JP2009048060A - Holographic recording composition, holographic recording medium, and information recording method - Google Patents

Abstract

To provide means capable of producing a high-quality holographic recording medium with high productivity.
A photopolymerizable matrix binder precursor, a photopolymerization initiator that can be excited by light irradiation to initiate a polymerization reaction of the photopolymerizable matrix binder precursor, and a photosensitive recording material enclosed in a micro container. Holographic recording composition. The micro container has an impermeability to at least a part of light included in a wavelength region capable of exciting the photopolymerization initiator, and is included in a wavelength region capable of exposing the photosensitive recording material. A wall membrane that is permeable to at least a portion thereof. A holographic recording medium comprising a recording layer formed from the holographic recording composition. A method for manufacturing the medium and a method for recording information on the medium.
[Selection figure] None

Description

  The present invention relates to a holographic recording composition suitable for producing a holographic recording medium, particularly a volume holographic recording medium. Furthermore, the present invention relates to a holographic recording medium formed using the holographic recording composition and a method for recording information on the medium.

  Conventionally, development of a holographic optical recording medium using a holographic principle has been advanced. Information is recorded on a holographic optical recording medium by superimposing information light containing image information and reference light in a recording layer made of a photosensitive composition, and writing interference fringes formed at that time on the recording layer. Done. On the other hand, when information is reproduced, reference light is incident on the recording layer on which information is recorded at a predetermined angle, whereby light diffraction of the reference light due to the formed interference fringes occurs and information light is reproduced.

  In recent years, volume holography, particularly digital volume holography, has been developed in practical use for ultra-high density optical recording and has attracted attention. Volume holography is a method of writing interference fringes in three dimensions by actively utilizing the thickness direction of the optical recording medium. Increasing the thickness increases the diffraction efficiency and increases the recording capacity by using multiple recording. There is a feature that can be achieved. Digital volume holography is a computer-oriented holographic recording method that uses a recording medium and a recording method similar to those of volume holography, but restricts image information to be recorded to a binarized digital pattern. In this digital volume holography, for example, image information such as an analog picture is once digitized, developed into two-dimensional digital pattern information, and recorded as image information. At the time of reproduction, the digital pattern information is read and decoded so that the original image information is restored and displayed. As a result, even if the S / N ratio (signal-to-noise ratio) is somewhat poor during reproduction, the original information can be reproduced with high fidelity by performing differential detection or performing error correction by encoding binary data. Can be reproduced (see Patent Document 1).

As a method for producing a holographic recording medium, a method using a photopolymer-type hologram photosensitive composition is widely used. The above method is a method of forming a recording layer by applying a coating solution formed by dissolving a photopolymer in a solvent on a substrate and then removing the solvent (solvent coating type), a thermosetting binder, a photopolymer, After the above mixture is applied on a substrate, the binder is cured by heating to form a recording layer (in situ polymerization hardening type) (see, for example, Patent Documents 2 and 3).
Japanese Patent Laid-Open No. 11-311936 JP-T-2005-502918 Japanese Patent Laid-Open No. 5-107999

  In the volume holography recording medium, it is advantageous to increase the thickness of the recording layer in order to improve signal strength (sensitivity) and reduce material consumption per recording (improving multiplexing performance). Further, the increase in the film thickness improves the signal position selectivity and reduces crosstalk, so that the multiplexing performance can be improved. However, in the solvent coating type manufacturing method, it is difficult to form a recording layer having a film thickness of 200 μm or more, for example, due to restrictions on solvent removal. On the other hand, according to the in situ polymerization hardening film manufacturing method, a thick recording layer suitable for volume holography can be formed.

  In the conventional in situ polymerization hardening type production method, a thermosetting binder is used as a matrix binder, and thus heating is necessary for the curing reaction. However, when a high temperature is applied during production of the medium, there is a problem that the substrate is distorted or warped. On the other hand, if the heating temperature is set to a relatively low temperature in order to avoid the above problem, the reaction takes a long time and the productivity is lowered.

  Accordingly, an object of the present invention is to provide means capable of producing a high-quality holographic recording medium with high productivity.

As a result of intensive studies to achieve the above object, the present inventor has obtained the following knowledge.
In the conventional in situ polymerization dura mater type production method, a thermal reaction is used for the dura mating reaction. Therefore, either time or heating is required to complete the reaction. On the other hand, if a photopolymerizable (photocurable) resin can be used as a matrix binder, such as a UV curable resin used in a UV hard coat or a protective layer of a disk, it can be heated at a high temperature or for a long time. The recording layer can be formed without undergoing treatment. In addition, since a conventional optical disc manufacturing machine can be used for the hardened film by light irradiation, productivity can be greatly improved.
However, the holographic recording medium includes a photosensitive hologram recording material. For this reason, in a hard film by light irradiation, the hologram recording material is affected by the light irradiated during the hard film processing, and it is difficult to ensure sufficient recording performance. For example, in the photopolymer type recording method, if the photosensitive wavelength of the recording material is longer than the matrix curing wavelength (hardening wavelength), the recording material is consumed at the time of hardening and the recording material is consumed. It becomes difficult to obtain sufficient recording characteristics due to the recording reaction.
Therefore, the present inventor has further studied, and the photopolymerizable binder in the holographic recording medium can be used by protecting the photosensitive recording material from light irradiation during the dural reaction with a micro container such as a microcapsule. I found a new thing.
The present invention has been completed based on the above findings.

That is, the means for achieving the above object is as follows.
[1] A photopolymerizable matrix binder precursor, a photopolymerization initiator that can be excited by light irradiation to initiate a polymerization reaction of the photopolymerizable matrix binder precursor, and a photosensitive recording material encapsulated in a micro container A graphic recording composition comprising:
The micro container is
It is impervious to at least a part of light contained in a wavelength range capable of exciting the photopolymerization initiator, and at least a part of light contained in a wavelength range capable of exposing the photosensitive recording material. The said composition for holographic recording which has a wall film which has permeability | transmittance with respect.
[2] A holographic recording medium having a recording layer formed from the holographic recording composition according to [1].
[3] A method of manufacturing a holographic recording medium according to [2],
The production method comprising polymerizing a photopolymerizable matrix binder precursor by irradiating the holographic recording composition according to [1] with light having an impermeability to the micro container wall film. .
[4] An information recording method for recording information on a recording layer by irradiating the holographic recording medium according to [2] with light having transparency through the wall of the micro container.

  According to the present invention, the curing process of the matrix binder can be performed by light irradiation, and thereby it is possible to provide a high-quality holographic recording medium with high productivity.

[Holographic recording composition]
The holographic recording composition of the present invention is encapsulated in a photopolymerizable matrix binder precursor, a photopolymerization initiator that can be excited by light irradiation to initiate a polymerization reaction of the photopolymerizable matrix binder precursor, and a micro container. Photosensitive recording material. The micro container has an impermeability to at least a part of light included in a wavelength region capable of exciting the photopolymerization initiator, and is included in a wavelength region capable of exposing the photosensitive recording material. A wall membrane that is permeable to at least a portion thereof.
The holographic recording composition of the present invention is suitable as a volume holographic recording composition. As described above, holographic recording is information recording in which information light containing information and reference light are superimposed in a recording layer and information is recorded by writing an interference image formed at that time in the recording layer. Volume holographic recording is an information recording method in which an interference image is three-dimensionally written on a recording layer in holographic recording.
In the present invention, “recording material” refers to a component that can record interference fringes as refractive index modulation by light irradiation for information recording and a component that contributes to the formation of the interference fringes. In addition, the “photosensitive recording material” means a substance having photosensitivity among the above recording materials. For example, the wavelength dispersibility of the refractive index is changed by a photopolymerizable monomer, a photopolymerization initiator, and a light stimulus described later. Dyes or dye systems to be used, substance systems capable of changing the wavelength dispersibility of the dyes by light stimulation, and the like.
Below, the detail of each component contained in the composition for holographic recording of this invention is demonstrated.

Micro container In the holographic recording composition of the present invention, the photosensitive recording material is contained in a micro container. In the present invention, the “encapsulation” means that the substance inside the micro container surrounded by the micro container wall film is held in a state where movement to the outside is restricted.
The state in which movement to the outside is restricted means that the micro container containing the photosensitive recording material is dispersed in a matrix that is compatible with the inclusion (photosensitive recording material) but does not contain the inclusion, After being held for a predetermined time under various conditions, the inclusions in the matrix excluding the microcontainers are not detected at all with respect to the expected detection amount when it is assumed that the total amount of inclusions has leaked, or 10 on a mass basis. % Or less, preferably 5% or less, more preferably 3% or less. The said conditions can be set according to the storage conditions etc. which are requested | required of the substance which should use a micro container. Specifically, for example, about 1 to 100 parts by mass of a micro container per 100 parts by mass of the matrix is dispersed and held for about 24 hours under acceleration conditions of about 30 ° C. to 40 ° C. or room temperature of about 20 ° C. to 25 ° C. After that, the leak can be analyzed.
Examples of the method for quantifying the inclusion leaked from the micro container include gas chromatography, liquid chromatography, and mass spectrometry. Further, if the inclusion contains a specific element, an elemental analysis method or a trace amount detection method suitable for the specific element may be applied. As the matrix, it is preferable to use a matrix binder precursor that is actually used in a holographic recording composition, or a similar substance.
The micro container wall film preferably restricts the movement of all substances in the micro container including the photosensitive recording material to the outside, and the mass transfer from the outside to the inside of the micro container, specifically, photopolymerization. It is further preferable to limit the movement of the matrix precursor and the photopolymerization initiator into the micro container.

  Further, the wall film of the micro container is a partition wall that can restrict specific stimulation from the outside, in particular, in the present invention, that at least light stimulation having a specific wavelength is transmitted to the inside as described later. By this wall film (partition wall), it is possible to continuously wrap the inclusions and limit physical contact with the outside. The micro container may have a visually clear interface between the inclusion and the exterior, or may not have a visually clear interface with either the inclusion or the exterior, In some cases, a wall film (partition) is formed with a gentle interpenetrating state with the inclusion or the outside. In the present invention, whether or not the micro container has a visually distinct interface with the outside or the inside or both. Is not particularly limited. Visually clear means that a discontinuous surface is clearly observed in the material distribution when scanning from inside to outside of a micro container using an electromagnetic wave or electron beam, such as an optical microscope or an electron microscope. Point to.

  In addition, as a method for confirming that the wall film restricts a specific stimulus from the outside from being transmitted to the inside (having impermeability to light of a specific wavelength), the specific stimulus, in particular, In the present invention, as will be described later, a method of confirming whether or not the substance is changed by the stimulus by sufficiently applying a light stimulus of a specific wavelength to a micro container containing the substance sensitive to the stimulus. Can be used. For example, a photodegradable substance sensitive to ultraviolet rays is sealed in a micro container, and after irradiating the micro container with ultraviolet light, the decrease in the photodegradable substance or the decomposition product of the photodegradable substance is analyzed and analyzed separately. It is possible to determine whether or not the micro container restricts this ultraviolet light stimulation by comparing with the analysis result when the same photodegradable substance not contained in the micro container is irradiated with the same amount of ultraviolet light. it can. Details of the external stimulus to be applied will be described later. In addition to gas chromatography, liquid chromatography, and mass spectrometry, analysis of the decrease in specific substances and degradation products include methods commonly used for identification and quantification of substances such as nuclear magnetic resonance spectra, infrared, and ultraviolet-visible absorption spectra. Can be used.

On the other hand, as a method for confirming that the wall film allows a specific light stimulus to be transmitted to the inside as described later (having transparency to light of a specific wavelength), the above method is also used. Can be used. Specifically, light of a specific wavelength is sufficiently irradiated to a micro container containing a substance sensitive to the light of the specific wavelength (however, the transmission of other specific wavelengths of light is limited), and the substance is It is possible to use a method for confirming whether or not it is changed by stimulation.
The micro container contained in the composition for holographic recording of the present invention is 100% on a mass basis with respect to the quantitative result in the case where no light stimulus is given at all for the light stimulus whose transmission is to be described later. A quantitative result within the range of 90% is preferable, and a quantitative result of 100% to 95% is more preferable. For light stimulation to be transmitted, which will be described later, the quantitative result is preferably less than 90% on a mass basis, more preferably the quantitative result is less than 80%, and the quantitative value in the range of up to 70%. The result is particularly preferred.

