JPH05165005A - Information recording medium and information record reproducing method - Google Patents

Abstract

PURPOSE:To easily provide an elctro-optical effect, enable the recording and memory of analog information eliminate needs for a deflecting plate for information reproduction, simplify an optical system for readout, enable the production of a large-area information recording medium, thereby providing an image with high resolution and no unevenness. CONSTITUTION:A first information recording medium is hardened and formed by means of an ultraviolet ray irradiation, after a mixed solution consisting of a liquid crystal and an ultarviolet ray hardening type resin moulding matrial is applied onto an electrode layer 13 to form an information recording layer 11, and the outer surface of which is a skin layer consisted of only an ultraviolet ray hardening type resin. A second information recording medium is such that a transparent electrode 13' is furthermore provided on the information recording layer 11 of the first information recording medium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an information recording medium capable of recording information recording by a voltage applying exposure recording method using a photoconductor or information recording by voltage application as visible information, and an information recording / reproducing method thereof.

[0002]

2. Description of the Related Art In the conventional electrophotographic technology, 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 between a pair of electrodes and an insulating layer for aligning liquid crystal are sequentially laminated. Is known in which information is exposed with a voltage applied between electrodes to lower the resistance of the photoconductive layer in the information exposed portion to align the liquid crystal and obtain a visible image using a deflector.

This information recording medium needs to be made into a cell in order to enclose a liquid crystal, and in order to perform twisted nematic orientation in the initial stage, an insulating film having both surfaces of the cell oriented by rubbing treatment is provided, and further the cell is further provided. It is necessary to mix spacers to keep the gap constant, and it is not possible to obtain a high-resolution image. There is also an optical problem because a rigid and transparent support is required to form the gap or the cell.
Further, there is also a problem that such an alignment-processed material in the initial state cannot be detected unless a polarizing plate is used for reading.

On the other hand, recently, a polymer dispersion type liquid crystal has been developed for a liquid crystal layer in a liquid crystal cell, and in such a medium, it is held in a state of being sandwiched between two substrates having ITO electrodes. This medium is substrate / ITO electrode /
When used in a method of recording electrostatic information in the liquid crystal layer by a discharge phenomenon according to information light, which is composed of a liquid crystal layer and exposed to a voltage applied in a state of facing the photoconductor, a polymer dispersion type is used. There is a problem that liquid crystal seeps out on the surface of the liquid crystal and causes noise when recording information. Moreover, by directly forming the ITO electrode on the liquid crystal layer, a substrate / ITO electrode / liquid crystal layer / ITO electrode structure is formed. ,
When information is recorded by applying a voltage between both electrodes to orient the liquid crystal layer, the liquid crystal bleeds out and the I
There is a problem in that the TO electrode is cracked, floats and the like, and the conductivity is lowered. Further, when the electrode layer and the liquid crystal layer are formed by the laminating method, there are problems of gap uniformity and noise due to spacers.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an information recording medium and an information recording / reproducing method which can record information accurately without using a liquid crystal cell and which is easy to reproduce information. In particular, when using a polymer-dispersed liquid crystal as an information recording layer, it is an object to provide an information recording medium and an information recording / reproducing method that do not cause image unevenness due to oozing of the liquid crystal.

[0006]

A first information recording medium of the present invention is an information recording medium in which an information recording layer comprising a liquid crystal phase and an ultraviolet curable resin phase is provided on an electrode layer. The information recording layer is formed by applying a mixed solution of a liquid crystal and a UV-curable resin forming material onto the electrode layer and then curing it by UV irradiation, and the outer surface thereof is a skin layer consisting of only the UV-curable resin. It is characterized by being formed in.

The first information recording / reproducing method for an information recording medium of the present invention is an information recording medium having an information recording layer comprising a liquid crystal phase and an ultraviolet curable resin phase on an electrode layer.
The information recording layer is formed by applying a mixed solution of a liquid crystal and an ultraviolet curable resin forming material onto the electrode layer and then curing the same by irradiating with ultraviolet light, and the outer surface thereof is a skin composed of only the ultraviolet curable resin. The information recording medium formed in the layer and the photoconductor provided with the photoconductive layer on the electrode layer are arranged in contact with each other in a contact or non-contact manner, and a voltage is applied between both electrodes of the information recording medium and the photoconductor. The information is exposed from the side of the body or the information recording medium, information is recorded by orienting the liquid crystal phase according to the information, and the recorded information is reproduced as visible information by transmitted light or reflected light. To do.

The second information recording medium of the present invention is an information recording medium in which an information recording layer composed of a liquid crystal phase and an ultraviolet curable resin phase and an electrode layer are sequentially provided on the electrode layer, and at least One of the electrode layers is transparent, and the information recording layer is
It was formed by applying a mixed solution of liquid crystal and a UV-curable resin forming material on the electrode layer and then curing it by UV irradiation, and its outer surface was formed into a skin layer consisting of only UV-curable resin. Is characterized by.

The second information recording / reproducing method for an information recording medium of the present invention is an information recording medium in which an information recording layer comprising a liquid crystal phase and an ultraviolet curable resin phase and an electrode layer are sequentially provided on the electrode layer. At least one of the electrode layers is transparent, and the information recording layer is formed by applying a mixed solution of a liquid crystal and an ultraviolet curable resin forming material onto the electrode layer and then curing it by ultraviolet irradiation. The information recording medium having an outer surface formed on a skin layer made of only an ultraviolet curable resin is applied with a voltage in a pattern between both electrodes to align the liquid crystal phase according to the pattern. When recording and reproducing recorded information, visible information is reproduced by transmitted light or reflected light.

