazole or a derivative thereof, poly-N-vinylpyrrolidone or a derivative thereof, a copolymer of styrene and maleic anhydride or a half ester thereof, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, acrylic A copolymer having a monomer selected from the group of copolymerizable monomers such as nitrile as a polymerization component is used.

Preferred is poly-N-vinylcarbazole or a derivative thereof, for example, poly-N-vinylcarbazole, vinylcarbazole-styrene copolymer,
Vinylcarbazole-vinyl chloride copolymer, vinylcarbazole-methylmethacrylate copolymer, vinylcarbazole-vinylanthracene copolymer, vinylcarbazole-vinylpyridine copolymer, vinylcarbazole-acrylate copolymer, vinylcarbazole-ethylacrylate Copolymer, vinylcarbazole-acrylonitrile copolymer, vinylcarbazole-butylacrylate copolymer, vinylcarbazole-nitrovinylcarbazole copolymer, nitrated poly-N-vinylcarbazole, polyvinylaminocarbazole, vinylcarbazole-N-methyl Aminovinylcarbazole copolymer, halogen-substituted poly-N-vinylcarbazole, vinylcarbazole-dibromovinylcarbazole copolymer, polyiodovinyl Carbazole, Po Revenge alkylidene vinylcarbazole, poly propenyl carbazole, and the like.

Next, the photopolymerizable compound (host monomer) will be described. Examples of the host monomer include a monomer having at least one ethylenically unsaturated double bond in one molecule, an oligomer, a prepolymer, and a mixture thereof. Specific examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with aliphatic polyhydric amine compounds.

More specifically, the unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and halogen-substituted unsaturated carboxylic acids thereof such as chlorinated unsaturated carboxylic acids. Examples thereof include acids, brominated unsaturated carboxylic acids, and fluorinated unsaturated carboxylic acids. Examples of the salts of unsaturated carboxylic acids include sodium salts and potassium salts of the above-mentioned acids.

As the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol are used. Diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol di Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol te Laacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanate Nurate, polyester acrylate oligomer, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, tetramethylene glycol dimethacrylate, propylene glycol dimethacrylate, Opentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, hexanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, tetraethylene glycol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol Tetramethacrylate,
Dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, sorbitol pentamethacrylate, sorbitol hexamethacrylate, bis- [p- (3-methacryloxy 2-Hydroxypropoxy) phenyl] dimethylmethane, bis-
[P- (acryloxyethoxyphenyl] dimethylmethane, 2-hydroxypropyl methacrylate, etc. may be mentioned.

As the itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol itaconate, 1,4
-Butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

As the clonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Examples thereof include sorbitol tetracrotonate.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.

As the halogenated unsaturated carboxylic acid,
2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H, 1H, 2H, 2H-heptadeca Examples thereof include fluorodecyl methacrylate.

As the amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, methylenebisacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebisacrylamide, 1,6-hexamethylenemethacrylamide, diethylenetriamine. Examples thereof include trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and acrylamidobutyraldehyde dimethyl acetal.

As another example, Japanese Patent Publication No. 48-417.
No. 08, the polyisocyanate compound having two or more isocyanate groups in one molecule, the following general formula CH ₂ ═C (R) COOCH ₂ CH (R ₁ ) OH (wherein R and R ₁ are hydrogen atoms). Or a vinyl urethane compound having two or more polymerizable vinyl groups in one molecule, to which a vinyl monomer having a hydroxyl group represented by (denoting a methyl group) is added.

Further, urethane acrylates described in JP-A-51-37193, JP-A-52-304
90, Japanese Patent Publication No. 49-43191, and Japanese Patent Laid-Open No. 4
Polyester acrylates, epoxy resins and (meth) as described in JP-A 8-64183, respectively.
Mention may be made of polyfunctional acrylates such as acrylics and methacrylates.

Halides of epoxy acrylates such as fluorides and bromides can also be used. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association magazine Vol. 20, No. 7, pages 300 to 308 can also be used.

Esters of phenols and unsaturated carboxylic acids such as tribromophenol acrylate, tribromophenol methacrylate, tetrabromophenol acrylate, tetrabromobisphenol A di (meth) acrylate and the like can also be used.

Further, the following structural formula

[Chemical 1]

[Chemical 2] Triacrylates represented by, for example, manufactured by Toagosei Kagaku Kogyo Co., Ltd., trade name, Aronix M-315 and M-325, and 2,2'-bis (4-acryloxydiethoxyphenyl) propane (Shin Nakamura Chemical Co., Ltd.
Product, trade name, NK ester A-BPE-4), tetramethylolmethane tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, NK ester A-TMMT) and the like can also be used.

