WO2005029201A1 - ホログラフィック記録メディア、ホログラフィック記録方法およびホログラフィック情報メディア - Google Patents
ホログラフィック記録メディア、ホログラフィック記録方法およびホログラフィック情報メディア Download PDFInfo
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- WO2005029201A1 WO2005029201A1 PCT/JP2004/013591 JP2004013591W WO2005029201A1 WO 2005029201 A1 WO2005029201 A1 WO 2005029201A1 JP 2004013591 W JP2004013591 W JP 2004013591W WO 2005029201 A1 WO2005029201 A1 WO 2005029201A1
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- KGDQKMRJLRNYEX-UHFFFAOYSA-N tridecyl 2-sulfanylpropanoate Chemical compound SC(C(=O)OCCCCCCCCCCCCC)C KGDQKMRJLRNYEX-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/001—Phase modulating patterns, e.g. refractive index patterns
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/026—Recording materials or recording processes
- G03H2001/0264—Organic recording material
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/12—Photopolymer
Definitions
- the present invention relates to a holographic recording medium capable of large-capacity and high-speed transfer, and further relates to a holographic recording method and holographic information on which information is recorded.
- a recording method in this holographic recording for example, a recording method using a holographic recording medium in which transparent substrates are arranged on both sides of a holographic recording layer (for example, US Pat. No. 5,719,691) and A recording method using a holographic recording medium having a reflective surface disposed on one side of a holographic recording layer (for example, JP-A-2002-123949) and the like have been proposed.
- Such a holographic recording medium records information by changing a refractive index in a holographic recording layer in the medium by holographic exposure, and detects a change in a refractive index in the recorded medium.
- the basic principle is that information is reproduced by reading.
- the holographic recording layer is made of a material using an inorganic material (for example, UK Patent No. 9,929,953), and is structured by light. (For example, Japanese Patent Application Laid-Open No. H10-340479) or a material using diffusion polymerization of a photopolymer (for example, US Pat. No. 4,942,112).
- the material using the photopolymer described in Patent Document 5 uses a volatile solvent when producing the recording layer forming composition, so that the thickness of the recording layer is at most about 150 ⁇ . Is restricted to In addition, the volume shrinkage of 4-10% caused by polymerization adversely affected the reliability of reproducing the recorded information.
- a holographic recording layer forming composition utilizing the same (for example, U.S. Pat. No. 5,759,721).
- the recording layer-forming composition is a liquid substance other than the monomer that causes photo-induced thione polymerization
- the island-shaped monomer formed by photo-polymerization of the monomer in the recording layer by holographic exposure is used.
- drawbacks such as the possibility that the part may move, and the volume of the liquid substance expands due to changes in the environmental temperature inside the device.
- radical polymerization is used for recording in holographic exposure, and a binder is formed after the formation of the medium in order to retain the radically polymerizable monomer before the exposure (for example, a thread-forming material (for example, U.S. Pat. No. 6,103,454) has been proposed.
- a thread-forming material for example, U.S. Pat. No. 6,103,454
- Use of such a composition can increase the thickness of the holographic recording layer and reduce volume shrinkage. Can be done, but it is still not enough.
- a hologram recording photosensitive composition using a binder having a high degree of polymerization in advance instead of a binder-forming compound (for example, International Publication No. 3Z081)
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a holographic recording medium, a holographic recording method, a holographic recording method, and a holographic recorded holographic recording medium having high sensitivity and excellent storage stability. Decide to provide information media.
- one embodiment of the present invention provides: (1) a binder-forming compound, a compound having an ethylenically unsaturated bond between the first base material and the second base material, A holographic recording medium having a holographic recording layer containing a photopolymerization initiator capable of initiating a polymerization reaction of a compound having the formula (I) and a sensitizing dye capable of spectrally sensitizing the photopolymerization initiator.
- the binder-forming compound comprises a combination of at least one compound selected from the following (1) to (8):
- the content of the compound having an ethylenically unsaturated bond is 11 to the entire composition.
- a holographic recording medium wherein the photopolymerization initiator contains at least a compound represented by the following general formula (1).
- A represents an unsubstituted or alkyl-substituted cyclopentagel group
- B represents an unsubstituted or substituted arene group
- X— represents a fluorine atom-containing anion.
- the binder-forming compound includes (1) a compound having an isocyanate group and a compound having a hydroxyl group, or (7) a compound having an oxysilane group and a compound having a mercaptan group.
- the holographic recording medium according to the above (1) characterized by the following.
- the binder-forming compound includes (1) a compound having an isocyanate group and a compound having a hydroxyl group, and the compound having an isocyanate group has three or more isocyanate groups in the compound. 0 mass% or more 65 mass.
- the compound having an isocyanate group containing at least 3 isocyanate groups in an amount of 30% by mass or more and 65% by mass or less based on the entire compound having the isocyanate group is used.
- the holographic recording medium according to (3), wherein the compound having an isocyanate group has a molecular weight of 200 to 500.
- the compound having a hydroxyl group is a compound having two or more hydroxyl groups in a molecule having a molecular weight of 100 to 2,000.
- the compound having an ethylenically unsaturated bond includes a compound having a (meth) acryloyl group in a molecule.
- a compound having a refractive index of at least 1.55 or more is 50% by mass based on the whole compound having an ethylenically unsaturated bond. / 0 to 10.0% by mass.
- a holographic recording medium according to (I) A holographic recording medium according to (I).
- the thickness of the first base material is D1
- the thickness of the second base material is D2
- the thickness of the holographic recording layer is Dh.
- the thickness Dh of the holographic recording layer is 200 ⁇ or more and 2.0 mm or less, 0.15 Dh / (D 1 + D 2) ⁇ 2.0, and the relationship of D 1 ⁇ D 2 is satisfied.
- the first base material is transparent, and an antireflection treatment is performed on a surface of the first base material opposite to a surface in contact with the holographic recording layer.
- the holographic recording medium according to the above (1).
- the holographic recording medium according to the above (1) wherein the material of the first base material is glass.
- the holographic recording medium according to (1) wherein a reflective layer having a reflectance of 70% or more is laminated on the second base material.
- the holographic recording medium according to (1) wherein the holographic recording medium has a disk shape or a card shape. It is a recording media.
- the binder-forming compound is exposed before the holographic recording medium is subjected to holographic exposure.
- Holographic exposure was performed by injecting information light and reference light from the first substrate side based on the information, and the photopolymerization initiator was activated.
- the holographic recording method is characterized in that information is recorded on a holographic recording medium by diffusion-polymerizing a compound having an ethylenically unsaturated bond with the active species in a holographic recording layer.
