JPH02245758A - Internal accumulation type electrostatic charge image recording medium - Google Patents

Abstract

PURPOSE:To enhance image quality and resolution and to enable optionally repeating reproduction of information in an image quality in accordance with any purpose by laminating on a support an electrode layer and near above it a single layer or plural layers comprising fine photoconductive particles or fine conductive particles and on this or these layers an insulating layer. CONSTITUTION:The electrostatic charge image recording medium 3 is formed by laminating on the support 15 the electrode layer 13, near above this the single layer or plural layers of the line photoconductive particles 16 or the fine conductive particles 16, and on this or these layers the insulating layer 11 having a prescribed specific resistivity, and after having accumulated information the ends of the medium 3 are sealed with protective layers 10, thus permitting the electric charge of the information accumulated in the fine particles 16 to be permanently preserved and surface potential induced by this charge to be easily detected by inserting through the protective layer 10 and measuring the potential difference between the electrode 13 electrostatic charge image recording medium 3 to optionally repeat reproduction of the information high in quality and resolution in accordance with any purpose.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention records an image electrostatically by exposure when voltage is applied,
The present invention relates to an internal storage type electrostatic image recording medium that allows image reproduction at any time.

(Prior art) Silver halide photography is conventionally known as a high-sensitivity photographing technique.In this photography method, the image is recorded on a film through a developing process, and silver halide is used to reproduce the image. This is accomplished by using an emulsion (photographic paper) or by optically scanning a developed film and reproducing it on a cathode ray tube (hereinafter referred to as CRT).

In addition, electrodes are deposited on the photoconductive layer, the entire surface of the photoconductive layer is charged by corona charging in a dark place, and then exposed to strong light to make the photoconductive layer conductive in the areas exposed to the light, and the charges in those areas are An electrostatic latent image is optically formed on the surface of the photoconductive layer by leaking and removing the residual electrostatic charge, and a toner having a charge of the opposite polarity (or a charge of the same polarity) as the residual electrostatic charge is attached, There is an electrophotographic technique in which electrostatic transfer is performed on paper, etc., and then developed.This is mainly used for copying, but it cannot be used for photography due to its low sensitivity, and the photoconductive layer as a recording medium. Since the retention time of the electrostatic charge is short, it is common to develop the toner immediately after forming the electrostatic latent image.

[Problem to be solved by the invention]

However, with electrophotographic technology, visualization of the obtained electrostatic latent image is easier and faster than with silver halide photography, but the storage time of the latent image is extremely short, and developer dissociation properties, image quality, etc. are inferior to silver halide photography. . Furthermore, TV photographing technology requires line-sequential scanning in order to extract and record electrical image signals obtained by an image pickup tube. Line-sequential scanning is performed using an electron beam in the image pickup tube and a magnetic head for video recording, but since resolution depends on the number of scanning lines, it is significantly degraded compared to planar analog recording such as silver halide photography.

TVJL imaging systems that utilize solid-state image sensors (CCDs, etc.), which have been developing in recent years, are essentially the same in terms of resolution, and the problems inherent in these technologies are that image recording is of high quality and
If the resolution was high, the processing steps would be complicated, and if the steps were simple, there would be a lack of memory function or a basic deterioration of image quality.

In addition, information can be reproduced as visible information by providing a thermoplastic material layer with a selenium particle layer on a transparent electrode, corona charging the entire surface, imagewise exposure, and thermal development, and the accumulated charge information is extremely permanent. However, it requires corona charging to record the information, and it also visualizes and reproduces the information.

The present inventors first arranged a photoreceptor made of a photoconductive layer with an electrode provided on its front surface, and a charge retention medium made of an insulating layer with an electrode provided on its rear surface, facing the photoreceptor. After image exposure is performed from the photoconductor side or the charge retention medium side with a voltage applied between both electrodes, the charge retention medium is separated and the surface potential stored as image information on the charge retention medium is amplified to reproduce the image. An electrostatic image recording medium to be outputted, wherein the insulating layer of the charge holding medium contains a layer of photoconductive or conductive fine particles, and has a function of accumulating charge in the fine particles. About issue # (Special application 1986)
No. 3-239490).

The present invention aims to improve the electrostatic image recording medium, and in particular to improve the retention characteristics of accumulated information charges. Our goal is to provide an electrostatic image recording medium that does not erase the information charges accumulated in the image.It has high quality and high resolution, has a simple information recording method, and can be stored for a long time. An object of the present invention is to provide an electrostatic image recording medium that can arbitrarily and repeatedly reproduce images, codes, and (1,0) information with image quality that suits the purpose, and an electrostatic image recording method thereof.

[Means for Solving the Problems] The internal storage type electrostatic image recording medium of the present invention includes an electrode layer provided on a support, and then photoconductive fine particles,
Alternatively, conductive fine particles are laminated in a single layer or in multiple layers, and an insulating layer is further laminated on the fine particle layer.

The photoconductive fine particles are laminated directly on the electrode layer or on the electrode layer via an insulating layer having a thickness of 1000 Å or less.

The constituent materials of the electrostatic image recording medium of the present invention, the constituent materials of the photoreceptor used for recording on the electrostatic image recording medium, the method for forming the same, and the electrostatic image recording and reproducing method will be described below.

1 and 2 are cross-sectional views of the electrostatic image recording medium 3 of the present invention, and FIGS. 3 and 4 show information on the electrostatic image recording medium shown in FIGS. 1 and 2, respectively. In Figure 0, which is a cross-sectional view of an electrostatic image recording medium showing the storage state after recording, 3 is the electrostatic image recording medium, 10 is a protective layer, 11 is an insulating layer, and 11' is an insulating layer with a film thickness of 1000 Å or less The layer 13 is an electrostatic image recording medium electrode, 15 is a support, and 16 is a fine particle.

The electrostatic image recording medium 3 records information as a distribution of electrostatic charges for each particle 16. Information recorded accordingly;
Alternatively, depending on the recording method, the shape of this electrostatic image recording medium can take various shapes. For example, an electrostatic camera (
When used in Japanese Patent Application No. 63-121591 filed by the same applicant, it is in the form of a general film (single frame or continuous frame) or a disk, and when digital information or analog information is recorded using a laser, etc. It can be tape-shaped, disk-shaped, or card-shaped.

The support 15 supports the electrostatic image recording medium 3 with strength, and its material and thickness are not particularly limited as long as it has a certain level of strength that can support the fine particles. A rigid body such as a flexible plastic film, paper, glass, or plastic sheet may be used, and light transmittance may also be required. Specifically, when the electrostatic image recording medium 3 takes the form of a flexible film, tape, or disk, a flexible plastic film is used, and when strength is required, a rigid sheet or glass is used. Inorganic materials such as

A case where the electrostatic image recording medium 3 takes the form of a flexible film, tape, or disk will be explained. First, the fifth
The one shown in Figure (a) is of a type in which the insulating layer 11, which is the recording section, is continuous.

This is made by forming an insulating layer on a support such as a plastic film provided with an electrode layer, leaving both sides of the support or the entire surface of the support. This electrostatic image recording medium has a length that is at least twice as long as one screen to be recorded (for example, one frame when taken with a camera, or within a track of digital information recording). Naturally, it also includes a structure in which a plurality of electrostatic image recording media are joined together in the longitudinal direction, and in this case, there may be a slit band where an insulating layer is missing between adjacent insulating layers.