Four compounds having the following structural formulas and manufactured by France SNPE are also effective.

[Chemical 3] (Product name, ACTICRYL CL 9 manufactured by SNPE)
93)

[Chemical 4] (Product name, ACTICRYL CL 9 manufactured by SNPE)
59)

[Chemical 5] (Product name, ACTICRYL CL 9 manufactured by SNPE)
60)

[Chemical 6] (Product name, ACTICRYL CL 1 manufactured by SNPE)
039)

Examples of the photopolymerization initiator include benzoin alkyl ethers, ketals, oxime esters, benzophenone, thioxanthone derivatives, quinone, aromatic ketones such as thioacridone, and 1,3-di (t-butyldioxycarbonyl). Benzene, iodonium salts, dianine, rhodamine, safranine, malite green,
Alkyl or alkyl borates such as methylene blue, iron-arene complexes, bisimidazoles, N-arylglycines and the like can be used.

In order to increase the sensitivity of the photopolymerization initiator,
It is desirable to use a system to which a visible light sensitizing dye is added. Examples of visible light sensitizing dyes include aromatic amines such as Michler's ketone, xanthene dyes, thiopyrylium salts, merosinin / quinoline dyes, coumarin / ketocoumarin dyes, acridine orange, benzoflavin, dianine,
Phthalocyanine, porphine, rhodamine, safranine, malachite green, methylene glycol and the like are used.

Particularly preferred is the following general formula

[Chemical 7] (Wherein R ₄ , R ₅ and R ₆ are each a hydrogen atom, a chlorine atom, a lower dialkylamino group, a lower dialkenylamino group or an alicyclic amino group, and X is a total number of hydrogen atoms and heteroatoms of 5 to 9). Heterocyclic groups or —COY groups, wherein Y is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,
Lower alkoxy group, substituted or unsubstituted phenyl group, substituted or unsubstituted steryl group, or substituted or unsubstituted 3'-
Represents a coumarin group. Z represents a hydrogen atom or a cyano group. ) Is a polymerization initiator system composed of a coumarin compound and an organic peroxide.

In the above formula, R ₄ , R ₅ and R ₆ are preferably hydrogen atoms, chlorine atoms, lower alkoxy groups such as methoxy, ethoxy and butoxy, lower groups such as dimethylamino, diethylamino and N-methyl-N-propylamino. Examples thereof include an alicyclic amino group such as a dialkylamino group, N-monofolino and N-piperidino, a lower dialkenylamino group such as dipropenylamino, di, (α-methylpropenyl) amino group.

The heterocyclic group for X is 2-imidazole, 2-N-methylimidazole, 2-benzimidazole, 2- (4-phenyl) imidazole, 2-oxazole, 2-benzoxazole, 2- (4-phenyl). ) Oxazole, 2-thiazole, 2-benzthiazole, 2- (4-phenyl) thiazole, 2- (5-phenyl) thiadiazole, 2- (5-tolyl) thiadiazole, 2- (5-biphenyl) thiadiazole, 2-
Examples thereof include residues such as (5-phenyl) oxadiazole, 2- (5-p-methoxyphenyl) oxadiazole, and 2- (5-p-chlorophenyl) oxadiazole.

As Y in the --COY group, methyl, ethyl, propyl, hexyl, β-cyanoethyl,
A substituted or unsubstituted C ₁ -C ₆ alkyl group such as ethoxycarbonylmethyl, butoxycarbonylmethyl, phenyl, p-cyanophenyl, p-methylphenyl, p-
A substituted or unsubstituted phenyl group such as methoxyphenyl and m-hydroxycarbonylphenyl, a steryl group such as steryl, p-methoxysteryl, p-cyanosteryl, and m-chlorsteryl, and the following general formula

[Chemical 8] (In the formula, R ₁ , R ₂ , R ₃ and Z are the same as those in the chemical formula 7) and the 3-coumarino group and the like can be mentioned.

Specific examples of the coumarin compound include 3-acetyl-7-dimethylaminocoumarin and 3-benzoyl-
7-dimethyl-aminocoumarin, 3-benzoyl-5,
7-dimethoxycoumarin, methyl 7-diethylamino-
3-coumarinoyl acetate, 3-cinnamoyl-7-
Diethylaminocoumarin, 3,3'-carbonylbis (7-diethylamino) coumarin, 3,3'-carbonylbis (5,7-dimethoxyamino) coumarin, 7-diethylamino-5,7'-dimethoxy-3,3'- Biscoumarin, 3- (2'-benzimidazoyl) -7-diethylaminocoumarin, 3- (2'-benzoxazoyl) -7-diethylaminocoumarin, 3- (5'-phenylthiadiazoyl-2 ')- 7-diethylaminocoumarin, 3- (2'-benzthiazoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (4-cyano-7-diethylamino) coumarin and the like can be mentioned.