The wall film of the micro container has an impermeability to at least a part of light contained in a wavelength region capable of exciting a photopolymerization initiator capable of initiating polymerization of a photopolymerizable matrix binder precursor; and It has transparency to at least a part of light included in a wavelength range in which the photosensitive recording material contained in the micro container can be exposed.
The photosensitive wavelength of the photosensitive recording material is, for example, 350 to 800 nm, preferably 400 to 700 nm. On the other hand, the wavelength (photosensitive wavelength) that can excite the photopolymerization initiator is, for example, in the range of 250 to 500 nm, preferably 270 to 400 nm. However, the photopolymerization initiator may be particularly photosensitive in a wavelength range other than the above. Therefore, the micro container has an impermeability to light included in a wavelength range of 250 to 500 nm, preferably 270 to 400 nm, is not included in the wavelength range, and is 350 to 800 nm, preferably 400 Those having a wall film having transparency to light contained in a wavelength region of ˜700 nm, more preferably 405 to 650 nm can be used. According to the present invention, in a system in which the recording wavelength is longer than the hardening film wavelength and the recording material is consumed by short wavelength excitation during the hardening reaction when the recording material is not contained in the micro container, Good recording characteristics can be obtained by protecting the recording material with the container.

  As described above, in order to obtain a micro-container having the functions of (1) restriction of traffic of specific substances (partition properties) and (2) permeability and impermeability to light of a specific wavelength, an interfacial polymerization method, Various methods generally used as a method for producing microcapsules such as a submerged drying method, a coacervation method, and an interfacial precipitation method can be used. From the viewpoint of ease of production and sealing of the container, it is preferable to use an interfacial polymerization method or a submerged drying method. Specifically, the atomized core material is dispersed in a suitable medium and then covered with a fine film. When this method is used, a core substance containing at least a photosensitive recording material to be encapsulated in a micro container is used.

  In the interfacial polymerization method, a polymerization reaction at the interface is used to generate a container wall. In many cases, a condensation polymerization reaction is used. For example, when acid chloride is used as the oil-soluble wall agent, polyamine or polyphenol is used as the water-soluble wall agent, polyamide or polyether coating can be used as the wall material, and isocyanate can be used as the oil-soluble wall agent. . Alternatively, when a polyamine or polyol is used as the water-soluble wall agent, a polyurethane or polyurea coating can be produced. Examples of the interface generation method include a water-in-oil method and an oil-in-water method, and a disperser such as a ball mill, a homogenizer, or a dissolver can be used to make the container fine particles. Since most of the photosensitive recording materials are oil-soluble, it is preferable to use a homogenizer or a dissolver as a disperser from the viewpoint of the water-in-oil method and the particle size of the fine particles.

  As a specific example of the combination of the oil-soluble wall material and the water-soluble wall material in the interfacial polymerization method, a method of providing a coating of polyamide or polyether using acid chloride as the oil-soluble wall material, polyamine or polyphenol as the water-soluble wall material It is desirable to use a polyurethane or polyurea coating by using isocyanate as the oil-soluble wall agent and polyamine or polyol as the water-soluble wall agent. In the form in which acid chloride is reacted with polyamine or polyphenol, hydrogen chloride gas may be generated during the production process, and therefore, a method using isocyanate, polyamine, and polyol without generation of such stimulating gas is particularly preferable.

  Specific examples of the polyamine include triethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like. More detailed polyamines and the like are described in detail in Seisho (Polyurethane Handbook edited by Keiji Iwata, Nikkan Kogyo Shimbun (1987)).

  Specific examples of polyphenols include bisphenol A, bisphenol F, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, dihydroxydiphenyl ether, dihydroxybenzophenone, o-hydroxyphenol, m-hydroxyphenol, p-hydroxy. Phenol, biphenol, tetramethylbiphenol, ethylidene bisphenol, methyl ethylidene bis (methylphenol), α-methylbenzylidene bisphenol, cyclohexylidene bisphenol, allylated bisphenol, bis (mono or di-t-butylphenol) propane, methylene bis (2- Propenyl) phenol, propylene bis (2-propenyl) phenol, bis [(2- Lopenyloxy) phenyl] methane, bis [(2-propenyloxy) phenyl] propane, 4,4 ′-(1-methylethylidene) bis [2- (2-propenyl) phenol], 4,4 ′-(1- Methylethylidene) bis [2- (1-phenylethyl) phenol], 4,4 '-(1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene) And bis [2-methyl-6- (2-propenyl) phenol], 4,4 ′-(1-methyltetradecylidene) bisphenol, and the like.

  The isocyanate is preferably a compound having a bifunctional or higher functional isocyanate group. Specifically, xylene diisocyanate and its hydrogenated product, hexamethylene diisocyanate, tolylene diisocyanate and its hydrogenated product, and diisocyanates such as isophorone diisocyanate are the main raw materials. In addition to these dimers or trimers (burette or isocyanurate), polyfunctional as adducts of polyols such as trimethylolpropane and bifunctional isocyanates such as xylylene diisocyanate, trimethylolpropane A compound in which a high molecular weight compound such as a polyether having active hydrogen such as polyethylene oxide is introduced into an adduct of a polyol such as xylylene diisocyanate and a bifunctional isocyanate such as xylylene diisocyanate, benzene isocyanate And the like formalin condensates. The compounds described in JP-A-62-212190, JP-A-4-26189, JP-A-5-317694, Japanese Patent Application No. 8-268721, and the like are also preferable.

  Specific examples of the polyol include ethylene glycol, propylene glycol, and oligomers thereof, polymers (polyethylene glycol, polypropylene glycol), polytetramethylene glycol, glycerin, polyethylene glycol of glycerin, or modified products of polypropylene glycol, polyvinyl alcohol, and the like. Is mentioned.

  In the liquid drying method, the polymer and the core substance are dissolved in an organic solvent having a low boiling point and added to a continuous phase containing a hydrophilic colloid or an active agent to form a stable O / W emulsion, followed by reduced pressure or heating. The organic solvent is removed to produce a film. As the polymer, polyacrylate, polystyrene, polyvinyl alcohol, polyester, butyral resin, polyolefin, or a copolymer thereof can be used. In this case, the water-in-oil method is usually used. As the disperser, those described above can be used.

  As the polymer used in the above-mentioned liquid drying method, polyacrylate, polystyrene, polyvinyl alcohol, polyester, butyral resin, polyolefin, or a copolymer thereof may be used among polymers used as a binder as a recording material to be described later. Is possible.

  In both the interfacial polymerization method and the in-liquid drying method, the wall material of the micro container may also serve as a binder as a recording material.

In order to impart the above-described light blocking property to the wall film of the micro container, it is preferable to add a light absorber to the wall material or use a polymer having a light absorbing property as the wall material.
The light absorber only needs to be able to sufficiently block the irradiation wavelength region used for the dura mater, but in particular, the wavelength region having a molar extinction coefficient exceeding 1 (dm ³ · cm ⁻¹ · mol ⁻¹ ) is 470 nm or less. It is preferably 420 nm or less, more preferably 380 nm or less. Either a pigment type or a dye type may be used as the light absorber, but it is preferable to use a dye type in order to prevent optical scattering of the material.

  Specific examples of the light absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylic acid ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and oxalic acid anilide ultraviolet absorbers. It is done. Specific examples of these ultraviolet absorbers include JP-A Nos. 47-10537, 58-111942, 58-212844, 59-19945, 59-46646, 59. No. -109055, No. 63-53544, No. 36-10466, No. 42-26187, No. 48-30492, No. 48-31255, No. 48-41572, No. 48. No. -54965, No. 50-10726, U.S. Pat. No. 2,719,086, No. 3,707,375, No. 3,754,919, No. 4, Examples thereof include those described in 220,711 specification and the like. The amount of the light absorber used is not particularly limited as long as it is set according to the type of the light absorbing goods and the desired light blocking property. The range of 0.1 to 20% by mass, preferably about 1 to 15% by mass.

On the other hand, in the case of using a polymer having light absorption, the polymer preferably has a wavelength region having an absorbance of 1 or more per 10 μm of a single polymer film of 470 nm or less, and more preferably 420 nm or less. Those having a thickness of 380 nm or less are particularly preferable.
As the polymer having a light absorbing property, a polymer containing a skeleton of the light absorbing agent in the main chain, residue and / or side chain is preferably used.
Examples of the polymer containing a light absorber skeleton in the main chain include those represented by the following general formula XX. Examples of the polymer containing a skeleton of a light absorber in the residue and / or side chain include those represented by the following general formula YY. A polymer containing a skeleton of a light absorber in the main chain is synthesized by adding a functional group that forms a chemical bond x to the light absorber in advance as a raw material. On the other hand, a polymer containing a skeleton of a light absorber in the residue and / or side chain may be used as a raw material by previously imparting a functional group that forms a chemical bond x to the light absorber as described above. After synthesizing the chain polymer in advance, a chemical bond y may be formed to give the function.

(In general formula XX, X represents a linking group, for example, a urethane group, a urea group, an ester group, or an alkylene group such as —CH ₂ — or —CH ₂ CH ₂ —. A is a main skeleton of a repeating unit. And B represents a main skeleton of a repeating unit showing light absorption.)

(In general formula YY, X represents a linking group, for example, a urethane group, a urea group, an ester group, or an alkylene group such as —CH ₂ — or —CH ₂ CH ₂ —. A and B are independently selected. Represents a main skeleton of a repeating unit, Y represents an appropriate spacer group, and C represents a skeleton exhibiting light absorption.)

On the other hand, selective light transmission can be imparted to the wall film of the micro container by using a material having a high transparency with respect to the target wavelength (recording wavelength). In general, each material other than the above-mentioned light absorber generally does not have a significant absorption in the range of 350 to 800 nm, preferably 400 to 700 nm suitable as recording light. There is no problem. On the other hand, some of the above-mentioned light absorbers have a long maximum wavelength in the absorption spectrum, so care must be taken. In the present invention, it is particularly preferable to use a light absorber having a molar extinction coefficient of 0.1 (dm ³ · cm ⁻¹ · mol ⁻¹ ) or less at the central wavelength of the recording light source, and 0.05 ( it is preferable to use the ^{dm 3 · cm -1 · mol -1} ) or less is light absorbers, particularly preferable to use a light absorbing agent is ^{0.01 (dm 3 · cm -1 ·} mol -1) or less . Further, when a polymer having a light absorption property is used, the polymer preferably has an absorbance of 0.1 or less with respect to the central wavelength of a recording light source per 10 μm of a single coating film, and is 0.05 or less. Are more preferable, and those of 0.01 or less are particularly preferable.

  A dispersion stabilizer can be added in order to facilitate dispersion during the production of the microcontainer or to disperse the microcontainer in the matrix easily. The dispersion stabilizer is preferably a water-soluble polymer having a solubility in water of 5% or more at the temperature to be emulsified. For example, polyvinyl alcohol and its modified products, polyacrylic acid amide and its derivatives, ethylene-vinyl acetate copolymer Polymer, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, vinyl acetate-acrylic acid copolymer, Examples thereof include carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivatives, arabic gum, sodium alginate and the like. The dispersion stabilizer may or may not be covalently bonded to the wall material of the micro container. The dispersion stabilizer is preferably added in the range of 1 to 100% by mass, more preferably in the range of 5 to 70% by mass, and in the range of 10 to 50% by mass, based on the solid content mass of the micro container. It is particularly desirable to add at. In this range, it is possible to set the sufficient dispersion stability and the particle diameter at the time of dispersion to a desired range.

  The shape of the micro container may be any shape such as a spherical shape, an elliptical spherical shape, a flat plate shape, a rod shape, etc., but in consideration of the principle of the manufacturing method and the close-packed state in the matrix described later, it is spherical or elliptical. Preferably there is. Regarding the size of the micro container, for example, when the shape is spherical, the average particle size is preferably in the range of 50 nm to 30 μm, and in the range of 70 nm to 10 μm in terms of uniform dispersion in the matrix binder described later. More preferably, it is in the range of 100 nm to 5 μm. The average particle size can be measured using, for example, Japanese Industrial Standard JIS Z 8825-1 “Particle Size Analysis Laser Diffraction Method” or JIS Z 8826 “Particle Size Analysis Photon Correlation Method”. If a commercially available particle size measuring device is available, it may be used. In the present invention, a value using a particle size analyzer LA-950, which can be purchased from Horiba Seisakusho, is used. Even when the shape of the micro container is elliptical, the average particle diameter is obtained by using the value obtained by using the measuring instrument.

  When manufacturing micro-containers, it is unavoidable to produce micro-containers with a large particle size distribution and undesirable large particle sizes, such as filtration, dialysis, centrifugation, sedimentation methods, etc. It is also possible to remove only the micro container. Therefore, the above-mentioned desirable particle size range should be applied only to the micro container to be mixed with the matrix described later, and is included in the holographic recording composition of the present invention. The manufacturing method of the micro container containing the recording material does not limit the applicability to the present invention. However, in view of manufacturing costs and labor, it is preferable that a micro container having an average particle diameter in the above-mentioned preferable range can be formed without going through the process of removing the micro container having a large particle diameter.

