JP2908189B2 - Information recording apparatus and information recording / reproducing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical sensor capable of recording optical information on an information recording medium in the form of visible information or electrostatic information, an information recording apparatus comprising the optical sensor and the information recording medium, and The present invention relates to an information recording / reproducing method, and more particularly to an improvement of an optical sensor suitable for recording information on an information recording medium having a polymer dispersed liquid crystal as an information recording layer.

[0002]

2. Description of the Related Art In the conventional electrophotographic technique, there is known an information recording medium in which a liquid crystal cell in which a nematic liquid crystal is sealed on a photoconductive layer and an insulating layer for liquid crystal alignment are sequentially laminated between a pair of electrodes. It is known that a liquid crystal is aligned by lowering the resistance of a photoconductive layer in an information exposure section by applying information while a voltage is applied between the electrodes, and obtaining a visible image using a deflecting plate.

This information recording medium needs to be formed into cells in order to enclose the liquid crystal. In addition, in order to perform twist nematic alignment at the initial stage, an insulating film in which both surfaces of the cells are subjected to an alignment treatment by rubbing treatment or the like is provided. In order to keep the gap constant, it is necessary to mix spacers, so that a high-resolution image cannot be obtained. In addition, there is an optical problem because a rigid and transparent support is required for producing a gap or a cell.
Further, there is a problem that the alignment treatment in the initial state cannot be detected unless a polarizing plate is used for reading.

The inventor of the present invention has disclosed an optical sensor comprising a photoconductive layer having an electrode layer provided on the front surface thereof, and a polymer-dispersed liquid crystal layer having an electrode layer provided on the rear surface facing the optical sensor. The recording medium is placed on the optical axis and exposed while applying a voltage between the two conductive layers.The liquid crystal layer is oriented according to the incident optical image to record information. An information recording / reproducing method for reproducing as visible information by light has been filed (Japanese Patent Application Nos. 2-18623 and 3-10847). This information recording / reproducing method
The liquid crystal cell is capable of visualizing recorded information without using a polarizing plate. However, when a vinyl chloride resin or a vinyl acetate resin is used as a binder resin in the charge generation layer as an optical sensor used for recording information on this type of information recording medium, a recorded portion and an unrecorded portion are used. Has low contrast potential, and has a certain problem in the information forming ability of the optical sensor.

The present invention relates to an optical sensor used for forming information on an information recording medium having a liquid crystal phase and a resin phase as an information recording layer. The optical sensor has excellent information forming ability and improved information recording sensitivity. Another object is to provide an information recording apparatus and an information recording / reproducing method.

[0006]

[0007]

According to a first information recording apparatus of the present invention, a charge generation layer and a charge transport layer are sequentially provided on an electrode layer, and the charge generation layer comprises a polyvinyl chloride component and a polyvinyl acetate. A polyvinyl chloride component in the resin binder from 15% by weight to 68% by weight.
And the following general formula (1)

Embedded image (However, X in the formula may be the same or different selected from hydrogen, lower alkyl group, lower alkoxy group, nitro group, sulfonic acid group, hydroxyl group, carboxyl group, halogen atom, and n is 0 to 3 And R is an optionally substituted hydrocarbon ring group, heterocyclic group or alkyl group.) And an information recording layer on the electrode layer. A laminated information recording medium, wherein the information recording layer is an information recording medium comprising a liquid crystal phase and a resin phase, and at least one electrode layer is disposed on the optical axis as a transparent electrode layer via a spacer so as to face each other. The electrode layers are connected so that a voltage can be applied.

A second information recording apparatus according to the present invention is an information recording medium in which a charge generation layer, a charge transport layer, a dielectric layer, an information recording layer, and an electrode layer are sequentially provided on an electrode layer. Wherein the electrode is transparent, and the charge generation layer is a resin binder comprising a polyvinyl chloride component and a polyvinyl acetate component, wherein the polyvinyl chloride component is contained in the resin binder in an amount of 15% by weight to 68% by weight. And a charge generation material represented by the above general formula (1), and the information recording layer comprises a liquid crystal phase and a resin phase, and is connected between both electrode layers so that a voltage can be applied. And

In the information recording / reproducing method in the first and second information recording apparatuses, information is recorded by exposing the information while applying a voltage between the two electrodes, and orienting the liquid crystal phase according to the information. It is characterized in that information recording is reproduced as visible information by transmitted light or reflected light.

First, an optical sensor according to the present invention will be described. FIG. 1A is a diagram for schematically explaining the optical sensor by a cross-sectional view thereof, and FIG. 1B is a diagram showing another embodiment, in which 13 is an electrode layer, 14 ′ is a charge generation layer, 14 "is a charge transport layer, 15 is a substrate, and 17 is a charge injection control layer.

The charge generation layer 14 'and the charge transport layer 14 "are photoconductive layers, and when irradiated with light, photo carriers (electrons and holes) are generated in the irradiated portion, and the carriers move through the layer width. This is a conductive layer which can be formed, and is a layer whose effect is particularly remarkable when an electric field is present. The charge generation layer and the charge transport layer are sequentially laminated on the electrode layer.

The charge generation layer comprises a binder resin and a charge generation substance. Examples of the charge generating substance include quinone, azo, bisazo, trisazo, phthalocyanine, acid xansen dye, cyanine, styryl dye, pyrylium dye, perylene, methine, a-selenium, and a-. Silicon, azulhenium salt-based, squarium salt-based and the like can be mentioned, and they can be used alone or in combination.

Particularly, bisazo-based charge generating substances are preferable, and particularly, the following general formula (1):

[0014]

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(Wherein X in the formula may be the same or different selected from hydrogen, lower alkyl group, lower alkoxy group, nitro group, sulfonic group, hydroxyl group, carboxyl group, halogen atom, and n is An integer of 0 to 3 and R is a hydrocarbon ring group, a heterocyclic group, or an alkyl group which may be substituted.), And electrostatic information corresponding to the information pattern can be obtained with high sensitivity. In addition, not only can the charge-holding medium be provided with a high contrast ratio, but even after the formation of the photoconductive layer, the dark potential does not increase, so that the contrast ratio has excellent stability over time. .

Such a bisazo compound is exemplified below by a combination of the respective substituents in the general formula (1).

[0017]

[Table 1]

Preferred examples of the bisazo compound are shown below.

[0019]

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Next, the binder resin in the charge generation layer, which is a feature of the present invention, will be described. The binder resin includes a polyvinyl chloride component and a polyvinyl acetate component, and the polyvinyl chloride component is contained in the resin binder at a ratio of 15% by weight to 68% by weight. When the content ratio of the polyvinyl chloride component is in this range, the detailed reason is unknown, but the information recording layer is composed of a liquid crystal phase and a resin phase, and the information recording medium for recording information by the orientation of the liquid crystal phase is required. It has been found that when used for information recording, the optical sensor can have a large contrast potential.