Further, as shown in FIG. 5(b), there is a type in which the insulating layer 11 is discontinuous in the longitudinal direction.

This is made by forming an insulating layer discontinuously in the longitudinal direction on a support such as a plastic film, with or without leaving both sides of the support. Formed in layers. The size of this insulating layer depends on the exposure method of the image and information input device, but for example, when using a camera, it is 35 mm x 35 mm.
In the case of sub-ont input such as a laser beam, it is during the track of digital information recording. In the case of digital information recording, the insulating layer missing portion formed between adjacent insulating layers can be used as a tracking band when inputting and outputting information. Naturally, it also includes a structure in which a plurality of electrostatic image recording media are joined together in the longitudinal direction, and in this case, there may be a slit band where an insulating layer is missing between adjacent insulating layers.

Furthermore, as shown in FIG. 5(c), there is a type in which the insulating layer is discontinuous in the width direction.

This type is made by forming an insulating layer discontinuously in the width direction on a support such as a plastic film provided with an electrode layer, with or without leaving both sides of the support.
A plurality of strip-shaped insulating layers are formed on the support. The width of this insulating layer is equal to or an integral multiple of the width of the track of digital information to be recorded, and the missing part of the insulating layer formed between adjacent insulating layers is a tracking band during input/output of information. used as.

Furthermore, as shown in FIG. 5(d), there is a disc-shaped type.

In this type, an insulating layer is formed on the entire surface of a support such as a circular plastic film provided with an electrode layer, or with a continuous spiral-shaped missing portion of the insulating layer. In this electrostatic image recording medium, a circular cutout for driving an input/output device may be formed, and in the case of a digital information recording section, a continuous spiral cutout in the insulating layer may be formed to input information. It can be used as a tracking band during output.

The electrode 13 is formed on a support, and its material is not limited as long as it has a specific resistance value of 10' Ω·cow or less, and may be an inorganic metal conductive film, an inorganic metal oxide conductive film, or the like. Such electrostatic image recording medium electrodes are formed on the support by methods such as vapor deposition, sputtering, CVD, coating, plating, dipping, and electrolytic polymerization. In addition, the film thickness needs to be changed depending on the electrical properties of the material composing the electrode and the applied voltage during information recording, but for example, in the case of aluminum, it is about 100 to 3000, and the thickness of the film between the support and the insulating layer is It is formed on the entire surface between or in accordance with the formation pattern of the insulating layer.

The insulating layer 11 needs to have high insulation properties in order to suppress the movement of charges, and is required to have insulation properties with a specific resistance of 10 14 Ω·cm or more.

In the case of the electrostatic image recording medium shown in FIG. 1, the insulating layer is laminated by first forming fine particles 12 on the electrode by vapor deposition, and then depositing silica, alumina, etc. on the fine particle layer by vapor deposition, sputtering, etc. The layer can be formed by coating or dipping the resin or rubber dissolved in a solvent.

In the case of the electrostatic image recording medium shown in FIG. 2, an insulating layer 11' is first laminated on the electrode to a thickness of 1000 Å or less. This insulating layer 11° has the function of injecting charge from the electrode 13 into the fine particles by a tunneling phenomenon using an electric field formed by an image charge, and stably retaining the charge in the fine particles after injection. 1000Å
It is preferably formed by laminating silica, alumina, etc. by vapor deposition, sputtering, etc., with the following film thickness, and resin,
The rubber may be dissolved in a solvent and laminated by spinner coating.

As the resin, a thermoplastic resin, a thermosetting resin, an energy beam curing resin such as an ultraviolet curing resin or an electron beam curing resin, an engineering plastic, or rubber can be used.

Examples of thermoplastic resins include polyethylene, vinyl chloride resin, polypropylene, styrene resin, ABS resin,
Polyvinyl alcohol, acrylic resin, acrylonitrile-styrene resin, vinylidene chloride resin, AAS (
ASA) resin, ABS resin, cellulose conductor resin, thermoplastic polyurethane, polyvinyl butyral, poly-4-methylpentene-1, polybutene-1, rosin ester resin, etc., and fluororesins such as polytetrafluoroethylene, fluorinated Ethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, their disperdylane type or modified type (coating type), polyparaxylylene represented by the following structural formula (in addition, the above C type Not only those with the above structure, but also those in which one of the sites other than the main chain binding site in the benzene ring are substituted with chlorine, and the D type may be those in which two of the sites are substituted with chlorine, ) etc. are particularly preferred from the viewpoint of heat resistance and moisture resistance.

Examples of thermosetting resins include unsaturated polyester resins, epoxy resins, phenol resins, urea resins, melamine resins, diallyl phthalate resins, silicone resins, and energy ray-curable resins such as ultraviolet curable resins and electron beam curable resins. Examples of resins include radically polymerizable acrylate compounds, such as ester compounds of acrylic acid, methacrylic acid, or derivatives thereof, which have hydroxyl groups at both ends. Specifically, hydroxyethyl acrylate, hydroxyl Polymerization of propyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 4-hydroxycyclohexyl acrylate, 5-hydroxycyclooctyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, etc. In addition to (mek)acrylic acid ester compounds having one polymerizable unsaturated group, compounds having two polymerizable unsaturated groups represented by the formula % can be used.

Examples of the curable compound having two hydroxyl groups and one or more radically polymerizable unsaturated groups include glycerol methacrylate and the following general formula (where RSR' is a methyl group or hydrogen, and R is Short-chain diol residues such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, 1.6-hexanediol, etc.) can be used.

Engineering plastics include polycarbonate, polyamide, acetal resin, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polyimide resin, polysulfone, polyether sulfone,
Aromatic polyester, polyacrylate, etc. can be used.

In addition, as the insulating layer 11 laminated on the fine particles, a silicone film, a polyester film, a polyimide film, a fluorine-containing film, a polyethylene film, a polypropylene film, a polyparabanic acid film, a polycarbonate film, a polyamide film, etc. are attached via an adhesive or the like. It may be formed into a layer by doing this and used in the same manner as the above thermoplastic resin.

Note that the insulating layer 11 laminated on the fine particles 12 needs to be formed to a thickness of at least 1000 μm (0.1 μm) or more from the standpoint of insulation, and from the standpoint of flexibility, the thickness must be at least 1 μm.
00 μm or less is preferable.

The fine particles that store charge are formed from a photoconductive material or a conductive material.

Examples of photoconductive particulate materials include inorganic photoconductive materials such as amorphous silicon, crystalline silicon, amorphous selenium, crystalline selenium, cadmium sulfide, and zinc oxide, and organic photoconductive materials such as polyvinyl carbazole, fucrocyanine, and azo pigments. used.

In addition, as conductive materials, Group 1A (alkali metals), Group IB (copper group), Group IIA (alkaline earth metals), Group IIB (zinc group), Group 1[[A] of the periodic table are used. (aluminum group), IIIB group (rare earths), ■B group (titanium group), VIB group (vanadium group), VIB group (chromium group), ■B group (manganese group), same ■group ( The IVA group (carbon group) includes carbon, silicon,
Germanium, tin, and lead, antimony and bismuth as members of the VA group (nitrogen group), and sulfur, selenium, and tellurium as members of the VIA group (oxygen group) are used in fine powder form. Among the above elements, metals include metal ions, fine powder alloys,
It can also be used in the form of an organometallic complex.

Furthermore, the above elements can be used in the form of oxides, phosphorus oxides, sulfides, and halides. In particular, carbon, gold, copper, aluminum, etc. are preferably used.

