JP2002236440A - Photosensitive composition for volume hologram recording and photosensitive medium for volume hologram recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a volume hologram recording material, a recording medium and a volume hologram which are excellent not only in the hologram recording performance but in various kinds of physical properties such as heat resistance, toughness and softness. SOLUTION: The photosensitive composition for volume hologram recording contains organic-inorganic hybrid polymers which are prepared by copolymerization of organic silicon compounds expressed by general formula (1): RmSi(OR')n and organic monomers having ethylenically unsaturated double bonds as the structural components of the main chains, and/or their hydrolyzed polymerization condensation products organic metal fine particles having photopolymerizable reactive groups and a photopolymerization initiator. In the formula, R is a 1-10C group having ethylenic double bonds, R' is a 1-10C alkyl group and m and n satisfy m+n=4, m>=1 and n>=1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive composition capable of recording a volume hologram, a volume hologram recording medium using the same, and a volume hologram produced using the recording medium.

[0002]

2. Description of the Related Art As a photosensitive composition for producing a volume hologram, the Omnidex series manufactured by DuPont is the only commercially available mass-produced product. This material contains a radical polymerization monomer, a binder polymer, a photoradical polymerization initiator, and a sensitizing dye as main components, and utilizes a difference in refractive index between the radical polymerization monomer and the binder polymer. That is, when the photosensitive composition formed in the form of a film is subjected to interference exposure, radical polymerization is started in a portion where light is strong, and a concentration gradient of a radical polymerization monomer is generated with the exposure. Diffusion transfer of the polymerized monomer occurs. As a result, depending on the intensity of the interference light, the density of the radical polymerizable monomer is increased and decreased, and appears as a difference in refractive index. Although this material system has the best performance as a currently reported photopolymer for volume holograms, problems have been pointed out with respect to heat resistance and transparency.

Further, a material system using both radical polymerization and cationic polymerization has been reported. For example, Japanese Patent No. 28731
No. 26 discloses a system using a monomer having a diallyl fluorene skeleton as a high refractive index radical polymerizable monomer and a cationic polymerizable monomer having a smaller refractive index than the radical polymerizable monomer. In this system, the high refractive index component is polymerized by radical polymerization at the time of hologram exposure, and then the image is fixed by cationic polymerization at the fixing exposure.

Further, a material system utilizing cationic polymerization is
For example, it is disclosed in US Pat. This material system has the advantage that there is no oxygen inhibition in the radical polymerization system, but the sensitivity of cationic polymerization (Photosp
Eed) is poor, and there is a problem that it is difficult to provide sensitivity in a long wavelength region.

Further, Japanese Patent No. 2953200 discloses a material system using an inorganic substance network and a photopolymerizable monomer in combination. When an inorganic material capable of forming a network is used as a binder, there is an advantage that heat resistance, environmental friendliness, and mechanical strength are excellent, and a large difference in refractive index from a photopolymerizable organic monomer can be obtained. The hologram recording film formed by the system is rather brittle and has poor flexibility, processability, and coating suitability, and poor compatibility between the inorganic binder and the organic monomer. There is a problem that it is difficult to do.

Japanese Patent No. 2953200 also discloses that an organic group is introduced into an inorganic substance network to impart flexibility to an inorganic binder, thereby improving the brittleness of a hologram recording film. However, Patent 29
No. 53200 discloses that an organic group is introduced into an inorganic network by hydrolysis and polycondensation of an organic metal compound having an organic moiety in a side chain or an organic metal compound having a functional group polymerizable with an organic monomer. It is just that. That is, according to the disclosure of Japanese Patent No. 2953200, the network structure of the inorganic network itself is composed of chains of inorganic compounds connected to each other, and the organic group is introduced into the network structure of the inorganic network as a pendant side chain. It does not essentially change the rigid structure of the inorganic network.

Further, Japanese Patent Application Laid-Open No. 2000-508783 discloses a material in which ultrafine metal particles are dispersed in a solid matrix as a hologram recording material. However, the matrix needs to have fluidity, and the solidity is poor. was there.

[0008]

Various material systems have been disclosed for forming a volume hologram recording film.
It is not enough to apply to a wide range of fields such as optical elements, not only hologram recording performance such as refractive index difference, sensitivity and transparency, but also heat resistance, film strength, environmental resistance, mechanical strength, flexibility There is a demand for a material system that sufficiently satisfies various performances including physical properties such as workability, workability, and coating suitability.

The present invention has been accomplished in view of the above circumstances, and it is an object of the present invention to provide a hologram recording material excellent in various performances, a volume hologram recording medium using the same, and a volume hologram.