- the whole holographic recording medium may be further stabilized by irradiating heat.
- a holographic recording method as described in (14) above which is characterized by the following.
- the first base material side may be used based on information to be recorded on the holographic recording medium.
- the holographic exposure is performed by injecting information light and reference light from the holographic recording medium, the photopolymerization initiator is activated, and the compound having an ethylenically unsaturated bond is diffused and polymerized by the active species, whereby information is recorded on the holographic recording medium.
- an embodiment of the present invention provides a holographic information recording medium in which information is recorded on the holographic recording layer in the holographic recording medium according to (1).
- the holographic information recording layer comprises a region mainly composed of a binder formed from the binder-forming compound and a compound having an ethylenically unsaturated bond.
- FIG. 1 is a schematic diagram showing the principle of a measuring device used for measuring a shrinkage ratio.
- the holographic recording medium of the present invention is a holographic recording medium in which a holographic recording layer is sandwiched between a first base material and a second base material, wherein the holographic recording layer has a compound having an isocyanate group and a hydroxyl group.
- a compound having an isocyanate group and a compound having an amino group, a compound having a phenolic group and a carboxyl group, a compound having an unsaturated ester group and a compound having an amino group, a compound having an unsaturated ester group and a mercaptan Compounds having a group, compounds having a vinyl group and compounds having a silicon hydride group, compounds having an oxysilane group and compounds having a mercaptan group, and oxsilane, oxetane, tetrahydrofuran, oxepane, monocyclic acetanol, and bicyclic acetal Lactone, cyclic orthoester, compound having at least one group selected from cyclic carbonate in the molecule and at least one kind of binder selected from thermal cationic polymerization initiators
- the photopolymerization initiator capable of initiating the polymerization reaction of the compound having an ethylenically unsaturated bond is at least a compound represented by the general formula (I). It is characterized by containing the compound represented by 1).
- the binder-forming compound refers to a precursor that is not a polymer as a binder when the recording composition is prepared, and will be described later in detail by using such a binder-forming compound. It is possible to prevent the recording medium from shrinking before and after the above-described holodographic exposure, and to increase the thickness of the recording layer when the holographic recording medium is manufactured.
- the binder-forming compound of the present invention does not polymerize or cross-link between the binder-forming compounds. Or by polymerizing or crosslinking after holographic exposure to form a binder.
- the binder-forming compound include a compound having an isocyanate group and a compound having a hydroxyl group, a compound having an isocyanate group and a compound having an amino group, a compound having a carposimido group and a carboxyl group, and an unsaturated ester group.
- At least one combination may be used as appropriate, and further, a compound having an isocyanate group and a compound having a hydroxyl group, which can be polymerized or cross-linked to a binder under mild conditions in the above selection.
- a compound having an oxysilane group and a compound having a mercaptan group is more preferable.
- the compound having an isocyanate group used for crosslinking the compound having an isocyanate group and the compound having a hydroxyl group used in the present invention can be used without any particular limitation, and is a photopolymerization component described in detail above.
- a compound having two or more isocyanate groups in a molecule is more preferable.
- a recording medium it is produced by sandwiching a recording composition that is liquid at room temperature or liquid at a temperature of 100 ° C. or less with a predetermined thickness between two substrates. A liquid or a compound having a melting point of 100 ° C. or less is more preferable.
- Such a compound having a sosinate group include, for example, 1,8-diisocyanate-41-isocyanate methylenoloctane, 2-isocyanateethyl-2,6-diisocyanate, and benzene-1-one , 3,5-triisocyanate, 1-methinolebenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene -2,4,6-triisocyanate, diphenylmethane-2,4 , 4'-triisomethane, triphenylmethane-1,4'-triisocyanate, bis (isocyanatotolyl) phenyl / lemethane, dimethylene diisocyanate, tetramethylene diisocyanate , Hexanemethylene diisocyanate, 2,2-dimethy ⁇ / pentanediisocyanate, 2,2,4-trimethyolepentanediisocyanate
- an isocyanate compound having three or more isocyanate groups in a molecule and the proportion of the isocyanate group in the compound is 30% by mass or more and 65% by mass or less is used. It is more preferable to use it because the shrinkage of the recording medium before and after the holographic exposure described later can be prevented.
- Such an isocyanate compound having three or more isocyanate groups in the molecule and in which the proportion of the isocyanate group occupying the compound is 30% by mass or more and 65% by mass or less in the compound is a compound that satisfies this condition.
- a holographic recording medium in which a recording layer composed of a holographic recording composition described in detail below is laminated, and the holographic information used after the recording is completed.
- Media like CDs and DVs, can have a variety of ambient temperatures under fluorescent lights, windowsills, or left behind. Therefore, it is preferable that the coloring of the recording layer is suppressed under various conditions, and to suppress the coloring in this way, among the above-mentioned compounds, the aliphatic isocyanate compound is more preferable.
- the binder may be formed by self-crosslinking of the compound having an isocyanate group, which is an essential component described above.
- the isocyanate compound described in detail above is required. It is preferable to form a binder by a cross-linking reaction with a compound having a functional group that reacts with the isocyanate group in the molecule. Examples of such a compound that can react with the isocyanate compound include a compound having a hydroxyl group in the molecule. And compounds having a primary or secondary amino group, and compounds having an enamine structure.
- a compound having a hydroxyl group is preferable as a compound capable of reacting with the isocyanate compound, and a compound having two or more aliphatic alcoholic hydroxyl groups in the molecule is more preferable.
- a liquid composition at room temperature or a liquid composition at a temperature of 100 ° C. or less is provided with a predetermined thickness between two substrates. Since it is produced by being sandwiched between layers, compounds that are liquid at room temperature or have a melting point of 100 ° C or less are often used. Is more preferable.
- Such compounds having two or more alcoholic hydroxyl groups in the molecule include, for example, diethylene glycol ⁇ triethylene glycol ⁇ /, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2,2-dimethyl-1 , 3-propanediole, 2,2-getyl-1,3-propanediol, 2-butynole-2-ethyneol 1,3_propanediole, 1,2-butanediole, 1,4-butanediol , Polytetramethylene glycol, 1,5-pentanedionole, 2-methyl-2,4- ⁇ pentanediole, 3-methinole-1,5-pentanediol, 1,6-hexanediol, 2-ethynol-1, 3-hexanediolone, 2,5-dimethyl-2,5-hexanediol, 1,10-de
- the molecular weight of a compound having two or more aliphatic alcoholic hydroxyl groups in a molecule may be a compound having a volatility of the compound itself, a compound having an ethylenically unsaturated bond, a compound having a cationically polymerizable functional group, or a photopolymerization.