The information recording medium and the information recording / reproducing method of the present invention will be described below.

FIG. 1A is a diagram for schematically explaining a cross section of a first information recording medium of the present invention, in which 3 is an information recording medium, 11 is an information recording layer, and 13 is an electrode layer. , 15 are substrates.

Either one or both of the electrode layers 13 need only be transparent, and a metal thin film conductive film having a specific resistance value of 10 ⁶ Ω · cm or less, an inorganic metal oxide conductive film, a quaternary ammonium salt, etc. And the organic conductive film. The electrode layer 13 is formed by a method such as vapor deposition, sputtering, CVD, coating, plating, dipping, and electrolytic polymerization. The film thickness needs to be changed depending on the electrical characteristics of the material forming the electrodes and the applied voltage at the time of recording information. For example, an ITO film has a thickness of about 100 to 3000 Å, and the entire surface between the information recording layer and Alternatively, it is formed according to the formation pattern of the information recording layer.

The substrate 15 is a card, a film, a tape,
It strongly supports an information recording medium having a shape such as a disc, and it is not necessary to provide it when the information recording layer has a supporting property, but a certain level of strength capable of supporting the information recording layer is required. If it has, its material and thickness are not particularly limited, and for example, a flexible plastic film or a rigid body such as glass, plastic sheet, card, etc. is used. Specifically, when the information recording medium has a flexible film, tape, disk, or card shape, a flexible plastic film is used, and when strength is required, a rigid sheet or glass. Inorganic materials and the like are used.

If necessary, a layer having an antireflection effect is laminated on the other surface of the substrate on which the electrode layer 13 is provided, or a transparent substrate having a film thickness capable of exhibiting the antireflection effect is formed. The antireflection property may be imparted by adjusting or by combining both.

Next, the information recording layer 11 is composed of a liquid crystal phase and a resin phase, and a smectic liquid crystal, a nematic liquid crystal, a cholesteric liquid crystal or a mixture thereof can be used as the liquid crystal material. It is preferable to use a smectic liquid crystal from the viewpoint of so-called memory property, in which orientation is retained and information is retained permanently.

As the smectic liquid crystal, a liquid crystal substance exhibiting a smectic A phase such as a cyanobiphenyl type, a cyanoterphenyl type, a phenyl ester type having a long carbon chain at a terminal group of a substance exhibiting liquid crystallinity, or a fluorine type, a ferroelectric substance A liquid crystal substance 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 it with a smectic or cholesteric liquid crystal. For example, a Schiff base type, an azoxy type, an azo type, a benzoic acid phenyl ester type, Cyclohexyl acid phenyl ester type, biphenyl type, terphenyl type, phenylcyclohexane type,
Known nematic liquid crystals such as phenylpyridine type, phenyloxazine type, polycyclic ethane type, phenylcyclohexene type, cyclohexylpyrimidine type, phenyl type and tolan type can be used. Also, a microcapsule obtained by mixing a liquid crystal material with polyvinyl alcohol or the like can be used.

When selecting a liquid crystal material, it is preferable to use a material having a large anisotropy in the refractive index because the contrast can be obtained.

The material for forming the resin phase is an ultraviolet curable resin that is compatible with the liquid crystal material in the monomer or oligomer state, or is compatible with the solvent common to the liquid crystal material in the monomer or oligomer state. Those having solubility can be preferably used.

Examples of such UV-curable resins include acrylic acid esters and methacrylic acid esters, which are in the form of monomers and oligomers, such as dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate. Polypropylene glycol diacrylate, isocyanuric acid (ethylene oxide modified) triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, etc. Type, ester type oligomer, nonylphenol modified acrylate, N-vinyl-2-pyrrolidone,
Examples thereof include monofunctional monomers or oligomers such as 2-hydroxy-3-phenoxypropyl acrylate.

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

Examples of the photo-curing agent include 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck), 1-hydroxycyclohexylphenylketone (“Irgacure manufactured by Ciba Geigy”). 184 "), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (" Darocur 1116 "manufactured by Merck), benzyl dimethyl ketal (" Irgacure 65 manufactured by Ciba Geigy ").
1 "), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (" Irgacure 907 "manufactured by Ciba Geigy), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) “Kayacure DETX”) and ethyl p-dimethylaminobenzoate (“Kayacure EPA” manufactured by Nippon Kayaku Co., Ltd.), isopropyl thioxanthone (“Kunta Cure I manufactured by Ward Brekinsop”)
TX ”and a mixture of ethyl p-dimethylaminobenzoate and the like, but liquid 2-hydroxy-2-methyl-1-phenylpropan-1-one is a liquid crystal, and a polymer-forming monomer or oligomer. It is particularly preferable in terms of compatibility with the resin forming material.

The liquid crystal and the resin-forming material may be used so that the content of the liquid crystal is 10% by weight to 90% by weight, preferably 40% by weight to 80% by weight, and less than 10% by weight. Even if the liquid crystal phase is oriented by information recording, the light transmittance is low, and if it exceeds 90% by weight, bleeding of the liquid crystal or the like is reduced, resulting in image unevenness, which is not preferable. A large amount of liquid crystal is present in the information recording phase to improve the contrast ratio and reduce the operating voltage.

The information recording layer is formed by mixing a mixed solution of a resin forming material and liquid crystal on a blade coater,
It is formed by applying and curing by a coating method such as a roll coater or a spin coater. In addition,
If necessary, a leveling agent may be added to improve the coating suitability of the solution and improve the surface property.