[0010]

Means for Solving the Problems In order to achieve the above object, the photosensitive composition for volume hologram recording provided by the present invention is represented by at least the following general formula (1) as a main chain constituent. Organic-inorganic hybrid polymer obtained by copolymerizing an organosilicon compound and an organic monomer having an ethylenically unsaturated double bond, and / or a hydrolytic polycondensate thereof, having a photopolymerization-reactive group and refraction of the polymer It is characterized by containing organometallic fine particles having a ratio different from that of the hydrolyzed polycondensate of the organic-inorganic hybrid polymer, and a photopolymerization initiator.

RmSi (OR ') n General formula (1) (In the above formula, R may be the same or different, and an ethylenic double bond-containing group having 1 to 10 carbon atoms, and R' may be the same or different. Represents an alkyl group having 1 to 10 carbon atoms, m
+ N = 4, m ≧ 1, and n ≧ 1. )

[0012] A method of applying a volume type hologram recording photosensitive composition containing the above-mentioned organic-inorganic hybrid polymer or a partially hydrolyzed polycondensate thereof as a binder polymer to a substrate, followed by hydrolysis and polycondensation. Applying a photosensitive composition for volume hologram recording containing a hydrolysis-condensation product of an organic-inorganic hybrid polymer onto a substrate,
By drying, a hologram recording material layer excellent in various performances is formed, and a photosensitive medium for volume hologram recording is obtained.

The thus obtained photosensitive medium for volume hologram recording of the present invention comprises at least an organosilicon compound represented by the following general formula (1) and an ethylenically unsaturated double bond as main components. An organic-inorganic hybrid polymer hydrolyzed polycondensate obtained by copolymerizing an organic monomer having the same, and a hydrolyzed polycondensate of the organic-inorganic hybrid polymer having a photopolymerization-reactive group and having a refractive index of the polymer. A volume hologram recording material layer containing at least organic metal fine particles different from the above and a photopolymerization initiator is provided on a substrate.

RmSi (OR ′) n General formula (1) (In the above formula, R may be the same or different, and an ethylenic double bond-containing group having 1 to 10 carbon atoms, and R ′ may be the same or different. Represents an alkyl group having 1 to 10 carbon atoms, m
+ N = 4, m ≧ 1, and n ≧ 1. )

The hologram recording material layer of the photosensitive medium for volume hologram recording according to the present invention forms interference fringes by interference exposure to form a hologram layer, and a volume hologram is obtained.

In the present invention, an organic-inorganic hybrid polymer containing a main chain constituent unit derived from an organosilicon compound and / or a hydrolyzed polycondensate thereof is used as a binder polymer. Since the refractive index is much lower than that of the metal compound, it is possible to obtain a large difference in the refractive index between the organic metal fine particles as a refractive index modulating component described later, and the refractive index modulation amount (Δ
A large volume hologram of n) is obtained.

Furthermore, the inorganic main chain component derived from the organosilicon compound provides good dispersibility of the organometallic fine particles, and makes it easy to prepare a photosensitive composition for volume hologram recording into a uniform coating solution. .

Further, a hologram recording material layer formed by coating the photosensitive composition for volume hologram recording according to the present invention on a base film, and performing interference exposure thereon to generate interference fringes. The obtained hologram layer has a structure in which other components such as organometallic fine particles and a photopolymerization initiator enter gaps of a network structure formed by a hydrolyzed polycondensate of an organic-inorganic hybrid polymer.
Therefore, since a flexible part is inserted into the chain that forms the network structure, it has the flexibility of an organic polymer, the toughness and the heat resistance of an inorganic polymer as physical properties of the film, and has excellent workability in practical use. I have.

In one embodiment of the present invention, the photosensitive composition for volume hologram recording is characterized by containing an organosilicon compound represented by the following general formula (2).

R ″ mSi (OR ′ ″) n Formula (2) (In the above formula, R ″ may be the same or different and may be an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, a vinyl group, an acryloyl Group, a methacryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydrocarbon group having 1 to 10 carbon atoms having a hydroxyl group or a carboxyl group, R '''may be the same or different and may be an alkyl group having 1 to 10 carbon atoms. M + n = 4, m ≧ 1, and n ≧ 1.)

In another embodiment, the photosensitive composition for volume hologram recording comprises, as the hydrolyzed polycondensate, the organic-inorganic hybrid polymer and / or the hydrolyzed polycondensate and the above-mentioned general formula (2) ) Is mixed with a hydrolyzed polycondensate with an organosilicon compound.