- the molecular weight is 100 or more and 200 or less.
- the amount of the compound having two or more aliphatic alcoholic hydroxyl groups in the molecule cannot be specified unconditionally by the type and amount of the isocyanate compound, which is an essential component described above, but the amount of the compound having an isocyanate group
- the mole number of the isocyanate group in the holographic recording composition of the compound is N [mo 1], and the alcoholic water.
- the mole number of the hydroxyl group in the holographic recording composition of the compound is M [mo 1 ], It is usually 0.5 ⁇ NZM ⁇ 2.0, and more preferably 0.7 ⁇ N / M ⁇ 1.5 in terms of compatibility and control of crosslinking reaction. I like it.
- the urethane bond when a compound having an isocyanate group and a compound having two or more alcoholic hydroxyl groups in a molecule are reacted to form a urethane bond, the urethane bond may be reacted at a low temperature. It is preferable to add a known organic metal compound such as tin or lead as a curing catalyst.
- the compound having an oxysilane group or the compound having a mercaptan group in a molecule used in forming a binder by polymerizing a compound having an oxysilane group and a compound having a mercaptan group a known crosslinkable compound is particularly preferable.
- the recording composition which is liquid at room temperature or liquid at a temperature of 100 ° C or less is used. Since it is produced by sandwiching it with a predetermined thickness between two substrates, a compound that is liquid at room temperature or has a melting point of 100 ° C. or less is preferable, and two oxysilane groups or mercaptan groups are more preferable. Compounds having the above are more preferred.
- Specific examples of the above-mentioned compound having an oxysilane group include aliphatic polyglycidyl ether, polyalkylene glycol diglycidyl ether, tertiary carboxylic acid monoglycidyl ether, and polycondensate of bisphenol A and epichlorohydrin.
- the compounds described in “Chemical Products of 112,900”, Kagaku Kogyo Nippo Co., Ltd., pp. 778-787 can also be suitably used, and such compounds having an oxysilane group in the molecule can be used.
- the substances may be used in combination of two or more if necessary.
- Examples of the compound having a mercaptan group include, for example, thioglycolic acid, ammonium thioglycolate, monoethanolamine thioglycolate, sodium thioglycolate, methyl thioglycolate, octyl thioglycolate, and methoxybutyl thioglycolate.
- These thiol-containing compounds may be used alone or in combination of two or more.
- a prensted base or a Lewis base in order to perform polymerization under milder conditions.
- bases include, for example, pyridine, piperidine, dimethylaniline, 2,4,6-tris (dimethylamino Amines such as methyl) benzene and 2,4,6-tris (dimethylaminomethyl) phenol.
- an unsubstituted or alkyl-substituted cyclopentenyl group represented by A in the formula is used.
- the one bonded to the cycle pentagenenyl group is hydrogen or an alkyl group.
- the number of alkyl groups mentioned here is 0 to 5 with respect to the pentagenenyl group having a mouth, and the alkyl group is preferably a straight-chain, branched or cyclic one having 11 to 12 carbon atoms.
- the unsubstituted or substituted arylene group represented by B is a non-substituted or substituted arylene group having at least a benzene ring such as benzene, naphthalene, anthracene, phenanthrene, thalicene, pyrene, triphenylene, perylene or fluorene.
- a compound having a substituent or a substituent examples include a straight-chain, branched or cyclic alkyl group having 11 to 12 carbon atoms, _OR, -COR, -COOR, and the like.
- R represents a linear, branched or cyclic alkyl group having 11 to 12 carbon atoms.
- the anion represented by X— includes halogen, nitrate ion, hexafenoleo antimonate, hexafenoleo phosphate, triflate, tetrafluoroborate, and pentafluorohydroxyantimonate. And the like.
- Such a compound represented by the general formula (1) include, for example, ( ⁇ 6 -m-xylene) (775-cyclopentagenenyl) iron (1 +) tetrafluoroborate, ( ⁇ 6-0-xylene) (5-cyclopentagenenyl) iron (1+) triflate, ( ⁇ 6-o-xylene) ( ⁇ 5-cyclopentagenenyl) iron (1+) hexafluoroantimo , (776- ⁇ -xylenes).
- the aion containing a fluorine atom as the aion represented by ⁇ _ in the formula represents the stability of the complex itself and the recording layer. It is preferable because the liquid stability at the time of preparing the forming composition and the radical can be more effectively generated as a photopolymerization initiator.
- the photopolymerization initiator for photopolymerizing the compound having an ethylenic unsaturated bond of the present invention includes, in addition to the compound represented by the general formula (1) described in detail above, benzoin and benzoin, which are conventionally known.
- carbonyl compounds such as benzophenone, azo compounds such as azobisisobutyronitrile, sulfur compounds such as dibenzothiazolyl sulfide, peroxides such as benzoyl peroxide, 2-tribromomethanesulfonyl- Halides such as pyridine, quaternary ammonium salts or onium compounds such as substituted or unsubstituted diphenylbenzene salts and triphenylsulfonium salts, 2,2-bis (o-chlorophenyl) —4 Photopolymerization of bisimidazole compounds such as 1,4,5,5, -tetrapheninolebiimidazole and metal ⁇ complexes such as titanocene complexes
- An initiator may be used in combination, and the wavelength of an exposure light source used for holographic exposure described later and the wavelength of a laser light source used for holographic exposure of the photopolymerization initiator may be used.
- the sensitizing dye for sensitizing the spectral wavelength of the photopolymerization initiator used here, various dyes used in the art can be mentioned.
- Various colorants such as a compound, a porphyrin derivative, a phthalocyanine derivative and a pyromethene derivative may be used alone or in combination of two or more as needed.
- photopolymerization initiators or sensitizing dyes include, for example, US Pat. Nos. 5,027,436, 5,096,790, 5,147,758, 5, Nos. 204, 467, 5, 256, 520, 6, 01 1, 180, European Patent Nos. 255, 486, 256, 981, 277, 915, 318, 893, Nos.
- the photopolymerization initiator for photopolymerizing the compound having an ethylenically unsaturated bond described above depends on the molecular weight of the photopolymerization initiator and the ratio of the ethylenically unsaturated bond in the compound having an ethylenically unsaturated bond. Although it cannot be unconditionally determined, it is usually preferred to use 0.01 to 25 parts by mass of the compound having an ethylenically unsaturated bond.