The polyvinyl chloride component and the polyvinyl acetate component may be polyvinyl chloride or a mixture of a vinyl chloride-vinyl acetate copolymer and polyvinyl acetate, or may contain 15% by weight of the polyvinyl chloride component. It may be a vinyl chloride-vinyl acetate copolymer containing at a ratio of about 68% by weight. The polyvinyl chloride, polyvinyl acetate, and vinyl chloride-vinyl acetate copolymer used preferably have an average molecular weight of 1,000 to 100,000 from the viewpoint of applicability.

Further, an electron accepting substance may be added to the charge generating layer. 2,4,7-
Trinitrofluorenone, tetrafluoro-P-benzoquinone, tetracyanoquinodimethane, triphenylmethane, maleic anhydride, hexacyanobutadiene and the like can be used.

The binder resin can be used in a ratio of 0.1 to 10 parts by weight, preferably 0.3 to 1 part by weight, based on 1 part by weight of the charge generating substance. The electron accepting substance is contained in an amount of 0.001 to 1 part by weight of the charge generating substance.
It can be used in a proportion of 10 to 10 parts by weight.

The charge generation layer is formed by dissolving or dispersing the binder resin, the charge generation substance, and the electron accepting substance in a solvent, coating the mixture on an electrode, and drying. Examples of the solvent include dichloroethane, 1,1,2-trichloroethane, monochlorobenzene, tetrahydrofuran, cyclohexane, dioxane, 1,2,3-trichloropropane, ethyl cellosolve, 1,1,1, -trichloroethane, methyl ethyl ketone, chloroform, toluene and the like. Examples of the application method include a blade coating method, a dipping method, and a spinner coating method. The charge generation layer has a thickness of 0.01 μm to 1 after drying.
μm, preferably 0.1 μm to 0.3 μm.

Next, the charge transport layer will be described. The charge transport layer comprises a binder resin and a charge transporting substance.
The charge transporting substance is a substance having an excellent property of transporting charges generated in the charge generating layer under voltage application conditions, such as hydrazone, pyrazoline, styryl, stilbene, butadiene, azine, and enacine. Azole-based, PVK-based, carbazole-based, oxazole-based, triazole-based, aromatic amine-based, amine-based, triphenylmethane-based, and polycyclic aromatic compound-based compounds. Substances can also be used.

Among them, the compound number (2
Those of 4) to (33) are preferred. In the formula, Me represents a methyl group, Et represents an ethyl group, Pr represents an n- (or iso-) propyl group, and Bu represents an n- (or iso-, t-) butyl group.

[0027]

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[0028]

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As the binder resin, silicone resin, styrene-butadiene copolymer resin, epoxy resin, acrylic resin, saturated or unsaturated polyester resin,
Polycarbonate resin, polyvinyl acetal resin, phenol resin, polymethyl methacrylate (PMM
A) Resin, melamine resin, polyimide resin, vinyl chloride resin, vinyl acetate resin, etc., and it is preferable to use 0.05 to 1 part by weight based on 1 part by weight of the charge transporting substance. still,
A binder is not required when the binder itself serves as a charge transport material.

The charge transporting layer may contain the electron accepting substance described in the section of the charge generating layer in the same manner as the charge transporting substance in an amount of 0.001 to 10 parts by weight per 1 part by weight of the charge transporting substance. They can be blended in proportions. The charge transporting layer, the charge transporting substance, the binder resin, the electron accepting substance is dissolved or dispersed in the same solvent as described in the section of the charge generating layer, and coated on the charge generating layer by the same coating method, After a drying step, the film is formed to have a thickness of 1 to 50 μm after drying.

Next, the charge injection control layer will be described.
The charge injection control layer is provided, if necessary, between the electrode 13 and the charge generation layer 14 '. An optical sensor is disposed so as to face an information recording medium described later, and information exposure is performed while applying a voltage between both electrodes. In recording information on the information recording medium, the voltage applied to the information recording medium is adjusted by controlling the charge injection property or the charge injection prevention property from the electrode 13 to the charge generation layer 14 'in the optical sensor. It is provided for the purpose of doing so.

The purpose of providing such a charge injection control layer is as follows.
In particular, in the case of a polymer-dispersed liquid crystal layer as described later, it is necessary to set the sensitivity of the optical sensor in the operating voltage region of the liquid crystal. In such a case, the optical sensor and the information recording medium are required. When the information exposure is performed while applying a voltage between the potential and the potential (bright potential) applied to the information recording medium in the exposed portion and the potential applied to the information recording medium in the unexposed portion, that is, when the information is not exposed. Nevertheless, the phenomenon that charges move in the photosensitive layer as if they were exposed (dark potential)
(Contrast potential) must be large in the operating region of the liquid crystal in the information recording medium.

Therefore, it is necessary to match the sensor characteristics of the optical sensor with the characteristics of the information recording medium. For example, when the operating potential of the liquid crystal is low, it is necessary to lower the dark potential of the optical sensor. When the operating potential is high, there may be a dark potential in the optical sensor as long as the operating potential is lower than the operating potential of the liquid crystal. The charge injection control layer is appropriately provided depending on the characteristics of the information recording medium.

When it is necessary to keep the dark potential of the optical sensor low, a charge injection prevention layer is provided between the electrode 13 and the charge generation layer 14 '. There are two types of charge injection preventing layers, a layer using a so-called tunneling effect and a layer using a rectifying effect.

The layer utilizing the tunneling effect is formed of, for example, a single layer such as an inorganic insulating film, an organic insulating polymer film, an insulating monomolecular film, or the like, or a laminate of these layers. For example, As ₂ O ₃ , B ₂ O ₃ , Bi ₂ O ₃ , CdS, Ca
_{O, CeO 2, Cr 2 O} 3, CoO, GeO 2, HfO 2, Fe 2 O 3, La
₂ O ₃ , MgO, MnO ₂ , Nd ₂ O ₃ , Nb ₂ O ₅ , PbO, Sb ₂ O ₃ , Si
_{O 2, SeO 2, Ta 2} O 5, TiO 2, WO 3, V 2 O 5, Y 2 O 5, Y 2 O 3, Zr
O ₂ , BaTiO ₃ , Al ₂ O ₃ , Bi ₂ TiO ₅ , CaO-SrO, CaO-Y ₂ O ₃ ,
_{Cr-SiO, LiTaO 3, PbTiO} 3, PbZrO 3, ZrO 2 -Co, ZrO 2 -SiO
_{2, AlN, BN, NbN,} Si 3 N 4, TaN, TiN, VN, ZrN,
SiC, TiC, WC, Al ₄ C _{3 and the} like are formed by glow discharge, vapor deposition, sputtering and the like. The thickness of this layer is determined for each material used in consideration of the insulating property for preventing charge injection and the tunnel effect.