Next, a method for forming the fine particle layer will be explained.

What is shown in Figures 1 and 2 is amorphous silicon,
The zero-particle layer forming material is formed by depositing a fine particle layer of amorphous selenium, crystalline selenium, etc. on an electrode or an insulating layer using a low-pressure evaporation device, and the material is 10 Torr to 10"3 Torr. When evaporated under moderately low pressure, it aggregates and becomes ultrafine particles with a diameter of about 10 to 0.1 μm, and the fine particles are stacked on the surface of the electrode or insulating layer in a single layer or in multiple layers. be.

Next, the structure of the photoreceptor used in the present invention will be explained in the sixth section.
The explanation will be based on the photoreceptor 1 shown in FIG.

The photoconductive layer support 5 is made of the same material as the insulating layer support 15, but when used in a device that records information by entering light from the photoreceptor side, it is natural that the light is For example, when the light is used in a camera that uses natural light as incident light and enters from the photoreceptor side, a transparent glass plate or a plastic film or sheet with a thickness of about 1 mm is used.

The photoreceptor electrode 7 is formed on the photoconductive layer support 5, except when metal is used for the photoconductive layer support 5, and the material thereof has a specific resistance value of 10-Ω·C- or less. There are no limitations, and examples include an inorganic metal conductive film, an inorganic metal oxide conductive film, and the like. Such a photoreceptor electrode 7 is formed on the photoconductive layer support 5 by vapor deposition, sputtering, CVD, coating, plating, dipping, electrolytic polymerization, or the like. The thickness also depends on the electrical characteristics of the material that constitutes the photoreceptor electrode 7.
It is necessary to change the voltage depending on the applied voltage when recording information, but for example, in the case of aluminum, it is 100 to 30
Approximately 00 people. Similarly to the photoconductive layer support 5, when it is necessary to input information light to this photoreceptor electrode 7,
The above-mentioned optical properties are required, for example, when information light is visible light (
400-700 nm), I To (IntO
s-SnOz), SnO! Transparent electrodes coated by sputtering, vapor deposition, etc., or by making ink with their fine powders together with a binder, Au, AI, A
g.

Tetracyanoquinodimethane (TCNQ), a translucent electrode made by vapor deposition or sputtering of Ni, Cr, etc.
An organic transparent electrode coated with polyacetylene or the like is used.

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

Furthermore, when the information light is ultraviolet light (400 nm or less), the above electrode materials can basically be used, but electrode substrate materials that absorb ultraviolet light (organic polymer materials, soda glass, etc.) are not preferred. A material that transmits ultraviolet light, such as quartz glass, is preferred.

The photoconductive layer 9 is a photoconductive layer in which photocarriers (electrons, holes) are generated in the irradiated area when light is irradiated, and these carriers can move across the layer width, especially in the presence of an electric field. This is a layer where the effect is noticeable when The materials include inorganic photoconductive materials, organic photoconductive materials, organic-inorganic composite photoconductive materials, and the like.

Below, these photoconductive materials and methods of forming the photoconductive layer will be explained.

(A) Inorganic photoreceptor (photoconductor) Inorganic photoreceptor materials include amorphous silicon, amorphous selenium, cadmium sulfide, zinc oxide, and the like.

(a) Amorphous silicon photoreceptor The amorphous silicon photoreceptor is ■Hydrogenated amorphous silicon (a-Si:H)
■Fluorinated amorphous silicon (a-3t:F) without doping with impurities, -P by doping B, AI, Ga, In, TI, etc.
type (hole transport type), ・P, Ag, 5bSB
There is a type in which i, etc. is made N type (electron transport type) by doping.

The method for forming the photoreceptor layer is to introduce silane gas and impurity gas together with hydrogen gas into a low vacuum.
I Torr), the film can be formed by depositing it on an electrode substrate heated or not heated by glow discharge, it can be formed by a thermochemical reaction on a heated electrode substrate, or it can be formed by vapor deposition or sputtering of a solid raw material. It can be used as a single layer or in a laminated form. The film thickness is 1 to 50 μm.

Further, in order to prevent charges from being injected from the photoreceptor electrode 7 and charging as if the photoreceptor electrode 7 had been exposed to light even though it had not been exposed, a charge injection prevention layer may be provided on the surface of the photoreceptor electrode 7. This charge injection prevention layer is applied on the electrode substrate and on the top of the photoreceptor. (surface layer), an a-SiN layer, an a-
It is preferable to provide an insulating layer such as 1zOsN on the SiC layer, 5ift layer, and the like. If this insulating layer is made too thick, no current will flow when exposed to light, so it needs to be at least 1000 Å or less, and considering ease of fabrication, it should be 400 to 50 Å.
Approximately 0 people is desirable.

In addition, as a charge injection prevention layer, it is preferable to provide a charge transport layer on the electrode substrate that has a charge transport ability of opposite polarity to the polarity of the electrode substrate by utilizing a rectifying effect.If the electrode is negative, a hole transport layer, an electrode If is brass, an electron transport layer is provided.For example, a-3i, which is Si doped with boron.
: H(n'') improves hole transport properties, provides a rectifying effect, and functions as a charge injection prevention layer.

(b) Amorphous selenium ffi photomaterial Amorphous selenium photoreceptor includes: ■Amorphous selenium (a-Se) ■Amorphous selenium tellurium (a-5e-Te) ■Amorphous arsenic selenium compound (a JlslSe3)■
There is an amorphous arsenide selenium compound 'M + Te.

This photoreceptor was manufactured by vapor deposition and sputtering, and 5x01SA j! was used as a charge injection blocking layer. *01s
A SiC5SiN layer is provided on the electrode substrate by vapor deposition, sputtering, glow discharge method, or the like. Moreover, a laminated type photoreceptor may be formed by combining the above items (1) to (4).The film thickness of the photoreceptor layer is the same as that of an amorphous silicon photoreceptor.

(c) Cadmium sulfide (CdS) This photoreceptor is manufactured by coating, vapor deposition, and sputtering methods. In the case of vapor deposition, solid particles of CdS are placed on a tungsten board and vapor deposited by resistance heating, or by EB.
(electron beam) evaporation or, in the case of sputtering, deposited on the substrate in an argon plasma using a CdS target. In this case, CdS is usually deposited in an amorphous state, but a crystalline oriented film (oriented in the film thickness direction) can also be obtained by selecting sputtering conditions. For coating, Cd
It is preferable to disperse S particles (particle size 1 to 100 μm) in a binder, add a solvent, and coat on the substrate.

(d) Zinc oxide (Zn 2 O) This photoreceptor is produced by a coating method or a CVD method. As a coating method, ZnS particles (particle size 1~
100 IIm) is dispersed in a binder, a solvent is added, and coating is performed on a substrate. Also C
In the VD method, organic metals such as diethylzinc and dimethylzinc are mixed with oxygen gas in a low vacuum (10-''~ITorr) and chemically reacted on a heated electrode substrate (150~400°C) to form zinc oxide. It is deposited as a film.In this case as well, a film oriented in the film thickness direction is obtained.

(B) Organic photoreceptor Organic photoreceptors include single-layer photoreceptors and functionally separated photoreceptors.

(a) Single-layer photoreceptor A single-layer photoreceptor is made of a mixture of a charge-generating material and a charge-transporting material.