Recording Material The holographic recording composition of the present invention contains a photosensitive recording material, and may optionally contain components that do not have photosensitivity such as a binder but contribute to the formation of interference fringes. The photosensitive wavelength of the photosensitive recording material and the method of encapsulating the photosensitive recording material in the micro container are as described above. Further, the non-photosensitive recording material may be included in a micro container, and the wall material of the micro container may also serve as a binder as the recording material as described above.

  The recording material can be selected depending on the recording method. For example, a photopolymerizable photopolymer or a photodegradable photopolymer, a material that causes refractive index modulation based on the principle of substance diffusion, photochromic property or Materials that cause refractive index modulation using a photodispersible dye and change the wavelength dispersion of the refractive index, and photorefractive materials that use a change in birefringence due to a change in the orientation of liquid crystal molecules can be used. . From the viewpoint of sensitivity and easy formation of fine particles, a photopolymer type or coloring / decoloring type recording material is preferred. A plurality of recording materials may be included together.

-Photopolymer type recording material-
When the recording material is a photopolymer type, the micro container contains a photopolymerizable monomer as a photosensitive recording material, a photopolymerization initiator capable of polymerizing the photopolymerizable monomer, and further a binder. Can do. In this case, the photopolymerization initiator is sensitive by the exposure for recording, and the photopolymerizable monomer is polymerized in the binder to form an image (interference fringes).

As the photopolymerizable monomer, a monomer having a polymerization form such as radical polymerization, cationic polymerization, anion polymerization or the like can be used as appropriate, and radical polymerization is particularly preferable in terms of sensitivity and stability.
Examples of the radical polymerization monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In addition, vinyl esters, vinyl ethers, and styrenes can also be suitably used. Of these, esters and amides of the above unsaturated carboxylic acids, in particular, acrylic acid and methacrylic acid esters and amides are preferred from the viewpoints of sensitivity and stability.

  The acrylic acid and methacrylic acid esters and amides particularly preferably contain an aromatic ring in the structure. Specifically, the acrylic acid esters include phenyl acrylate, biphenyl acrylate, naphthyl acrylate, and benzyl acrylate. , Bisphenol A diacrylate, bisphenol F diacrylate, 9,9′-bisphenoxy fluorenediyl acrylate, and derivatives of phenyl acrylate include bromophenyl acrylate, dibromophenyl acrylate, tribromophenyl acrylate, pentabromophenyl acrylate, Chlorophenyl acrylate, dichlorophenyl acrylate, nonylphenyl acrylate, stearylphenyl acrylate, bisphenol A diacrelane Examples of the derivatives of tetrabromobisphenol A, tetrachlorobisphenol A diacrylate, and acryloyl groups of the acrylate esters described above are modified with ethylene glycol such as 2-acryloylethoxy group Is done. As the esters of methacrylic acid and the amides of acrylic acid and methacrylic acid, those obtained by appropriately replacing the acryloyl group of the compounds exemplified above with a methacryloyl group, an acrylamide group, and a methacrylamide group can be used. Moreover, what has a heterocyclic ring in a structure can also be utilized.

  Examples of the cationic polymerization and anionic polymerization monomers include glycidyl ethers, glycidyl esters, cyclohexene oxides, oxetanes, vinyl ethers, vinyl esters, styrenes, and the like.

  These photopolymerizable monomers are preferably included in the range of 1% by mass to 50% by mass, more preferably in the range of 2% by mass to 30% by mass, with respect to the total solid mass of the recording material. More preferably, it is contained in the range of mass% to 25 mass%. Within the above range, sufficient sensitivity and multiplexing performance can be ensured by having a sufficient density in the system, and sufficient storage stability and image retention can be obtained by not having an excessive density.

  There is no restriction | limiting in particular as a photoinitiator, A well-known polymerization initiator can be used. As the photopolymerization initiator, a single compound or a plurality of compounds may be used. The type of the initiator may be appropriately selected depending on the type of the photopolymerizable monomer and the polymerization type. As described above, radical polymerization is preferable from the viewpoints of sensitivity and stability, and it is preferable to use a photopolymerization initiator suitable for radical polymerization.

  Examples of the photo radical polymerization initiator include organic halogenated compounds, carbonyl compounds, organic peroxide compounds, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds. Oxime ester compounds, onium salt compounds, and the like.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-2 58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.K. P. Examples include the compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”. Among these, an oxazole compound substituted with a trihalomethyl group and an S-triazine compound are particularly preferable.

  More preferably, an s-triazine derivative having at least one mono, di, or trihalogen-substituted methyl group bonded to the s-triazine ring, specifically, for example, 2,4,6-tris (monochloromethyl)- s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, -(3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1 -(P-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p -Tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pheni Thio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -S-triazine, and the like.

  Examples of the carbonyl compound include benzophenone derivatives such as benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone; Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butyl) Acetophenone derivatives such as phenyl) ketone; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  As the azo compound, for example, an azo compound described in JP-A-8-108621 can be used.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butyl). Peroxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro Peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, , 5-Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxy Dicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, , 4′-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen dihydrogen) Phthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate), and the like.

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, Di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pen Fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoro Phen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3 Examples thereof include 4,5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453, and JP-A-1-152109.

  Examples of the hexaarylbiimidazole compound include JP-B-6-29285, US Pat. No. 3,479,185, US Pat. No. 4,311,783, US Pat. No. 4,622. 286, etc., specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (O-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ', 5, '-Tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4, Examples include 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, and JP-A-9-188710. , JP 2000-131837, JP 2002-107916, JP 764769, and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago” and the like. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 Described in Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527 Specific examples include organoboron transition metal coordination complexes described in Japanese Patent Application Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.

  Examples of the oxime ester compound include J.I. C. S. Perkin II (1979) 1653-1660; C. S. Perkin II (1979) pages 156-162, Journal of Photopolymer Science and Technology (1995) pages 202-232, compounds described in JP-A 2000-66385, compounds described in JP-A 2000-80068, specific examples Includes the following compounds.

  Examples of the onium salt compound include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Bal et al, Polymer, 21, 423 (1980), diazonium salt, US Pat. No. 4,069,055, ammonium salt described in JP-A-4-365049, US Pat. No. 4,069, No. 055, U.S. Pat. No. 4,069,056, phosphonium salts, European Patent No. 104,143, U.S. Pat. No. 339,049, U.S. Pat. No. 410,201 , Iodonium salts described in JP-A-2-150848 and JP-A-2-296514, European Patent 370,693, European Patent 390,214, European Patent 233,567 Specification, European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US US Patent No. 161,811, US Pat. No. 410,201, US Pat. No. 339,049, US Pat. No. 4,760,013, US Pat. No. 4,734,444 Specification, US Pat. No. 2,833,827, German Patent 2,904,626, German Patent 3,604,580, German Patent 3,604,581 Sulfonium salts described in the specification, V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Among these, the oxime ester compound, diazonium salt, iodonium salt, and sulfonium salt are particularly preferable in terms of reactivity and stability.

  These photopolymerization initiators are preferably included in the range of 0.05% by mass to 10% by mass, and in the range of 0.1% by mass to 5% by mass, with respect to the total solid content mass of the recording material. Is more preferable, and it is further more preferable that it is contained in the range of 0.5 mass% to 3 mass%. Within the upper range, sufficient sensitivity and multiplexing performance can be ensured by having a sufficient concentration in the system, and sufficient storage and transparency can be obtained by not having an excessive concentration.

  In order to further sensitize the polymerization initiator, a sensitization aid can also be included in the micro container. Examples of the sensitizing aid include coumarins having a substituent at the 3-position and / or 7-position, flavones, dibenzalacetones, dibenzalcyclohexanes, chalcones, xanthenes, and thioxanthenes. Porphyrins, phthalocyanines, acridines, anthracenes and the like can be used. Further, in order to adjust the photosensitive wavelength, a sensitizing dye can be included in a micro container. As the sensitizing dye, the compounds mentioned in the above sensitization aid, as well as cyanine dyes, merocyanine dyes, pyrylium salts, thiopyrylium salts, porphyrazines and the like can be used. However, the presence or absence of these additives does not limit the present invention. Moreover, what is necessary is just to set the usage-amount of the said additive suitably.

  A binder as a recording material can play a role of dispersing or dissolving a photopolymerizable monomer and a photopolymerization initiator in a micro container and three-dimensionally holding a generated image component. As the binder, oligomers and polymers having a molecular weight exceeding 1000 can be suitably used. The molecular weight is preferably 1000 or more, more preferably 2000 or more, and particularly preferably 5000 or more. The upper limit is not particularly limited, and is preferably an extent that does not hinder dissolution when producing a microcontainer, and is, for example, about 3000 to 8000, depending on the binder type used. In addition, the said molecular weight shall mean a mass mean molecular weight.

  Moreover, when a glass transition point (Tg) exists in a binder, the range of -80 degreeC-20 degreeC is preferable, the range of -60 degreeC-10 degreeC is further more preferable, and the range between -40 degreeC-0 degreeC is especially preferable. If it is within the above range, it is possible to achieve both a sufficient carrying / image holding force and a quick diffusion behavior of the monomer and the initiator and high performance. When the binder to be used is a mixture or copolymer of a plurality of polymer species, Tg is measured in the mixed or copolymerized state. Further, the molecular weight distribution of the binder does not particularly limit the present invention.