The charge injection preventing layer utilizing the rectifying effect is provided with a charge transporting layer having a charge transporting ability of a polarity opposite to that of the electrode substrate utilizing the rectifying effect. That is, such a charge injection prevention layer is formed of an inorganic photoconductive layer, an organic photoconductive layer, and an organic-inorganic hybrid photoconductive layer, and has a thickness of about 0.1 to 10 μm. Specifically, when the electrode is set to minus, amorphous silicon photoconductive layer doped with B, Al, Ga, In, etc., amorphous selenium, or oxadiazole, pyrazoline, polyvinylcarbazole,
Organic photoconductive layer formed by dispersing stilbene, anthracene, naphthalene, tridiphenylmethane, triphenylmethane, azine, amine, aromatic amine and the like in a resin,
If the electrode is set to positive, P, N, As, S
An amorphous silicon photoconductive layer doped with b, Bi, or the like, a ZnO photoconductive layer, or the like is formed by a method such as glow discharge, vapor deposition, sputtering, CVD, or coating. These photoconductive layers need to be formed of a photoconductive material that generates carriers having the same polarity on the electrode side. B, Al, Ga, I
When the silicon photoconductive layer doped with n or the like and the electrode is positive, the silicon photoconductive layer doped with P, N, As, Sb, Bi, etc., the selenium photoconductive layer, the organic photoconductive layer, etc. are glow-discharged and deposited. , Sputtering, CVD, coating and the like.

The electrode layer 13 needs to have transparency if the information recording medium described later is opaque. If the information recording medium has transparency, it may be transparent or opaque. Is a metal thin film conductive film, an inorganic metal oxide conductive film, an organic conductive film such as a quaternary ammonium salt or the like having a resistivity of 10 ⁶ Ω · cm or less. The electrode layer 13 is formed by a method such as vapor deposition, sputtering, CVD, coating, plating, dipping, and electrolytic polymerization. Further, the film thickness needs to be changed depending on the electric characteristics of the material constituting the electrode and the applied voltage at the time of information recording. For example, the thickness of the ITO film is about 100 to 3000 °, and the entire surface between the photoconductive layer and Alternatively, it is formed according to the formation pattern of the information recording layer.

The substrate 15 includes a card, a film, a tape,
This optically supports an optical sensor having a shape such as a disk. If the photoconductive layer itself has a supporting property, it is not necessary to provide the photoconductive layer. However, as long as the photoconductive layer has a certain strength capable of supporting the photoconductive layer, its material and thickness are not particularly limited. For example, a flexible plastic film or a rigid body such as glass, a plastic sheet, or a card is used.

If the electrode layer 13 is transparent, a layer having an antireflection effect may be laminated on the other surface of the substrate on which the electrode layer 13 is provided, or an antireflection effect may be obtained. It is advisable to adjust the transparent substrate to a film thickness that can be adjusted, or to provide an antireflection property by combining the two.

Next, a first information recording apparatus according to the present invention will be described. FIG. 2 is a diagram for schematically explaining an aspect of the first information recording apparatus by a cross section thereof. The information recording medium 3 in which an information recording layer 11 and an electrode layer 13 'are sequentially laminated.
And the above-described optical sensor 1 are disposed to face each other via a spacer 19, and both electrodes are connected so that a voltage can be applied.

The information recording medium 3 will be described. As the information recording medium in the invention, it is preferable that the information recording layer is a polymer dispersed liquid crystal composed of a liquid crystal phase and a resin phase.

As the liquid crystal forming the liquid crystal phase, a smectic liquid crystal, a nematic liquid crystal, a cholesteric liquid crystal, or a mixture thereof can be used. From the viewpoint of, it is preferable to use a smectic liquid crystal.

Examples of the smectic liquid crystal include a liquid crystal material exhibiting a smectic A phase such as a cyanobiphenyl-based, cyanoterphenyl-based, phenylester-based, and fluorine-based one having a long carbon chain at a terminal group of a substance exhibiting liquid crystallinity. A liquid crystal material exhibiting a smectic C phase used as a liquid crystal;
Alternatively, a liquid crystal substance exhibiting smectic H, G, E, F, or the like can be given.

A nematic liquid crystal may be used, and the memory property can be improved by mixing with a smectic or cholesteric liquid crystal. For example, Schiff base type, azoxy type, azo type, phenyl benzoate type, Cyclohexylic acid phenyl ester type, biphenyl type, terphenyl type, phenylcyclohexane type,
Known nematic liquid crystals such as phenylpyridine, phenyloxazine, polycyclic ethane, phenylcyclohexene, cyclohexylpyrimidine, phenyl and tolane can be used. Further, a mixture obtained by mixing a polyvinyl alcohol or the like with a liquid crystal material to form a microcapsule can also be used. When a liquid crystal material is selected, a material having a different direction of the refractive index is preferable because contrast can be obtained.

As a material for forming the resin phase, for example,
UV-curable resins that are compatible with the liquid crystal material in the form of monomers or oligomers, or monomers,
Those having compatibility with a liquid crystal material and a common solvent in an oligomer state can be preferably used. Examples of such UV-curable resins include acrylic acid esters and methacrylic acid esters, and in the form of monomers and oligomers, for example, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, polypropylene glycol Polyfunctional monomers such as diacrylate, isocyanuric acid (ethylene oxide-modified) triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, etc. or polyfunctional urethanes, esters Oligomer, nonylphenol-modified acrylate, N-vinyl-2-pyrrolidone, 2-hydroxy-3-phenoxy Monofunctional monomers or oligomers such as acrylate and the like.

The solvent is not particularly limited as long as it is a common solvent, and examples thereof include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as chloroform, and methyl cellosolve. Examples thereof include alcohol derivative solvents and ether solvents represented by dioxane.

The photo-curing agent which can be used for curing the ultraviolet-curable resin is, for example, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one (“Darocur 1173” manufactured by Merck) and 1-hydroxycyclohexylphenyl ketone (“Irgacure 18” manufactured by Ciba Geigy)
4 "), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (" Darocure 1116 "manufactured by Merck), benzyldimethyl ketal (" Irgacure 651 "manufactured by Ciba-Geigy), 2-
Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (“Irgacure 907” manufactured by Ciba-Geigy) and 2,4-diethylthioxanthone (“Kayacure DETX” manufactured by Nippon Kayaku Co., Ltd.) Ethyl p-dimethylaminobenzoate (Kayacure E manufactured by Nippon Kayaku Co., Ltd.
PA ") and isopropylthioxanthone (" Kuntacure ITX "manufactured by Ward Brekinsop Co., Ltd.) and p
A mixture with ethyl dimethylaminobenzoate, and the like, but 2-hydroxy-2-methyl-1-
Phenylpropan-1-one is particularly preferred in terms of compatibility with liquid crystal materials, polymer-forming monomers or oligomers.