When a photosensitive medium for volume hologram recording is produced using the photosensitive composition for volume hologram recording according to any of these embodiments, the volume hologram recording material layer contains the organic resin as a binder. It contains a hydrolyzed polycondensate of an inorganic hybrid polymer and / or a hydrolyzed polycondensate thereof and an organosilicon compound represented by the general formula (2).

By incorporating the above organosilicon compound, a large amount of Si, which is an inorganic component, is present in the photosensitive composition for volume hologram recording, so that the dispersibility of the organometallic fine particles is further improved. .

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive composition for volume hologram recording provided by the present invention comprises at least an organosilicon compound represented by the following general formula (1) as a main chain constituent and an ethylenically unsaturated double compound. An organic-inorganic hybrid polymer obtained by copolymerizing an organic monomer having a bond, and / or a hydrolyzed polycondensate thereof, a polymer having a photopolymerization-reactive group, and a polymer having a refractive index of the above-mentioned organic-inorganic hybrid polymer. It contains organometallic fine particles different from the decomposition polycondensate and a photopolymerization initiator.

RmSi (OR ') n General formula (1) (In the above formula, R may be the same or different, and an ethylenic double bond-containing group having 1 to 10 carbon atoms, and R' may be the same or different. Represents an alkyl group having 1 to 10 carbon atoms, m
+ N = 4, m ≧ 1, and n ≧ 1. )

[0026] A photosensitive composition for volume hologram recording containing the above-mentioned organic-inorganic hybrid polymer or a partially hydrolyzed polycondensate thereof as a binder polymer is coated on a substrate and then subjected to hydrolysis and polycondensation. Applying a photosensitive composition for volume hologram recording containing a hydrolysis-condensation product of an organic-inorganic hybrid polymer onto a substrate,
By drying, a hologram recording material layer excellent in various performances can be obtained.

The organic-inorganic hybrid polymer has at least the following general formula (1) RmSi (OR ') n general formula (1) as a main chain constituent component (wherein R may be the same or different and may have 1 to 1 carbon atoms) 10 ethylenic double bond-containing groups, R ′ may be the same or different and represent an alkyl group having 1 to 10 carbon atoms;
+ N = 4, m ≧ 1, and n ≧ 1. ) And an organic monomer having an ethylenically unsaturated double bond are copolymerized, preferably a random copolymer.

Examples of the organosilicon compound of the general formula (1) include various vinylalkoxysilanes, for example, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane, vinyltriallyloxysilane,
Vinyltetraethoxysilane, vinyltetramethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like are preferably used.

Examples of the organic monomer having an ethylenically unsaturated double bond include acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester, but are not limited thereto.

The organic-inorganic hybrid polymer is prepared by adding the ethylenic double bond-containing group of the organometallic compound represented by the general formula (1) and the ethylenically unsaturated double bond of the organic monomer by a general method. It can be produced by a polymerization reaction. For example, an organometallic compound and an organic monomer may be used as aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, methanol, ethanol, and isopropanol. Add an initiator such as benzoyl peroxide and azoisobutyronitrile into a solvent such as alcohols, radical polymerize it with heating, then remove the solvent to produce an organic-inorganic hybrid polymer. can do.

When this organic-inorganic hybrid polymer is hydrolyzed and polycondensed by a sol-gel reaction, different molecules of the organic-inorganic hybrid polymer or organometallic compound portions in the same molecule are cross-linked to form a network (network structure). I do. This network structure is composed of a chain of a main chain component derived from an organosilicon compound and a main chain component derived from an organic monomer. Therefore, it is structurally different from the inorganic binder polymer disclosed in Japanese Patent No. 2953200 in which an organic group is introduced as a side chain in a pendant manner on a network in which only inorganic compounds are linked, and the organic-inorganic hybrid polymer is a chain forming a network. Since a flexible portion is inserted in the inside, it has both the toughness and heat resistance of an inorganic polymer as well as the flexibility of an organic polymer as film properties, and is practically more processed than that disclosed in Japanese Patent No. 2953200. Excellent aptitude.

In the present invention, an organic silicon compound is particularly used as an inorganic main chain constituent unit of the organic-inorganic hybrid polymer. One of the indexes of the hologram performance is a refractive index modulation amount (Δn) calculated by Kogelnik theory. Δn indicates the refractive index difference in the refractive index distribution formed according to the interference light incident on the light-sensitive material. The larger the Δn, the better the hologram. Since the organosilicon compound has a very low refractive index as compared with other organometallic compounds, by using an organosilicon compound as an inorganic main chain constituent unit of an organic-inorganic hybrid polymer, it serves as a refractive index modulation component described later. Since a large difference in the refractive index from the organometallic fine particles can be obtained, Ko is smaller than the conventional combination using an organic binder polymer and an organic monomer as a refractive index modulating component.
The refractive index modulation amount (Δ
n) is large, which is advantageous in terms of performance.