Further, it is necessary to heat the liquid crystal to a temperature at which the liquid crystal maintains an isotropic phase or more so that the liquid crystal and the ultraviolet curable resin forming material are completely compatible with each other. When the information recording layer is UV-cured, if the liquid crystal is UV-cured at a temperature not higher than the isotropic phase, a problem arises because the liquid crystal and the UV-curable resin material are partially phase-separated. That is, the liquid crystal domain grows too much, the skin layer is not completely formed on the surface of the information recording layer, the phenomenon of liquid crystal bleeding occurs, and the ultraviolet curable resin is matted, which makes it difficult to accurately capture information. Is not preferable. In addition, 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 the solvent is evaporated, heating is required to maintain the isotropic phase, in particular, there is a problem that the wettability with respect to the electrode layer is lowered and a uniform information recording layer cannot be obtained.

Further, a fluorine type surfactant is added for the purpose of maintaining the wettability with respect to the electrode layer. Examples of such a fluorine-based surfactant include Sumitomo 3M Ltd.
Made, Fluorard FC-430, Fluorard FC-43
1, N- (n-propyl) -N- (β-acryloxyethyl) -perfluorooctyl sulfonic acid amide [Mitsubishi Materials Corporation EF-125M], N- (n-propyl) -N- (β -Methacryloxyethyl) -perfluorooctyl sulfonic acid amide [Mitsubishi Materials Corporation
EF-135M], perfluorooctane sulfonic acid [Mitsubishi Materials EF-101], perfluorocaprylic acid [Mitsubishi Materials EF-20]
1], N- (n-propyl) -N-perfluorooctane sulfonic acid amide ethanol [Mitsubishi Materials Corporation
EF-121] manufactured by Mitsubishi Materials Co., Ltd.
102, same EF-103, same EF-104, same EF-1
05, the same EF-112, the same EF-121, the same EF-12
2A, EF-122B, EF-122C, EF-
122A3, EF-123A, EF-123B, EF-132, EF-301, EF-303, E
F-305, EF-306A, EF-501, E
F-700, EF-201, EF-204, EF
-351, EF-352, EF-801, EF-
802, EF-125DS, EF-1200, E
F-L102, same EF-L155, same EF-L174,
The same EF-L215 etc. are mentioned. In addition, 3- (2-perfluorohexyl) ethoxy-1,2-dihydroxypropane [MF-100 manufactured by Mitsubishi Materials Corporation], N
-N-propyl-N-2,3-dihydroxypropyl perfluorooctyl sulfonamide [MF-110 manufactured by Mitsubishi Materials Corporation], 3- (2-perfluorohexyl) ethoxy-1,2-epoxypropane [Mitsubishi Materials MF-120], Nn-propyl-N
-2,3-epoxypropyl perfluorooctyl sulfonamide [MF-130 manufactured by Mitsubishi Materials Corporation],
Perfluorohexyl ethylene [Mitsubishi Materials Corporation
MF-140], N- [3-trimethoxysilyl) propyl] perfluoroheptylcarboxylic acid amide [MF-150 manufactured by Mitsubishi Materials Corporation], N- [3-trimethoxysilyl) propyl] perfluoroheptylsulfone. Examples include amide [MF-160 manufactured by Mitsubishi Materials Corporation] and the like. The fluorine-based surfactant is used in a proportion of 0.1 to 20% by weight based on the total amount of the liquid crystal and the resin forming material.

Further, the solid content concentration in the coating solution for forming the information recording layer is preferably 10 to 60% by weight, and at the time of curing, the curing conditions such as the kind and concentration of the resin, the coating layer temperature, and the ultraviolet irradiation conditions are appropriately selected. By setting
As the outer surface layer, it is possible to excellently form a skin layer composed only of a resin layer having no liquid crystal phase.

Since the film thickness of the information recording layer affects the resolution, the film thickness after drying is 0.1 μm to 10 μm, preferably 3 μm.
The thickness may be set to μm to 8 μm, and the operating voltage can be lowered while maintaining high resolution. If the film thickness is too thin, the contrast of the information recording portion will be low, and if it is too thick, the operating voltage will be high, such being undesirable.

By forming the skin layer on the outer surface of the information recording layer, it is possible to increase the use ratio of the liquid crystal in the information recording layer and to prevent the liquid crystal from seeping out.

The photoreceptor of the present invention will be described below. The photoreceptor can be a single-layer photoreceptor or a laminated photoreceptor. The single-layer type photoconductor is formed by laminating a mixture of a charge generating substance and a charge transporting substance on an electrode, and the laminated type photoconductor separates the charge generating layer and the charge transporting layer to generate a charge. It is a type in which a layer and a charge transport layer are sequentially laminated on an electrode.

In the photoconductor used in the present invention, the following general formula (1)

[0032]

[Chemical 2] (However, X in the formula may be the same or different selected from hydrogen, a lower alkyl group, a lower alkoxy group, a nitro group, a sulfonic acid group, a hydroxyl group, a carboxyl group, and a halogen atom, and n is 0 to 3 And R is a hydrocarbon ring group, a heterocyclic group, or an alkyl group which may be substituted.) As a charge generating substance, and an electron-accepting substance is used as a monolayer. Type photoconductor, it is added together with the bisazo compound, and in the case of the layered photoconductor, it is added together with the bisazo compound in the charge generation layer, or added together with the charge generation layer and also in the charge transport layer. It is something.

The photosensitive member used in the present invention can not only provide electrostatic information corresponding to the information pattern to the charge holding medium with high sensitivity and high contrast, but also after forming the photosensitive member. Since the dark potential does not increase over time, the stability of the contrast ratio with time is excellent.

First, the bisazo compounds which can be preferably used in the present invention are exemplified below by the combination of the respective substituents in the above general formula (1).