The content ratio of the liquid crystal material and the resin is such that the content of the liquid crystal is 10% by weight to 90% by weight, preferably 40% by weight.
The amount is preferably 80% by weight, and if it is less than 10% by weight, the light transmittance is low even if the liquid crystal phase is oriented by information recording, and if it exceeds 90% by weight, phenomena such as oozing of the liquid crystal may occur. This causes image unevenness, which is not preferable. When a large amount of liquid crystal is present in the information recording layer, the contrast ratio can be improved and the operating voltage can be reduced.

The information recording layer is formed by applying a mixed solution of a resin forming material and a liquid crystal, a photo-curing agent or the like dissolved or dispersed in a solvent onto the electrode layer using a blade coater, a roll coater, or a spin coater. Apply by method,
It is formed by curing with light or heat. If necessary, a leveling agent may be added to improve the applicability of the solution and improve the surface properties.

In forming the information recording layer, it is necessary to heat the mixed solution to a temperature higher than the temperature at which the liquid crystal maintains an isotropic phase, and to completely dissolve the liquid crystal and the ultraviolet-curable resin-forming material. An information recording layer in which the resin phase and the liquid crystal phase are uniformly dispersed can be obtained. When the information recording layer is cured with ultraviolet light at a temperature lower than the temperature at which the liquid crystal exhibits an isotropic phase, there is a problem that the phase separation between the liquid crystal and the ultraviolet-curable resin material is increased. That is, the liquid crystal domain grows too much, the skin layer is not completely formed on the surface of the information recording layer, and the liquid crystal seeps out, or the ultraviolet curable resin is matted, making it difficult to capture information accurately. Undesirably, the ultraviolet curable resin may not be able to hold the liquid crystal and may not even form the information recording layer. On the other hand, when heating is necessary to maintain the isotropic phase when evaporating the solvent, there is a problem that the wettability to the electrode layer is particularly reduced, and a uniform information recording layer cannot be obtained.

It is preferable to add a fluorine-based surfactant to the information recording layer for the purpose of maintaining the wettability to the electrode layer. Examples of such a fluorine-based surfactant include Florad FC-430, Florad FC-431, and N- (n-propyl) -N- (β-acryloxyethyl) -perfluoro manufactured by Sumitomo 3M Co., Ltd. Octylsulfonic acid amide [EF-125M manufactured by Mitsubishi Materials Corporation], N-
(N-propyl) -N- (β-methacryloxyethyl)
-Perfluorooctylsulfonic acid amide [EF-135M manufactured by Mitsubishi Materials Corporation], perfluorooctanesulfonic acid [EF-101 manufactured by Mitsubishi Materials Corporation],
Perfluorocaprylic acid [EF manufactured by Mitsubishi Materials Corporation]
-201], N- (n-propyl) -N-perfluorooctanesulfonic acid amide ethanol [EF-121 manufactured by Mitsubishi Materials Corporation], and EF-102, EF-103 manufactured by Mitsubishi Materials Corporation, and EF-103 manufactured by Mitsubishi Materials Corporation. EF-104, E
F-105, EF-112, EF-121, EF
-122A, EF-122B, EF-122C, EF-122A3, EF-123A, EF-123
B, EF-132, EF-301, EF-30
3, EF-305, EF-306A, EF-50
1, EF-700, EF-201, EF-20
4, EF-351, EF-352, EF-80
1, EF-802, EF-125DS, EF-1
200, EF-L102, EF-L155, EF
-L174 and EF-L215. Also,
3- (2-perfluorohexyl) ethoxy-1,2-
Dihydroxypropane [MF- manufactured by Mitsubishi Materials Corporation]
100], Nn-propyl-N-2,3-dihydroxypropyl perfluorooctylsulfonamide [MF-110 manufactured by Mitsubishi Materials Corporation], 3- (2-perfluorohexyl) ethoxy-1,2-epoxy Propane [MF-120 manufactured by Mitsubishi Materials Corporation], Nn-propyl-N-2,3-epoxypropyl perfluorooctylsulfonamide [MF-120 manufactured by Mitsubishi Materials Corporation]
130], perfluorohexyl ethylene [MF-140 manufactured by Mitsubishi Materials Corporation], N- [3-trimethoxysilyl) propyl] perfluoroheptylcarboxylic acid amide [MF-150 manufactured by Mitsubishi Materials Corporation], N-
[3-Trimethoxysilyl) propyl] perfluoroheptylsulfonamide [Mitsubishi Materials Corporation MF-
160]. The fluorine-based surfactant is added at a ratio of 0.1 to 20% by weight based on the total amount of the liquid crystal and the resin-forming material.

The solid content concentration in the coating solution for forming the information recording layer is preferably 10 to 60% by weight. Upon curing, the curing conditions such as the type and concentration of the resin, the temperature of the coating layer, and the conditions for irradiating ultraviolet rays are appropriately adjusted. By setting
A skin layer composed of only a resin layer having no liquid crystal phase as an outer skin layer can be favorably formed, whereby the use ratio of liquid crystal in the information recording layer can be increased,
In addition, bleeding of the liquid crystal can be eliminated.

The above description has been made of the UV-curable resin as the resin material. However, as other resin materials, for example, a solvent-soluble thermosetting resin having compatibility with a common solvent with the liquid crystal material, for example, an acrylic resin , Methacrylic resin, polyester resin, polystyrene resin, and copolymers based on these, such as epoxy resin, silicone resin, and the like.

Since the thickness of the information recording layer affects the resolution, the thickness after drying is 0.1 μm to 10 μm, preferably 3 μm.
The operating voltage can be reduced while maintaining high resolution. If the film thickness is too thin, the contrast of the information recording section is low, and if it is too thick, the operating voltage is undesirably high.

When the information recording layer itself has a supporting property and the support is omitted, a skin layer is formed on the surface of the information recording layer. Even when laminated by a method or the like, cracks do not occur and conductivity can be prevented from lowering. In this case, after providing the electrode layer on the information recording layer provided on the temporary support, the temporary support may be peeled off to obtain an information recording medium.

The electrode layer 13 'in the information recording medium is provided on the substrate 15 by using the same material and the same laminating method as the electrode layer 13 in the above-mentioned optical sensor. As shown in FIG. 2, this information recording medium is disposed opposite to the above-mentioned optical sensor via a spacer 19, and the two electrode layers 13, 1
3 'is connected via a voltage source V to form a first information recording device. The electrode layers 13 and 13 'in the information recording device are:
Any one or both may be transparent.

As the spacer, a resin film such as polyester such as polyethylene terephthalate, polyimide, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyamide, polypropylene, cellulose acetate, ethyl cellulose, polycarbonate, polystyrene, polytetrafluoroethylene, etc. It may be formed by using, or may be formed by applying and drying each of the above resin solutions. Also, aluminum,
A metal material such as selenium, tellurium, gold, or platinum may be formed by evaporation. The thickness of the spacer is a gap distance between the optical sensor and the information recording medium and affects the distribution of the voltage applied to the information recording layer. Therefore, the thickness of the spacer is preferably at least 100 μm or less, and more preferably 3 μm to 30 μm.