Charge-generating substances> Substances that easily generate charges by absorbing light, such as azo pigments, disazo pigments, trisazo pigments, phthalocyanine pigments, perylene pigments, pyrylium dyes, cyanine dyes, and methine. A dye system is used.

<Charge transport material system> A material with good transport properties for ionized charges, such as hydrazone type, pyrazoline type, polyvinylcarbazole type,
There are carbazole-based, stilbene-based, anthracene-based, naphthalene-based, tridiphenylmethane-based, azine-based, amine-based, aromatic amine-based, etc.

Alternatively, a charge-transfer complex may be obtained by forming a complex with a charge-generating substance and a charge-transporting substance.

Normally, photoreceptors have photosensitivity determined by the light absorption properties of the charge-generating substance, but when a charge-generating substance and a charge-transporting substance are mixed to form a complex, the light absorption properties change; for example, polyvinylcarbazole (PVK) Trinitrofluorenone (TNF) is only felt at wavelengths around 400 nm, but PVK-TNF complexes are only felt at wavelengths around 650 nm.
You will be able to feel up to the wavelength range.

The thickness of such a single-layer photoreceptor is preferably 10 to 50 μm.

(b) Functionally separated photoreceptor Charge generating materials easily absorb light but have the property of trapping light, while charge transporting materials have good charge transport properties but poor light absorption properties. Therefore, it is a type in which a charge generation layer and a charge transport layer are laminated in order to separate the two and fully exhibit their respective characteristics.

<Charge generation layer> Examples of substances forming the charge generation layer include azo, disazo, trisazo, phthalocyanine, acidic xanthene dye, cyanine, styryl dye, biryllium dye, perylene, methine, a-5e, a-5
i, azulenium salts, squalium bases, etc.

Charge Transport Layer> Examples of substances forming the charge transport layer include oxadiazole, hydrazone, pyrazoline, PVK, carbazole, oxazole, triazole, aromatic amine, amine, and triphenylmethane. type, polycyclic aromatic compound type, etc.

The method for manufacturing a functionally separated photoreceptor is to first dissolve the charge generating substance in a solvent and apply it on the electrode, then dissolve the charge transport layer in the solvent and apply it to the charge transport layer, and then remove the charge generating layer from zero.
．． The thickness of the charge transport layer is preferably 1 to 10 um, and the thickness of the charge transport layer is 10 to 50 um.

In addition, in the case of either a single-layer photoconductor or a functionally separated photoconductor, silicone resin, styrene-butadiene copolymer resin, epoxy resin, acrylic resin, saturated or unsaturated polyester resin, polycarbonate resin, polyvinyl is used as a binder. Acetal resin, phenol resin, polymethyl methacrylate (PMMA) resin, melamine resin, polyimide resin, etc. are used as charge-generating materials and charge-generating materials, respectively.
0.1 to 10 parts to make it easier to adhere. As the coating method, a dipping method, a vapor deposition method, a sputtering method, etc. can be used.

Next, the charge injection prevention layer will be described in detail.

The charge injection prevention layer prevents dark current (
This can be provided to prevent charge injection from the electrode), that is, a phenomenon in which charges move in the photosensitive layer as if it had been exposed even though it had not been exposed.

There are two types of charge injection prevention layers: a layer that utilizes a so-called tunneling effect and a layer that utilizes a rectification effect. First, in a device that utilizes the so-called tunneling effect, when only a voltage is applied, current does not flow to the photoconductive layer or the surface of the insulating layer due to this charge injection prevention layer, but when light is incident, the current does not flow to the surface of the photoconductive layer or the insulating layer. 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, causing a tunnel effect and current flowing through the charge injection prevention layer. . Such a charge injection prevention layer is formed of a single layer such as an inorganic insulating film, an organic insulating polymer film, an insulating monomolecular film, or a stack of these. Examples of the inorganic insulating film include AszOi, B2O3, etc. ,BizO,,CdS,C
aO, CeO2, CrzOx, Coo, Ge01
,)1fO,,FezO3,LazO= ,11go
, MnO2, Nd2O2, Nb2O%, PbO, 5b
zOs, Stow, 5eO1, Taxes, Ti
0g, WOs, VzOs, y, o,, Y2O1, Zr
O,, BaTiO2, AIto.

, Old 2Tie, , CaO-5rO, Ca0-YzOs
, Cr-5in, LiTa01, PbTiO3, Pb
ZrO3, Zr0z-Co, Zr0l-5iO1,
AtN,,ON,NbN,5isNa,Ta
N, TiN, VN, ZrN.

It is formed of SiC, TiC, WC, Al4C3, etc. by glow discharge, vapor deposition, sputtering, etc. The thickness of this layer is determined depending on the material used, taking into account the insulating properties to prevent charge injection and the tunnel effect. Next, the charge injection prevention layer utilizing a rectifying effect is provided with a charge transporting layer having a charge transporting ability of opposite polarity to the polarity of the electrode substrate using a rectifying effect. That is, such a charge injection prevention layer is formed of an inorganic photoconductive iS layer, an organic photoconductive layer, and an organic-inorganic composite photoconductive layer, and has a thickness of about 0.1 to IO .mu.m. Specifically, if the electrode is negative, B, AI, C.

a, amorphous silicon photoconductive layer doped with In, etc., amorphous selenium, or oxadiazole, birapurine, polyvinylcarbazole, stilbene, anthracene, naphthalene, tridiphenylmethane, triphenylmethane, azine, amine, aromatic amine, etc. in the resin. When the electrode is positive, an amorphous silicon photoconductive layer doped with P, N, As, Sb, Bi, etc., a ZnO photoconductive layer, etc. are formed by glow discharge, vapor deposition, sputtering, etc. It is formed by a method such as CVD or coating.

In order to produce an electrostatic image recording device using the photoreceptor and electrostatic image recording medium formed in this way, the photoconductive layer surface of the photoreceptor and the electrostatic image recording medium surface are brought into contact, or
Alternatively, they are stacked facing each other in a non-contact state. In the case of non-contact, it is preferable to maintain non-contact mechanically or to face the photoreceptor and the electrostatic image recording medium with a spacer interposed at the end of the medium. . Although it depends on what kind of information input means is used, it goes without saying that spacers may be placed at appropriate locations on the surface of the photoreceptor and the surface of the electrostatic image recording medium. In the case of non-contact, the distance between the photoreceptor and the electrostatic image recording medium is 1 to 5
A suitable value is 0 μm, and the spacer can be made of an organic material such as plastic or an inorganic material such as glass.

Next, an electrostatic image recording method will be explained.

6 and 7 are diagrams for explaining the electrostatic image recording method on the electrostatic image recording medium shown in FIG. 2 of the present invention.
The figure shows the case where the fine particles are photoconductive fine particles, and Figure 7 shows the case where the fine particles are conductive fine particles. In the figure, 1 is the photoreceptor, 5 is the photoconductive layer support, 7 is the photoreceptor electrode, and 9 is the photoconductive Layer 17 is a power source.

First, in the electrostatic image recording method shown in FIG.
A transparent photoreceptor electrode 7 made of O is formed, and 10
The photoreceptor 1 is constructed by forming a photoconductive layer N9 of about μm. As shown in FIG. 6(a), for this t light body l,
The electrostatic image recording medium 3 is placed with a gap of about 10 μm in between.