[0035]

[Table 1] Among these, preferable bisazo compounds are exemplified below.

[0036]

[Chemical 3] Next, the charge transport material forming the charge transport layer is a material having a good property of transporting charges generated by the charge generating material, and examples thereof include hydrazone-based, pyrazoline-based, PVK-based, carbazole-based, oxazole-based, triazole-based, aromatic compounds. There are group amine type, amine type, triphenylmethane type, polycyclic aromatic compound type and the like, and any substance having hole transporting property and electron transporting property can be used.

Among them, the compound number (2
Those of 4) to (33) are preferable.

[0038]

[Chemical 4]

[0039]

[Chemical 5] Next, as the electron-accepting substance added to the charge generation layer, or the charge generation layer and the charge transport layer, 2,4,7-trinitrofluorenone, tetrafluoro-P-benzoquinone, tetracyanoquinodimethane, and tricyanoquinodimethane Phenylmethane,
Maleic anhydride, hexacyanobutadiene, etc. can be used.

Next, a method for producing the photoconductor will be described.

First, in the laminated type photoreceptor, the charge generating substance and the electron accepting substance are mixed in an amount of 0.001 part by weight to 10 parts by weight with respect to 1 part by weight of the charge generating substance. A charge generating layer is formed by dispersing and dissolving in a medium, applying and drying on the electrode, and then forming a charge generating layer on the charge generating layer. Or by mixing 0.001 part by weight to 10 parts by weight of the electron-accepting substance with respect to 1 part by weight of the charge-transporting substance, dispersing and dissolving in an appropriate medium, coating and drying. The charge transport layer is formed by coating and drying. The thickness of the charge generation layer after drying is preferably 0.1 to 10 μm, and the thickness of the charge transport layer is preferably 1 to 50 μm.

In the single-layer type photoreceptor, the charge generating substance and the charge transporting substance may be mixed in a ratio of 1: 100 to 100: 100 (parts by weight), and the electron accepting substance may be the charge generating substance and the charge transporting substance. The total amount of the substance is 0.
It is advisable to mix them in a proportion of 001 parts by weight to 10 parts by weight, and they are dispersed or dissolved in a medium and applied on an electrode and dried to form a layer. The film thickness is preferably 1 to 50 μm.

Further, a charge transfer complex may be formed by forming a complex with a charge generating substance and a charge transporting substance. Normal,
The photoconductor has a photosensitivity determined by the light absorption property of the charge generating substance. However, when the charge generating substance and the charge transporting substance are mixed to form a complex, the light absorbing property is changed. For example, polyvinylcarbazole (PVK) is used in the ultraviolet region. However, trinitrofluorenone (TNF) feels only around 400 nm wavelength, but PVK-TNF complex becomes sensitive up to 650 nm wavelength region.

In both the single layer type and the laminated type, a binder can be used in forming the photoconductive layer. As the binder, a silicone resin, a styrene-butadiene copolymer resin, an epoxy resin, an acrylic resin can be used. , Saturated or unsaturated polyester resin, polycarbonate resin, polyvinyl acetal resin, phenol resin, polymethylmethacrylate (PMMA) resin, melamine resin, polyimide resin, vinyl chloride resin, vinyl acetate resin, etc. It is recommended to use 0.1 to 10 parts by weight for 1 part by weight of each material of the transport material. The binder is not necessary when it itself serves as a binder as a charge generating substance or a charge transporting substance.

As the solvent, 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 can be mentioned.

As a coating method, a blade coating method, a dipping method, a spinner coating method or the like can be used.

In the photoconductor of the present invention, the photoconductive layer is not necessarily provided in order to reduce the sensitivity, but a photoconductive layer may be laminated on the electrode via a charge injection preventing layer as a means for suppressing the change with time.

The charge injection prevention layer is provided on at least one of both surfaces of the photoconductive layer, or both surfaces, a dark current when a voltage is applied to the photoconductive layer (for example, charge injection from an electrode), that is, not exposed. Nevertheless, it is provided in order to prevent the phenomenon that charges move in the photoconductive layer as if exposed.

There are two types of charge injection prevention layers, one utilizing the so-called tunneling effect and the other utilizing the rectifying effect. First, in the case of utilizing the so-called tunneling effect, the current does not flow to the photoconductive layer or the surface of the insulating layer due to the charge injection prevention layer only by applying the voltage, but when light is incident, it corresponds to the incident portion. Since one of the charges (electrons or holes) generated in the photoconductive layer is present in the charge injection prevention layer, a high electric field is applied to cause a tunnel effect and a current flows through the charge injection prevention layer. ..

Such a charge injection prevention layer is formed by a single layer such as an inorganic insulating film, an organic insulating polymer film, an insulating monomolecular film, or by laminating these layers. As ₂ O ₃ , B ₂ O ₃ , Bi ₂ O ₃ , CdS, CaO, CeO ₂ ,
Cr ₂ O ₃ , CoO, GeO ₂ , HfO ₂ , Fe ₂ O ₃ , La ₂ O ₃ , MgO, Mn
_{O 2, Nd 2 O 3,} Nb 2 O 5, PbO, Sb 2 O 3, SiO 2, SeO 2, Ta 2 O
₅ , TiO ₂ , WO ₃ , V ₂ O ₅ , Y ₂ O ₅ , Y ₂ O ₃ , ZrO ₂ , BaTiO ₃ , Al
₂ O ₃ , Bi ₂ TiO ₅ , CaO-SrO, CaO-Y ₂ O ₃ , Cr-SiO, LiTa
O ₃ , PbTiO ₃ , PbZrO ₃ , ZrO ₂ -Co, ZrO ₂ -SiO ₂ , AlN, B
N, NbN, Si ₃ N ₄ , TaN, TiN, VN, ZrN, SiC, TiC
, WC, Al ₄ C _3, etc. are formed by glow discharge, vapor deposition, sputtering or the like. The film thickness of this layer is determined for each material used in consideration of the insulating property for preventing charge injection and the tunnel effect.