The binder to be encapsulated in a micro container as a recording material (or used as a wall material) may be a non-three-dimensional crosslinked polymer or a three-dimensional crosslinked polymer.
Specific examples of the non-three-dimensional crosslinked polymer include, for example, polyvinylidene fluoride, polydimethylsiloxane, polytrifluoroethyl methacrylate, polyoxypropylene, polyvinyl isobutyl ether, polyvinyl ethyl ether, polyoxyethylene, polyvinyl butyl ether, and polyvinyl pentyl ether. , Polyvinyl hexyl ether, poly (4-methyl-1-pentene), cellulose acetate butyrate, poly (4-fluoro-2-trifluoromethylstyrene), polyvinyl octyl ether, poly (vinyl 2-ethylhexyl ether), polyvinyl decyl Ether, poly (2-methoxyethyl acrylate), polybutyl acrylate, poly (t-butyl methacrylate), polyvinyl dodecyl ether, poly (3 Ethoxypropyl acrylate), polyoxycarbonyltetramethylene, polyvinyl propionate, polyvinyl acetate, polyvinyl methyl ether, polyethyl acrylate, ethylene-vinyl acetate copolymer, (80% to 20% by weight vinyl acetate) cellulose propionate , Cellulose acetate propionate, benzyl cellulose, phenol-formaldehyde resin, cellulose triacetate, polyvinyl methyl ether (isotactic), poly (3-methoxypropyl acrylate), poly (2-ethoxyethyl acrylate), polymethyl acrylate, Polyisopropyl methacrylate, poly (1-decene), polypropylene, poly (vinyl sec-butyl ether), polydodecylmeta Relate, polyoxyethyleneoxy succinoyl, (polyethylene succinate) polytetradecyl methacrylate, ethylene-propylene copolymer (EPR-rubber), polyhexadecyl methacrylate, polyvinyl formate, poly (2-fluoroethyl methacrylate) , Polyisobutyl methacrylate, ethyl cellulose, polyvinyl acetal, cellulose acetate, cellulose tripropionate, polyoxymethylene, polyvinyl butyral, poly (n-hexyl methacrylate), poly (n-butyl methacrylate), polyethylidene dimethacrylate, poly (2- Ethoxyethyl methacrylate), polyoxyethylene oxymale oil, (polyethylene maleate) poly (n-propyl methacrylate), poly (3 3,5-trimethylcyclohexyl methacrylate), polyethyl methacrylate, poly (2-nitro-2-methylpropyl methacrylate), polytriethylcarbinyl methacrylate, poly (1,1-diethylpropyl methacrylate), polymethyl methacrylate, poly (2 -Decyl-1,3-butadiene), polyvinyl alcohol, polyethylglycolate methacrylate, poly (3-methylcyclohexyl methacrylate), poly (cyclohexyl α-ethoxyacrylate), methylcellulose, poly (4-methylcyclohexyl methacrylate), polydeca Methylene glycol dimethacrylate, polyurethane, poly (1,2-butadiene), polyvinyl formal, poly (2-bromo-4-trifluoromethylstyrene) Cellulose nitrate, poly (sec-butyl α-chloroacrylate), poly (2-heptyl-1,3-butadiene), poly (ethyl α-chloroacrylate), poly (2-isopropyl-1,3-butadiene, poly ( 2-methylcyclohexyl methacrylate), polypropylene, polyisobutene, polybornyl methacrylate, poly (2-tert-butyl-1,3-butadiene), polyethylene glycol dimethacrylate, polycyclohexyl methacrylate, poly (cyclohexanediol-1,4-di) Methacrylate), butyl rubber, polytetrahydrofurfuryl methacrylate), gutta percha (β), polyethylene ionomer, polyoxyethylene (high molecular weight), polyethylene, poly (1-methylcyclohexyl methacrylate) ), Poly (2-hydroxyethyl methacrylate), polyvinyl chloroacetate, polybutene, polyvinyl methacrylate, poly (N-butyl-methacrylamide), gutta percha (α), terpene resin, poly (1,3-butadiene), shellac, poly (Methyl α-chloroacrylate), poly (2-chloroethyl methacrylate), poly (2-diethylaminoethyl methacrylate), poly (2-chlorocyclohexyl methacrylate), poly (1,3-butadiene) (35% cis; 56% Trans; 7% 1,2-content), natural rubber, polyallyl methacrylate, polyvinyl chloride + 40% dioctyl phthalate, polyacrylonitrile, polymethacrylonitrile, poly (1,3-butadiene), butadiene-acrylonitrile copolymer Polymer, polymethylisopropenyl ketone, polyisoprene, polyester resin rigid (about 50% styrene), poly (N- (2-methoxyethyl) methacrylamide), poly (2,3-dimethylbutadiene) (methyl rubber), vinyl chloride -Vinyl acetate copolymer, polyacrylic acid, poly (1,3-dichloropropyl methacrylate), poly (2-chloro-1- (chloromethyl) ethyl methacrylate), polyacrolein, poly (1-vinyl-2-pyrrolidone) ), Chlorinated rubber, nylon 6; nylon 6,6; nylon 6,10, butadiene-styrene copolymer, block copolymer poly (cyclohexyl α-chloroacrylate), poly (2-chloroethyl α-chloroacrylate), Butadiene-styrene copolymer, poly (2-amino Noethyl methacrylate), polyfurfuryl methacrylate, polybutyl mercaptyl methacrylate, poly (1-phenyl-N-amyl methacrylate), poly (N-methyl-methacrylamide), cellulose, polyvinyl chloride, urea formaldehyde resin, poly (sec -Butyl α-bromoacrylate), poly (cyclohexyl α-bromoacrylate), poly (2-bromoethyl methacrylate), polydihydroabietic acid, polyabietic acid, polyethylmercaptyl methacrylate, poly (N-allylmethacrylamide), Poly (1-phenylethyl methacrylate), polyvinyl furan, poly (2-vinyltetrahydrofuran), poly (p-methoxybenzyl methacrylate), polyisopropyl methacrylate, Poly (p-isopropylstyrene), polychloroprene, poly (oxyethylene-α-benzoate-ω-methacrylate), poly (p, p'-xylylenyl dimethacrylate), poly (1-phenylallylmethacrylate), poly (p -Cyclohexylphenyl methacrylate), poly (2-phenylethyl methacrylate), poly (oxycarbonyloxy-1,4-phenylene-1-propyl, poly (1- (o-chlorophenyl) ethyl methacrylate), styrene-maleic anhydride Copolymer, poly (1-phenylcyclohexyl methacrylate), poly (oxycarbonyloxy-1,4-phenylene-1,3-dimethyl-butylidene-1,4-phenylene), poly (methyl α-bromoacrylate), Polybenzyl methacrylate, poly ( 2- (phenylsulfonyl) ethyl methacrylate), poly (m-cresyl methacrylate), styrene-acrylonitrile copolymer, poly (oxycarbonyloxy-1,4-phenyleneisobutylidene-1,4-phenylene), poly (O-methoxyphenyl methacrylate), polyphenyl methacrylate, poly (o-cresyl methacrylate), polydiallyl phthalate, poly (2,3-dibromopropyl methacrylate), poly (oxycarbonyloxy-1,4-phenylene-1) -Methyl-butylidene-1,4-phenylene), poly (oxy-2,6-dimethylphenylene), polyoxyethyleneoxyterephthaloyl, polyethylene terephthalate, polyvinylbenzoate, poly (oxycarbonyloxy-1,4-phenylenebutene) (Ridene-1,4-phenylene), poly (1,2-diphenylethyl methacrylate), poly (o-chlorobenzyl methacrylate), poly (oxycarbonyloxy-1,4-phenylene-sec-butylidene-1,4- Phenylene), polyoxypentaerythroxyphthaloyl), poly (m-nitrobenzyl methacrylate), poly (oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene), poly (N- (2 -Phenylethyl) methacrylamide), poly (4-methoxy-2-methylstyrene), poly (o-methylstyrene), polystyrene, poly (oxycarbonyloxy-1,4-phenylenecyclohexylidene-1,4- Phenylene), poly (o-methoxystyrene), polydiphenylmethyl methacrylate Rate, poly (oxycarbonyloxy-1,4-phenyleneethylidene-1,4-phenylene), poly (p-bromophenyl methacrylate), poly (N-benzylmethacrylamide), poly (p-methoxystyrene), poly Vinylidene chloride, polysulfide ("Thiocol"), poly (o-chlorodiphenylmethyl methacrylate), poly (oxycarbonyloxy-1,4- (2,6-dichloro) phenylene-isopropylidene-1,4- (2, 6-dichloro) phenylene), poly (oxycarbonyloxybis (1,4- (3,5-dichlorophenylene))) polypentachlorophenyl methacrylate, poly (o-chlorostyrene), poly (phenyl α-bromoacrylate) , Poly (p-divinylbenzene), poly (N-vinyl) Phthalimide), poly (2,6-dichlorostyrene), poly (β-naphthyl methacrylate), poly (α-naphthylcarbinyl methacrylate), polysulfone, poly (2-vinylthiophene), poly (α-naphthyl methacrylate), poly (Oxycarbonyloxy-1,4-phenylenediphenyl-methylene-1,4-phenylene), polyvinylphenyl sulfide, butylphenol formaldehyde resin, urea-thiourea-formaldehyde resin, polyvinylnaphthalene, polyvinylcarbazole, naphthalene-formaldehyde resin , Phenol-formaldehyde resin, and polypentabromophenyl methacrylate. These random copolymers and block copolymers are also preferably used.
Furthermore, as the three-dimensional cross-linking polymer, polyester resin, polyurethane resin, poly (meth) acrylate resin, novolac resin, polyimide resin, polyolefin resin, polycarbonate resin, polyvinyl chloride resin, polystyrene resin, epoxy resin, polyamide resin, and these These random copolymers and block copolymers can be suitably used.

  The binder may be a polymer already formed when the recording material is prepared, or may be a polymer formed by causing a reaction or cross-linking during the preparation process.

  These binders are preferably contained in the range of 99% by mass to 50% by mass, more preferably in the range of 95% by mass to 75% by mass, and more preferably in the range of 95% by mass to 75% by mass with respect to the total solid content mass of the recording material. More preferably, it is contained in the range of 80% by mass. If it is in the said range, by carrying | supporting a photopolymerizable monomer in sufficient quantity as a dispersion medium, the flow of a photopolymerizable monomer can be suppressed in an appropriate range, and resolution can be improved.

  The binder may also have a function as a micro container wall film. That is, in addition to the case where the above-mentioned photopolymerizable monomer, photopolymerization initiator, and binder are encapsulated in a micro container, the binder covers the outer periphery as a micro container wall film, and the photopolymerizable monomer and the light are contained inside. This is a case where a polymerization initiator is supported. In this case, if it is confirmed that the above two conditions (restriction of traffic and restriction of stimulation) are satisfied, in the present invention, the binder is a binder as one of the recording materials, and the micro container Assume that it is also a wall membrane. In this case, the glass transition point (Tg) is not particularly limited.

-Refractive index modulation type of dye-
When the recording material uses the change in the wavelength dispersion of the refractive index of the dye, the photosensitive container is made of a dye or dye system that changes the wavelength dispersion of the refractive index at least by light stimulation, or a dye. In addition, a substance capable of changing the wavelength dispersibility of the dye by light stimulation can be included, and a binder can be included.
In the present invention, the “dye that changes the wavelength dispersion of the refractive index by light stimulation” refers to wavelength dispersion of the refractive index directly by light stimulation with a single molecule without passing energy or atomic group exchange between molecules. It refers to dyes that change their nature, commonly called photochromic substances. The dye system refers to a reaction system in which the wavelength dispersion of the refractive index of a specific substance is changed by light stimulation with a plurality of molecules via exchange of energy and atomic groups between molecules.
Specific examples of the dye include diarylethene, spiropyran, fulgide, viologen, thioindigo, azobenzene derivative, norbornadiene, spirooxazine and the like.
The dye system includes at least a dye or a dye precursor and a trigger substance that triggers color development and may optionally include a sensitizing dye. Specific examples thereof are described in detail in JP-A-2005-309359.
The amount of the dye or dye system used can be 1 to 20% by mass, preferably 2 to 15% by mass, based on the total solid content of the recording material. If it exceeds this range, the light absorption becomes large and the ratio of the reproduced light to the incident reference light becomes weak and inefficient. Conversely, if it is less than this range, the refractive index and the modulation amount of absorption are small and sufficient sensitivity is obtained. There is a possibility that it cannot be obtained.

  Examples of the binder used as a recording material in a recording method using refractive index modulation of a dye include the same binders as exemplified in the photopolymer system. In this case, the glass transition point (Tg) of the binder is not limited. Further, like the photopolymer system, the binder can also serve as a micro container wall film. About the usage-amount of a binder, it is as above-mentioned.

The photopolymerizable matrix binder precursor holographic recording medium generally contains a polymer called a matrix and a polymer for holding a photopolymerization initiator, which is related to recording and storage. The matrix is used for the purpose of enhancing the effects of improving coating properties, film strength, and hologram recording characteristics. The above-mentioned micro container is preferably supported by a matrix in the recording layer. The holographic recording composition of the present invention contains a photopolymerizable component as a matrix binder precursor. After mixing the matrix binder precursor with the micro container, the matrix binder can be formed by polymerization (in situ polymerization) by light irradiation and curing. In situ polymerization means that at the stage of mixing and preparing the composition, only the precursor of the matrix binder is present in the composition, and the matrix binder itself is not present. It refers to a process in which the reaction of the precursor proceeds and a matrix binder is formed in the composition. As a result, the matrix binder precursor is consumed after in situ polymerization, and instead a matrix binder is formed. For example, when the precursor is in a liquid state and the generated matrix binder is a solid, the precursor is in a liquid state. The composition can be changed to a solid by external stimulation. If this principle is used, it is possible to fix the shape of the composition not only in the form of a film but also in any shape. In addition, in situ polymerization allows the shape to be fixed without using a solvent, so the production rate is limited by the rate of solvent volatilization and internal residual solvent cannot be removed. The problem can be solved, and it becomes possible to produce a super-thick film (for example, 500 μm or more) which could not be achieved conventionally.

  In the present invention, a photopolymerizable matrix binder precursor, specifically, a photocurable resin (photopolymer) is used as the matrix binder precursor. By using a photopolymerizable component, extremely rapid production (dura) is possible. For example, when a thermosetting resin is used, the progress of the thermal reaction is slower than the progress of the photoreaction, and there is a problem of removal of residual heat after curing and loss of thermal energy that was not used for curing. Continuous production is difficult, and usually batch production. Therefore, the use of a photocurable resin is particularly advantageous in terms of productivity and cost.

  The photopolymerizable matrix binder precursor is, for example, an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one ethylenically unsaturated bond, preferably two or more. It can be a photopolymerizable monomer. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These can be, for example, monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof, and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. Examples thereof include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. In addition, unsaturated carboxylic acid ester having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, or addition reaction product of amide with monofunctional or polyfunctional isocyanate, or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group, or an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. . As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylate ester, octyl acrylate, dodecyl acrylate, stearyl acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3 -Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, Taerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyania Examples include nurate and polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxy) phenyl] dimethyl methane, and the like.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Examples thereof include those having an aromatic skeleton described in JP-A No. 59-5241 and JP-A-2-226149, and those containing an amino group described in JP-A 1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula to a polyisocyanate compound having two or more isocyanate groups. Can be mentioned.
CH ₂ ═C (R _a ) COOCH ₂ CH (R _b ) OH... General formula (wherein R _a and R _b each independently represents a hydrogen atom or a methyl group.)
Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are polymerized. High speed is preferable.
Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. In addition, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like are also included. Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 can be suitably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  About the said addition polymeric compound, the detail of usage methods, such as the structure, single use or combined use, addition amount, etc. can be arbitrarily set according to final performance design. For example, it can be selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferred, and in many cases, a bifunctional or higher functionality is preferred. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both photosensitivity and intensity by using these together. In addition, the selection and use method of the addition polymerization compound is an important factor for the compatibility and dispersibility with other components in the composition (for example, a micro container, an initiator, and other additives). For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination.