- a sensitizing dye capable of spectrally sensitizing a photopolymerization initiator cannot be unconditionally defined by the molecular weight of the dye itself or the molar extinction coefficient, but is usually 0.01 to 25 to the photopolymerization initiator.
- the compound having an ethylenically unsaturated bond has a refractive index higher or lower than that of the binder-forming compound.
- Such compounds having a (meth) acryloyl group having a refractive index of 1.55 or more generally include, in the molecule, hetero atoms such as nitrogen, oxygen, sulfur and phosphorus, chlorine, bromine and boron.
- hetero atoms such as nitrogen, oxygen, sulfur and phosphorus, chlorine, bromine and boron.
- Compounds having a divalent or higher valence such as halogen atoms such as silicon or aromatic rings are mentioned.
- Such compounds include paracumylphenoxhetylene glycol acrylate and paracumylphenoxyethylene glycol meta- Acrylate, hydroxylated, 0—phenylphenol acrylate, hydroxyxylated) 3—naphthol acrylate, triblemofenyl acrylate, trypnole mophenyl methacrylate, trydophenyl methacrylate, polyethylene Oxide modified tetrapromobisphenol A diacrylate, Ethylene oxide-modified tetrabromobisphenol A dimethatalylate, bis (4-methacryloylthiophenyl) sulfide, JP-A-6-310132, JP-A-200-344444 And compounds having a fluorene skeleton described in JP-A-2003-29604 and the like.
- the purpose of providing a refractive index difference between the binder formed from the binder-forming compound and the diffusion polymer of the compound having an ethylenically unsaturated bond is not hindered.
- (Meta) having a refractive index of less than 1.55 for the purpose of adjusting the compatibility and viscosity when preparing the holographic recording layer composition and controlling diffusion polymerization during holographic exposure.
- a compound having an atariloyl group may be further added. Examples of such a compound having a (meth) acryloyl group include substituted or unsubstituted phenol and norphenol as a compound having one (meth) atalyloyl group.
- (meth) acrylate of 2-ethylhexanol and (meth) acrylate of alkylene oxide adducts of these alcohols.
- Compounds having two (meth) acryloyl groups include substituted or unsubstituted bisphenol A, bisphenol F, fluorene and di (meth) acrylate of isocyanuric acid, as well as alkylene oxide addition of these alcohols.
- Compounds having three (meth) acryloyl groups include pentaerythritol, trimethylolpropane and tri (meth) atalylate of isocyanuric acid, and tri (meth) acrylate of an alkylene oxide adduct of these alcohols.
- Examples of the compound having four or more (meth) atalyleinole groups include pentaerythritol and dipentaerythritol poly (meth) atalylate.
- a conventionally known monomer (oligomer) containing a (meth) atalyloyl group such as a urethane acrylate having a urethane bond as a main chain or a polyester acrylate having an ester bond as a main chain, is appropriately selected in the present invention.
- a conventionally known monomer (oligomer) containing a (meth) atalyloyl group such as a urethane acrylate having a urethane bond as a main chain or a polyester acrylate having an ester bond as a main chain, is appropriately selected in the present invention.
- a conventionally known monomer (oligomer) containing a (meth) atalyloyl group such as a urethane acrylate having a urethane bond as a main chain or a polyester acrylate having an ester bond as a main chain
- the compounds having an ethylenically unsaturated bond in the molecule described above may be used alone or in combination of two or more, and usually at least 1.0% by mass in the holographic recording composition. , 50% by mass or less, and more preferably 4.0% by mass or more, 40% by mass or less.
- the compound having an ethylenically unsaturated bond is formed by diffusion polymerization of a compound having an ethylenically unsaturated bond to form a polymer having a high refractive index
- the compound having a refractive index of 1.55 or more as described above is usually preferably contained in an amount of 50 to 100% by mass, and more preferably 60 to 100% by mass.
- the first base material and the second base material used for the recording medium of the present invention are transparent and do not cause expansion or contraction or bending at the ambient temperature of use, and are incompatible with the above-mentioned recording composition.
- Any active material can be used without particular limitation.
- a substrate include quartz glass, soda glass, potash glass, lead crystal glass, borosilicate glass, aluminosilicate glass, titanium crystal glass, and crystallized glass.
- Various resins such as glass such as polycarbonate, polyimide such as polycarbonate, polyacetal, polyarylate, polyetheretherketone, polysulfone and polyethersulfone, polyamide-amide-polyetherimide, polyamide, and cyclic olefin ring-opening polymer. Can be mentioned.
- the information light and the reference light are considered from the viewpoints of thickness fluctuation with respect to environmental temperature and humidity during holographic exposure, gas permeability, and light transmittance of the light source wavelength used during holographic exposure.
- the material of the first base material on the incident side is more preferably glass.
- the second substrate is preferably made of glass, but if the holographically recorded information is read out by a CCD, a device provided with a focus correction mechanism may be used to expand or contract the thickness or thickness.
- a substrate made of resin may be used instead of a substrate such as glass whose fluctuation is suppressed.
- the transmittance of light incident on the first substrate on the side where the information light and the reference light are incident is preferably 70% or more, and more preferably 80% or more of the light reaching the holographic recording layer. This is more preferable because of low loss of the resin.
- an anti-reflection treatment is applied to the first substrate surface opposite to the surface on which the holographic recording layer is laminated.
- the treatment is not particularly limited as long as the refractive index of the first substrate is also low, but for example, inorganic metals such as AlF3, MgF2, AlF3'MgF2, and CaF2
- Organic fluorine such as fluoride, vinylidene fluoride, homopolymers, copolymers, graft polymers, block polymers containing fluorine atoms such as Teflon (R), and modified polymers modified with functional groups containing fluorine atoms Compounds and the like are preferable because they have a lower refractive index than those described in detail above as the base material.
- the method of providing a layer made of a fluorine-based compound on a base material cannot be unequivocally determined depending on the type of the support-fluorine-based compound, but a sol-gel method, a vacuum evaporation method, and a sputtering method
- a known method such as a CVD method or a coating method, or a method described in JP-A-7-27902, JP-A-2001-123264, JP-A-2001-264509 or the like can be appropriately selected and used. .
- Such an antireflection layer cannot be unconditionally defined by the surface treatment or material of the base material, but is usually in the range of 0.001 to 20 and preferably in the range of 0.005 to 10 um.
- a second base material holographic recording layer is laminated on a recording medium such as used in a holographic recording / reproducing apparatus described in JP-A-2002-123949, WO 99/57719, and the like. It is preferable that a reflection layer is provided on the surface or on the opposite surface. When such a reflection layer is provided, the reflectance is preferably set to 70% or more with respect to the wavelength of the light to be reflected. % Is more preferable.