Next, as shown in FIG. 7(b), the electrode 7.
A voltage is applied between 13. In the dark, since the photoconductive Ji9 is a high resistance material, no change occurs between the electrodes as long as the voltage applied to the gap is equal to or lower than the discharge start voltage according to Paschen's law. Further, when a voltage equal to or higher than the discharge starting voltage is applied to the gap by an external power source, a discharge occurs, charge is accumulated on the surface of the electrostatic image recording medium, and this state continues until the voltage drops to the discharge starting voltage, resulting in fogging charge. When light 18 is incident from the photoreceptor 1 side, the photoconductive layer 9 in the area where the light is incident exhibits conductivity, a discharge occurs, and charges are accumulated on the surface of the electrostatic image recording medium. Further, even if there is a uniform fog charge in advance, charge is further accumulated in the portion where light is incident.

Next, the power supply 17 is turned off, the electrostatic image recording medium 3 is peeled off from the photoreceptor 1, and the entire surface is exposed to light 20 as shown in FIG. Electron and hole carriers are generated, and the opposite charge induced in the electrode 13 by the image charge formed at the part where the light is incident moves through the insulating layer 11° by the created electric field by a tunneling phenomenon, and the particle This neutralizes the opposite charges in the layer and allows charges of the same polarity as the image charge to be accumulated in a stable state. In addition, when exposing the entire surface, it is necessary to expose the particle layer to generate electrons and hole carriers, so when exposing from the insulating layer side, the electrode may be opaque, but the insulating layer may be transparent or semi-transparent. It needs to be a transparent layer, and it is better to use transparent resin.
Further, when the entire surface is exposed from the electrode side, it is necessary to use a transparent inorganic conductive layer such as ITO1 tin oxide, or a transparent electrode such as a vapor deposited film of gold or the like.

Next, the case where the fine particles are conductive fine particles will be explained with reference to FIG.

As shown in FIG. 7(b), when light 18 is incident from the photoreceptor 1 side, a discharge is generated between the surface of the electrostatic image recording medium and charges are accumulated on the surface of the electrostatic image recording medium. Due to the electric field formed by the charges, opposite charges induced in the electrode move through the insulating layer 11' by a tunneling phenomenon, and are permanently stored in the conductive particle layer as information charges. When the exposure is completed, the voltage is turned off and the electrostatic image recording medium 3 is then taken out, thereby completing the formation of the electrostatic latent image.

Further, in the electrostatic image recording medium shown in FIG.
In this case, information charges can be accumulated in the particles as in the case of the electrostatic image recording medium shown in FIG. 2 above.

Note that the photoreceptor 1 and the electrostatic image recording medium 3 may be of a contact type instead of a non-contact type as described above, and in the case of a contact type, charges are drawn to the electrostatic image recording medium electrode 13 at the stage of exposure. It passes through the photoconductive N9 and reaches the surface of the electrostatic image recording medium.
The particles stop at the surface of the insulating layer 11, and information charges are accumulated in the particles in the same manner as described above.

The electrostatic image recording medium in which information charges are accumulated in the particles in this way is sealed by coating the electrode terminals with an insulating resin to form a protection 1110, as shown in FIGS. 3 and 4. This allows the information charges in the particles to be retained permanently.

When this electrostatic image recording method is used for planar analog recording,
Similar to silver salt photography, high resolution can be obtained, and the charges of the formed particle layer 12 are protected in the insulating layer and stored for a long period of time without being discharged.

Methods for inputting information to the electrostatic image recording medium of the present invention include a method using a high-resolution electrostatic camera and a recording method using a laser. First of all, a high-resolution electrostatic camera uses a photoreceptor 1 consisting of a photoconductive layer 9 with a photoreceptor electrode 7 on the front surface, instead of the photographic film used in ordinary cameras, and a photoreceptor 1 on the rear surface facing the photoreceptor 1. An electrostatic image recording medium consisting of an insulating layer 11 provided with an electrostatic image recording medium electrode 13 constitutes a voice recording member, and a voltage is applied to the image electrode to make the photoconductive layer conductive according to the incident light. It forms an electrostatic latent image of an incident optical image in fine particles by accumulating charges on an insulating layer according to the amount of light, and a mechanical shutter can also be used.
It is also possible to use an electric shutter, and the electrostatic latent image can be retained for a long time regardless of whether it is in a bright or dark place.

In addition, a color filter is used to separate the optical information into R, G, and B light components using a prism and extract it as parallel light.
Color photography is performed by forming one frame with three sets of electrostatic image recording media separated into R, G, and B, or by arranging R, G, and B images on 1,000 planes and making one frame with one set. You can also do it.

For recording methods using lasers, the light sources include argon laser (514,488 nm), helium-neon laser (633 nm), and semiconductor laser (780 nm).
nm, 810 nm, etc.), and a voltage is applied to the photoreceptor and the electrostatic image recording medium with their surfaces brought into close contact with each other or facing each other with a fixed interval. In this case, it is best to set the photoreceptor electrode to the same polarity as the carrier of the photoreceptor. In this state, laser exposure corresponding to image signals, character signals, code signals, and line drawing signals is performed by scanning. Analog recording, such as the
Halftone dots are formed by controlling the dot generator, and halftone dots are formed by applying dot generator ON-OFF control to laser light. Note that the spectral characteristics of the photoconductive layer in the photoreceptor do not need to be panchromatic (it only needs to be sensitive to the wavelength of the laser light source).

Next, a method for reproducing an electrostatic image recorded on an electrostatic image recording medium will be explained.

FIG. 8 is a diagram showing an example of a potential reading method in an electrostatic image recording and reproducing method, and the same numbers as in FIG. 1 indicate the same contents. In the figure, 21 is a potential reading section, 23 is a detection electrode, 25 is a guard electrode, 27 is a capacitor, and 29 is a voltmeter.

To reproduce information from an electrostatic image recording medium that has accumulated information charges, it is necessary to peel off the protective layer 10 that seals the electrode terminals to expose the electrodes and read the potential difference with the surface potential. This is done by making use of the characteristics of the terminal to pierce the terminal and contact it with the electrode, and then reading the potential difference between the surface potential and the surface potential.

When the potential reading section 21 is placed to face the surface of the electrostatic image recording medium, an electric field generated by the charges accumulated in the fine particle layer acts on the detection electrode 23, and an amount equal to the charge on the electrostatic image recording medium is generated on the detection electrode surface. An induced charge of . Since the capacitor 27 is charged with an equal amount of charge of opposite polarity to this induced charge, a potential difference corresponding to the accumulated charge is generated between the electrodes of the capacitor, and by reading this value with a voltmeter 29, the potential of the information charge is determined. be able to. Then, the potential reading section 21
By scanning the electrostatic latent image on the surface of the electrostatic image recording medium, the electrostatic latent image can be output as an electrical signal. Note that if only the detection electrode 23 is used, the electric field (electric line of force) due to charges in a wider range than the area facing the detection electrode of the electrostatic image recording medium will act, reducing the resolution, so a guard electrode 25 grounded around the detection electrode is used. You may also be able to place
Since the electric lines of force are oriented perpendicular to the surface,
Electric lines of force only act on the portion facing the detection electrode 23, and the potential of the portion approximately equal to the area of the detection electrode 23 can be read. The accuracy and resolution of potential reading vary greatly depending on the shape and size of the detection electrode and guard electrode, as well as the distance from the electrostatic image recording medium, so it is necessary to find and design optimal conditions according to the required performance.