  Depending on the material constituting the wall film of the micro container, if the matrix binder precursor is excessively low in molecular weight, the matrix binder precursor penetrates the wall film and causes the wall film to expand, so that the partition wall of the micro container May decrease. In general, the molecular weight of the matrix binder precursor is preferably about 300 to 3000, more preferably about 400 to 2000, depending on the material constituting the wall film of the micro container.

  The content of the photopolymerizable matrix binder precursor in the holographic recording composition of the present invention can be, for example, 30 to 95% by mass, preferably 40 to 90% by mass, and 50 to 80%. It is more preferable to set it as the mass%.

Photopolymerization initiator The holographic recording composition of the present invention includes a photopolymerization initiator that can be excited by light irradiation and initiate a polymerization reaction of the photopolymerizable matrix binder precursor together with the photopolymerizable matrix binder precursor. . There is no restriction | limiting in particular as said photoinitiator, Various well-known photoinitiators can be used. As the photopolymerization initiator, a single compound may be used, or a plurality of compounds may be used in combination. The kind of photopolymerization initiator can be selected according to the kind of photopolymerizable matrix binder precursor and the polymerization type. As described above, radical polymerization is preferable from the viewpoints of sensitivity and stability, but cationic polymerization is also preferably used as necessary. Moreover, you may use together radical polymerization and cationic polymerization. The photosensitive wavelength of the photopolymerization initiator is as described above.

  Examples of the photo radical polymerization initiator include organic halogenated compounds, carbonyl compounds, organic peroxide compounds, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds. Oxime ester compounds, onium salt compounds, and the like. Specific examples thereof include the same compound group as the photopolymerization initiator as the recording material described above.

  These photopolymerization initiators are preferably included in a range of 0.05% by mass to 10% by mass, and 0.1% by mass to 5% by mass with respect to the total solid mass of the above-mentioned photopolymerizable matrix binder precursor. % Is more preferable, and it is even more preferable that it is included in the range of 0.5% by mass to 3% by mass. If it is within the above range, sufficient sensitivity and curing rate can be ensured by having sufficient concentration in the system, and masking effect on drawing components can be prevented by not having excessive concentration, and sufficient drawing at the time of drawing Sensitivity can be secured.

Other Components In addition to the components described above, the holographic recording composition of the present invention can optionally contain additives as necessary. Examples of the additive include already polymerized binder polymer, surfactant, sensitizer, filler, stabilizer, release agent and the like. These additives may be present inside or outside the micro container, but are preferably present at least outside the micro container.
By adding a binder polymer that has already been polymerized, the adhesiveness between the matrix binder and the support (substrate), flexibility, rigidity, tackiness, and the like for the recording layer formed from the holographic recording composition of the present invention, It can be added to impart optical properties. In addition, the surfactant prevents repelling of the composition on the substrate, uneven coating, and increase in surface variation of the film thickness when the recording layer is formed by applying the holographic recording composition of the present invention on the substrate. Can be added. A sensitizer can be added to sensitize photopolymerization. In addition, the stabilizer can be added to prevent the matrix binder from being decomposed or denatured during long-term storage, storage under high temperature and high humidity conditions, or storage under a large amount of light exposure conditions. In particular, the mold release agent facilitates peeling of the film from the molding roll when the film is directly formed without applying the holographic recording composition of the present invention on the substrate, and the film is broken or the film is formed on the roll. Can be added to prevent sticking.
These additives may be included in the micro container, but it is preferable that at least a part of the additive is present outside the micro container in view of the expected function.
Moreover, although the usage-amount of the said additive is not specifically limited, For example, it can be set as about 0.01-10 mass% with respect to the composition whole quantity.

  The holographic recording composition of the present invention can be used as various holographic recording compositions capable of recording information by irradiation with light containing information, and particularly as a volume holographic recording composition. Is preferred.

[Holographic recording medium and manufacturing method thereof]
The present invention relates to a holographic recording medium having a recording layer formed from the holographic recording composition of the present invention.
The present invention further relates to a method for producing the holographic recording medium of the present invention. The manufacturing method includes polymerizing a photopolymerizable matrix binder precursor by irradiating the composition for holographic recording of the present invention with light that the micro-container wall film is impermeable. A matrix binder can be formed by this polymerization reaction.
Details of the holographic recording medium and the method for manufacturing the same of the present invention will be described below.

In the holographic recording medium of the present invention, the presence of a support (substrate) is not essential, but in order to improve production ease, strength as a product form, designability, weather resistance, handling in normal use From the viewpoint of properties, it is preferable to form the recording layer on a support. The recording layer can be formed on any support. Further, the support may be provided only on one side of the recording layer, or may be provided on both sides, or may envelop the entire recording layer. The shape of the support can be freely selected from a plate shape, a disk shape, a film shape, a cylinder shape, a net shape, a box shape, etc. Among them, a shape known as a substrate for an optical recording medium is preferable. That is, it is a disc shape and has a concentric clamp hole at the center or a rectangular card shape.
Moreover, the magnitude | size of a support body can be set arbitrarily.

  There is no restriction | limiting in particular as a material of a support body, Both an inorganic material and an organic material can be used suitably. When light used for recording and reproduction is incident through the substrate, it is preferable to use a material that is sufficiently transparent in the wavelength range of the light used, and for purposes such as strength, designability, weather resistance, and handling properties in normal use. It is preferable to use a material that can sufficiently reinforce the property.

Examples of the inorganic material include metal plates such as glass, quartz, silicon, and aluminum plates, and metal films. In addition, these materials such as steel wire glass may be used in combination.
Examples of the organic material include acetate resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and acrylic resins. Polynorbornene resin, cellulose resin, polyarylate resin, polystyrene resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic resin, polylactic acid resin, plastic film laminated paper And synthetic paper. These materials may be mixed or combined.
Said inorganic material and organic material may be used individually by 1 type, and may use 2 or more types together. Among these, polycarbonate resins, acrylic resins, and polyolefin resins (particularly polycycloolefin resins) are preferable from the viewpoints of moldability, optical properties, and cost.

  Moreover, it is also possible to perform arbitrary surface treatment to said material. For example, in order to improve the adhesion with the recording layer, the surface is subjected to surface roughening by brush grain, sand grain, transfer grain, corona treatment, etc., or a gap layer or an adhesive layer is provided for the same purpose. In order to provide light reflectivity, it is possible to provide a thin film on the transparent substrate by vapor deposition or sputtering, or to provide an uneven shape for focusing servo or addressing servo.

  As a method for coating the composition on the support, conventionally known coating methods, that is, an inkjet method, a spin coating method, a kneader coating method, a bar coating method, a blade coating method, a curtain coating method, a roll coating method, a flow, and the like. A coating method, a printing method, a dip coating method, a casting film forming method, a gravure printing method, an ink jet printing method, and a screen lean method can be used. A casting method can also be used. As a method of forming a recording layer without using a support, a composition that has been batch-cured in advance is pulverized by an arbitrary method, and the obtained powder or granule is press-molded and injection-molded to form a composition layer alone. The method of obtaining a molding can be mentioned. From the viewpoint of omitting the heat treatment process, it is preferable to use the method exemplified as the method using the support. In this case, it is possible to obtain an extremely excellent production speed as compared with the conventional method requiring heat treatment or solvent removal. it can. In addition, as a method suitable for forming an ultra-thick recording layer, the method described in JP-A-2005-17589 can also be applied. However, the present invention is not necessarily limited to the method exemplified above, and a method suitable for the properties of the recording layer composition to be used should be appropriately selected.

  By using the light that the microcontainer wall film is impermeable as the light that is irradiated to polymerize the photopolymerizable matrix binder precursor to the composition, the photosensitive recording material contained in the microcontainer Hardening can be performed without degrading performance. The wavelength to be irradiated should be appropriately selected depending on the composition to be used, but the viewpoints of manufacturing cost, maintenance of equipment, and availability of equipment should also be considered. That is, from the viewpoints of irradiation energy and acquisition / maintenance costs, ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, DEEP-UV lamps, excimer lamps, and LEDs are preferable. 400 to 300 nm for lamps, 365 nm emission line, 320 to 250 nm for high pressure mercury lamps and DEEP-UV lamps, 320 to 250 nm for low pressure mercury lamps, 308 nm for excimer lamps In the case of LED, it is 365 nm. The use of excimer lamps or LEDs is preferred because of power consumption and illuminance efficiency.

  When using a light source that emits a wavelength exceeding the preferred range for use in the dura, that is, in terms of the type of light source, it is outside the above range of ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, DEEP-UV lamp It is desirable to remove the light of the wavelength with an optical filter. In the case of an excimer lamp or LED, the emission spectrum is in a very narrow range, so that a filter is generally not necessary.

The amount of irradiation energy should be determined appropriately according to the correlation between the irradiation energy of the composition used and the progress of curing, and from the viewpoint of dura, a sufficient amount of irradiation energy should be secured. and degradation since there is a risk of inducing, preferably 10 to 10000 mJ / cm ² as the range of the irradiation energy, more preferably 30~5000mJ / cm ^2, particularly preferably 50~2000mJ / cm ^2, 80~1000mJ / cm ² is most preferred. If the illuminance of the light source to be used is excessively high, the operating cost is high, and if it is low, the production speed is hindered. Therefore, the illuminance at the outermost surface of the irradiated material is 0.1 to 1000 mW / cm ^2. The range of 0.5 to 500 mW / cm ² is more preferable, and the range of 1 to 200 mW / cm ² is particularly preferable. When it is difficult to secure the illuminance with a single light source, it is possible to obtain the illuminance within the above range by simultaneously irradiating a plurality of the same type of light sources. The irradiation time is determined from the required irradiation energy and the illuminance of the light source used. From the viewpoint of rapid production, a range of approximately 0.01 seconds to 30 minutes is preferable, and a range of 0.1 seconds to 20 minutes. Further preferred is a range of 1 second to 10 minutes. At the time of curing, it is preferable to work in a clean atmosphere in order to prevent adhesion and mixing of foreign substances. A so-called class 1000 clean atmosphere is preferable, and a class 100 clean atmosphere is more preferable. However, the present invention is not limited to these.

  When a photopolymer material, particularly a radical polymerization type photopolymer, is used as the matrix binder precursor, it is preferable to reduce the oxygen concentration in the atmosphere, and the concentration is 0.1 to 10% in terms of volume fraction in the atmosphere. A range is preferable and the range of 1 to 5% is more preferable. In particular, when using ionic polymerization (cationic polymerization, anionic polymerization), it is desirable to reduce the humidity in the atmosphere, and the humidity is preferably in the range of 10 to 40% as relative humidity at 25 ° C., and in the range of 20 to 35%. Is more preferable. As a method of maintaining the above atmosphere, the entire area including the steps related to curing is isolated and filled with an atmosphere of constant humidity or constant oxygen concentration, or only the apparatus that performs irradiation for curing is isolated and constant humidity or constant oxygen concentration Or a method of spraying an atmosphere having a constant humidity or a constant oxygen concentration to locally keep the atmosphere constant in the step of performing irradiation for curing. However, in some cases, such as when the matrix binder is effectively isolated from the external atmosphere by the substrate or medium configuration, an atmosphere with reduced oxygen or humidity may not be required.

  The holographic recording medium of the present invention includes the recording layer (holographic recording layer), and preferably includes a lower substrate, a filter layer, a holographic recording layer, and an upper substrate. And other layers such as a reflective film, a filter layer, a first gap layer, and a second gap layer.

  The holographic recording medium of the present invention is capable of recording / reproducing information using the principle of hologram, and is a volume for recording a large amount of information such as a relatively thin planar hologram or a three-dimensional image for recording information such as two dimensions. It may be a hologram, may be a transmission type or a reflection type, or may be a mixture thereof. The holographic recording medium of the present invention is suitable as a volume holographic recording medium for which high recording density is required because high capacity information recording is possible.

  Further, the recording method of the hologram on the holographic recording medium of the present invention is not particularly limited, and for example, an amplitude hologram, a phase hologram, a blazed hologram, a complex amplitude hologram, or the like may be used. Among these, information recording in the volume holographic recording area is performed by irradiating the volume holographic recording area with information light and reference light as a coaxial light beam, and recording information by an interference pattern due to interference between the information light and the reference light. The so-called coaxial recording system is particularly preferable.