Further, since the organic-inorganic hybrid polymer contains an inorganic main chain component derived from an organosilicon compound, the organic metal fine particles have a good dispersibility, and the photosensitive material for volume hologram recording is excellent. It is easy to prepare the composition into a uniform coating liquid.

Further, Japanese Patent Application Laid-Open No. 2000-508783 discloses a system in which reactive metal fine particles are dispersed in a solid matrix. However, the solid matrix has a high fluidity and is practically suitable for processing. However, in the present invention, since the organic-inorganic hybrid polymer is used as the binder polymer, the processability is improved.

The photosensitive composition for volume hologram recording of the present invention may use, as a binder polymer, a partially or completely hydrolyzed condensate of the organic-inorganic hybrid polymer or an organic-inorganic hybrid polymer. And a partially or completely hydrolyzed condensate thereof.

The photosensitive composition for volume hologram recording of the present invention may be used as a binder polymer by mixing the above-mentioned organic-inorganic hybrid polymer and various organic polymers depending on the use. As the organic polymer, for example, polyacrylate, polymethacrylate or a partial hydrolyzate thereof, polyvinyl acetate or a partial hydrolyzate thereof, polyvinyl alcohol or a partial acetalized product thereof, triacetyl cellulose, polyisoprene, polybutadiene , Polychloroprene, silicone rubber, polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinylcarbazole or a derivative thereof, poly-N-vinylpyrrolidone or a derivative thereof, styrene and anhydrous Maleic acid copolymer or its half ester, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, acrylonitrile, ethylene, propylene, vinyl chloride Le can be exemplified a copolymer of at least one polymerization component copolymerizable monomers groups such as vinyl acetate.

In order to further improve the refractive index difference between the binder and the organometallic fine particles, an organic silicon compound represented by the following general formula (2) may be added to the photosensitive composition for volume hologram recording. it can.

R ″ mSi (OR ″ ′) n Formula (2) (In the above formula, R ″ may be the same or different and may be an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, a vinyl group, an acryloyl Group, a methacryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydrocarbon group having 1 to 10 carbon atoms having a hydroxyl group or a carboxyl group, R '''may be the same or different and may be an alkyl group having 1 to 10 carbon atoms. M + n = 4, m ≧ 1, and n ≧ 1.)

When the organosilicon compound represented by the general formula (2) is added to the photosensitive composition for volume hologram recording, a network is formed together with the organic-inorganic hybrid polymer by a sol-gel reaction in the presence of water and an acid catalyst. In order to form, not only lower the refractive index of the binder,
It also has the effect of improving the toughness and heat resistance of the film. According to the compounding of the organosilicon compound represented by the general formula (2), a large amount of Si which is an inorganic component is present in the photosensitive composition for volume hologram recording, so that the dispersibility of the organometallic fine particles is further improved. There is also an effect.

Examples of the organosilicon compound of the general formula (2) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n
-Propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-
Propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldi Ethoxysilane, dimethylmethoxysilane, dimethylethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, vinyltrichlorosilane, vinyl Lutris (β-methoxyethoxy) silane, vinyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-amino Propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-chloropropyltrimethoxysilane and the like are preferably used.

The organic-inorganic hybrid polymer and the organosilicon compound represented by the general formula (2) usually form a network in which both are mixed and then hydrolyzed and polycondensed to form a mixed network. Is mixed after partial hydrolysis polycondensation of one or both,
It is also possible to form a network in which both are mixed by further performing hydrolysis and polycondensation after mixing.

The organic metal fine particles are components (refractive index modulation components) for forming interference fringes by modulating the refractive index of the strongly exposed portion during interference exposure. The organometallic fine particles have at least one photopolymerizable reactive group, and the refractive index of a polymer obtained by polymerizing the organometallic fine particles is a hydrolyzed polycondensate of the organic-inorganic hybrid polymer. Those having a different refractive index, preferably a difference in refractive index between the two.
One that is 0 or more is used.

The organometallic fine particles are provided on the surface of the metal fine particles,
A compound in which at least one functional group capable of being photopolymerized such as photoradical polymerization or photocation polymerization is bonded.

The metal component of the organometallic fine particles is not particularly limited as long as a difference in refractive index from that of the organic-inorganic hybrid polymer can be obtained. However, since the organosilicon compound is an organometallic compound having a relatively low refractive index, the organic silicon compound is not used. In order to increase the difference in the refractive index from the organic-inorganic hybrid polymer containing the main chain constituent component derived from the silicon compound, it is preferable to use organic metal fine particles made of a metal component having a refractive index as high as possible. As a metal component with a high refractive index,
For example, Ti, Zr, Zn, In, Sn and the like can be exemplified.