- the material of such a reflective layer is not particularly limited as long as a desired reflectance can be obtained.
- the layers can be laminated by providing a thin film of a metal or the like on the surface of the substrate.
- a metal thin film for example, to form such a reflective layer, it can be laminated as a metal thin film, a metal single crystal or a polycrystal by a known method such as a vacuum deposition method, an ion plating method, and a sputtering method.
- the metals used for laminating the metal thin film include anolemmium, dumbbell, antimony, indium, selenium, tin, tantalum, chromium, lead, gold, silver, platinum, nickel, niobium, germanium, silicon, molybdenum, Metals such as manganese, tungsten, and palladium can be used alone or in combination of two or more.
- the thickness of the metal thin film layer may be any thickness as long as a desired reflectance can be obtained,
- any one of them is used.
- a physical pattern may be formed on one surface of the substrate, and such a pattern or a forming method is described in, for example, JP-A-2003-178564, JP-A-2003-228885. No. 2003-33 1464, No. 2004-126306, No. 2004-126040, No. 2004-126041, No. 2004-1 273 79, No. 62, 100, U.S. Patent Publication No. 2004/0042375, 2004/006 7419, and the like can be appropriately selected and formed.
- a recording medium with a high storage capacity can be manufactured by making the holographic recording layer as thick as possible.
- the thickness of the first base material is Dl
- the thickness of the second base material is D2
- the thickness of the thick recording layer is Dh
- the thickness of the holographic recording layer cannot be increased, or even if the thickness of the recording layer is increased, the thickness of the base material increases.
- the entire recording medium becomes thick.
- the mass of the recording medium alone is heavy, which may cause a load on the drive system of the apparatus, which is not preferable.
- Dh / (D 1 + D 2)> 2.0 it is possible to reduce the thickness of the recording medium while securing the thickness of the recording layer.
- the thickness of the recording layer becomes thicker, the surface accuracy of the recording medium, the thickness unevenness of the recording layer at the operating temperature, the thickness fluctuation of the recording layer when unexpected stress is applied, and the first base material.
- the second substrate may be displaced, which is not preferable.
- the relation between the thickness D2 of the second base material is D1 ⁇ D2, and in order to ensure the flatness of the recording medium, the ratio of the thickness of D1 to D2 is 0. More preferably, it is in the range of 20 ⁇ D1 / D2 ⁇ 1.00.
- the thickness D h of the holographic recording layer cannot be determined unconditionally due to the diffraction efficiency, dynamic range, spatial resolution, etc. of the recording layer, but it is usually 200 ⁇ or more.
- the recording layer may have uneven thickness.
- the shape of the recording medium is not particularly limited as long as it is suitable for the holographic recording / reproducing apparatus used for the recording medium.
- US Pat. Disc-shaped ones are preferred for use in the apparatus described in 711, 691, JP-A-2002-123939, etc., and International Publication No. If the device described in 719 is used, a card-like device is preferable.
- a method for producing a recording medium includes mixing a holographic recording layer forming composition by mixing a holographic recording composition by heating at room temperature or, if necessary, under safelight. After being prepared and degassed to suppress polymerization inhibition at the time of holographic exposure, the holographic recording layer-forming composition at room temperature or, if necessary, heated, is applied to the first substrate, and then A recording medium can be manufactured by laminating the two base materials so that air bubbles do not enter so as to have a predetermined thickness of the recording layer, and finally sealing the end.
- the first base material and the second base material are fixed to a mold under a safelight so as to have a predetermined gap, and the holographic recording composition heated at room temperature or heated as necessary does not allow bubbles to enter.
- the recording medium can be manufactured by filling the space between the first base material and the second base material by injection molding or suctioning under reduced pressure so that air bubbles do not enter, and finally sealing the end.
- under safelight refers to an operation in a state where the wavelength of light at which the photopolymerization initiator becomes active is cut.
- the holographic recording layer forming composition may be applied to a second substrate instead of the first substrate described above, And the second base material. Further, when sealing the first base material, the holographic recording layer and the end of the second base material, the liquid base such as a moisture-curable adhesive capable of sealing is used.
- the sealing material may be crosslinked and sealed, or may be sealed in advance using an end sealing material on a ring for ensuring a predetermined thickness of the holographic recording layer.
- the holographic recording method of the present invention it is desired to perform recording after reacting a binder-forming compound with the holographic recording medium described above in detail before the holographic exposure to form a binder. Based on the information, information light and reference light are incident from the first base material side and holographic exposure is performed to activate the photopolymerization initiator, and the compound having an ethylenic unsaturated bond by the active species is holographically exposed. It is characterized by recording information on holographic recording media by diffusion polymerization in the recording layer.
- a recording layer forming composition is prepared without a solvent for dilution.
- a uniform film thickness is obtained or the composition is wound during preparation of the composition. It is difficult to remove air bubbles. Therefore, when the recording layer forming composition is prepared, fluidity is required at room temperature or in a heated state.
- the recording layer forming composition is liquid at room temperature and has low viscosity, it is difficult to secure the flatness as a recording medium, or the ethylenically unsaturated bond after recording information by holographic exposure. It is not preferable because the polymer formed by the compound having a combination may be displaced in the recording layer. .
- a binder is formed on the holographic recording medium containing the above-mentioned essential components by crosslinking the binder-forming compound before the holographic exposure.
- the polymer formed by diffusion polymerization of the compound having the compound having a saturated bond can be prevented from moving in the holographic recording layer.
- holographic exposure is performed based on the information to be recorded, and the photopolymerization initiator is activated.
- Information can be recorded on a holographic recording medium by diffusing and polymerizing a compound having an unsaturated bond.
- the crosslinking reaction for forming the above-mentioned binder in the present recording method may be performed by crosslinking all combinations of functional groups that can be reacted, or by crosslinking only a part of the combination within a range that does not cause a practical problem. good.
- the ethylenic acid remaining in the recording layer may be exposed to light and heat, if necessary, for the purpose of fixing the recorded holographic information. It is preferable that the compound having an unsaturated bond is photopolymerized with a photopolymerization initiator, and that the uncrosslinked functional groups of the remaining binder-forming compound are thermally crosslinked.
- the light used for exposure is exposed to the entire recording medium at a time.
- the light may be applied before, at the same time as, or after the simultaneous exposure, or a plurality of heat treatments may be performed. They may be combined.
- an information light and a reference light are made to enter the holographic recording medium described above in detail from the first base material side based on the information to be recorded.