Next, the second information recording device will be described. FIG. 3 is a cross-sectional view showing a second information recording apparatus according to the present invention. In FIG. 3, reference numeral 20 denotes a dielectric layer, and the same reference numerals as those in FIG. 2 denote the same contents.

In the second information recording device, the optical sensor and the information recording medium in the first information recording device are combined with the dielectric layer 20.
And are directly laminated. The second information recording device is particularly suitable when the photoconductive layer in the optical sensor is formed by applying a solvent, and when the information recording layer is directly laminated on the photoconductive layer, the information is interacted with each other. The liquid crystal in the recording layer is eluted, and when the information recording layer is coated and formed on the photoconductive layer, it is possible to prevent image unevenness due to elution of the photoconductive material by the solvent for forming the information recording layer. , The optical sensor and the information recording medium can be integrated.

In forming the dielectric layer 20, it is necessary that the dielectric layer 20 has no solubility in any of the organic photoconductive layer forming material and the information recording layer forming material, and it is necessary that the dielectric layer 20 does not have conductivity. is necessary. In the case of having conductivity, the space charge is diffused and the resolution is deteriorated, so that the insulating property is required. However, the dielectric layer lowers the distribution voltage applied to the liquid crystal layer or deteriorates the resolution.
On the contrary, when the thickness is reduced, not only the occurrence of image noise due to the interaction with time, but also the problem of penetration due to defects such as pinholes at the time of layer coating is caused. Since the permeability due to defects such as pinholes differs depending on the solid content ratio of the material to be laminated and the type of solvent and the viscosity, the thickness of the material to be laminated is appropriately set, but is preferably at least 10 μm or less. , Preferably 0.1 to 3 μm. Further, in consideration of the voltage distribution applied to each layer, a material having a high dielectric constant as well as a thin film is preferable.

As a material for forming the dielectric layer, inorganic materials such as SiO ₂ , TiO ₂ , CeO ₂ , Al ₂ O ₃ , GeO ₂ , Si ₃ N ₄ ,
It is preferable to use AlN, TiN, or the like, and to form a layer by vapor deposition, sputtering, chemical vapor deposition (CVD), or the like. Alternatively, a water-soluble resin having low compatibility with an organic solvent, for example, an aqueous solution of polyvinyl alcohol, aqueous polyurethane, water glass, or the like may be used, and the layers may be laminated by a spin coating method, a blade coating method, a roll coating method, or the like. Further, a fluorine resin which can be applied may be used. In this case, the resin may be dissolved in a fluorine-based solvent and applied by a spin coating method, or may be laminated by a blade coating method, a roll coating method or the like.

The fluorine resin which can be applied is represented by a general formula

[0063]

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And / or a general formula

[0065]

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(Where n is 1 or 2) a fluorine-containing thermoplastic resin having a molecular weight such that the intrinsic viscosity at 50 ° C. is at least 0.1 at 50 ° C. , General formula

[0067]

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And / or a general formula

[0069]

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(Where n is 1 or 2) a cyclic structure repeating unit (a) represented by the following general formula:-(CF ₂ -CFX)-(where X is F, Cl, -O-CF ₂ CF ₂ CF ₃ , -O-CF ₂ CF (CF ₃ ) OCF ₂ C
It consists of a repeating unit (b) represented by F ₂ SO ₃ F, —O—CF ₂ CF ₂ CF ₂ COOCH ₃ ), contains at least 80% by weight of the repeating unit (a), and has an intrinsic viscosity at 50 ° C. Is at least 0.1
It is possible to suitably use a fluorine-containing thermoplastic resin as follows.

The repeating unit (a) has the general formula CF ₂ CFCF—O
-(CF ₂ ) _n It is obtained by radically cyclopolymerizing perfluoroallyl vinyl ether or perfluorobutenyl vinyl ether represented by CF = CF ₂ (where n is 1 or 2).

Those containing the repeating unit (a) and the repeating unit (b) are represented by the general formula: CF ₂ = CF—O— (CF ₂ ) _n
CF = CF ₂ (where n is 1 or 2) and a general formula, CF ₂ = CFX (where X is F, C
1, -O-CF ₂ CF ₂ CF ₃ , -O-CF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ F, -O-CF ₂
It is obtained by radical polymerization with a monomer represented by CF ₂ CF ₂ COOCH ₃ ). These resins are disclosed, for example, in JP-A-1-131215.

Further,

[0074]

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(Provided that the dioxonol component content represented by the number m of repeating units is 20 to 90 mol%), and the melt viscosity at a temperature 90 to 110 ° C. higher than the glass transition temperature is 10 ² to 10 ^4. A fluorine-containing thermoplastic resin having a Pa · sec may be used.

This fluorine-containing thermoplastic resin is, for example, manufactured by DuPont [trade name “Teflon” AF1600, containing about 65 mol% of dioxonol units, glass transition temperature 160
° C, melt viscosity 2657 Pa · sec (250 ° C, 100sec
^-1 , measured value according to ASTM D3835), water absorption of 0.
01% or less], manufactured by the company [Teflon AF240
0, containing about 85 mol% of dioxonol units, glass transition temperature 240 ° C., melt viscosity 540 Pa · sec (350 ° C.,
100 sec ^-1 measured by ASTM D3835),
Water absorption of 0.01% or less] is specifically exemplified.

The fluororesin does not necessarily need to be a perfluororesin, but may be any one which is hardly soluble in a general-purpose solvent and soluble in a fluorine-based solvent. When selecting a coating type transparent insulating material, the solvent does not dissolve the photoconductive layer,
In addition, when the information recording layer is applied and formed, it is necessary that the material does not dissolve in the material constituting the information recording layer or does not dissolve in the solvent used for application. Does not need to dissolve the photoconductive layer at the time of film formation. Examples of a material for forming a film by a vapor deposition method include polyethylene, polypropylene, poly (monochlorotrifluoroethylene), and polytetrafluoroethylene. Further, as a material to be formed by the CVD method, polyparaxylene represented by the following structural formula,

[0078]

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(The C type is not limited to the above structure, but one of the benzene rings other than the main chain bonding site is substituted with chlorine, and the D type is two of those substituted with chlorine. Etc.) can be used.

Next, a method for recording information on the first and second information recording devices of the present invention will be described. FIG. 4 is a diagram for explaining an information recording method in the first information recording device of the present invention, and the same applies to an information recording method in the second information recording device.

First, a voltage is applied between the electrodes 13 and 13 'by a power supply. When recording on the information recording medium, the information recording medium is heated, for example, by resistance heating (not shown) embedded in the support, and the liquid crystal is heated to a temperature indicating a liquid crystal phase, thereby further improving the memory performance. Can be done.

While applying a voltage between the electrodes 13 and 13 ′,
When the information light 18 is incident, the photocarriers generated in the photoconductive layer including the charge generation layer 14 'and the charge transport layer 14 "in the portion where the information light 18 is incident are moved by the electric field formed by the two electrodes, and the voltage is reduced. The redistribution is performed, the liquid crystal phase in the information recording layer is oriented, and recording is performed according to the pattern of the information light 18. A voltage may be applied for a predetermined time while the information light 18 is incident.