FIG. 9 is a diagram showing a schematic configuration of an electrostatic image reproduction method, in which 61 is a potential reading device, 63 is an amplifier, and 65 is a CR
T, 67 is a printer.

In the figure, a potential reading device 61 detects the charge potential, and an amplifier 63 amplifies the detected output, which can be displayed on a CRT 65 and printed out using a printer 67. In this case, it is possible to arbitrarily select and output the part to be read at any time, and it is also possible to reproduce it repeatedly.

Furthermore, since the electrostatic latent image is obtained as an electrical signal, it can also be used for recording on other recording media, etc., if necessary.

Next, a color filter used to form a color image will be explained.

Figure 10 is a diagram showing a color separation optical system using a prism. In the figure, 71, 73.75 are prism blocks, 77.79
．． 81 is a filter, and 83.85 is a reflecting mirror.

The color separation optical system consists of three prism blocks, and a part of the light information incident on the a-plane of the prism block 71 is separated and reflected on the b-plane, and further reflected on the a-plane, and a B color light component is extracted from the filter 77. It will be done. The remaining optical information enters the prism block 73, travels to the zero plane, where some of it is separated and reflected, and the rest goes straight to the filters 79.
．． From 81, the G color photoacid component and the R color light component are taken out. Then, by reflecting the G and B color light components with the reflecting mirrors 83.85, the R, G, and B light can be extracted as parallel light.

By placing a filter 91 as shown in FIG. 11 in front of the photoreceptor 1 and photographing,
Either three sets of electrostatic image recording media separated into R, G, and B form one frame as shown in (b), or one set is arranged as RlG and B images on one plane as shown in FIG. 11 (c). You can also make it into one frame.

[Function] The electrostatic image recording medium of the present invention includes an electrode provided on a support,
Next, photoconductive fine particles or conductive fine particles are laminated in a single layer or multiple layers near the electrode, and an insulating layer having a specific resistance value of 10" to 10" ΩcmO is further laminated on the fine particle layer. The surface of the electrostatic image recording medium is placed in contact or non-contact with the photoconductive layer surface of the photoreceptor, and a voltage is applied between both electrodes to expose the image. When the zero particle layer on the surface of an electrostatic image recording medium in which information charges are accumulated is made of photoconductive fine particles, when the electrostatic image recording medium is peeled off from the photoreceptor and exposed to light over the entire surface, carriers are generated in the particle layer in the exposed area. ,
Due to the electric field formed by the information charges accumulated on the surface of the electrostatic image recording medium, charges corresponding to the information charges are injected from the electrodes of the electrostatic image recording medium into the photoconductive fine particle layer, and are accumulated as information charges. be. When the particle layer is made of conductive fine particles, the electric field formed by the charges on the surface of the electrostatic image recording medium causes the electrode to charge 7! l
(Accumulated in the conductive particle layer and stored as information charge in the conductive fine particle layer in the insulating layer. After information storage, the electrode terminal is sealed with a protective layer, so that the information charge accumulated in the fine particles is permanently stored.) is maintained.

The accumulated information charge is extremely stable because it is accumulated inside the insulating layer, and since the particle layer is laminated under the insulating layer, even if it is immersed in water, it will not be accumulated in the particle layer after drying. Since the surface charge is induced again by the charge, it is possible to prevent the information charge from attenuating due to moisture in the air or the like.

Further, when reproducing information, the potential difference can be easily detected by peeling off the protective layer or inserting the protective layer and measuring the potential difference between the electrode and the surface potential.

Examples will be described below.

Method for producing an electrostatic image recording medium [Example 1] Vacuum deposition (10-'
T.

Al electrodes are laminated to a thickness of 1,000 layers using the rr) method. Then, on the two electrodes, a Sing insulating layer is deposited to a thickness of 500 mm using a sputtering method.Next, this substrate is heated to 100°C with a heater plate, and selenium is deposited under low vacuum (3 Torr) in that state. A single layer of selenium particles having an average diameter of 0.5 μm was provided on the Sing insulating layer. Furthermore, silicone resin (TSR-
144 manufactured by Toshiba Silicon Co., Ltd.) was applied with a spinner coat (1000 rpm X30S),
After drying at 60°C for 3 hours, an insulating layer with a thickness of 10 μm was provided to produce an electrostatic image recording medium of the present invention.

[Example 2] (When the fine particles in Example 1 are conductive fine particles) Under the same conditions as in Example 1, using gold instead of selenium as the deposition material, low vacuum deposition was performed by resistance heating in a crucible. Ta. As a result, black fine gold particles with an average particle diameter of 0.2 μm were formed in a single layer on the surface of the silicone resin, and then, as in Example 1, a 50% xylene solution of silicone resin i (TSR-144 manufactured by Toshiba Silicon Co., Ltd.) was added to the surface of the silicone resin. ) (
11000rp x 30s) and 60°C13
After drying for hours, an insulating layer with a thickness of 10 μm was provided to produce an electrostatic image recording medium of the present invention.

[Example 3] (In the case of providing a fine particle layer directly on an electrode) An Al electrode is laminated to a thickness of 1000 nm on a 1 mm thick glass substrate by vacuum evaporation (10-' Torr). Next, this substrate is heated to 100"C with a heater plate, and selenium is deposited on the A2 electrode under low vacuum (3 Torr) in that state, thereby forming a single layer of selenium particles with an average diameter of 06.5 μm on the electrode. Further, xylene 50 of silicone resin (TSR-144 manufactured by Toshiba Silicon Co., Ltd.) was provided on the selenium particle layer.
% solution by spinner coating (1000 rpm
), and after drying at 60°C for 3 hours, the film thickness was 10. cr
An electrostatic image recording medium of the present invention was prepared by providing an insulating layer of m.

[Example 4] In the selenium deposition of Example 1, as a result of increasing the deposition time from 60 seconds to 300 seconds, multiple layers of crystalline selenium were formed on the 5iO1 insulating layer. This was confirmed by optical microscopy. Thereafter, an electrostatic image recording medium was obtained in the same manner as in Example 1.

[Reference Example 1]...Single-layer organic photoreceptor (PVK-TN
F) Production method Poly-N-vinylcarbazole Log (manufactured by Anan Perfumery Co., Ltd.), 10 g of 2,4.7-trinitrofluorenone,
2 g of polyester resin (binder: Byron 200 manufactured by Toyobo Co., Ltd.), 90% tetrahydrofuran (THF)
A mixed solution having a composition of g was prepared in a dark place, and IntOs-
A photosensitive layer having a photoconductive layer with a film thickness of about 10 μm was obtained by applying 5 nOi to a spuntered glass substrate (lam thickness) with a film thickness of about 1000 μm using a doctor blade and drying with ventilation at 60° C. for about 1 hour. I got it. In addition, in order to completely dry the sample, it was further air-dried for one day before use.

[Reference Example 2] A method for manufacturing an amorphous silicon aSi:H-free 99 photoreceptor will be explained with reference to FIG.

■Substrate cleaning Corning's 7059 glass (23X16XO39L, optically polished) with a SnO□ thin film photoreceptor electrode layer on one surface is ultrasonically cleaned in trichloroethane, acetone, and ethanol for 10 minutes each in this order. .

■ Preparation of the device After setting the cleaned substrate on the anode 106 in the reaction chamber 104 so as to ensure sufficient heat conduction, the inside of the reaction chamber is heated to 10-' Torr level, and the reaction chamber is evacuated with P. Then, the gas pipe is baked out at 1508° C. to 350° C. for about 1 hour, and the device is cooled after baking out.