The size of the metal fine particles is not particularly limited.
About 200 nm is preferable.

Examples of the photoradical polymerizable functional group include an addition-polymerizable ethylenically unsaturated double bond, which is formed by coating a metal fine particle with an ethylenically unsaturated double bond-containing coupling agent. It can be introduced by processing. As the ethylenically unsaturated double bond-containing coupling agent, for example, vinyl silane, acryloyl silane,
A silane coupling agent such as methacryloylsilane can be used.

Examples of the photocationically polymerizable functional group include cyclic ethers represented by an epoxy ring and an oxetane ring;
Thioethers, vinyl ethers and the like can be used, and can be introduced by subjecting metal fine particles to surface treatment with a coupling agent containing these functional groups. As the epoxy ring-containing coupling agent, for example, β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
A silane coupling agent such as γ-glycidoxypropyltrimethoxysilane can be used.

The photopolymerization initiator is used for initiating or accelerating the polymerization of the organometallic fine particles by interference exposure. According to the type of polymerization reaction, a photoradical polymerization initiator or a photocationic polymerization initiator may be used. Select and use as appropriate.

As the photoradical polymerization initiator, 1,3-di (t-butyldioxycarbonyl) benzophenone,
3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, N-phenylglycine,
Examples thereof include 2,4,6-tris (trichloromethyl) -s-triazine, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, and imidazole dimers.

Examples of the cationic photopolymerization initiator include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, aromatic phosphonium salts, and mixed ligand metal salts, for example, (η ⁶ -benzene) (η ^5- (Cyclopentadienyl) iron (II), a silanol-aluminum complex, and the like.

The photopolymerization initiator is preferably decomposed after recording the hologram from the viewpoint of stabilizing the recorded hologram. For example, in the case of an organic peroxide system, the initiator is easily decomposed by irradiation with ultraviolet rays, which is preferable.

For recording a hologram, a visible laser beam, for example, an argon ion laser (458 nm, 488 nm) is used.
m, 514.5 nm), krypton ion laser (6
47.1 nm) and laser light from a YAG laser (532 nm) are used, but a sensitizing dye can be added for the purpose of improving the sensitivity at each laser light wavelength.

As sensitizing dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes Dyes and pyrylium salt dyes are exemplified. Sensitizing dyes having an absorption wavelength in the visible light region, when high transparency is required such as optical elements,
It is preferable that the hologram be made colorless by decomposition or the like by heating or irradiation with ultraviolet rays after the hologram recording.

The organometallic fine particles as the refractive index modulating component are 10 to 1000 parts by weight based on 100 parts by weight of the organic-inorganic hybrid polymer as the binder polymer.
It is preferably used in a proportion of 10 to 100 parts by weight.

The organosilicon compound of the general formula (2), if necessary, is used in an amount of 10 to 100 parts by weight, preferably 20 to 70 parts by weight, based on 100 parts by weight of the binder polymer.

The photopolymerization initiator is the binder polymer 10
1 to 10 parts by weight, preferably 5 to 10 parts by weight with respect to 0 parts by weight
Used in parts by weight.

The sensitizing dye is used in an amount of 0.01 to 1 part by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the binder polymer.
It is used in a proportion of 0.5 parts by weight.

Each of the above-mentioned materials was subjected to acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, , 4-dioxane,
By dissolving in 1,2-dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol, or the like, or a mixed solvent thereof, a coating liquid as a photosensitive composition for volume hologram recording according to the present invention can be prepared. it can.

The above coating solution is applied to an appropriate substrate film by a method such as a spin coater, a gravure coater, a comma coater, and a bar coater. The thickness of the volume hologram recording material layer is 1 to 100 μm, preferably 10 to 4 μm.
The thickness is preferably set to 0 μm.

The base film of the photosensitive medium for volume hologram recording has transparency, and is a polyethylene film, a polypropylene film, a polyethylene fluoride film, a polyvinylidene fluoride film,
Polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl alcohol film, polyvinyl alcohol film, polymethyl methacrylate film, polyether sulfone film, polyether ether ketone film, polyamide film, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film And a resin such as a polyester film such as a polyethylene terephthalate film and a polyimide film, and has a thickness of 2 to 200 μm, preferably 10 to 50 μm.

The hydrolysis-polycondensation reaction (sol-gel reaction) of the photosensitive composition for volume hologram recording can be carried out at an arbitrary timing before or after application to the substrate film in the presence of a suitable amount of water at -10. ° C to 35 ° C, preferably 0 ° C to 2
Leaving at 5 ° C. for 15 minutes to 12 hours facilitates progress and completion.