The ratio of the organic peroxide to the coumarin compound is 1 to 100 parts by weight of the organic peroxide to 1 part by weight of the coumarin compound, preferably 1 part by weight of the coumarin compound to the organic peroxide. It is used in a proportion of 1 to 50 parts by weight.

The composition ratio of each component constituting the record carrier is such that the binder polymer is 100 parts by weight, the host monomer is 10 parts by weight to 300 parts by weight, and the photopolymerization initiator and the visible light sensitizing dye are combined to be 1 part by weight. ~ 100 parts by weight. Particularly preferably, 30 parts by weight to 150 parts by weight of the host monomer, 100 parts by weight of the binder polymer, and 1 part by weight to 30 parts by weight of the photopolymerization initiator and the visible light sensitizing dye are used in combination. ..

In addition to the above composition, components such as an oxygen scavenger, a thermal polymerization inhibitor, a plasticizer and an ultraviolet absorber may be added to the record carrier.

In the present invention, the above composition is prepared, for example, by using benzene, chlorobenzene, tetrahydrofuran, 1,4.
-Dissolve in a solvent such as dioxane, 1,2-dichloroethane, dichloromethane or chloroform to prepare a desensitizing solution, and apply it on a plate or film made of glass or a transparent resin. Then, it is dried to evaporate the solvent and obtain a record carrier.

As the method of applying the photosensitive solution, there are spinner coating, blade coating, roll coating, etc., and the coating is performed after drying so that the film thickness becomes 0.1 μm to 100 μm. The film thickness is adjusted by the concentration of the composition in the solvent, the film thickness at the time of coating, and the like, but in some cases, coating and drying may be repeated several times to obtain a thick film.
In addition, the support itself of the binder polymer may be used to form itself into a film.

Further, if the surface of the record carrier which is in contact with air is coated with an aqueous solution of polyvinyl alcohol or the like to block the air, polymerization inhibition by oxygen does not occur and sensitivity can be improved.

The record carrier thus obtained is sensitive to a laser beam having a bright line at, for example, 457.9 nm, 488 nm, 514.5 nm, 528.7 nm, for example, 488 nm.
1 to 50 for argon ion lasers with wavelengths of
The energy of 0 mJ / cm ² gives diffraction efficiency in a practical range.

Next, the hologram forming method of the present invention will be described. The hologram forming method of the present invention comprises a step of exposing a record carrier to radiation, a step of developing using a developing solution containing a guest monomer and a photo or thermal polymerization initiator, and partially substituting a host monomer with the guest monomer. Depending on the light or heat curing process of the recorded record carrier.

In the process of exposing the record carrier to radiation,
The radiation that can be used is preferably a radiation using a laser beam, a mercury lamp, or the like as a light source. When forming a hologram, for example, when forming a mirror for a specific wavelength, a Lippmann hologram forming apparatus as shown in FIG. 1 and a Deniseuk type hologram forming apparatus as shown in FIG. 2 are used. Moreover, even if light with a wavelength of about 500 nm emitted from an argon laser is used, if an optical system using a glass block as shown in FIG. 3 or FIG. Mirrors can be formed that reflect light rays. 1 to 4
Where, 1 is an argon laser, 2 is a half mirror,
3 is a mirror, 4 is a special filter, 5 is a record carrier, 6 is a lens, 7 is a matching solution, and 8 is a glass block.

Next, the developing step is carried out by immersing the record carrier on which the hologram latent image is formed in a developing solution containing a guest monomer and a photo or thermal polymerization initiator. In this developing step, in the recording carrier, an unpolymerized host monomer or a low polymerization degree component of the host monomer is eluted into a developing solution according to the formed hologram pattern, and a guest monomer and light or The developing solution containing a thermal polymerization initiator is permeated to replace the unpolymerized host monomer or the low polymerization degree component of the host monomer with the guest monomer, or to add the guest monomer to the host monomer.

The solvent in the developing solution does not dissolve much the polymer of the binder polymer and the host monomer in the record carrier on which the hologram latent image is formed by exposure.
Alternatively, it must be one that is hardly dissolved and that can rapidly elute unpolymerized host monomers and low-polymerization components of the host monomers. It may also have a function of causing the record carrier to swell or contract.