- Exposure to activate the photopolymerization initiator record the information on the holographic recording medium by diffusing and polymerizing the compound having an ethylenically unsaturated bond with this active species, and record the information on the holographic recording medium
- the recorded information is stabilized by further performing heat and light irradiation on the entire holographic recording medium.
- This embodiment differs from the first embodiment described above in that, when the recording layer forming composition is prepared, the composition, which flows in a heated state but does not flow at room temperature, has a shear stress.
- This is an effective recording method for a holographic recording medium in which a recording layer is formed by a recording layer forming composition having a gelling or thixotropy at room temperature unless added. In such a recording medium, there is practically no problem in securing the flatness of the recording medium and preventing the movement of the polymer formed by diffusion polymerization of the compound having an ethylenically unsaturated bond.
- the compound having an ethylenically unsaturated bond remaining in the recording layer by light and heat for the purpose of further improving the preservability of recorded information
- the light used for exposure is exposed to the entire recording medium at a time, as in the first embodiment described above. It may be a deviation or a combination of several heat treatments.
- any apparatus capable of recording / reproducing on the recording medium of the present invention can be used.
- a recording and reproducing apparatus include, for example, U.S. Patent Nos. 5,719,691, 5,838,467, 6,163,391, 6,414, No. 296, U.S. Publication No. 2002-136143, JP-A-9-305978, JP-A-10-124872, JP-A-11-21 9540, JP-A-2000-98862, JP-A-2000-298837, JP-A-2001-23 No. 169, 2002-83431, 2002-123949, 2002-123948, 2003-43904, WO 99/57719, 02Z05270, 02Z75727, etc. Can be done.
- the photopolymerization initiator in the recording medium was activated to enable holographic recording, and that the recording was performed.
- Any laser light source that can read holograms can be used without particular limitation. Examples of such light sources are a semiconductor laser in the blue-violet region, an argon laser, a He—Cd laser, a frequency doubled YAG laser, He—Ne lasers, Kr lasers, semiconductor lasers in the near infrared region, and the like can be given.
- holographic recording media before recording and holographic recording media with little recorded information and with the possibility of additional recording when the wavelength of the light source normally used for holographic recording is assumed to be I nm, ( ⁇ +
- recording is performed by exposing the recording medium to laser light by exposing the recording medium to a case or cassette that can at least block light of 100 nm or less, preferably ( ⁇ + 200) nm or less. Only information is recorded by taking out the case ⁇ from the cassette and irradiating it with a laser beam under light shielding.
- the recording medium on which information is recorded by the holographic recording method of the present invention can be taken out of a light-shielding case or cassette such as the above-mentioned light-shielding case, and can be handled in a light room like a CD or DVD. Can be used as information media.
- a holographic information recording layer is sandwiched between a first base material and a second base material, and the holographic information recording layer has a compound having an isocyanate group and a compound having a hydroxyl group, A compound having an isocyanate group and a compound having an amino group, a compound having a carbodiimide group and a carboxyl group, a compound having an unsaturated ester group and a compound having an amino group, a compound having an unsaturated ester group and a compound having a mercaptan group Compounds, compounds having a vinyl group and a compound having a silicon hydride group, compounds having an oxysilane group and compounds having a mercaptan group, and oxolane, oxetane, tetrahydrofuran, oxepane, monocyclic acetal, bicyclic acetal, ratatone, Cyclic orthoester, ring Condition A region mainly composed of
- the refractive index is 1.55 or more.
- the refractive index of a region mainly containing a binder is higher than that of a region mainly containing a radical polymer formed by radical polymerization containing at least a compound having an ethylenically unsaturated bond as a monomer unit.
- Information is recorded by lowering the refractive index of the region mainly containing the binder than the refractive index of the region mainly containing the radical polymer.
- the information recording layer on which information is recorded under normal handling conditions is unlikely to change, so that there is almost no deterioration in readout by the reproducing apparatus over time.
- the binder-forming compound (A-1-1-3) used in preparing the holographic recording layer-forming composition the compound having an ethylenically unsaturated bond (B-1-1-10), 'The combination initiator (C-115) and the dye (D-1-1-3) are shown below.
- A-4) Urethane curing catalyst (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.)
- A-5) Polypropylene glycol diglycidyl ether (Epolite 200P, manufactured by Kyoeisha Chemical Co., Ltd.)
- Solution 1 was prepared by mixing 48.92 g of the binder-forming compound (A-5 above) and 8.74 g of the binder-forming compound (A-7 above) under safelight.
- B-5 a compound having an ethylenically unsaturated bond
- the composition finally prepared was deaerated with nitrogen, and the gas components contained in the ultrasonic cleaning device were removed. Was removed, and a holographic recording layer forming composition 1 for comparison was prepared.
- holographic recording layer forming composition 1 In the holographic recording layer forming composition 1 described above, the compound having an ethylenically unsaturated bond and the photopolymerization initiator were changed to the compounds and addition amounts shown in Table 1, and further added to the solution 1 as shown in Table 1.
- Holographic recording layer forming composition 2-9 was prepared in the same manner as holographic recording layer forming composition 1 except that the amount of sensitizing dye was dissolved. ⁇ table 1
- binder-forming compound (A-3 above) was added to 36.
- Omg of 2,6-di (t-butyl) —4-methylphenol and 67. lmg of urethane curing catalyst (previous Solution A-4) was mixed and dissolved to prepare solution 2.
- 7.92 g of a binder-forming compound (A-1), 23.75 g of a binder-forming compound (A-2) 8.00 g of a compound having an ethylenically unsaturated bond (see above) B-1) and 2.00 g of a compound having an ethylenically unsaturated bond (B-4) are mixed and dissolved to prepare a solution B.
- a holographic recording layer-forming composition 1 124 was prepared in the same manner as the holographic recording layer-forming composition 10 except that the sensitizing dye in the amount described in Table 2 was dissolved in Solution 2. .
- a binder-forming compound (A-8.90 g of a compound having an ethylenically unsaturated bond (B_l 1.00 g of a compound having an ethylenically unsaturated bond) (Solution B-0.93 g of photoinitiator (C-2 above) and 9.6 mg of sensitizing dye (D-3) were mixed and dissolved to prepare solution C.
- a mouth graphic recording layer forming composition 26-30 was prepared in the same manner as the recording layer forming composition 25.
- a compound having an ethylenically unsaturated bond was dissolved in the isocyanate compound shown in Table 4, and then a photopolymerization initiator was dissolved in this solution.