In the above-mentioned hydrolysis polycondensation, it is preferable to use a catalyst. The catalyst is preferably an acid such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid.
It can be used as an aqueous solution of 0.0N, preferably about 0.005 to 5.0N.

For the photosensitive medium for volume hologram recording, for example, a coating solution of the photosensitive composition for volume hologram recording is applied to a base film, and the coating film is sufficiently hydrolyzed and polycondensed. Thereafter, it is obtained by drying and forming a film (volume hologram recording material layer) of the photosensitive composition for volume hologram recording.

Also, the coating liquid of the photosensitive composition for volume hologram recording is partially or completely hydrolyzed and polycondensed, and then applied to an appropriate base film and dried. A photosensitive medium for volume hologram recording is obtained.

The organic-inorganic hybrid polymer as the binder polymer may be mixed with other materials after being subjected to hydrolysis and polycondensation in advance.

When the organic silicon compound of the general formula (2) is used as the auxiliary binder, the organic-inorganic hybrid polymer and the organic silicon compound may be hydrolyzed and polycondensed and then mixed with other materials. Further, as a modified example, one or both of the organic-inorganic hybrid polymer and the organosilicon compound are partially hydrolyzed and polycondensed alone beforehand, and then mixed with other components to prepare a coating liquid. Alternatively, it may be completely polycondensed after coating.

The water and the catalyst such as acid and alkali necessary for the hydrolysis and polycondensation reactions may be mixed in the solvent at the same time as the respective materials, or may be added later. For example, when performing hydrolysis and polycondensation after coating, it may be added to the coating liquid immediately before coating, and when performing hydrolysis and polycondensation before coating, hydrolysis is performed. May be added immediately before performing the polycondensation reaction.

When the volume hologram recording material layer after drying has tackiness, a film exemplified as the above-mentioned base film can be laminated as a protective film. In this case, the contact surface of the laminate film with the volume hologram recording material layer may be subjected to a release treatment so as to be easily peeled off later.

The thus obtained photosensitive medium for volume hologram recording has a hologram recording material layer provided on a base film, and the hologram recording material layer is composed of a hydrolyzed polycondensate of an organic-inorganic hybrid polymer. Or, an organic-inorganic hybrid polymer and an organic silicon compound are mixed and hydrolyzed polycondensate, an organometallic fine particle as a refractive index modulating component, and a photopolymerization initiator are contained as essential components. It has a structure in which other components such as organometallic fine particles and a photopolymerization initiator enter into gaps in a network of a hydrolyzed polycondensate in which a decomposed polycondensate or an organic-inorganic hybrid polymer and an organic metal compound are mixed.

The volume hologram can be formed on the photosensitive medium for recording a volume hologram according to the present invention by performing interference exposure by a conventionally known method.

For example, a hologram master is faced to and adhered to a hologram recording material layer of a photosensitive medium for volume hologram recording, and visible light or ionizing radiation such as ultraviolet light or an electron beam is used from the transparent base film side. A volume hologram is formed by performing the interference exposure.

Further, in order to promote the refractive index modulation by interference exposure or to complete the polymerization reaction, after the interference exposure, a process such as overall exposure with ultraviolet light or heating can be appropriately performed.

The volume hologram recording mechanism of the photosensitive composition for volume hologram recording in the present invention is considered to be the same as the mechanism conventionally known. That is, when the photosensitive composition formed in the form of a film is subjected to interference exposure, the organometallic fine particles as a refractive index modulating component start photopolymerization in a portion where light is strong, and the organometallic fine particles as a refractive index modulating component are thereby accompanied. A concentration gradient of the fine particles is generated, and the diffusion and movement of the organometallic fine particles occur from a portion where light is weak to a portion where light is strong. As a result, depending on the intensity of the interference light,
The organometallic fine particles or a polymer thereof are made dense and dense, and appear as a difference in refractive index. This refractive index difference becomes an interference fringe, and a volume hologram is formed.

In this manner, the hologram recording material layer of the photosensitive medium for volume hologram recording according to the present invention forms interference fringes by interference exposure and becomes a hologram layer, and a volume hologram is obtained.

In the present invention, the difference in the refractive index between the interference fringes of the hologram layer is caused by the difference between the portion containing the organic-inorganic hybrid polymer as the binder polymer at a high ratio and the portion containing the organic metal fine particles or the polymer thereof at a high ratio. However, since the organic-inorganic hybrid polymer used in the present invention contains Si as an inorganic component and has a very low refractive index, a large difference in the refractive index from the organometallic fine particles can be obtained. It is possible to obtain a volume hologram having a large refractive index modulation amount (Δn).