Next, the charge injection preventing layer utilizing the rectifying effect is formed by providing the charge transporting layer having the charge transporting ability of the polarity opposite to that of the electrode substrate by utilizing the rectifying effect. As such a charge injection prevention layer, an inorganic photoconductive layer,
It is formed of an organic photoconductive layer and an organic-inorganic hybrid type photoconductive layer, and its film thickness is about 0.1 to 10 μm. Specifically, when the electrode is negative, an amorphous silicon photoconductive layer doped with B, Al, Ga, In, etc., an amorphous selenium photoconductive layer, a polyvinylcarbazole photoconductive layer, or oxadiazole, pyrazoline, polyvinylcarbazole, Stilbene, anthracene, naphthalene, tridiphenylmethane, triphenylmethane, azine, amine,
An organic charge transport layer formed by dispersing an aromatic amine or the like in a resin, and when the electrode is positive, P, N, As, Sb, B
amorphous silicon photoconductive layer doped with i, etc., Zn
An O photoconductive layer, a polyvinylcarbazole-trinitrofluorenone organic photoconductive layer, and the like are formed by methods such as glow discharge, vapor deposition, sputtering, CVD, and coating.

The photosensitive member support is not particularly limited in thickness and material as long as it has a certain strength capable of supporting the photosensitive member. For example, a flexible plastic film, metal foil or paper. Alternatively, a rigid body such as glass, a plastic sheet, a metal plate (which can also serve as an electrode) is used. However, when it is used in a device that records information by making light incident from the photoconductor side, it is naturally necessary to have a property of transmitting that light. For example, when it is used in a camera that makes natural light incident light and enters it from the photoconductor side. Has a thickness of 1
A transparent glass plate of about mm or a plastic film or sheet is used.

The photoreceptor electrode is formed on the photoreceptor support except when a metal support is used.
The material is not limited as long as the specific resistance value is 10 ⁶ Ω · cm or less, and it is an inorganic metal conductive film, an inorganic metal oxide conductive film, an organic conductive film such as a quaternary ammonium salt, or the like. Such a photoreceptor electrode is formed on the photoreceptor support by vapor deposition, sputtering, CVD, coating, plating, dipping, electrolytic polymerization, or the like. The film thickness needs to be changed depending on the electrical characteristics of the material forming the photoconductor electrode and the applied voltage at the time of recording information. For example, in the case of aluminum, it is about 100 to 3000 Å. Similar to the support, this photoconductor electrode is required to have the above-mentioned optical characteristics when it is necessary to transmit information light. For example, if the information light is visible light (400 to 700 nm), IT
Transparent electrodes such as O (In ₂ O ₃ -SnO ₂ ), SnO _{2 and the} like, which are coated by sputtering, vapor deposition, or fine powders thereof formed into an ink with a binder, Au, Al,
Semi-transparent electrode made of Ag, Ni, Cr, etc. by vapor deposition or sputtering, tetracyanoquinodimethane (TCN)
Q), an organic transparent electrode coated with polyacetylene or the like is used.

The above electrode material can also be used when the information light is infrared (700 nm or more) light, but in some cases, a colored visible light absorbing electrode can be used to cut visible light.

Further, when the information light is ultraviolet (400 nm or less) light, the above electrode material can be basically used, but the electrode substrate material absorbs ultraviolet light (organic polymer material,
Soda glass and the like) are not preferable, and materials such as quartz glass that transmit ultraviolet light are preferable.

An antireflection film may be formed on the light incident surface. This antireflection film can be formed as a single layer or a laminated layer of an inorganic material such as magnesium fluoride or titanium oxide by vapor deposition, sputtering or the like.

Next, an information recording method on the first information recording medium of the present invention will be described.

FIG. 2 is a view for explaining the method of recording information on the information recording medium shown in FIG. 1A, in which 1 is a photoconductor, 5 is a photoconductive layer support, and 7 is a photoconductor electrode. , 9 are photoconductive layers, and 17 is a power source.

First, 1000 Å thick indium tin oxide (ITO) was formed on a photoconductive layer support 5 made of 1 mm thick glass.
Form a transparent photoconductor electrode 7 consisting of
The photoconductive layer 9 having a thickness of about m is formed to form the photoconductor 1.

As shown in FIG. 2A, the information recording medium 3 is arranged on the photoconductor 1 with a gap of about 10 μm.

Then, a voltage is applied between the electrodes 7 and 13 by the power source 17 as shown in FIG. In a dark place, the photoconductive layer 9 is a high resistance material.

In this state, when the light 18 is incident from the side of the photoconductor 1, the photoconductive layer 9 in the portion where the light is incident becomes conductive and becomes a low resistance element, an electric field acts on the information recording layer, and the information recording layer is formed. The alignment of the liquid crystal occurs in.

Further, when forming the information charges, some liquid crystals have different operating voltages and ranges. Therefore, when setting the applied voltage and the applied voltage time, the voltage is distributed among the photoconductor, the air gap, and the information recording medium. May be appropriately set to set the voltage distribution applied to the information recording layer to the operating voltage region.

The method of recording information on the information recording medium of the present invention enables planar analog recording and can obtain a high resolution because the alignment at the liquid crystal level can be obtained, and the exposure pattern can be changed by the alignment of the liquid crystal phase. It is visualized and held.

