JPH01295897A - Static charge recording card - Google Patents

Abstract

PURPOSE:To accumulate data of high quality and high resolution, and to preserve said data as electrostatic latent images for a long period, by laminating onto a card base material a static charge recording body obtained through the lamination of an insulating layer on electrodes, in a manner that said insulating layer becomes the upper surface of said recording body. CONSTITUTION:An insulating layer 11 is laminated on a static charge recording electrode 13 thereby to form a static charge recording body 3 on a card base material. When the static charge recording body 3 is used together with a photoreceptor, data is recorded on the surface of the insulating layer 11 or thereinside as a distribution of static charges. The static charge recording electrodes 13 are formed wholly in the interval between a static charge recording body support 15 and the insulating layer 11 or, on the support 15 in accordance with the forming pattern of the insulating layer. The material of the electrodes is not limited if only the specific resistance thereof is not higher than 10<6>OMEGA.cm. Since the insulating layer 11 laminated on the electrodes 13 records data on the surface thereof or thereinside in the form of a distribution of static charges, a high insulative property is required in order to restrict the move of the charges, and therefore the specific resistance of the insulating layer should be not lower than 10<14>OMEGA.cm.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrostatic charge recording card in which information is stored on an insulating layer, or the charge is accumulated by being developed with a toner.

[Conventional technology]

Currently, we are in the age of cards, and various cards such as cash cards and credit cards are in circulation, but most of them are magnetic recording cards, and the most commonly used are business card-sized cards, which are convenient to carry. ing. However, since a magnetic recording card of this size does not have much storage capacity, the actual situation is that its use is limited to storing verification codes such as personal identification numbers, account numbers, and registration numbers. - It is well known that so-called optical cards, which record information mechanically, have an extremely large amount of recorded information compared to conventional magnetic recording cards, but there are problems with the information recording materials, making them economically A highly versatile optical card has not yet been put into practical use.

The recording section in an optical card is formed by laminating a thin film of anti-resistance metal on a conductive material, but current optical disk technology has a resolution of 2.3 μm, and usually has a resolution of 25 to 25 μm. It has a storage capacity of over 1 million bits.

[Problem that the invention seeks to solve]

However, in optical cards, the information units are formed by laminating reflective metal on a substrate, so advanced manufacturing technology is required, and problems still exist when reproducing data.

The present invention differs from such an information recording means in an optical card, and is extremely easy to manufacture by recording information as a charge on the upper surface of an electrostatic charge recording body in which an insulating material is laminated on an electrode. Moreover, the processing process is simple, it can be stored for a long time, and the stored characters, line drawings, images, codes, and (1,0) information can be repeatedly played back at will with the image quality that suits the purpose. Our objective is to provide a high-quality, high-resolution electrostatic charge recording card.

[Means for solving problems]

In the present invention, an electrostatic charge recording material in which an insulating layer is laminated on an electrode is laminated on a card base material with the insulating layer facing upward. It is either exposed and embedded in the card base material, or it is laminated by being attached onto the card base material with the insulating layer facing upward. In addition, this electrostatic charge recording medium is laminated in a state in which information is recorded or in a state in which information is not recorded, and the recording storage form of this electrostatic charge recording medium is either electric charge or The toner is stored in a developed state, and the electrode portion of the electrostatic charge recording material is partially exposed at an appropriate location on the card base material in order to write information after the card is manufactured.

Next, the structure of the electrostatic recording medium according to the present invention will be explained.

FIG. 1(a) is a perspective view of the ROM type electrostatic charge recording card of the present invention, and FIG. 1(b) is a cross-sectional view taken along line A-A in FIG. Figure 3 (a) is a diagram of the DRAWROM type electrostatic charge recording card of the present invention, and the same figure (opening) is a sectional view taken along line B-B, and Figure 2 is a diagram of the electrostatic charge recording card used in the present invention. 1 is a cross-sectional view of a recording medium, where ■ is an electrostatic charge recording card, 4 is a card base material, 11 is an insulating layer, 13 is an electrostatic charge recording body electrode, 14 is an exposed electrode portion, 15 is an electrostatic charge recording body support, 16 indicates a protective film.

The electrostatic charge recording body 3 is insulated on the electrostatic charge recording electrode 13.
It is used together with a photoreceptor to record information as a distribution of electrostatic charges on the surface of the insulating layer 11 or inside it.