The hologram recording material layer of the photosensitive medium for volume hologram recording according to the present invention forms an interference fringe by interference exposure and becomes a hologram layer. It has a network structure of a hydrolyzed polycondensate of an inorganic hybrid polymer or a hydrolyzed polycondensate in which an organic-inorganic hybrid polymer and an organosilicon compound are mixed. Therefore, since a flexible part is inserted into the chain that forms the network structure, it has the flexibility of an organic polymer, the toughness and the heat resistance of an inorganic polymer as physical properties of the film, and has excellent workability in practical use. I have.

[0077]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preparation of Organic-Inorganic Hybrid Polymer Starting Solution Ethyl methacrylate and γ-methacryloxypropyltrimethoxysilane (KBM503; Shin-Etsu Chemical Co., Ltd.)
Was adjusted to a molar ratio of 6: 4, benzene was used as a solvent, and benzoyl peroxide was used as an initiator, and the mixture was polymerized under reflux for 8 hours. After completion of the reaction, the mixture was purified by removing unreacted substances and benzene, and dried under reduced pressure to obtain an organic-inorganic hybrid polymer.

The organic-inorganic hybrid polymer obtained above is dissolved in acetone, and water, hydrochloric acid and tetraethoxysilane (KBE04; manufactured by Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound are added. -An inorganic hybrid polymer starting solution was obtained.

2. Preparation of Volume Hologram Next, a photosensitive composition solution for volume hologram recording having the following composition was prepared.

<Volume type photosensitive composition solution for hologram recording>-Starting solution of organic-inorganic hybrid polymer prepared as described above: 100 parts by weight (solid content)-Zirconia fine particles having an ethylenically unsaturated double bond introduced therein (γ -Zirconia fine particles treated with methacryloxypropyltrimethoxysilane): 60 parts by weight 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals Co., Ltd.): 2 parts by weight 3-Ethyl-5- [ (3-Ethyl-2 (3H) -benzothiazolylidene) ethylidene] -2-thioxo-4-
Oxazolidinone (NK-1473; manufactured by Hayashibara Biochemical Laboratory): 0.02 parts by weight Methanol: 30 parts by weight Methyl ethyl ketone: 30 parts by weight A polyethylene terephthalate (PET) film having a thickness of 38 μm (Toray) Co., Ltd. using a bar coater to form a gel-like hologram recording material layer on a dry mirror having a dry film thickness of 20 μm using a bar coater. Was prepared.

Next, the hologram recording material layer side of the photosensitive medium for volume hologram recording is laminated on a mirror,
514.5 nm argon ion laser light was incident from the ET side to perform interference exposure to record a volume hologram.

Next, the interference fringes were fixed by heating and UV polymerization to obtain a volume hologram. As a result of calculation from the spectral evaluation result, the refractive index modulation amount Δn was 0.051.

[0083]

According to the present invention, not only the hologram recording performance such as the refractive index difference, sensitivity and transparency, but also the volume having the flexibility of an organic polymer, the toughness and the heat resistance of an inorganic polymer as film properties. Hologram recording material, volume hologram recording medium, and volume hologram can be provided, and application to a wide range of fields such as optical elements is expected.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 85/00 C08G 85/00 4J100 G03F 7/004 501 G03F 7/004 501 511 511 521 521 7/028 7 / 028 7/033 7/033 7/075 501 7/075 501 521 521 F term (reference) 2H025 AA10 AA13 AB20 AC01 AC08 BH05 CA01 CA27 CA28 CA39 CA41 CA43 CB34 CC20 2K008 AA00 AA11 DD13 FF17 4J011 PA99 PC02 SA21 SA SA87 SA88 UA01 VA01 WA01 4J026 AB44 BA42 4J031 CA69 CA83 4J100 AP21P CA01 FA02 JA32 JA37

Claims (12)