■a-3i: Heat the heater at 108°C so that the temperature of the glass substrate on which H(n”) is deposited is 350°C.
! II. The internal pressure of the reaction chamber 104 was brought to 200 sT by controlling the rotational speed of the needle pulp and PMB using the P H3/S i H4-1000 ppse gas that had been heated and mixed in advance in the tank 101.

After the flow internal pressure becomes constant so that it becomes rr, Matc
40W Rf P through hing Box 103
power 102 (13,56 KHz) is input to form plasma between the cathode and anode. Deposition is carried out for 4 minutes, then Rf input is stopped and the needle pulp is closed.

As a result, approximately 0.0. A 2 μm a-3i:H(n”) film was deposited on the substrate.

■a-3i: Deposition of H 5iHn100% gas in the same way as ■
When the internal pressure becomes constant, 4 mTorr is applied through Matching Box 103.
0W RfPower 102 (13,56KHz)
to form a plasma and maintain it for 70 minutes.

When the deposition is completed, the input of Rf is stopped and the needle pulp is closed. l1eater l After O8Off, the board is cold, so take it out.

As a result, approximately 18.8. A um film was deposited on the a·si:H(n′) film.

In this way, a photoreceptor with a SnO,/a-3i:H(n'') blocking layer/a-3t:H (non-dope) of 20 μm was fabricated.

(Reference Example 2)...Production method of amorphous selenium-tellurium inorganic photoreceptor A-5e-
A Te thin film was deposited on an ITO glass substrate using a resistance heating method at a vacuum level of 10-' Torr. The film thickness was 1 μm.

Furthermore, while maintaining the degree of vacuum, S is heated using the same resistance heating method.
Evaporate only e to 10uma on the a-5e-Te layer.
-5g layers were laminated.

[Reference Example 3] Method for producing a functionally separated photoreceptor (method for forming a charge generation layer) A mixed solution having a composition of 0.4 g of chlorodiane blue and 40 g of dichloroethane was placed in a 250 ml stainless steel container, and a glass Peas No.3.180mJ! was added and pulverized for about 4 hours using a vibrating mill (Yasuyo Denki Seisakusho KED9-4) to obtain chlorocyan blue with a particle size of ~5 μm. After filtering the glass peas, 0.4 g of polycarbonate, Nipilon E-2000 (Mitsubishi Gas Chemical) was added and stirred for about 4 hours. This solution was applied using a doctor blade to a glass substrate (film thickness) on which about 1000 InO03-5nO□ had been sputtered to obtain a charge generation layer having a film thickness of ltIm. Drying was carried out at room temperature for one day.

[Method for forming charge transport layer]

4-Dibenzylamino-2-methylbenzaldehyde-
0.1 g of 1,1'-diphenylhydrazone.

Polycarbonate (Kneepilon E-2000) 0,
1 g.

A mixed solution having a composition of 2.0 g of dichloroethane was applied onto the charge generation layer using a doctor blade, and a mixture of about 10μ
A charge transport layer of m was obtained. Drying was performed at 60°C for 2 hours.

[Reference Example 4] (Formation method of charge generation layer) Butyral resin (Water Chemistry, 5LE) was added to 10 g of butyl acetate.
C) 0.25g, azulenium C having the following structural formula
10. Mix 0.5 g of salt and 133 g of glass peas, stir with a touch mixer for 1 day, then disperse and apply with a doctor blade or applicator on ITO layered on a glass plate. It was dried at 60°C for 12 hours or more.The film thickness after drying was 1 μm or less.

(Method for forming a charge transport layer) 9.5 g of tetrahydrofuran, 0.5 g of polycarbonate (Mitsubishi Gas Chemical Co., Ltd., Nipiron E2000) and a hydrazone derivative represented by the following structural formula (Anan Perfume Co., Ltd., CTC1).
91) (hereinafter referred to as margin) and 0.5 g of the mixture was applied onto the charge generation layer using a doctor blade and dried at 60°C for 12 hours or more. The film thickness was 10 μm or less.

[Reference Example 5] (Method for forming a charge generation layer) 20 g of tetrahydrofuran, 0.5 g of butyral resin (5LEC, manufactured by Building Blocks Chemical), and 0.2 g of titanyl phthalocyanine.
5g, 4.10-dibromoanthrone 0.25g
, Glass Peas No. 1 was stirred for 1 day with 33 g of 1 touch mixer, dispersed well, and then laminated on a glass plate with a doctor blade or applicator.
It was coated on top and dried at 60°C for 2 hours or more. The film after drying had a film thickness of 1 am or less.

(Preparation method of charge transport layer) Dissolve 0.5 g of polycarbonate (Mitsubishi Gas Chemical, Nipiron E2000) and 0.5 g of the above hydrazone derivative (Anan Perfume, CTCI91) in 9.5 g of dichloroethane, and use a doctor blade to generate the above charge. Apply on layer, 6
It was dried at 0°C for 2 hours or more. 11! The thickness was 10 μm or more.

[Reference Example 6]... Method for producing a functionally separated photoreceptor provided with a charge injection prevention layer (method for forming a charge injection prevention layer) Soluble polyamide (
Toagosei Chemical Co., Ltd., FS-175SV10) was applied at a thickness of 0.5 to lum using a spin coater and dried at 60° C. for 2 hours or more.

(Method for forming charge generation layer) Add butyral resin (Building Chemical, 5LE) to 10 g of butyl acetate.
C) 0.25g of the azulenium C1og salt described above.
5 g and Glass Peas No. 133 g were mixed, stirred for 1 day with a touch mixer, dispersed well, applied on the charge injection prevention layer using a doctor blade or applicator, and dried at 60° C. for 2 hours or more. . The film after drying had a thickness of 1 μm or less.

(Method for forming a charge transport layer) 9.5 g of tetrahydrofuran, 0.5 g of polycarbonate (Mitsubishi Gas Chemical Co., Ltd., Nipiron E2000), and 0.5 g of the above-mentioned hydrazone derivative (CTC191, manufactured by Anan Kaori Co., Ltd.)
was dissolved and applied onto the charge generation layer using a doctor blade, and dried for over 12 hours at 60"C. Film thickness: 10μ.
m or less.

[Reference Example 7] (Method for forming charge injection prevention layer) Soluble polyamide (
Toagosei Kagaku, FS-175SV10) with a spin coater to a thickness of 0.5 to 1 μm! ! ! The cloth was dried at 60° C. for 2 hours or more.

(Method for forming a charge generation layer) 20 g of tetrahydrofuran, 0.5 g of butyral resin (5LEC, manufactured by Building Blocks Chemical), and 0.2 g of titanyl phthalocyanine.
5g, 4.10-dibromoanthrone 0.25g
, Glass Peas No. 1, 33g, 1 with a touch mixer
Stir for several days, disperse well, and apply the mixture onto the charge injection prevention layer using a doctor blade or applicator.
It was dried at 60°C for 2 hours or more. The film after drying had a thickness of 1 μm or less.

(Method for forming a 1-it cargo transport layer) 0.5 g of polycarbonate (Mitsubishi Gas Chemical, Nipiron E2000) was added to 9.5 g of dichloroethane as a solvent.
The above hydrazone derivative (Anan Perfume, CTC191) 0.
5 g was dissolved and applied onto the charge generation layer using a doctor blade, and dried at 60°C for 12 hours or more. Film thickness is 10
It was more than μm.