As the information input method, there are a high resolution electrostatic camera method and a laser recording method. The information light may be incident from the photoconductor side or the information recording medium side. First, a high-resolution electrostatic camera forms a recording member by the photoconductor 1 and the information recording medium 3 instead of the photographic film used in a normal camera, and an optical shutter can also be used. Electrical shutters may also be used.

Further, the optical information is separated into R, G, and B light components by the prism and the color filter, and taken out as parallel light.
Color imaging can also be performed by forming a frame or by arranging R, G, and B images on one plane to form one frame.

As a recording method using a laser, an argon laser (514.488 nm) was used as a light source,
A helium-neon laser (633 nm) or a semiconductor laser (780 nm, 810 nm, etc.) can be used, and the photoreceptor and the information recording medium are planarly brought into close contact with each other or the surfaces thereof are opposed to each other at a constant interval and a voltage is applied. In this state, laser exposure corresponding to an image signal, a character signal, a code signal, and a line drawing signal is performed by scanning. An analog recording such as an image is performed by modulating the light intensity of the laser, and a digital recording such as a character, a code, or a line drawing is performed by ON / OFF control of the laser light. In the case of halftone dot formation in an image, laser light is subjected to dot generator ON-OFF control. Incidentally, the spectral characteristics of the photoconductive layer in the photoconductor do not have to be panchromatic, as long as it has sensitivity to the wavelength of the laser light source.

In addition, instead of the photoconductor, corona charging, or a method of applying a voltage with a needle electrode or a pattern electrode in a contact or non-contact state, or information recording by an ion printer using an ion head You can also

The information recorded by the orientation of the liquid crystal is visible information that can be visually read, but it can be magnified and read by a reflection type projector, and further reflected by laser scanning or CCD. Information can be read with high accuracy by reading with light or transmitted light.

The information recording medium of the present invention records electrostatic information in a state where the electrostatic information is visualized by the orientation of the liquid crystal and has a memory property. This memory property is erased when the liquid crystal is heated to a temperature near its isotropic phase transition and can be reused.

Next, the second information recording medium will be described.

FIG. 1B is a view showing a cross section of the second information recording medium of the present invention, in which 13 'is an electrode layer,
The same reference numerals as those in FIG. 1A indicate the same contents.

In this information recording medium, an electrode layer 13 'is further provided in a pattern on the surface of the information recording layer in the first information recording medium. As such an electrode layer 13 ', the materials described in the above-mentioned electrode layer 13 can be used, and for example, an ITO layer may be provided by a sputtering method or a vapor deposition method.

Usually, when a mixture of a curable resin and a liquid crystal is used and the resin is cured to form a film, the liquid crystal oozes out on the film surface. For example, even if ITO is laminated by a sputtering method or a vapor deposition method, The ITO film is cracked and the conductivity is lowered.

In the second information recording medium of the present invention, since the skin layer consisting of only the ultraviolet curable resin is present on the surface of the information recording layer, the liquid crystal does not seep out and the IT layer is formed on the information recording layer.
Even if O or the like is directly provided by a vacuum deposition method, a sputtering method, or the like, the electrode layer can be prevented from cracking, and the conductivity is not deteriorated. In addition, heat resistance and sputtering resistance can be improved. Further, since the electrode layer is integrated with the information recording layer as compared with the first information recording medium, it is possible to make the gap between the electrodes uniform.

Information recording on the second information recording medium is performed by applying a voltage between the electrodes 13 and 13 'to orient the liquid crystal layer at the location where the electrode 13' is present. Alternatively, the electrode layers 13 and 13 'may be formed into a matrix and recorded in a pattern by manipulating the voltage. Alternatively, both electrodes may be uniformly provided on both sides of the information recording layer and a low voltage may be applied between both electrodes. Alternatively, the pattern of laser light may be recorded by heating the information recording layer in a pattern using laser light or the like and lowering the operating voltage in the heated portion to about the applied voltage. For information reproduction, for example, when transmitted light is used, light is transmitted through the information recording section, whereas light is scattered at a portion where information is not recorded, and a contrast with the information recording section can be obtained. Is.

[0077]

The first information recording medium of the present invention holds liquid crystal in the information recording layer and does not cause liquid crystal bleeding phenomenon on its surface, and is combined with a photoconductor or the like. When used in the information recording method described above, it is possible to record electrostatic information without image irregularity without disturbance of information recording by the liquid crystal on the surface of the information recording layer. Further, since the information recording layer can be uniformly thinned by the coating technique, the gap between the information charges formed on the information recording layer and the electrode layer can be made evenly small, and a large area information recording medium can be manufactured. Yes, high resolution images can be recorded and reproduced.

Further, in the case of the second information recording medium, since the phenomenon of liquid crystal seepage on the surface of the information recording layer can be prevented, even if an electrode layer such as an ITO film is formed by a vapor deposition method or the like, wrinkles, There is no occurrence of cracks and the like, and deterioration of conductivity can be prevented. Further, since the electrode layer can be directly provided on the information recording layer, the gap between both electrodes can be made uniform.

Each information recording medium of the present invention can easily obtain the electro-optical effect, and can record and store analog information. In addition, it is opaque due to light scattering when the electric field due to the information charge is not applied, and when the electric field due to the information charge is applied, the liquid crystal phase is aligned and the information recording section is made transparent, so that a deflector plate is not required for information reproduction. Therefore, the optical system for reading can be simplified.

Examples will be described below. In the examples, “part” means “part by weight” and “%” means “% by weight”.