Specifically, for example, benzene, toluene,
Xylene, ethylbenzene, n-propylbenzene, cumene, phenol, cresol, chlorobenzene, dichlorobenzene, nitrobenzene, benzyl alcohol,
Benzyl chloride, benzyl bromide, α-methylnaphthalene, α-chloronaphthalene and other benzene and naphthalene derivatives, and n-pentane, n-hexane,
Alkanes such as n-heptane, n-octane, isooctane and cyclohexane, cycloalkanes, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol Alcohols such as, ethers such as diethyl ether, methyl ethyl ether and diisopropyl ether, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, methyl acetate, ethyl formate and methyl propionate are used. You may use the mixed solvent of.

Next, the compound (guest monomer) capable of undergoing light or heat polymerization in the developing solution will be described. First,
As the guest monomer that can be photo- or heat-polymerized, those described as the host monomer can be used. In addition, styrene, nitrostyrene, dichlorostyrene,
Styrenes such as dibromostyrene can also be used.

The same compound as the host monomer may be used as the guest monomer, but by using a monomer having a difference in optical refractive index between the guest monomer and the host monomer, a high diffraction efficiency can be obtained when a hologram is formed. Can be obtained, and the larger the difference in optical refractive index, the higher the diffraction efficiency of the hologram. Also,
The guest monomer is preferably liquid at 25 ° C. to 100 ° C. or capable of being a solvent in the developing solution.

Examples of the photo or thermal polymerization initiator include aromatic ketones such as benzoin alkyl ethers, ketals, oxime esters, benzophenone, thioxanthone derivatives, quinone and thioacridone when a guest monomer is cured by photopolymerization. , 1,3-di (t-butyldioxycarbonyl) benzene, iodonium salts, dianine, rhodamine, safranine, malachite green methylene blue and other alkyl or alkyl borates, iron-arene complexes, bisimidazoles, N-arylglycines Etc. can be used.

Further, methyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, t-butyl peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α ′ -Bis (t-butylcumylperoxyisopropyl) benzene, t-butylperoxyisopropyl carbonate, benzoyl peroxide,
Di (t-butylperoxy) isophthalate, di (t-
Butylperoxy) terephthalate, di (t-butylperoxy) phthalate, t-butylperoxybenzoate, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 2,5-dimethyl An organic peroxide such as -2,5- (dibenzoylperoxy) hexane can be used as a polymerization initiator for both photopolymerization and thermal polymerization.

Further, as the thermal polymerization initiator, an azo radical polymerization initiator such as azobisisobutyronitrile (AIBN) can be used.

In the developing step, in addition to the above steps, the unpolymerized host monomer of the record carrier and the low-polymerized components of the host monomer may be first removed using only the solvent, and then immersed in the guest monomer. In this case, the polymerization initiator is dissolved in the guest monomer.

The concentration of the guest monomer in the developing solution is appropriately set, but is 10% by weight or more, preferably 35% by weight or more.
A range of 60% by weight is good. If it is less than 35% by weight, the amount of the solvent becomes excessive, and after the recording carrier is pulled up from the developing solution, a large amount of the solvent remains inside the recording carrier, so that the recording carrier swells or contracts and the hologram becomes uneven. On the other hand, if the guest monomer concentration exceeds 60% by weight, the ratio of the solvent becomes too small, so that it cannot be sufficiently extracted with the host monomer during the development process, resulting in a dark hologram, which is not preferable. In addition, the concentration of the polymerization initiator depends on the guest monomer.
1 to 100 parts by weight is preferable with respect to 100 parts by weight.

The interval of interference fringes can be controlled by appropriately selecting the solvent or guest monomer in the developing solution.

After the development processing is completed, the surface of the record carrier is adhered with a transparent glass or resin plate or film.
The polymerization proceeds more rapidly, but the surface may be left as it is, unless particularly required.

The record carrier is then subjected to a curing step. In the curing step, the guest carrier is cured by irradiating the record carrier with light such as ultraviolet rays or heating to fix the hologram. When the surface of the record carrier is not covered before curing, the surface of the record carrier can be covered with a suitable glass or resin plate or film after fixing the hologram.

[0054]

[Operation] Next, the operation will be described. In the hologram forming method, it is important that a clean hologram that is bright and has no cloudiness can be stably and promptly obtained. If the method according to the present invention is used, the guest monomer can be rapidly cured, and since it is not necessary to perform curing by irradiation with light having a large energy density or heating at a high temperature, the characteristics of the hologram are not changed by the curing treatment, A very large cure is obtained.