  Below, the detail of the board | substrate and each layer which may be contained in the holographic recording medium of this invention is demonstrated one by one.

-Board-
The details of the substrate are as described above. The substrate is usually provided with a plurality of address-servo areas as linearly extending positioning areas at predetermined angular intervals, and a sector-shaped section between adjacent address-servo areas is a data area. . In the address-servo area, information for performing focus servo and tracking servo by the sampled servo method and address information are recorded in advance by embossed pits (servo pits) or the like (preformat). Note that the focus servo can be performed using the reflective surface of the reflective film. As information for performing the tracking servo, for example, a wobble pit can be used. In the case where the holographic recording medium has a card shape, the servo pit pattern may be omitted.

  There is no restriction | limiting in particular as thickness of a board | substrate, According to the objective, it can select suitably, 0.1-5 mm is preferable and 0.3-2 mm is more preferable. If the thickness of the substrate is 0.1 mm or more, the distortion of the shape during storage of the disc can be suppressed, and if it is 5 mm or less, the mass of the entire disc increases and an excessive load is applied to the drive motor. It can be avoided.

-Recording layer-
The recording layer is formed from the holographic recording composition of the present invention, and information can be recorded using holography. There is no restriction | limiting in particular as thickness of a recording layer, According to the objective, it can select suitably. If the thickness of the recording layer is in the range of 1 to 1,000 μm, a sufficient S / N ratio can be obtained even if shift multiplexing of 10 to 300 is performed, and if it is in the range of 100 to 700 μm, this is remarkable. This is advantageous. Furthermore, as described above, according to the holographic recording composition of the present invention, a thick recording layer (for example, 500 μm or more) suitable for volume holography can be easily formed with high productivity.

-Reflective film-
The reflective film can be formed on the servo pit pattern surface of the substrate.
As a material for the reflective film, a material having a high reflectance with respect to information light and reference light is preferably used. When the wavelength of light used as information light and reference light is 400 to 780 nm, for example, it is preferable to use Al, Al alloy, Ag, Ag alloy, or the like. When the wavelength of light used as information light and reference light is 650 nm or more, it is preferable to use Al, Al alloy, Ag, Ag alloy, Au, Cu alloy, TiN, or the like.
In addition, by using an optical recording medium that reflects light and can be added or erased as a reflective film, for example, a DVD (digital video disk), it is possible to rewrite to what area the hologram has been recorded. It is also possible to additionally write and rewrite directory information such as in which part an error exists and how the alternation process was performed without affecting the hologram.

The method for forming the reflective film is not particularly limited and can be appropriately selected according to the purpose. Various vapor deposition methods such as vacuum deposition, sputtering, plasma CVD, photo CVD, ion plating An electron beam evaporation method or the like is used. Among these, the sputtering method is excellent in terms of mass productivity and film quality.
The thickness of the reflective film is preferably 50 nm or more, and more preferably 100 nm or more so that sufficient reflectance can be achieved.

-Filter layer-
The filter layer can be provided on the servo pits of the substrate, on the reflective layer, or on the first gap layer described later.
The filter layer has a wavelength selective reflection function that reflects only light of a specific wavelength from among a plurality of types of light rays, transmits the first light, and reflects the second light. In particular, even if the incident angle changes, the selective reflection wavelength does not shift, and the function of preventing irregular reflection from the reflection film of the recording medium by the information light and the reference light and the generation of noise are also provided. By laminating filter layers, optical recording with high resolution and excellent diffraction efficiency can be performed.
There is no restriction | limiting in particular as a filter layer, According to the objective, it can select suitably, For example, a dichroic mirror layer, a coloring material containing layer, a dielectric material vapor deposition layer, a single layer or two or more cholesteric layers, and as needed It is possible to form a laminate in which at least one of the other layers appropriately selected is laminated. Although the thickness is not specifically limited, For example, it is about 0.5-20 micrometers.
The filter layer may be directly laminated on the substrate together with the recording layer or the like, or may be laminated on a substrate such as a film to produce a filter layer, which may be laminated on the substrate.

-First gap layer-
The first gap layer is provided between the filter layer and the reflective film as necessary, and is formed for the purpose of smoothing the lower substrate surface. It is also effective for adjusting the size of the hologram generated in the recording layer. That is, since it is necessary for the recording layer to form an interference area for the recording reference light and the information light to a certain extent, it is effective to provide a gap between the recording layer and the servo pit pattern.

The first gap layer can be formed, for example, by applying a material such as an ultraviolet curable resin on the servo pit pattern by spin coating or the like and curing it. Moreover, when using what apply | coated and formed on the transparent base material as a filter layer, this transparent base material will work | function also as a 1st gap layer.
There is no restriction | limiting in particular as thickness of a 1st gap layer, According to the objective, it can select suitably, 1-200 micrometers is preferable.

-Second gap layer-
The second gap layer is provided between the recording layer and the filter layer as necessary.
There is no restriction | limiting in particular as a material of a 2nd gap layer, According to the objective, it can select suitably, For example, a triacetyl cellulose (TAC), a polycarbonate (PC), a polyethylene terephthalate (PET), a polystyrene (PS) Transparent resin films such as polysulfone (PSF), polyvinyl alcohol (PVA), polymethyl methacrylate = polymethyl methacrylate (PMMA), etc., or JSR brand name ARTON film or Nippon Zeon brand name ZEONOR Examples thereof include norbornene resin films. Among these, those having high isotropic properties are preferred, and TAC, PC, trade name ARTON, and trade name ZEONOR are particularly preferred.
There is no restriction | limiting in particular as thickness of a 2nd gap layer, According to the objective, it can select suitably, 1-200 micrometers is preferable.
Hereinafter, the holographic recording medium of the present invention will be described in more detail based on specific embodiments. However, the present invention is not limited to the following specific embodiments.

<First embodiment>
FIG. 1 is a schematic cross-sectional view showing the configuration of the holographic recording medium according to the first embodiment. In the holographic recording medium 21 according to the first embodiment, a servo pit pattern 3 is formed on a polycarbonate resin substrate or glass substrate 1, and the servo pit pattern 3 is coated with aluminum, gold, platinum, or the like to be a reflective film 2 is provided. In FIG. 1, the servo pit pattern 3 is formed on the entire surface of the lower substrate 1. However, the servo pit pattern may be formed periodically. The height of the servo pit pattern 3 is usually 1750 mm (175 nm), which is sufficiently smaller than the thicknesses of the substrate and other layers.

  The first gap layer 8 is formed by applying a material such as an ultraviolet curable resin on the reflective film 2 of the lower substrate 1 by spin coating or the like. The first gap layer 8 is effective for protecting the reflective film 2 and adjusting the size of the hologram generated in the recording layer 4. That is, providing a gap between the recording layer 4 and the servo pit pattern 3 is effective for forming a recording reference light and information light interference region in the recording layer 4 to a certain size.

  A filter layer 6 is provided on the first gap layer 8, and a holographic recording medium 21 is configured by sandwiching the recording layer 4 between the filter layer 6 and the upper substrate 5 (polycarbonate resin substrate or glass substrate).

In FIG. 1, the filter layer 6 transmits only red light and does not transmit light of other colors. Therefore, since the information light, the recording and reproduction reference light are green or blue light, the light does not pass through the filter layer 6 and does not reach the reflection film 2 but becomes return light and is emitted from the incident / exit surface A. Become.
The filter layer 6 is a multilayer deposited film in which high refractive index layers and low refractive index layers are alternately stacked.
The filter layer 6 made of this multilayer deposited film may be directly formed on the first gap layer 8 by vacuum deposition, or a film in which the multilayer deposited film is formed on the substrate is punched into a holographic recording medium shape. May be.

  The holographic recording medium 21 in the present embodiment may have a disk shape or a card shape. In the case of a card shape, there is no need for the servo pit pattern. In the holographic recording medium 21, the lower substrate 1 is 0.6 mm, the first gap layer 8 is 100 μm, the filter layer 6 is 2 to 3 μm, the recording layer 4 is 0.6 mm, and the upper substrate 5 is 0.6 mm. The total thickness is about 1.9 mm.

Next, an optical system that can be used for recording and reproducing information on the holographic recording medium 21 will be described with reference to FIG.
First, light (red light) emitted from the servo laser is reflected almost 100% by the dichroic mirror 13 and passes through the objective lens 12. The servo light is irradiated onto the holographic recording medium 21 by the objective lens 12 so as to focus on the reflective film 2. That is, the dichroic mirror 13 transmits light having a wavelength of green or blue, and reflects light having a wavelength of red almost 100%. The servo light incident from the light incident / exit surface A of the holographic recording medium 21 passes through the upper substrate 5, the recording layer 4, the filter layer 6, and the first gap layer 8, is reflected by the reflective film 2, and again The first gap layer 8, the filter layer 6, the recording layer 4, and the upper substrate 5 are transmitted through the incident / exit surface A. The returned return light passes through the objective lens 12, is reflected almost 100% by the dichroic mirror 13, and servo information is detected by a servo information detector (not shown). The detected servo information is used for focus servo, tracking servo, slide servo, and the like. If the hologram material constituting the recording layer 4 is not sensitive to red light, even if the servo light passes through the recording layer 4 or the servo light is irregularly reflected by the reflective film 2, Has no effect. Further, since the return light of the servo light reflected by the reflection film 2 is reflected almost 100% by the dichroic mirror 13, the servo light is detected by the CMOS sensor or the CCD 14 for detecting the reproduced image. In addition, there is no noise with respect to the reproduction light.

  The information light and the recording reference light generated from the recording / reproducing laser pass through the polarizing plate 16 to become linearly polarized light, pass through the half mirror 17 and pass through the quarter wavelength plate 15. It becomes circularly polarized light. Through the dichroic mirror 13, the objective lens 12 irradiates the holographic recording medium 21 with information light and recording reference light so as to generate an interference pattern in the recording layer 4. The information light and the recording reference light enter from the incident / exit surface A and interfere with each other in the recording layer 4 to generate an interference pattern there. Thereafter, the information light and the recording reference light pass through the recording layer 4 and enter the filter layer 6, but are reflected to the bottom surface of the filter layer 6 to become return light. That is, the information light and the recording reference light do not reach the reflective film 2. This is because the filter layer 6 is a multilayer deposited layer in which a plurality of high refractive index layers and low refractive index layers are alternately stacked, and has a property of transmitting only red light.

<Second Embodiment>
FIG. 2 is a schematic cross-sectional view showing the configuration of the holographic recording medium according to the second embodiment. In the holographic recording medium 22 according to the second embodiment, a servo pit pattern 3 is formed on a polycarbonate resin or glass substrate 1, and the surface of the servo pit pattern 3 is coated with aluminum, gold, platinum, etc. Is provided. The height of the servo pit pattern 3 is the same as that of the first embodiment in that it is normally 1750 mm (175 nm).

  The difference in structure between the second embodiment and the first embodiment is that the second gap layer 7 is provided between the filter layer 6 and the recording layer 4 in the holographic recording medium 22 according to the second embodiment. It is that. The second gap layer 7 has a point where information light and reproduction light are focused. If this area is filled with a photopolymer, excessive consumption of monomers due to overexposure occurs, resulting in a decrease in multiple recording capability. Therefore, it is effective to provide a non-reactive and transparent second gap layer.

  A filter layer 6, which is a multilayer deposited film in which a plurality of high refractive index layers and low refractive index layers are alternately stacked, is formed on the first gap layer 8 after the first gap layer 8 is formed. The thing similar to embodiment can be used.

  In the holographic recording medium 22 of the second embodiment, the lower substrate 1 is 1.0 mm, the first gap layer 8 is 100 μm, the filter layer 6 is 3 to 5 μm, the second gap layer 7 is 70 μm, and the recording layer 4. Is 0.6 mm, the upper substrate 5 is 0.4 mm thick, and the total thickness is about 2.2 mm.