[Reference Example 8] (Method for forming photoreceptor electrode layer) Indium tin oxide (ITO1 specific resistance 1
00Ω·cm”) was deposited by sputtering.

Further, it can be similarly deposited by the EB method.

(Method for Forming Charge Injection Prevention Layer) Silicon dioxide was deposited on the photoreceptor electrode layer by sputtering.

The film thickness can be from 100 to 3,000, and aluminum oxide may be used instead of silicon dioxide, and the EB method can be used instead of the sputtering method.

(Method for Forming Charge Generation Layer) Selenium-tellurium (tellurium content: 13% by weight) was deposited on the charge injection prevention layer by resistance heating. Film thickness is 2
It is less than μm.

(Method for Forming Charge Transport Layer) Granular selenium was used on the charge generation layer and deposited by resistance heating. The film thickness is 10 μm or less.

[Example 5] Electrostatic image recording and reproducing method As shown in Figure 6, a single layer organic photoreceptor (PVK) prepared in Reference Example 1 was used.
-TNF) 1 and the electrostatic image recording medium produced in Example 1 were grounded using a 10 μm thick polyester film as a spacer, with the surface of the electrostatic image recording medium facing the photoconductive layer surface of the photoreceptor. Then, a DC voltage of 700 V was applied between both electrodes, with the photoreceptor side being positive and the resin layer side being negative.

In addition, in the case of an amorphous silicon photoreceptor, it is preferable to apply a voltage with the photoreceptor side being negative, and in the case of an amorphous selenium photoreceptor, with the voltage being positive.

With voltage applied, exposure is performed from the photoreceptor side for 1 second using a halogen lamp with an illuminance of 1000 lux as a light source. After the exposure is complete, the electrostatic image recording medium is taken out and the entire surface is exposed to light to complete the formation of the electrostatic latent image. do.

Next, the exposed portion of the electrode 13 was sealed by coating with silicone resin, and then the medium was immersed in water.

After immersing in water, remove the medium and evaporate the water, then use the protective WA
As a result of peeling off the IO and measuring the potential difference between the electrode and the medium surface as shown in Figure 8, a surface potential of 50 V was measured on the medium surface using a surface potentiometer, but the surface potential in the unexposed area was It was O■.

Furthermore, when the surface potential of the electrostatic image recording medium was measured in a dark place before the entire surface was exposed, a surface potential of 100 V was measured in the exposed area, indicating that charges were accumulated in the selenium particles due to the entire surface being exposed.

Next, during exposure, the resolution pattern film was brought into close contact with the photoreceptor glass substrate side, and after similar exposure, the electrostatic image recording medium was placed on the surface of the surface potential measurement probe with a micro area of 50 x 50 μm, as shown in Figure 8. Perform XY axis scanning, 5
As a result of processing potential data in units of 0 μm and enlarging and displaying it on a CRT by potential-luminance conversion, a resolution pattern of up to 1100 μm could be confirmed on the CRT. After exposure, the electrostatic image recording medium was left at a room temperature of 25°C and 35% for 3 months.
As a result of performing a similar potential scanning reading, a resolution pattern display with no change was obtained at all (immediately after exposure).

Also, as an exposure method, using a normal camera, -700
The copy was photographed outdoors in the daytime with a voltage of V applied, exposure f-1, 4, and shutter speed 1/60 seconds. After exposure, the electrostatic image recording medium was scanned in the XY axes with a 50×50 μm micro-area surface potential measurement probe surface.
As a result of processing potential data in units of 0 μm and enlarging and displaying it on a CRT by potential-luminance conversion, an image with gradation was formed.

〔Effect of the invention〕

The electrostatic image recording medium of the present invention includes an electrode provided on a support,
Next, photoconductive fine particles or conductive fine particles are laminated in a single layer or a plurality of layers near the electrode, and an insulating layer having an IQ of 14 to 101@Ω·cmO resistivity is further laminated on the fine particle layer. The information charges accumulated in the microparticles are permanently retained by sealing the electrode terminals with a protective layer after information accumulation.

The accumulated information charge is extremely stable because it is accumulated inside the insulating layer, and even if it is immersed in water, after drying, the surface charge will be induced again on the surface of the electrostatic image recording medium by the charge accumulated in the fine particle layer. Therefore, it is possible to prevent information charges from attenuating due to moisture in the air.

In addition, the induced surface potential can be easily detected by a potential reading method that measures the potential difference between the electrode and the surface potential by peeling off the protective layer or inserting a protective layer, and furthermore, the electrostatic latent image It is possible to output an electric signal corresponding to the image and display it on a CRT or print it out using a printer.

In addition, since the information storage means is a unit of electrostatic charge, the information stored on the electrostatic image recording medium is of high quality and high resolution, and furthermore, it requires only 5 processing steps and can be stored for a long time. In addition, the stored information can be repeatedly reproduced at any desired image quality depending on the purpose.

[Brief explanation of drawings]

1 and 2 are cross-sectional views of the electrostatic image recording medium of the present invention, and FIGS. 3 and 4 are cross-sectional views showing the storage state of the electrostatic image recording medium of the present invention after electrostatic image recording, FIG. 5 is a perspective view showing various flexible electrostatic image recording media, FIGS. 6 and 7 are diagrams for explaining the method of recording an electrostatic image on an electrostatic image recording medium according to the present invention, and FIG. 9 is a diagram showing an example of a DC amplification type potential reading method, FIG. 9 is a diagram showing a schematic configuration of an electrostatic image recording and reproducing method using the electrostatic image recording medium of the present invention, and FIG. 10 is a color separation optical system. FIG. 11 is an explanatory diagram for forming a color electrostatic latent image, and FIG. 12 is a diagram for explaining the method for producing an a-3t:H photoreceptor. 1 is a photoconductor, 3 is an electrostatic image recording medium, 5 is a photoconductive layer support, 7 is a photoconductor bridge, 9 is a photoconductive layer, IO is a protective layer, 1
1.11' is an insulating layer, 12 is an insulating layer missing part, 13 is an electrostatic image recording medium electrode, 15 is an insulating layer support, 16 is a fine particle, 17 is a power source, 18 is a pattern exposure light, and 20 is an entire surface exposure light. , 21 is a potential reading section, 23 is a detection electrode, 25 is a guard electrode, and 27 is a capacitor. Applicant Dainippon Printing Co., Ltd. Agent Patent attorney (1) Nobuhiko (5 others) Figure 1, Figure 5 (a) Figure 2, Figure 3I, Figure 4 (b) Figure 5I12I (C) (d) 1ri Fig. 7 (a) (b) (C) Fig. 6 (b) +muu↓1 output↓hi20 (d) Fig. 1o Fig. 11: Jumping one

Claims (3)

[Claims] (1) An electrode layer was provided on a support, then photoconductive fine particles or conductive fine particles were laminated in a single layer or multiple layers near the electrode layer, and an insulating layer was further laminated on the fine particle layer. Internal storage type electrostatic image recording medium. (2) The internal storage type electrostatic image recording medium according to claim 1, wherein the photoconductive fine particles are directly laminated on the electrode layer. (3) The internal storage type electrostatic image recording medium according to claim 1, wherein the photoconductive fine particles or the conductive fine particles are laminated on an electrode layer with an insulating layer having a thickness of 1000 Å or less interposed therebetween.