[0055]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples. Example 1 The following composition: Poly-N-vinylcarbazole (manufactured by Anan Fragrance Co., Ltd., trade name, Tubicor-210, average molecular weight 800,000) --- 1.0 g Tribromophenol methacrylate (Daiichi Kogyo Seiyaku ), Trade name, New Frontier BR-31) --- 0.5 g * 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone --- 0.08 g * 3,3'- Carbonyl bis (7-diethylaminocoumarin) --- A composition having 0.003 g was dissolved in 15 g of 1,4-dioxane, and
The solution was filtered through a 25 μm filter to obtain a photosensitive solution.

This sensitizing solution was applied on a glass plate having a thickness of 1.5 mm by 0.1
After forming a film having a thickness of 4 mm (mm) and drying at 74 ° C. for 30 minutes, a record carrier having a thickness of 10 μm was obtained. The surface of the record carrier is polyvinyl alcohol (Kuraray Co., Ltd., polymerization degree 500
A 10% aqueous solution with a saponification degree of 88%) is 2000 r with a spin coater.
It was spun on for 20 seconds at pm and dried. Then, using the optical system shown in FIG. 2, the hologram was exposed with light having a wavelength of 488 nm by an argon laser so that the exposure energy was 10 mJ / cm ² . After the exposure, the polyvinyl alcohol film on the surface of the record carrier was removed. Then, development processing was performed. The developer is 3,2,3,3-tetrafluoropropyl acrylate (trade name, viscoat 4F, manufactured by Osaka Organic Chemical Industry Co., Ltd.), with respect to 100 parts by weight of 3,
A composition composed of 8 parts by weight of 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 100 parts by weight of acetone was used. The record carrier was immersed in the developer having the above composition for 20 seconds and then pulled up.

The hologram obtained is left as it is,
When it was cured with natural light in the room, the curing was completed in about 30 minutes. The maximum diffraction efficiency of the hologram was 85%, and the diffraction wavelength for recording the maximum diffraction efficiency was 480 nm.

Comparative Example 1 In Example 1, the developing solution was made to have a composition containing no polymerization initiator, and the developing treatment was performed in the same manner. Then, leaving it as it is, curing the hologram with natural light in the room,
After 1 hour, the curing had hardly progressed, and after 24 hours, the curing had been completed. However, since it took a long time to cure, dust and the like adhered to the surface and became dirty. The maximum diffraction efficiency of the hologram in this case was 85%, and the diffraction wavelength for recording the maximum diffraction efficiency was 480 nm.

Example 2 In Example 1, the record carrier was taken out of the developer, and 2
The acetone was evaporated by leaving it for about a minute. Then attach a 0.5 mm thick glass plate to the hologram surface,
Heat treatment was performed in an oven at ℃ for 10 minutes. As a result, the hologram was hardened, and the maximum diffraction efficiency of 83% and the diffraction wavelength for recording the maximum diffraction efficiency of 480 nm were obtained.

Comparative Example 2 In Example 2, a developing solution containing no polymerization initiator was used for the developing treatment, and the same heating treatment was performed. However, even if it is heated for 30 minutes, curing does not end, so the temperature
The temperature was raised to 120 ° C. and heating was continued for 30 minutes. As a result, the hologram was cured, but the maximum diffraction efficiency was 47%, and the diffraction wavelength for recording the maximum diffraction efficiency was 570 nm, which was lower than that of the hologram of Example 2.

[0061]

As described above, according to the present invention, by including the guest monomer and the photo or thermal polymerization initiator in the developing solution, the curing of the guest monomer after the development processing is promptly completed. Further, since it is not necessary to cure under conditions such as high intensity light irradiation or heating at a high temperature, it is possible to obtain an effect that the efficiency of the hologram is not lowered and the diffraction wavelength is not shifted.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a Lippmann type exposure optical system for exposing a mirror hologram that reflects a specific visible ray.

FIG. 2 is a schematic diagram of a Denishuke type exposure optical system for exposing a mirror hologram that reflects a specific visible ray.

FIG. 3 is a schematic diagram of a Lippmann exposure optical system for exposing a mirror hologram that reflects a specific infrared ray.

FIG. 4 is a schematic diagram of a Deniseuk type exposure optical system for exposing a mirror hologram that reflects a specific infrared ray.

[Explanation of symbols]

 1 Argon Laser 2 Half Mirror 3 Mirror 4 Special Filter 5 Record Carrier 6 Lens 7 Matching Solution 8 Glass Block

Claims (1)

[Claims] 1. A record carrier comprising a binder polymer, a photopolymerizable compound, and a photopolymerization initiator is exposed to a laser light interference pattern, and then the record carrier is subjected to a photopolymerizable or heat-polymerizable compound and a photopolymerizable compound. A method for forming a hologram, which comprises immersing in a developer containing an initiator to perform a developing treatment, and then curing the record carrier by heat or light.