- a solution in which a sensitizing dye and a urethane curing catalyst (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) are dissolved in a compound having two or more hydroxyl groups in the molecule is dissolved in the photopolymerization initiator.
- Holographic recording composition 31 1-46 was prepared by adding nitrogen to the solution and deaeration of the last prepared composition with nitrogen, and then removing the contained gas components by vacuum degassing. . [Table 4]
- first substrate and a second substrate one side of 0.5 mm (dl, d2) glass is made to have a reflectance of 0.1% with incident light perpendicular to the wavelength of 532 nm.
- Anti-reflection treatment was applied.
- a polyethylene terephthalate sheet was used as a spacer so that the recording layer thickness (Dh) shown in Table 4 was obtained on the surface of the first base material which had not been subjected to the antireflection treatment.
- Attach the graphic recording composition to the first substrate, and in the next V do not wrap the air layer over the holographic recording composition on the non-reflective surface of the second 'substrate.
- the first base material and the second base material were bonded via a spacer.
- the ends were sealed with a moisture-hardening adhesive, and heat-treated under the heat treatment conditions described in Table 5 to produce a holographic recording medium.
- One side of 0.5 mm (d 1) thick glass, perpendicular to 532 nm wavelength By subjecting the first substrate to anti-reflection treatment so that the reflectance by light becomes 0.1%, one side of the glass with a thickness of 5 mm (d 2) is exposed to a wavelength of 532 nm.
- the second substrates were each produced by performing aluminum vapor deposition so that the reflectance by vertical incident light became 90%.
- a polyethylene terephthalate sheet was formed into a spacer so that the recording layer had a thickness (D h) shown in Table 5 on the surface of the first base material which had not been subjected to the anti-reflection treatment.
- the described holographic recording layer forming composition is applied to the first base material, and then the aluminum-deposited surface of the second base material is bonded onto the holographic recording composition so that an air layer is not wound.
- the first base material and the second base material were bonded via a spacer. Finally, the end was sealed with a moisture-curable adhesive, and heat-treated under the heat treatment conditions shown in Table 6 to produce a holographic recording medium.
- a digital pattern is displayed on a holographic recording medium equipped with an Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under a safelight.
- Holograms were obtained by holographic exposure of this digitally patterned with an energy of cm 2 .
- the generated reproduction light was read by a CCD, and the minimum exposure amount at which a good digital pattern was reproduced was measured as the sensitivity (S11).
- the holographic recording media stored at 50 for 1 week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S12).
- the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
- a digital pattern is displayed on a holographic recording device equipped with a Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under safelight.
- a hologram was obtained by holographic exposure with this digital patterned at an energy of j / cm 2 .
- the holographic recording medium was treated under a 70,000 lux sunshine fader for 5 minutes, and then heated at 100 ° C. for 5 minutes.
- the Nd: YAG laser (532 nm) as a reference beam under safe light
- the processed recording medium is read using a CCD to read the generated reproduction light, and the minimum exposure amount at which a good digital pattern can be reproduced is determined by the sensitivity ( S 21).
- the holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S22).
- the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
- the holographic recording medium produced as described above was not stored for 1 week at 50 ° C under shading, and a series of multiple holograms were written.
- the sensitivity (recording energy) was measured and evaluated according to the following method, and the results obtained are shown in Table 9.
- a digital pattern is displayed on a holographic recording device equipped with a Nd: YAG laser (532 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under a safelight.
- a hologram was obtained by performing holographic exposure with this digital pattern at an energy of jZcm 2 .
- the holographic recording medium was treated under a 70,000 lux sunshine dome for 5 minutes, and then heated at 100 ° C for 5 minutes.
- the Nd: YAG laser (532 nm) as a reference beam under safe light
- the processed reproduction medium was read by a CCD and the minimum exposure required to reproduce a good digital photo pattern was obtained.
- the light intensity was measured as sensitivity (S31).
- the holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S32).
- the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
- the digital pattern was displayed on a holographic recording medium that had not been stored at 50 ° C for 1 week under a safelight using a holographic manufacturing apparatus equipped with a blue-violet semiconductor laser (405 nm) ⁇ . Hologram by this digitally patterned holographic exposure with energy of Om j / cm 2 Got. Next, the holographic recording medium was treated under a 70,000 lux sunshine feed meter for 5 minutes, and then heated at 100 ° C. for 5 minutes. The processed recording medium is read under a safelight using a semiconductor laser (405 nm) in the blue-violet region as a reference beam, and the generated reproduction light is read by a CCD. Was measured as the sensitivity (S41). The holographic recording medium stored at 50 ° C for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S42).
- the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
- the holographic recording medium prepared as described above was not stored for 1 week at 50 ° C under shading, and the holographic recording medium was not stored according to the procedure described in Japanese Patent Application Laid-Open No. 2002-123939. Then, a series of multiple holograms were written, and the sensitivity (recording energy) was measured and evaluated according to the following method. The obtained results are shown in 11.
- Holographic recording with a blue-violet semiconductor laser (405 nm) on a holographic recording medium that has not been stored at 50 ° C for 1 week under safelight A digital pattern was displayed on the apparatus, and a hologram was obtained by performing holographic exposure with the digital pattern at an energy of 0.1 to 30 mj / cm 2 .
- the holographic recording medium was treated under a 70,000 lux sunshine feed meter for 5 minutes, and then heated at 100 ° C. for 5 minutes.
- the processed recording medium is read under a safelight using a semiconductor laser (405 nm) in the blue-violet region as a reference beam, and the generated reproduction light is read by a CCD.
- the holographic recording medium stored at 50 ° C. for one week was evaluated in the same manner as described above, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S52).
- the recording medium of the present invention has higher sensitivity before and after storage than the comparative example.
- the holographic information media prepared in Table 8, Table 9, Table 10 and Table 11 in which the recorded information is fixed are stored under the following conditions, and before and after storage, digital data is created by a method suitable for each information medium.
- the patterns were reproduced and evaluated, and the difference between the minimum exposure light amount before and after storage at which a good digital pattern was reproduced was evaluated by the following method. The obtained results are shown in Table 12.
- the holographic information media was stored at 80 ° C for 2 weeks, and the minimum exposure sensitivity difference (ASh) before and after storage was determined.
- ASh Minimum exposure sensitivity difference (S2h)-Minimum exposure sensitivity before storage (S1h)
- the samples were stored at a temperature of 35 ° C under a sunshine fadeometer of 70,000 lux for 1 week, and the minimum exposure sensitivity difference (ASw) before and after storage was determined.