Since the operating voltage and the range vary depending on the liquid crystal, when setting the applied voltage and the applied voltage time, the voltage distribution in the information recording medium is appropriately set, and the voltage distribution applied to the information recording layer is determined by the liquid crystal. It is preferable to set the operation voltage range. According to this information recording method, planar analog recording is possible, and recording at the liquid crystal level is obtained, so that high-resolution recording is achieved, and the exposure pattern is maintained as a visible image by the orientation of the liquid crystal phase.

The information recording method includes a method using a camera and a method using a laser. As a method using a camera, an information recording medium is used instead of a photographic film used in a normal camera, and a recording member is used. An optical shutter can be used, and an electric shutter can also be used. It is a good thing. Further, the optical information is separated into R, G, and B light components by a prism and a color filter, extracted as parallel light, and one frame is formed by three sets of R, G, and B information recording media, or
By arranging the R, G, and B images on a plane to form one frame in one set, color photography can also be performed.

Further, as a recording method using a laser,
The light source is an argon laser (514.488n)
m), a helium-neon laser (633 nm), a semiconductor laser (780 nm, 810 nm, etc.) can be used,
Laser exposure corresponding to an image signal, a character signal, a code signal, and a line drawing signal is performed by scanning. Analog recording such as an image is performed by modulating the light intensity of a laser, and digital recording such as characters, codes, and line drawings is performed by ON-OFF control of a laser beam. In the case where halftone dots are formed in an image, the laser light is formed by performing dot generator ON-OFF control. Note that the spectral characteristics of the photoconductive layer in the optical sensor need not be panchromatic, as long as they have sensitivity to the wavelength of the laser light source.

As shown in FIG. 5, the exposure information recorded on the information recording medium separates the information recording medium in the case of the first information recording device, and is not changed in the case of the second information recording device. When information is reproduced by transmitted light in the state of (1), light A is transmitted because the liquid crystal is oriented in the direction of the electric field in the information recording portion, whereas light B is scattered in a portion where information is not recorded, and information is recorded. The contrast with the recording unit can be obtained. Information recorded by these information recording devices may be read by reflected light.

The information recorded by the orientation of the liquid crystal is visible information that can be read visually, but it can also be read by enlarging it with a projector, and can be transmitted or reflected using laser scanning or a CCD. Thus, information can be read with high accuracy, and scattered light can be prevented by using a schlieren optical system as necessary.

The information recording medium in the first and second information recording apparatuses of the present invention records electrostatic information in a state where the electrostatic information is visualized by the orientation of the liquid crystal. The information once oriented and visualized is not erased, and a memory property is provided. Further, when the memory is heated to a high temperature near the isotropic phase transition, the memory can be erased, so that it can be used for information recording again.

As described above, the optical sensor of the present invention is suitable for recording information on an information recording medium having a polymer-dispersed liquid crystal as an information recording layer.

[0090]

In the present invention, the liquid crystal in the information recording medium is aligned by arranging the optical sensor and the information recording medium to face each other, and exposing the information while applying a voltage. The optical sensor and the information recording device are required to have a high contrast ratio in the operating voltage range of the liquid crystal, in which information is recorded by making the film transparent and contrasting with an unexposed portion. If the electric field is equal to or lower than the operating voltage of the liquid crystal due to the generation of photocarriers of the optical sensor due to the image information light, the liquid crystal in the information recording layer does not align and is opaque due to light scattering, whereas When an electric field equal to or higher than the operating voltage is applied, the liquid crystal in the information recording layer is oriented and the information recording portion can be made transparent. According to the information recording mode of the present invention, an analog image can be recorded by modulating an electric field, a deflecting plate is not required for reproducing information, and an optical system for reading information can be simplified. .

The inventors of the present invention have argued that, for the optical sensor comprising a vinyl chloride resin and a vinyl acetate resin as the binder of the charge generation layer, the detailed reason is unknown, but the information is determined by the resin composition of the charge generation layer of the optical sensor. It has been found that the voltage distributed to the recording layer is greatly affected. In particular, when the vinyl chloride resin component is present in the resin binder at a ratio of 15% by weight to 68% by weight, the potential difference between the exposed part and the unexposed part. Can provide a high contrast ratio, can provide an excellent contrast ratio, can provide an optical sensor having excellent light sensitivity, and can be an excellent information recording apparatus and information recording / reproducing method.

Hereinafter, the embodiments will be described.
"Parts" indicates parts by weight, and "%" indicates% by weight.

[0093]

Example 1 The following structure was used as a charge generating material

[0094]

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Is mixed with 196 parts of a mixed solvent of dioxane: cyclohexane = 1: 1, and the mixture is sufficiently kneaded by a mixer. A coating solution was prepared. The composition ratio between the vinyl chloride resin and the vinyl acetate resin in the copolymer resin was changed over the range of 85:15 to 15:85 as shown in Table 2 below.

This coating solution was applied to an ITO transparent electrode (film thickness: about 5
(00A, 80 Ω / □) on the ITO surface side of a glass substrate, and dried at 100 ° C. for 1 hour to form a 0.3 μm-thick charge generation layer.

Next, a charge transport material having the following structure

[0098]

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Butadiene derivative (trade name: T-4)
05; Takasago Perfume Co., Ltd.) and 1 part of a styrene-butadiene copolymer resin (trade name: Clearen 730L; Denki Kagaku Kogyo) are combined with monochlorobenzene: dichloromethane:
It was mixed and dissolved with 27.3 parts of a mixed solvent of 1,1,2-trichloroethane = 1: 1: 2 to prepare a coating solution. This solution was applied on the charge generation layer and dried at 80 ° C. for 2 hours to form a charge transport layer having a thickness of 20 μm.

The electrical characteristics of the optical sensor thus obtained were evaluated using a measuring circuit shown in FIG. As shown in the figure, using a capacitor C ₁ and resistor R ₁ as corresponding to the information recording medium of the present invention. Also, gold is vapor-deposited on the optical sensor 1 to form an electrode layer, which is connected to the capacitor C ₁ and the resistor R ₁ ,
R ₁ and C ₁ were set to 400 MΩ and 120 pF, respectively.
In this measurement circuit, a voltage of 400 V is applied so that the optical sensor side becomes positive,
20-lux light of 500-600 nm from the O-plane
After irradiating for ms, the light irradiation was stopped, and thereafter, voltage application was continued for 100 ms including the light irradiation time. The current flowing in R ₁ to cancel the voltage applied from the time of light irradiation was monitored,
Was calculated potential accumulated in C _1. Fig. 7 shows the measurement results.
Is shown as a clear part. The horizontal axis represents time and the vertical axis represents the voltage applied to the C _1.