  Next, when information is recorded or reproduced, red servo light and green information light and recording and reproduction reference light are applied to the holographic recording medium 22 of the second embodiment having the above-described structure. Is irradiated. The servo light enters from the incident / exit surface A, passes through the recording layer 4, the second gap layer 7, the filter layer 6, and the first gap layer 8 and is reflected by the reflective film 2 to become return light. The return light again passes through the first gap layer 8, the filter layer 6, the second gap layer 7, the recording layer 4, and the upper substrate 5 in this order, and is emitted from the incident / exit surface A. The emitted return light is used for focus servo, tracking servo, and the like. If the hologram material constituting the recording layer 4 is not sensitive to red light, even if the servo light passes through the recording layer 4 or the servo light is irregularly reflected by the reflective film 2, Has no effect. Green information light or the like enters from the incident / exit surface A, passes through the recording layer 4 and the second gap layer 7, is reflected by the filter layer 6, and becomes return light. The return light again passes through the second gap layer 7, the recording layer 4 and the upper substrate 5 in this order, and exits from the incident / exit surface A. Also during reproduction, not only the reproduction reference light but also the reproduction light generated by irradiating the reproduction reference light onto the recording layer 4 is emitted from the incident / exit surface A without reaching the reflection film 2. The optical operation in the vicinity of the holographic recording medium 22 (the objective lens 12, the filter layer 6, the CMOS sensor or the CCD 14 as a detector in FIG. 3) is the same as in the first embodiment, and a description thereof will be omitted.

[Information recording method]
Furthermore, the present invention relates to a method for recording information on the holographic recording medium of the present invention. In the information recording method of the present invention, information is applied to the recording layer by irradiating the holographic recording medium of the present invention with light (light that can sensitize the photosensitive recording material) that the micro container wall film has transparency. Record. Specifically, interference fringes can be formed in the recording layer by the light irradiation.

  Preferably, the holographic recording medium of the present invention is a volume holographic recording medium. Details of the volume hologram recording method are described in “Introduction Principle and Practice of Holography” (Toshihiro Kubota, Asakura Shoten, 1995). In any of the principles, information on the phase, angle, and intensity of light is stored in the recording layer by recording the interference fringe in the recording layer using the interference fringe formed by coherent light. After that, by irradiating only the light for reproduction, the phase, angle, and intensity information recorded in the recording layer is reproduced, as if the recorded image exists in three dimensions. It gives a virtual image. For example, if an arbitrary image is recorded using this principle, it is possible to reproduce a three-dimensional image like a stereoscopic photograph, and an arbitrary signal obtained by binarizing an arbitrary signal by an arbitrary coding method. If an image signal (for example, a barcode or a two-dimensional barcode) is recorded, arbitrary information can be reproduced as an information recording medium.

  For recording information on the recording layer in the information recording method of the present invention, it is preferable to use a coherent light source as described above. As a light source that can be actually used, a laser principle such as a pulse laser or a continuous wave laser is used. Light source. The wavelength of the light source that can be used is, for example, in the range of 350 nm to 800 nm, preferably in the range of 400 nm to 700 nm, as described for the photosensitive wavelength of the photosensitive recording material. The light source may be a solid laser, a semiconductor laser, a gas laser, or a liquid laser. Preferred laser beams include, for example, a 532 nm YAG laser double wave, a 355 nm YAG laser triple wave, and GaN near 405 to 415 nm. Lasers, 488 nm or 515 nm Ar ion laser, 632 nm or 633 nm HeNe laser, 647 nm Kr ion laser, 694 nm ruby laser, 636 nm, 634 nm, 538 nm, 534 nm, 442 nm HeCd laser, and the like. It is also preferable to use a nanosecond or picosecond order pulse laser.

The information to be recorded is not particularly limited, and may be an image or a signal. As described above, the information to be recorded may or may not be binarized by an arbitrary coding method. In particular, when a binarized signal is reproduced by an arbitrary coding method, it is possible to perform an arbitrary process regarding a decoding process for the reproduced image or signal.
Energy irradiated when recording should be appropriately set to the luminance of the image to be obtained, its intensity, as illuminance on the recording layer surface, and 0.1μW / cm ² ~1.0W / cm ² it is preferred to, more preferably, to ^{1.0μW / cm 2 ~500mW / cm 2} , and particularly preferably to ^{10μW / cm 2 ~100mW / cm 2} . Within the above range, the time required for recording can be sufficiently shortened, so that a practical recording transfer rate can be ensured.

Next, the method for recording information on the holographic recording medium of the present invention will be described in more detail.
In order to record information on the recording layer formed from the holographic recording composition of the present invention, the recording layer is irradiated with information light and reference light to thereby form an interference image (interference fringe) on the recording layer. Then, the interference image can be fixed by irradiating the recording layer with the interference image with fixing light.
Here, as the information light and the reference light, the micro-container wall film is irradiated with light having transparency so that the photosensitive recording material contained in the micro-container is exposed to form an interference image, and then the formed image Can be fixed.

  Thereafter, information can be reproduced by irradiating the formed interference image with reference light. When reading (reproducing) the written information, the recording layer is irradiated with only the reference light in the same arrangement as during recording, and the reproduction light having an intensity distribution corresponding to the optical characteristic distribution formed inside the recording layer is obtained. The light is emitted from the recording layer. In the present invention, as the light for reproducing information, the micro container wall film should be irradiated with light having transparency. In general, since a wavelength longer than the recording wavelength often has transparency, the wavelength of light for reproduction is preferably longer than the recording wavelength. Among them, it is very preferable to use light having the same wavelength as that of the recording light, in particular, the same light source as that of the recording light. In this case, this also leads to simplification of the mechanism of the recording / reproducing apparatus to be used. preferable.

Next, an optical recording / reproducing apparatus suitably used for recording and reproducing information on the holographic recording medium of the present invention will be described with reference to FIG.
The optical recording / reproducing apparatus 100 shown in FIG. 4 maintains a spindle 81 to which the holographic recording medium 20 is attached, a spindle motor 82 that rotates the spindle 81, and the rotational speed of the holographic recording medium 20 at a predetermined value. A spindle servo circuit 83 that controls the spindle motor 82 is provided.

  The optical recording / reproducing apparatus 100 records information by irradiating the holographic recording medium 20 with information light and recording reference light, and irradiates the holographic recording medium 20 with reproduction reference light. A pickup 31 for detecting reproduction light and reproducing information recorded on the holographic recording medium 20, and a drive device 84 that enables the pickup 31 to move in the radial direction of the holographic recording medium 20. I have.

  The optical recording / reproducing apparatus 100 uses a detection circuit 85 for detecting a focus error signal FE, a tracking error signal TE, and a reproduction signal RF from an output signal of the pickup 31, and a focus error signal FE detected by the detection circuit 85. Based on this, the actuator in the pickup 31 is driven to move the objective lens (not shown) in the thickness direction of the holographic recording medium 20 to perform focus servo, and the tracking error detected by the detection circuit 85. Based on the signal TE, an actuator in the pickup 31 is driven to move the objective lens in the radial direction of the holographic recording medium 20 to perform tracking servo, a tracking error signal TE and a controller to be described later. It controls the drive unit 84 based on a command from over La and a slide servo circuit 88 for performing a slide servo for moving the pickup 31 in the radial direction of the holographic recording medium 20.

  The optical recording / reproducing apparatus 100 further decodes the output data of the CMOS or CCD array in the pickup 31 to reproduce the data recorded in the data area of the holographic recording medium 20 or the reproduction signal from the detection circuit 85. A signal processing circuit 89 that reproduces a basic clock from RF and discriminates an address; a controller 90 that controls the entire optical recording / reproducing apparatus 100; and an operation unit 91 that gives various instructions to the controller 90. I have. The controller 90 inputs the basic clock and address information output from the signal processing circuit 89, and controls the pickup 31, spindle servo circuit 83, slide servo circuit 88, and the like. The spindle servo circuit 83 receives the basic clock output from the signal processing circuit 89. The controller 90 includes a CPU (Central Processing Unit), a ROM (Read Only Memory), and a RAM (Random Access Memory), and the CPU executes a program stored in the ROM using the RAM as a work area. The function of the controller 90 can be realized.

  Hereinafter, the present invention will be further described based on examples. However, this invention is not limited to the aspect shown in the Example.

[Production Example 1]
Preparation of micro container As an oil phase component, EO-modified diacrylate of tetrabrominated bisphenol A (New Frontier BR-42M manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.95 g, adduct of trimethylolpropane and xylylene diisocyanate (Takenate D-110N manufactured by Mitsui Takeda Chemical Co., Ltd.) 10 g, 0.05 g of 2-methoxyhexyl paramethoxycinnamate as an ultraviolet absorber, 0.1 g of titanocene compound (Irgacure 784 manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 0.1 g of a surfactant (Takemoto Yushi Co., Ltd., Pionein A41C) was dissolved in 18.4 g of ethyl acetate. As an aqueous phase component, 37.5 g of a 4 mass% aqueous solution of polyvinyl alcohol (PVA205 manufactured by Kuraray) was prepared. The oil phase component and the aqueous phase component were emulsified at 12000 rpm for 10 minutes using a homogenizer. Thereafter, 26 g of purified water was added and stirred at 60 ° C. for 3 hours. The prepared liquid was observed with an inspection optical microscope (ECLIPSE E600PL manufactured by Nikon Corporation), and it was confirmed that spherical micro-containers were dispersed in the liquid. When this dispersion was analyzed using a laser particle size analyzer (LA-920, manufactured by Horiba, Ltd.), the average particle size was 0.35 μm. The aqueous dispersion of the micro container thus obtained was transferred to an aluminum bat and heated for one day in an oven at 60 ° C. to remove moisture, thereby obtaining 12 g of a block-shaped solid of the micro container that was dried. All of the above work was performed under safelight.

[Production Example 2]
An aqueous dispersion of a spherical micro container was obtained in the same manner as in Production Example 1 except that 2-ethylhexyl paramethoxycinnamate was not added. When this dispersion was analyzed using a laser particle size analyzer (LA-920, manufactured by Horiba, Ltd.), the average particle size was 0.37 μm. The aqueous dispersion of the micro container thus obtained was transferred to an aluminum bat and heated for one day in an oven at 60 ° C. to remove moisture, thereby obtaining 12 g of a block-shaped solid of the micro container that was dried. All of the above work was performed under safelight.

[Production Example 3]
An aqueous dispersion of a spherical micro container was obtained in the same manner as in Production Example 1 except that 5,10,15,20-tetraphenylporphyrin zinc complex was used as the ultraviolet absorber. When this dispersion was analyzed using a laser particle size analyzer (LA-920 manufactured by Horiba, Ltd.), the average particle size was 0.32 μm. The aqueous dispersion of the micro container thus obtained was transferred to an aluminum bat and heated for one day in an oven at 60 ° C. to remove moisture, thereby obtaining 12 g of a block-shaped solid of the micro container that was dried. All of the above work was performed under safelight.

[Example 1]
Preparation of Volume Hologram Recording Composition As a matrix binder precursor, 5 g of polyethylene glycol diacrylate (Aronics M-260 manufactured by Toagosei Co., Ltd., viscosity at 25 ° C .: 100 cps), 10 g of polyester diacrylate (manufactured by Toagosei Co., Ltd.) Aronics M-6200, viscosity at 25 ° C .: 2400 cps), 0.9 g of ethyl-2,4,6-trimethylbenzoylethoxyphenyl osphine oxide (Lucirin LR 8893 manufactured by BASF Corporation) as a photopolymerization initiator, and further mixed Then, 10 g of the micro container containing the recording material prepared in Production Example 1 was added, and the mixture was stirred and mixed until there was no lump. The liquid of the obtained composition was poured into a space of a glass cell composed of two glass plates having a thickness of 5 cm square and a thickness of 1.0 mm, which were overlapped through a 500 μm PET resin spacer, and a UV lamp (wavelength 365 nm) was irradiated for 10 seconds (light quantity 100 mJ / cm ² ) to obtain a recording medium. The composition after irradiation was completely adhered to the substrate and cured.

Evaluation of Volume Hologram Recording Medium Two-beam interference fringe recording based on Japanese Industrial Standards Committee TR Z 0019: 2002 “Hologram Recording Material—Photopolymer Optical Characteristic Measurement Method” provided in the form of a vibration isolator for optical measurement Using a measurement device, an Nd ³⁺ YAG laser (wavelength 532 nm) is a light source for recording measurement, a HeNe laser (wavelength 630 nm) is a probe light source for detection, and interference fringes are set so that the total irradiation amount on the medium surface is 1000 mJ / cm ^2. Exposure was performed. As a result, it was possible to obtain a diffraction efficiency of 2% in the probe light for detection from the recording medium of this example.

[Example 2]
As a matrix binder precursor in Example 1, 15 g of polypropylene glycol diglycidyl ether (Epolite 400P manufactured by Kyoeisha Chemical Co., Ltd., viscosity at 25 ° C .: 15 cps), 0.9 g of triphenylsulfonium hexafluorophosphate as a photopolymerization initiator (Tokyo) A recording medium injected into a glass cell was obtained in the same manner as in Example 1 except that the reagent purchased from Kasei Kogyo Co., Ltd. was used. The composition after irradiation was completely adhered to the substrate and cured.
As a result of evaluating the obtained recording medium in the same manner as in Example 1, it was possible to obtain a diffraction efficiency of 2% in the probe light for detection.