[0081]

Example 1 Multifunctional monomer (dipentaerythritol hexaacrylate, manufactured by Toagosei Co., Ltd., M-40
0) 40 parts, photocuring initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Merck, Darocur 1173) 2 parts, smectic liquid crystal (S-6 manufactured by BDH) 60 parts, Surfactant (Florard FC-43
0, manufactured by Sumitomo 3M) 3 parts was uniformly dissolved in 195 parts of xylene, and an ITO film was formed on the glass substrate (thickness of about 2,000 Å) by a sputtering method on a glass substrate (1.1 mm thick) ITO
After coating with a blade coater on the film side, drying at 50 ° C. for 3 minutes, and then vacuum drying at 50 ° C. for 3 minutes,
Immediately, ultraviolet rays of 300 mJ / cm ² were irradiated to cure the polyfunctional monomer. The film thickness was 6 μm.

The cross section of this information recording layer was extracted with liquid crystal using hot methanol and dried, and then the internal structure was observed with a scanning electron microscope (Hitachi, Ltd., S-800, 10000 times). However, as shown in FIG. 4, the surface of the layer is covered with an ultraviolet curable resin having a thickness of 0.6 μm, and a resin particle phase having a particle diameter of 0.1 μm is contained in the liquid crystal phase forming a continuous layer inside the layer. It can be seen that it has a filled structure.

Next, an ITO film was formed as an upper electrode on the cured information recording layer by sputtering to about 500 Å.
The information recording medium of the present invention was produced by forming a film having a thickness of.

A lead wire is attached between both electrodes of this medium,
A voltage of 400 V DC was applied to the terminals for 0.1 second. The transmittance of 633 nm light was 40% before the voltage was applied, but became 80% after the voltage was applied.

Further, this transparent state was kept at room temperature for one year or more, and showed a good memory property. Next, when the information recording medium after applying the voltage was placed on a hot plate at 60 ° C. and immediately cooled to room temperature after 10 seconds, the liquid crystal did not seep out and the whole was returned to the scattering state before applying the voltage. ,
Reusable.

[0086]

Example 2 The smectic liquid crystal (BD
Example 6 was repeated except that smectic liquid crystal (S1 manufactured by BDH) was used instead of S-6) manufactured by H company, 105 parts of xylene was used, and the coating layer temperature was dried at 32 ° C. When an information recording medium was prepared and tested in the same manner as in Example 1, the same performance as in Example 1 was exhibited.

[0087]

Example 3 (Production of Photoreceptor) A charge generating material is represented by the following formula.

[0088]

[Chemical 6] A solution in which 3 parts of a bisazo pigment and 1 part of a polyvinyl acetal resin were mixed in a mixed solvent of dioxane: cyclohexane = 1: 1 to make a solid content of 2% and 100 g was sufficiently dispersed by a ball mill to prepare an ITO transparent electrode (film thickness). Approximately 500Å, resistance value 80Ω / sq.) Is applied to the ITO side of a glass substrate using a blade coater with a 2 mil gap, and 10
After drying at 0 ° C. for 1 hour, a charge generation layer having a thickness of 0.3 μm was formed.

Next, 15 parts of p-diethylaminobenzaldehyde-N-phenyl-benzylhydrazone as a charge transporting material and 10 parts of a polycarbonate resin (trade name: Iupilon S-100, manufactured by Mitsubishi Gas Chemical Co., Inc.) were added to dichloromethane: 1,1. , 2-trichloroethane = 4: 6 mixed solvent to adjust the solid content to 17.8%,
The charge generation layer was coated with a blade coater having a gap thickness of a mil and dried at 80 ° C. for 2 hours to form a charge transport layer having a film thickness of 10 μm, thereby preparing an organic photoreceptor.

On the other hand, in the information recording medium of Example 1, an information recording medium without an upper electrode was prepared, and the photoreceptor and the polyester film having a thickness of 9 μm were used as spacers, and the photoreceptor side was positive and the information recording was performed. A DC voltage of 800 V was applied with the medium side being negative.

With the voltage applied, the illuminance of 10
The exposure using a halogen lamp of 00 lux as a light source is set to 0.
It was carried out for 1 second, and after the exposure was completed, the information recording medium was taken out and the information recording was completed. The exposed portion became transparent, and the transmittance of this portion was 90%.

Further, as an exposure method, a normal camera is used, and in the same manner as described above, the exposure is f = 1.4 with a voltage applied of 800 V through the gap, the shutter speed is 1/60 seconds, and an image of a copy is photographed outdoors or in the daytime. I went. When the information recording medium was taken out after the exposure, an image having gradation was formed.

Further, this medium was read by a film scanner using a CCD sensor and output by a sublimation transfer printer, and as a result, a hard copy having gradation was obtained.

[0094]

Example 4 (Preparation of Photoreceptor) 3 parts of the bisazo pigment represented by the above [Chemical Formula 6] as a charge generating material, a mixed resin of vinyl chloride resin and vinyl acetate resin (manufactured by Denka Co., Ltd., # 1000
D) 1 part with 100 g of a solution of dioxane: cyclohexane = 1: 1 with a solid content of 1.3% was sufficiently dispersed with a ball mill to prepare an ITO transparent electrode (thickness: about 500Å, resistance value: 80 Ω / sq.) Is applied to the ITO side of a glass substrate using a blade coater with a 2 mil gap and dried at 100 ° C. for 1 hour to give a film thickness of 0.3 μm.
The charge generation layer of was formed.

Next, 1,1-bis (4-diethylaminophenyl-1,3-butadiene 1) was used as a charge transport material.
0 parts and polystyrene resin (Denka: trade name MW-
1) 1 part was adjusted to a solid content of 15% with a mixed solvent of dichloromethane: 1,1,2-trichloroethane = 4: 6, and this solution was applied onto the charge generation layer with a blade coater having a gap thickness of 5 mils. It was applied and dried at 80 ° C. for 2 hours to form a charge transport layer having a film thickness of 20 μm, and an organic photoreceptor was produced.