Next, in the same measuring circuit, for the case of applying only the voltage in the same manner without applying light, calculates a potential to be similarly stored in C _1, shows a similarly results in FIG. 7 as a dark potential .

Of the two curves in FIG. 7, the upper line represents the potential change in the bright part, and the lower line represents the potential change in the dark part. The potential difference between the part and the dark part was defined as the contrast potential. The higher the contrast potential, the better the optical sensor.

Optical sensors were prepared by changing the binder resin composition of the charge generation layer in the optical sensors as shown in the following table, and the contrast potential of each optical sensor was determined using the above-described measuring circuit. The measurement results are shown in the following table.

[0104]

[Table 2]

[0105]

EXAMPLE 2 3 parts of the bisazo pigment used in Example 1 as a charge generating substance, 1 part of a vinyl chloride / vinyl acetate copolymer resin and 1 part of a blend resin with a vinyl acetate resin were used.
Dioxane: cyclohexane = 1: 1 mixed solvent 196
And the mixture was sufficiently kneaded with a mixer to prepare a coating solution for the charge generation layer. At that time, the composition ratio (weight ratio) of the vinyl chloride resin and the vinyl acetate resin in this blend binder resin was changed as shown in Table 3 below in the range of 85:15 to 15:85.

This coating solution was applied to an ITO transparent electrode (film thickness: about 5
(00A, 80 Ω / □) on the ITO surface side of a glass substrate, and dried at 100 ° C. for 1 hour to form a 0.3 μm-thick charge generation layer. Next, a charge transport layer having a thickness of 20 μm was formed on the charge generation layer in the same manner as in Example 1.

The electrical characteristics of the optical sensor thus obtained were measured under the same conditions as in Example 1 (R ₁ and C ₁ in FIG. 6).
Are 400 MΩ and 120 pF, respectively, and 40
0 V was applied). The measurement results are shown in the following table.

[0108]

[Table 3]

[0109]

Comparative Example 1 In Example 1, the binder in the charge generation layer was vinyl chloride resin (reagent; manufactured by Aldrich).
In addition, an optical sensor was produced in the same manner as in Example 1 except that THF was used as the solvent. Example 1 of this optical sensor
When evaluated in the same manner, the contrast potential was 3.3.
V.

[0110]

Comparative Example 2 In Example 1, the binder in the charge generation layer was vinyl acetate resin (reagent; manufactured by Aldrich).
An optical sensor was produced in the same manner as in Example 1 except that the above conditions were satisfied. When this optical sensor was evaluated in the same manner as in Example 1, the contrast potential was 12.4 V.

As can be seen from Tables 2 and 3, when the vinyl chloride-vinyl acetate copolymer or the mixture of the vinyl chloride / vinyl acetate copolymer and the polyvinyl acetate was used, the chloride in the resin binder was not changed. It can be seen that when the composition ratio of vinyl resin to vinyl acetate resin is in the range of 15:85 to 68:32, the contrast potential is improved. Also, from Comparative Examples 1 and 2, it can be seen that the contrast potential is low when the binder resin is vinyl chloride resin alone or vinyl acetate resin alone.

[0112]

Example 3 (Preparation of information recording medium) 4 parts of dipentaerythritol hexaacrylate, 6 parts of smectic liquid crystal S6 (trade name, manufactured by Merck Ltd.), fluorinated surfactant Florard FC-
430 (trade name; manufactured by 3M) 0.2 part, photopolymerization initiator "Darocur 1173" (trade name; manufactured by Merck) 0.2
Of the mixture was adjusted to 30% solids with xylene.

This solution was applied to an ITO transparent electrode (thickness: about 500).
A, IT on a glass substrate having a resistance value of 80Ω / □)
On the O-surface side, a 50 μm cap-thick blade coater was used, and the coating was maintained at 50 ° C. and 0.3 mJ / cm ² of U was applied.
By irradiating V light, an information recording medium having an information recording layer having a thickness of about 6 μm was manufactured. Liquid crystal was extracted from the cross section of the information recording layer using hot methanol, dried, and then scanned with a scanning electron microscope (S-800, 1000, manufactured by Hitachi, Ltd.).
0), the surface of the layer was found to be 0.6
The layer is covered with an ultraviolet curable resin having a thickness of μm, and the inside of the layer has a particle size of 0.3 μm.
It was found that it had a structure filled with 1 μm resin particles.

(Preparation of First Information Recording Apparatus) The optical sensor prepared in Example 1 was prepared as described above, with the charge generation layer containing 50% by weight of a polyvinyl chloride component in a resin binder in a resin binder. The information recording medium was a polyimide film having a thickness of 9 μm as a spacer, and the information recording medium and the optical sensor were arranged opposite to each other and grounded. Next, the gray scale is projected and exposed from the optical sensor side at an exposure amount of 0.1 to 10 lux, and at the same time, a direct current voltage of 900 V is applied between both electrodes, and the optical sensor layer side is positive and the information recording medium layer side is negative. For 2 seconds.

As a result, a transmitted image corresponding to the gray scale was formed on the information recording layer, and an image in which a sufficient contrast was obtained even on the low exposure side of the gray scale could be confirmed by the transmitted light. Further, the information recording medium was read by a scanner using a CCD line sensor and output by a sublimation printer. As a result, a high-resolution hard copy having gradation was obtained.

[0116]

Comparative Example 3 In Example 3, the binder in the charge generation layer was vinyl chloride resin (reagent; manufactured by Aldrich).
An information recording device was produced in the same manner as in Example 3 except that THF was used as the solvent. When this information recording apparatus was evaluated in the same manner as in Example 3, sufficient contrast was not obtained on the low exposure side of the gray scale.

[0117]

Comparative Example 4 In Example 3, the binder in the charge generation layer was vinyl acetate resin (reagent; manufactured by Aldrich).
An information recording device was produced in the same manner as in Example 3 except that the above-mentioned was used. When this information recording apparatus was evaluated in the same manner as in Example 3, sufficient contrast was not obtained on the low exposure side of the gray scale.

[0118]

Example 4 An optical sensor having the charge generation layer containing 50% by weight of a polyvinyl chloride component in a resin binder was prepared.

The following structure was formed on the charge transport layer of this optical sensor.

[0120]

Embedded image

Diparaxylylene having the above formula was vaporized and polymerized under vacuum to form a poly (monochloroparaxylylene) film having a thickness of 0.6 μm to form a dielectric layer.

Further, on this dielectric layer, 4 parts of dipentaerythritol hexaacrylate, 6 parts of smectic liquid crystal S6 (trade name, manufactured by Merck), fluorine-based surfactant Florard FC-430 (trade name, 3M company) 0.2)
Parts, a mixture of 0.2 parts of a photopolymerization initiator “Darocure 1173” (trade name, manufactured by Merck) with xylene to obtain a solid content of 30 parts.
% Of the solution was applied with a blade coater having a cap thickness of 50 μm, and kept at 50 ° C.
By irradiating UV light of cm ² , an information recording layer having a thickness of about 6 μm was laminated. On this information recording layer, about 200 A of ITO was laminated as a transparent electrode by a sputtering method to produce a second information recording device of the present invention.