[Comparative Example 1]
Preparation of Volume Hologram Recording Composition As a matrix binder precursor, 5 g of polyethylene glycol diacrylate (Aronics M-260 manufactured by Toagosei Co., Ltd., viscosity at 25 ° C .: 100 cps), 10 g of polyester diacrylate (manufactured by Toagosei Co., Ltd.) Aronics M-6200, viscosity at 25 ° C .: 2400 cps), 0.9 g of ethyl-2,4,6-trimethylbenzoylethoxyphenyl osphine oxide (Lucirin LR 8893 manufactured by BASF Corporation) as a photopolymerization initiator, and further mixed , EO-modified diacrylate of tetrabrominated bisphenol A (New Frontier BR-42M manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), adduct of trimethylolpropane and xylylene diisocyanate (Mitsui Takeda Chemical) Takenate D-110N manufactured by Co., Ltd.) 0.83 g, 0.05 g of 2-ethylhexyl paramethoxycinnamate as an ultraviolet absorber, and 0.1 g of titanocene compound (Irgacure 784 manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator Mix until dissolved. The obtained composition was used as a recording medium in the same manner as in Example 1. The composition after irradiation was completely cured.

Evaluation of Volume Hologram Recording Medium When the obtained recording medium was evaluated in the same manner as in Example 1, no diffracted light was obtained in the detection probe light (diffraction efficiency 0%).

[Comparative Example 2]
Preparation of Volume Hologram Recording Composition As a matrix binder precursor, 39 g of a prepolymer composed of diisocyanatodicyclohexylmethane and polytetrahydrofuran (Baytec WE-180 manufactured by Bayer) and polypropylene oxide triol (Accor MN- manufactured by Mitsui Chemicals Polyurethane) 1000) 55 g, tribromophenyl acrylate (New Frontier BR-30 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 3.5 g, titanocene compound (Irgacure 784 manufactured by Ciba Specialty Chemicals) 0.79 g, dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.) )), 2,6-di-t-butylphenol (purchased as a reagent from Kanto Chemical Co., Ltd.) 0.02 g, ditertiary butyl peroxide (Tokyo Chemical Industry Co., Ltd.) (Purchased as a reagent) 0.03 g was uniformly mixed and poured onto a glass substrate in the same manner as in Example 1. As a result, the solution spontaneously generated heat and cured without waiting for light irradiation. It took 35 minutes to peel off the glass plates.

Evaluation of Volume Hologram Recording Medium When the obtained recording medium was evaluated in the same manner as in Example 1, a diffraction efficiency of 2% was obtained in the detection probe light.

[Comparative Example 3]
Preparation of volume hologram recording composition Polypropylene glycol diglycidyl ether 15 g (Epolite 400P manufactured by Kyoeisha Chemical Co., Ltd., viscosity at 25 ° C .: 40 cps) as a matrix binder precursor, from dodecenyl succinic anhydride (Tokyo Chemical Industry Co., Ltd.) Purchased as a reagent, viscosity at 25 ° C .: 60 cps), except for using 2,4,6-tris (dimethylaminomethyl) phenol (purchased as a reagent from Tokyo Chemical Industry Co., Ltd.) as a curing catalyst In the same manner as in Example 1, a volume hologram recording composition was prepared. An attempt was made to produce a recording medium using the obtained composition in the same manner as in Example 1, but the composition did not cure even after light irradiation. Therefore, the newly prepared composition was heated in an oven at 80 ° C. for 6 hours without light irradiation. As a result, the composition was completely cured and a recording medium could be obtained.
When the obtained recording medium was evaluated in the same manner as in Example 1, it was possible to obtain a diffraction efficiency of 2% in the detection probe light.

[Comparative Example 4]
As a matrix binder precursor, dodecyl acrylate (Kyoeisha Chemical Co., Ltd. light acrylate LA, viscosity at 25 ° C .: 5 cps), polyester diacrylate 10 g (Toagosei Co., Ltd. Aronics M-6200, viscosity at 25 ° C .: 2400 cps) The composition was prepared in the same manner as in Example 1 except that the above was used, and a recording medium was produced. As in Example 1, a recording medium in which the composition was completely cured could be obtained. .
When the obtained recording medium was evaluated in the same manner as in Example 1, it was possible to obtain only a diffraction efficiency of 0.1% in the detection probe light.

[Comparative Example 5]
A composition was prepared in the same manner as in Example 1 except that the micro container manufactured in Production Example 2 was used, and a recording medium was produced. As in Example 1, the composition was completely cured. The medium could be obtained.
When the obtained recording medium was evaluated in the same manner as in Example 1, diffracted light could not be obtained from the detection probe light (diffraction efficiency 0%).

[Comparative Example 6]
A composition was prepared in the same manner as in Example 1 except that the micro container manufactured in Production Example 3 was used, and a recording medium was produced. As a result, the recording medium was completely cured as in Example 1. Could get.
The obtained recording medium was evaluated in the same manner as in Example 1. As a result, the diffraction efficiency in the detection probe light was 1%.

Confirmation of the partition properties of the micro container In order to confirm that the micro container has the desired partition properties, first, the micro container is dispersed and mixed in the matrix binder precursor composition to be used, and is sufficiently shielded from light for 2 hours. The matrix binder was sufficiently agitated in a state where it was not photocured, and then the supernatant obtained by sedimenting the microvessel using a centrifuge was taken and analyzed by liquid chromatography. The micro container and the matrix binder precursor were mixed in a combination and mass ratio of the above examples and comparative examples. During the analysis, the presence or absence of a photopolymerizable monomer and a photopolymerization initiator contained in the micro container was confirmed. The results are shown in Table 1 below. However, Comparative Examples 1 and 2 were not confirmed because they did not contain a micro container.

Confirmation of selective blocking property and permselectivity of micro container In order to confirm that micro container has desired selective blocking property and permselectivity, light for duranium (wavelength 365 nm) and recording are directly applied to micro container. The light (wavelength 532 nm) was irradiated at an irradiation dose of 20 J / cm ² , and then the light-irradiated micro-container was dispersed in ethyl acetate and stirred for 2 hours to extract the extracted light. The polymerizable monomer and the photopolymerizable initiator were quantified by liquid chromatography. Table 2 below shows the results of expressing the quantified increase / decrease of the two components as a percentage of the amount before irradiation.

[Example 3]
A bar coater (# 30) was set in an automatic coating machine (G-7 manufactured by Techno Supply Co., Ltd.), and the composition of Example 1 was prepared from a polyethylene terephthalate (PET) resin sheet (manufactured by FUJIFILM Corporation, Product name: Fujitac, 150 μm thick). Immediately after coating, the entire surface was irradiated with light for 10 seconds using a UV lamp (wavelength 365 nm) (light quantity 100 mJ / cm ² ), and as a result of film hardening, a recording layer having a smooth surface hardened on the PET sheet. (Photosensitive composition) was obtained.

[Comparative Example 7]
Except that the composition of Comparative Example 2 was used as the composition, coating and hardening treatment were performed on the PET resin in the same manner as in Example 5. However, spontaneous curing occurred during coating and the bar coater was fixed. However, the application could not be completed.

Evaluation Results As shown in Table 1, the partition walls of the micro container manufactured in Production Example 1 were extremely good. Further, as shown in Table 2, when the micro-container manufactured in Production Example 1 was irradiated with light for hardening, a photosensitive recording material (photopolymerizable monomer and photopolymerization initiator) contained in the micro-container was used. Was hardly consumed. From this result, it was shown that the micro container wall membrane manufactured in Production Example 1 is impermeable to the light for dura mater. On the other hand, as shown in Table 2, when the micro container manufactured in Production Example 1 was irradiated with recording light, almost all of the photopolymerizable monomer and all of the photopolymerization initiator were consumed. From this result, it was shown that the micro container wall film produced in Production Example 1 has transparency to recording light.
On the other hand, in Comparative Example 1, the recording layer was formed using the composition in which the photosensitive recording material was not encapsulated in the micro container but dispersed in the photocurable matrix binder precursor. The diffraction efficiency was lowered due to consumption of the photosensitive recording material.
Comparative Example 2 was a sample in which a recording layer was formed using the spontaneous heat generation of the matrix binder precursor, and Comparative Example 3 was subjected to film hardening by heating using a thermosetting matrix binder precursor. It is a sample. In any case, it took a long time for the dura mater as compared with the dura treatment by light irradiation.
In Comparative Example 4, the partition wall property of the micro container wall film was insufficient, the photopolymerization initiator contained in the micro container leaked to the outside, and the photopolymerization initiator concentration inside the micro container decreased, so that the recording performance was The diffraction efficiency decreased, and sufficient diffraction efficiency could not be obtained. In Comparative Example 4, the reason why the partition wall of the micro container wall film was insufficient was that dodecyl acrylate permeated the wall film of the micro container and caused the wall film to swell and extract substances inside the micro container. It is thought that there is.
Comparative Example 5 is a sample in which a recording layer was formed using the composition containing the micro container produced in Production Example 2. As shown in Table 2, in the micro container manufactured in Manufacturing Example 2, since the light for the dura was transmitted through the micro container wall film and the photosensitive recording material contained in the micro container was consumed, interference fringes were formed in the recording layer. It was not possible to obtain diffracted light capable of forming
Comparative Example 6 is a sample in which a recording layer was formed using the composition containing the micro container manufactured in Manufacturing Example 3. As shown in Table 2, since the micro container manufactured in Manufacturing Example 3 does not have sufficient transparency for recording light, interference fringe formation by light irradiation cannot be performed satisfactorily. High diffraction efficiency could not be obtained.
Further, as shown in Example 3, the composition of Example 1 was excellent in suitability for the coating process and suitable for continuous production.
On the other hand, as shown in Comparative Example 7, the composition of Comparative Example 2 was unsuitable for continuous production because it was cured during coating.
The results of diffraction efficiency in the examples were almost the same as the results of Comparative Examples 2 and 3 used as known materials. Thereby, it was shown that this invention has the industrial advantage by coexisting quick continuous production and the performance equivalent to the conventional material. On the other hand, the media of Comparative Examples other than Comparative Examples 2 and 3 are inferior to Comparative Examples 2 and 3, and although some effects are recognized in terms of rapid production, they are inferior to conventional materials. It lacked industrial advantage.

  According to the holographic recording composition of the present invention, volume holographic recording media can be continuously mass-produced.

It is a schematic sectional drawing which shows an example of the holographic recording medium concerning 1st embodiment. It is a schematic sectional drawing which shows an example of the holographic recording medium concerning 2nd embodiment. It is explanatory drawing which shows an example of the optical system which can be used for recording and reproduction | regeneration of the information to a holographic recording medium. It is a block diagram showing an example of the whole structure of the recording / reproducing apparatus used suitably for the recording and reproduction | regeneration of the information to the holographic recording medium of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Lower substrate 2 Reflective film 3 Servo pit pattern 4 Recording layer 5 Upper substrate 6 Filter layer 7 Second gap layer 8 First gap layer 12 Objective lens 13 Dichroic mirror 14 Detector 15 1/4 wavelength plate 16 Polarizing plate 17 Half Mirror 20 Holographic recording medium 21 Holographic recording medium 22 Holographic recording medium 31 Pickup 81 Spindle 82 Spindle motor 83 Spindle servo circuit 84 Drive device 85 Detection circuit 86 Focus servo circuit 87 Tracking servo circuit 88 Slide servo circuit 89 Signal processing circuit 90 Controller 91 Scanning unit 100 Optical recording / reproducing device A Input / output surface FE Focus error signal TE Tracking error signal RF reproduction signal

Claims (4)

For holographic recording comprising a photopolymerizable matrix binder precursor, a photopolymerization initiator that can be excited by light irradiation to initiate a polymerization reaction of the photopolymerizable matrix binder precursor, and a photosensitive recording material enclosed in a micro container A composition comprising:
The micro container is
It is impervious to at least a part of light contained in a wavelength range capable of exciting the photopolymerization initiator, and at least a part of light contained in a wavelength range capable of exposing the photosensitive recording material. The said composition for holographic recording which has a wall film which has permeability | transmittance with respect. A holographic recording medium having a recording layer formed from the holographic recording composition according to claim 1. A method for producing a holographic recording medium according to claim 2,
The said manufacturing method including superposing | polymerizing a photopolymerizable matrix binder precursor with respect to the composition for holographic recording of Claim 1 by irradiating the light which the said micro container wall film has impermeability. . An information recording method for recording information on a recording layer by irradiating the holographic recording medium according to claim 2 with light having transparency through the wall of the micro container.

Images