On the other hand, in the information recording medium of Example 2, an information recording medium without an upper electrode was prepared, and the photoreceptor and the polyester film having a film thickness of 9 μm were used as spacers and the photoreceptor side was positive and the information recording was performed. A DC voltage of 800 V was applied with the medium side being negative.

With the voltage applied, the illuminance of 10
The exposure using a halogen lamp of 00 lux as a light source is set to 0.
It was carried out for 1 second, and after the exposure was completed, the information recording medium was taken out and the information recording was completed. The exposed portion became transparent, and the transmittance of this portion was 90%.

Further, an ordinary camera was used as an exposure method, and an illuminance of 2000 lux from the photosensitive member side and an exposure f =
4. The subject was photographed at a shutter speed of 1/30 seconds. When the information recording medium was taken out after the exposure, an image having gradation was formed.

Further, this medium was read by a film scanner using a CCD sensor and output by a sublimation transfer printer, and as a result, a hard copy having gradation was obtained.

[0100]

Comparative Example Instead of the resin forming material in Example 1,
A bisphenol A resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.), which is a thermosetting resin, and an aliphatic curing agent (B-002, manufactured by the same company) were used, except that the resin was heated to 60 ° C. and cured. An information recording medium was produced in the same manner as in Example 1.

When information was recorded on this information recording medium in the same manner as in Example 1, spot-like stains were generated on the information recording surface,
It was found that the liquid crystal was seeped out.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an information recording medium of the present invention.

FIG. 2 is a diagram for explaining an information recording method on the first information recording medium of the present invention.

FIG. 3 is a scanning electron micrograph, which is a drawing and shows a grain structure in a cross section of an information recording layer of an information recording medium of the present invention.

[Explanation of symbols]

1 is a photoconductor, 3 is an information recording medium, 5 is a photoconductive layer support,
7 is a photoconductor electrode, 9 is a photoconductive layer, 11 is an information recording layer, 1
3, 13 'are electrode layers, 15 is a substrate, 17 is a power source, 18 is pattern exposure

Claims (6)

[Claims] 1. An information recording medium in which an information recording layer comprising a liquid crystal phase and an ultraviolet curable resin phase is provided on an electrode layer, the information recording layer comprising a liquid crystal and an ultraviolet curable resin forming material. An information recording medium, which is formed by applying a mixed solution onto an electrode layer and then curing the same by irradiation with ultraviolet rays, and forming an outer surface of the skin layer on a skin layer made of only an ultraviolet curable resin. 2. An information recording medium in which an information recording layer comprising a liquid crystal phase and an ultraviolet curable resin phase is provided on an electrode layer, wherein the information recording layer is liquid crystal, an ultraviolet curable resin forming material and fluorine. It is characterized in that it is formed by applying a mixed solution with a surface-active agent on an electrode layer and then curing it by irradiating with ultraviolet rays, and the outer surface thereof is formed into a skin layer consisting of only an ultraviolet curable resin. Information recording medium. 3. An information recording medium having an information recording layer comprising a liquid crystal phase and an ultraviolet curable resin phase on an electrode layer, wherein the information recording layer comprises a liquid crystal and an ultraviolet curable resin forming material. An information recording medium is formed by applying the mixed solution on the electrode layer and then curing it by ultraviolet irradiation, and the outer surface of the information recording medium is formed on a skin layer consisting of only an ultraviolet curable resin, and a photoconductive film is formed on the electrode layer. A layered photoconductor is arranged in contact or non-contact with each other, and information is exposed from the photoconductor or the information recording medium side while applying a voltage between both electrodes of the information recording medium and the photoconductor. An information recording / reproducing method characterized in that information is recorded by orienting the phases, and the reproduced information is reproduced as visible information by transmitted light or reflected light. 4. The information recording / reproducing method according to claim 3, wherein the photoconductor contains a compound represented by the following general formula (1) in its photoconductive layer. General formula (1) (However, X in the formula may be the same or different selected from hydrogen, a lower alkyl group, a lower alkoxy group, a nitro group, a sulfonic acid group, a hydroxyl group, a carboxyl group, and a halogen atom, and n is 0 to 3 And R is a hydrocarbon ring group, a heterocyclic group, or an alkyl group which may be substituted.) 5. An information recording medium in which an information recording layer comprising a liquid crystal phase and an ultraviolet curable resin phase and an electrode layer are sequentially provided on the electrode layer, at least one of the electrode layers being transparent, The information recording layer is formed by applying a mixed solution of a liquid crystal and a UV-curable resin forming material onto the electrode layer and then curing it by UV irradiation, and the outer surface thereof is a skin layer consisting of only the UV-curable resin. An information recording medium characterized by being formed on. 6. An information recording medium in which an information recording layer comprising a liquid crystal phase and an ultraviolet curable resin phase and an electrode layer are sequentially provided on the electrode layer, and at least one of the electrode layers is transparent, and The information recording layer is formed by applying a mixed solution of a liquid crystal and a UV-curable resin forming material onto the electrode layer and then curing it by UV irradiation, and the outer surface thereof is a skin layer consisting of only the UV-curable resin. Information is recorded on the information recording medium formed on the disk by applying a voltage in a pattern between both electrodes to orient the liquid crystal phase according to the pattern, and transmitted light or reflected light is used when reproducing the recorded information. An information recording / reproducing method characterized by reproducing as visible information by light.