[Claims] An organic-inorganic hybrid polymer obtained by copolymerizing at least an organic silicon compound represented by the following general formula (1) and an organic monomer having an ethylenically unsaturated double bond as a main chain constituent component, and / or Or a hydrolyzed polycondensate thereof, having a photopolymerization-reactive group and having a refractive index of the polymer different from the hydrolyzed polycondensate of the organic-inorganic hybrid polymer, and containing a photopolymerization initiator. 1. A photosensitive composition for volume hologram recording, comprising: RmSi (OR ′) n General formula (1) (In the above formula, R may be the same or different, and may have 1 to 10 carbon atoms, an ethylenic double bond-containing group, and R ′ may be the same or different and have 1 carbon atom. Represents an alkyl group of 10 to 10;
+ N = 4, m ≧ 1, and n ≧ 1. ) 2. The composition according to claim 1, further comprising an organosilicon compound represented by the following general formula (2).
The photosensitive composition for volume hologram recording according to the above. R ″ mSi (OR ″ ′) n General formula (2) (In the above formula, R ″ may be the same or different and may be an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, vinyl group, acryloyl group, methacryloyl Group, an epoxy group, an amide group, a sulfonyl group, a hydrocarbon group having 1 to 10 carbon atoms having a hydroxyl group or a carboxyl group, and R ′ ″ may be the same or different and represent an alkyl group having 1 to 10 carbon atoms, m + n = 4, m ≧ 1, n ≧ 1.) 3. The hydrolyzed polycondensate is the hydrolyzed polycondensate of the organic-inorganic hybrid polymer and / or the hydrolyzed polycondensate and an organosilicon compound represented by the following general formula (2). 2. The method of claim 1, wherein
The photosensitive composition for volume hologram recording according to the above. R ″ mSi (OR ″ ′) n General formula (2) (In the above formula, R ″ may be the same or different and may be an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, vinyl group, acryloyl group, methacryloyl Group, an epoxy group, an amide group, a sulfonyl group, a hydrocarbon group having 1 to 10 carbon atoms having a hydroxyl group or a carboxyl group, and R ′ ″ may be the same or different and represent an alkyl group having 1 to 10 carbon atoms, m + n = 4, m ≧ 1, n ≧ 1.) 4. The photosensitive composition for volume hologram recording according to claim 1, further comprising a sensitizing dye. 5. The method according to claim 1, wherein the organometallic fine particles are a compound having an ethylenically unsaturated double bond capable of addition polymerization as a photopolymerization-reactive group, and the photopolymerization initiator is a photoradical polymerization initiator. The volume type hologram recording photosensitive composition according to any one of claims 1 to 4, wherein 6. The organic metal fine particle is a compound having a cationically polymerizable group as a photopolymerization reactive group, and the photopolymerization initiator is a photocationic polymerization initiator. 4. The photosensitive composition for volume hologram recording according to any one of 4. 7. A photosensitive medium for volume hologram recording, wherein a film of the photosensitive composition for volume hologram recording according to claim 1 is provided on a substrate. 8. An organic-inorganic hybrid polymer obtained by copolymerizing at least an organosilicon compound represented by the following general formula (1) and an organic monomer having an ethylenically unsaturated double bond as a main chain constituent component. Decomposition polycondensate, containing at least a photopolymerization initiator having a photopolymerization-reactive group and having a refractive index of the polymer different from the hydrolytic polycondensate of the organic-inorganic hybrid polymer. A photosensitive medium for volume hologram recording, wherein a volume hologram recording material layer is provided on a substrate. RmSi (OR ′) n General formula (1) (In the above formula, R may be the same or different, and may have 1 to 10 carbon atoms, an ethylenic double bond-containing group, and R ′ may be the same or different and have 1 carbon atom. Represents an alkyl group of 10 to 10;
+ N = 4, m ≧ 1, and n ≧ 1. ) 9. The hydrolytic polycondensate contained in the volume hologram recording material layer is the same as the organic-inorganic hybrid polymer and / or the hydrolyzed polycondensate and an organic compound represented by the following general formula (2). 9. The photosensitive medium for volume hologram recording according to claim 8, which is a hydrolytic polycondensate with a silicon compound. R ″ mSi (OR ″ ′) n General formula (2) (In the above formula, R ″ may be the same or different and may be an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, vinyl group, acryloyl group, methacryloyl Group, an epoxy group, an amide group, a sulfonyl group, a hydrocarbon group having 1 to 10 carbon atoms having a hydroxyl group or a carboxyl group, R ′ ″ may be the same or different and represent an alkyl group having 1 to 10 carbon atoms, m + n = 4, m ≧ 1, n ≧ 1.) 10. The volume hologram recording material layer,
9. The composition according to claim 8, further comprising a sensitizing dye.
Or a photosensitive medium for volume hologram recording according to 9. 11. The organic metal fine particle is a compound having an ethylenically unsaturated double bond capable of addition polymerization as a photopolymerization-reactive group, and the photopolymerization initiator is a photoradical polymerization initiator. 11. The method according to claim 8, wherein
The photosensitive medium for volume hologram recording according to any one of the above. 12. The organic metal fine particles are compounds having a cationically polymerizable group as a photopolymerizable group, and
The photosensitive medium for volume hologram recording according to any one of claims 8 to 10, wherein the photopolymerization initiator is a photocationic polymerization initiator.