At the same time, a gray scale is projected and exposed from the photoconductive layer side of the information recording apparatus at an exposure amount of 0.1 to 10 lux, and at the same time, a DC voltage of 600 V is applied between the two electrodes to make the photoconductive layer side positive, When a negative voltage was applied for 0.1 second, a transmitted image corresponding to a gray scale was formed on the information recording layer, and an image in which a sufficient contrast was obtained even on the low exposure side of the gray scale was confirmed by transmitted light.

Further, the information recording medium was read by a scanner using a CCD line sensor and output by a sublimation printer. As a result, a high-resolution hard copy having gradation was obtained.

[0125]

Comparative Example 5 In Example 4, the binder in the charge generation layer was vinyl chloride resin (reagent; manufactured by Aldrich).
An information recording device was produced in the same manner as in Example 4 except that THF was used as the solvent. When this information recording apparatus was evaluated in the same manner as in Example 4, sufficient contrast was not obtained on the low exposure side of the gray scale.

[0126]

Comparative Example 6 In Example 4, the binder in the charge generation layer was vinyl acetate resin (reagent; manufactured by Aldrich).
An information recording device was produced in the same manner as in Example 4 except that the above-mentioned was used. When this information recording apparatus was evaluated in the same manner as in Example 4, sufficient contrast was not obtained on the low exposure side of the gray scale.

[Brief description of the drawings]

FIG. 1A is a diagram for schematically explaining a photosensor by a cross-sectional view thereof, and FIG. 1B is a diagram showing another embodiment.

FIG. 2 is a diagram schematically illustrating an aspect of a first information recording device according to the present invention by using a cross section thereof.

FIG. 3 is a diagram for schematically explaining an aspect of a second information recording device according to the present invention by a cross section thereof.

FIG. 4 is a diagram for explaining an information recording method in the information recording device of the present invention.

FIG. 5 is a diagram for explaining a method of reproducing information recorded on an information recording medium in the information recording device of the present invention.

FIG. 6 is a diagram for explaining a measurement circuit used for evaluating the electrical characteristics of the optical sensor according to the present invention.

FIG. 7 is a diagram showing an evaluation result obtained by the evaluation method shown in FIG. 6;

[Explanation of symbols]

1 is an optical sensor, 3 is an information recording medium, 11 is an information recording layer, 13 and 13 'are electrode layers, 14' is a charge generation layer, 1
4 "charge transport layer, 15 a substrate, a charge injection preventing layer 17, the electrode layer, 18 is the information beam, 19 a spacer, 20 is a dielectric layer, C ₁ is a capacitor, R ₁ is the resistance.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-155525 (JP, A) JP-A-4-70864 (JP, A) JP-A-52-72243 (JP, A) JP-A-62-1987 2267 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G02F 1/13 505 G02F 1/1333

Claims (4)

(57) [Claims] 1. A charge generation layer and a charge transport layer are sequentially provided on an electrode layer, and the charge generation layer comprises a polyvinyl chloride component and a
A resin binder comprising a vinyl acetate component,
The polyvinyl chloride component in the resin binder 15 wt%
To 68% by weight and the following general formula (1) : (Where X in the formula is hydrogen, lower alkyl group, lower alcohol
Xy group, nitro group, sulfonic group, hydroxyl group, carboxy
The same or different selected from
And n is an integer of 0 to 3, and R may be substituted
Hydrocarbon, heterocyclic or alkyl groups
You. A) an optical sensor comprising a charge generating substance represented by the following formula: and an information recording medium comprising an information recording layer laminated on an electrode layer, wherein the information recording layer comprises a liquid crystal phase and a resin phase. An information recording apparatus, wherein at least one electrode layer is disposed as a transparent electrode layer on the optical axis via a spacer, and both electrode layers are connected so that a voltage can be applied. Wherein electrode layers a charge generating layer on successively provided a charge transport layer, charge generation layer, a polyvinyl chloride component and port
A resin binder comprising a vinyl acetate component,
The polyvinyl chloride component in the resin binder 15 wt%
To 68% by weight and the following general formula (1) : (Where X in the formula is hydrogen, lower alkyl group, lower alcohol
Xy group, nitro group, sulfonic group, hydroxyl group, carboxy
The same or different selected from
And n is an integer of 0 to 3, and R may be substituted
Hydrocarbon, heterocyclic or alkyl groups
You. A) an optical sensor comprising a charge generating substance represented by the following formula: and an information recording medium comprising an information recording layer laminated on an electrode layer, wherein the information recording layer comprises a liquid crystal phase and a resin phase. At least one of the electrode layers is disposed as a transparent electrode layer on the optical axis via a spacer, and information is exposed while applying a voltage between the two electrodes. An information recording / reproducing method which performs recording and reproduces as visible information by transmitted light or reflected light when reproducing the information recording. 3. A charge-generating layer on the electrode layer, a charge transport layer, a dielectric layer, the information recording layer, an information recording medium in which the electrode layer is sequentially provided, is at least one of the electrodes transparent, also the The charge generation layer consists of a polyvinyl chloride component and polyvinyl acetate.
A polyvinyl chloride component which is contained in the resin binder at a ratio of 15% by weight to 68% by weight , and has the following general formula (1) : (Where X in the formula is hydrogen, lower alkyl group, lower alcohol
Xy group, nitro group, sulfonic group, hydroxyl group, carboxy
The same or different selected from
And n is an integer of 0 to 3, and R may be substituted
Hydrocarbon, heterocyclic or alkyl groups
You. An information recording device comprising a charge generating substance represented by the formula (1), wherein the information recording layer comprises a liquid crystal phase and a resin phase, and is connected between both electrode layers so that a voltage can be applied. 4. A charge-generating layer on the electrode layer, a charge transport layer, a dielectric layer, the information recording layer, an information recording medium in which the electrode layer is sequentially provided, is at least one of the electrodes transparent, also the The charge generation layer consists of a polyvinyl chloride component and polyvinyl acetate.
A resin binder comprising a polyvinyl chloride component in a proportion of 15% by weight to 68% by weight in the resin binder and the following general formula (1) : (Where X in the formula is hydrogen, lower alkyl group, lower alcohol
Xy group, nitro group, sulfonic group, hydroxyl group, carboxy
Group, is the same or different selected from halogen atoms
And n is an integer of 0 to 3, and R may be substituted
Hydrocarbon, heterocyclic or alkyl groups
You. ) Wherein the information recording layer further comprises a liquid crystal phase and a resin phase, wherein the information recording medium comprises a liquid crystal phase and a resin phase. Information is recorded by orienting the phase,
An information recording / reproducing method, wherein information is reproduced as visible information using transmitted light or reflected light when reproducing information.