- ASw Minimum exposure sensitivity difference
- S2w Minimum exposure sensitivity after storage (S2w)-Minimum exposure sensitivity before storage (S1w)
- the holographic information medium of the present invention shows good results without a decrease in sensitivity for reproduction.
- the holographic recording medium produced as described above is written with a series of multiplexed holograms according to the procedure described in US Pat. No. 5,719,691, and the sensitivity (recording energy), The contraction resistance and the contrast of the refractive index were measured and evaluated, and the obtained results are shown in Table 13.
- the holographic recording media was treated under a sunshine feed meter of 70,000 lux for 5 minutes and then heated at 100 ° C. for 5 minutes.
- Nd: YAG laser (532 nm) as a reference beam
- the read-out light generated is read by a CCD under safe light and the minimum exposure amount at which a good digital pattern can be reproduced is determined. (S1) was measured.
- the shrinkage resistance is indicated by a shrinkage rate measured by the following method.
- FIG. 1 is a schematic diagram showing the principle of a measuring device for measuring a shrinkage ratio. That is, the emission point of the white illumination light source that illuminates the holo-drama 3 is 01, and the viewpoint of the observer is 02.
- a white illumination light source 4 is installed at a light emitting point 01
- a spectroscope 5 is installed at a viewpoint 02.
- the spectrometer 5 is connected to a bass computer 6, and a moving pinhole plate 7 having a pinhole 8 through which only a part of light is transmitted is provided on the upper surface of the hologram 3 for measuring the luminance distribution of the spectral wavelength. Is installed.
- the movable pinhole plate 7 is configured to be attached to an XY stage (not shown) and move to an arbitrary position.
- the moving pinhole plate 7 Measure e c , ei, at each position of hologram 3 while moving.
- the hologram shrinkage at point P (1, J) is M (1, J)
- the hologram shrinkage M (1, J) is the average refractive index of the optical image recording material before recording.
- nr is the average refractive index of the hologram after the development processing is nc, it can be expressed by the following equation.
- ⁇ o is the incident angle on the holographic recording medium
- er is the incident angle of the reference light on the holographic recording medium.
- the contrast of the refractive index was determined from the diffraction efficiency measured according to the following method.
- the diffraction efficiency was measured using an ART25C type spectrophotometer manufactured by JASCO Corporation. A photomultimeter with a 3 mm wide slit was placed on a 20 cm radius circle centered on the sample. It was installed in. Monochromatic light having a width of 0.3 mm was incident on the sample at an angle of 45 degrees, and diffracted light from the sample was detected. The ratio of the largest value other than the specularly reflected light to the value when directly incident light is received without placing the sample is defined as the diffraction efficiency, and the refractive index contrast ( ⁇ ) is calculated from the diffraction efficiency of the obtained hologram.
- the refractive index contrast ( ⁇ ) is calculated from the diffraction efficiency of the obtained hologram.
- the recording medium of the present invention has high sensitivity, low shrinkage ratio, and high contrast as compared with the comparative example, and shows good results.
- the hologram was obtained by performing a quick exposure.
- the holographic recording media was treated under a sunshine feedmeter of 70,000 lux for 5 minutes and then heat-treated at 100 ° C. for 5 minutes.
- Nd: YAG laser (532 nm) as a reference beam under safe light
- this processed recording medium was read using a CCD to read out the generated reproduction light, and the minimum exposure amount at which a good digital pattern could be reproduced was measured as the sensitivity (S 1).
- the holographic information media created in Tables 13 and 14 in which the recorded information is fixed are stored under the following conditions, and before and after the storage, the digital pattern is reproduced and evaluated by a method suitable for each information medium.
- the difference between before and after the storage of the minimum exposure amount at which a good digital pattern was reproduced was evaluated by the following method, and the obtained results are shown in Table 15.
- the degree of coloring of the holographic information media was evaluated by the following method, and the obtained results are shown in Table 16. Knit preservation)
- the holographic information media was stored at 80 ° C for 2 weeks, and the minimum exposure sensitivity difference (ASh) before and after storage was determined.
- Minimum exposure sensitivity difference ( ⁇ Sh) Minimum exposure sensitivity after storage (S2h)-Minimum exposure sensitivity before storage (S1h)
- the samples were stored at a temperature of 35 ° C under a 70,000 lux sunshine fade meter for one week, and the minimum exposure sensitivity difference (ASw) before and after storage was determined.
- ASw Minimum exposure sensitivity difference
- S2w Minimum exposure sensitivity after storage (S2w)-Minimum exposure sensitivity before storage (S1w)
- the holographic information medium of the present invention shows good storage stability without lowering the sensitivity for reproduction as compared with the comparative example.
- a holographic information media was prepared by heating for a while. Then, it was stored under the following conditions, and before and after storage, the transmittance of each information medium was measured by Hitachi Spectrophotometer U-4100, manufactured by Hitachi High-Techno-Gee Corporation, and evaluated by the following method.
- the holographic information media was stored at 80 ° C for 2 weeks, and the transmittance difference ( ⁇ ) of 400 nm before and after storage was determined.
- Transmittance difference Transmittance before storage (Tl h)-Transmittance after storage (T2h) (Light storage stability)
- Transmittance difference (ATw) Transmittance before storage (Tlw)-Transmittance after storage (T2w)
- the holographic information medium of the present invention is less colored and shows better storage stability than the comparative example.
- a holographic recording medium having high sensitivity and excellent preservability, a holographic recording method, and a holographic information medium recorded with holographic recording are obtained.
Abstract
Description
Claims
Priority Applications (1)
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EP04773235A EP1666988A4 (en) | 2003-09-17 | 2004-09-10 | HOLOGRAPHIC RECORDING MEDIUM, HOLOGRAPHIC RECORDING METHOD, AND HOLOGRAPHIC INFORMATION MEDIUM |
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JP2003323809 | 2003-09-17 | ||
JP2003-323809 | 2003-09-17 | ||
JP2003396737 | 2003-11-27 | ||
JP2003-396737 | 2003-11-27 | ||
JP2004-58640 | 2004-03-03 | ||
JP2004058640A JP2005181953A (ja) | 2003-11-27 | 2004-03-03 | ホログラフィック記録メディア、ホログラフィック記録方法およびホログラフィック情報メディア |
JP2004-72139 | 2004-03-15 | ||
JP2004072139A JP4466141B2 (ja) | 2003-09-17 | 2004-03-15 | ホログラフィック記録用組成物、ホログラフィック記録メディア、ホログラフィック記録方法及びホログラフィック情報メディア |
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US (1) | US20050058911A1 (ja) |
EP (1) | EP1666988A4 (ja) |
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