If the electrostatic charge recording body support 15 has a certain level of strength that can strongly support the electrostatic charge recording body 3,
There are no particular restrictions on its material or thickness, such as flexible plastic film, metal foil, paper, glass, plastic sheet, or metal plate (which can also serve as an electrode).
A rigid body such as is used. Unless a metal plate is used as the electrostatic charge recording material support, an electrostatic charge recording material electrode is formed by laminating aluminum on the support to a thickness of approximately 1,000 layers by means such as vapor deposition, and then electrostatic charge recording material electrodes are formed. An electrostatic charge recording body is produced by laminating insulating layers that are charge recording body materials. Alternatively, the electrostatic charge recording material support 15 may be omitted and the electrostatic charge recording material electrode 13 and the insulating layer 11 may be directly laminated on the card base material 4 in this order. Alternatively, a metal plate may be used as the electrostatic charge recording body support, and may serve both as the electrostatic charge recording body support and the electrode.

The electrostatic charge recorder 3 is attached to or embedded in the card base material 4, as shown in FIG. 1 and FIG. 3, either after or before recording information. The material and thickness of the card base material 4 on which the electrostatic charge recording medium 3 is placed are not particularly limited as long as it has a certain level of strength that can support the electrostatic charge recording medium 3. For example, it may be a flexible material. plastic sheets such as polyvinyl chloride resin, glass,
A rigid body such as a ceramic or a metal plate (which can also serve as an electrode) is used.

The electrostatic charge recording material electrode 13 is formed on the entire surface between the electrostatic charge recording material support 15 and the insulating layer 11, or on the electrostatic charge recording material support 15 in accordance with the formation pattern of the insulating layer, and the material thereof is There is no limitation as long as the resistance is 106 Ω·cm or less, and inorganic metal doors, electric films, and inorganic metal oxides '474. membrane etc. are used. Such an electrostatic charge recording body electrode 13 is formed on the electrostatic charge recording body support 15 by vapor deposition, sputtering, CV
D. Formed by coating, plating, dipping, electrolytic polymerization, etc. Moreover, the thickness is about 100 to 3000 when aluminum is used.

Since the insulating layer 11 laminated on the electrostatic charge recording body electrode 13 records information as a distribution of electrostatic charges on its surface or inside thereof, it needs to have high insulation properties to suppress the movement of charges. , it is required to have insulation properties with a specific resistance of 1014 Ω·cm or more. Such an insulating layer 11
can be formed into a layer by dissolving resin or rubber in a solvent, coating, dipping, vapor deposition, or sputtering, and the thickness of the film is at least 1000 mm (0.1 μm) from the viewpoint of insulation. ) or more, and from the viewpoint of flexible building properties, it is preferably 100 μm or less.

Here, examples of the resin and rubber include polyethylene, polypropylene, vinyl resin, styrene resin, acrylic resin, nylon 66, nylon 6, polycarbonate, acetal homopolymer, fluororesin, cellulose resin, and phenol resin.

Urea resin, polyester resin, epoxy resin.

Flexible epoxy resin, melamine resin, silicone resin, phenoxy resin, aromatic polyimide, PPO, polysulfone, etc., as well as polyisoprene, polybutadiene, polychloroprene, isobutylene.

Extremely high nitrile, polyacrylic rubber, chlorosulfonated polyethylene, ethylene/propylene rubber.

Fluororubber, silicone rubber, polysulfide synthetic rubber.

A single rubber such as urethane rubber or a mixture thereof can be used. Also, by pasting 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. onto the electrostatic charge recording body electrode 13 via an adhesive or the like. Layers are formed by coating or dipping, or by adding necessary curing agents, solvents, etc. to thermoplastic resins, thermosetting resins, ultraviolet curable resins, electron beam curable resins, rubbers, etc. . Furthermore, a monomolecular film or a monomolecular cumulative film formed by the Langmuir-Blodget method can also be used.

Further, a charge retention reinforcing layer can be provided between the insulating layers 11 and the electrode surface or on the insulating layer ll. A charge retention enhancement layer is a layer in which charge is injected when a strong electric field (104V/Cm or more) is applied, but when a low electric field (10'V/Cm or more) is applied, charge is injected.
m or less) refers to a layer into which no charge is injected. As the charge retention enhancement layer, for example, 5i(h, Al2O2, Si
C, SiN, etc. can be used, and as an organic material, for example, a polyethylene vapor deposited film 9. A polyvaraxylene vapor deposited film can be used.

In addition, in order to hold static charge more stably, the insulating layer 11
It is preferable to add a substance having electron-donating properties (donor material) or a substance having electron-accepting properties (acceptor material) to the material. Donor materials include styrene, ren,
There are naphthalene-based, anthracene-based, pyridine-based, and azine-based compounds, specifically tetrathiofulvalene (TT
F), polyvinylpyridine, polyvinylnaphthalene, polyvinylanthracene, polyazine, polyvinylpyrene, polystyrene, etc. are used either singly or in combination. In addition, acceptor materials include halogen compounds, cyanide compounds, nitro compounds, etc. Specifically, tetracyanoquinodimethane (TCNQ), linitrofluorenone (TNF), etc. are used, and they are used singly or in combination. . The donor material and acceptor material are used by adding about 0.001 to 10% to the resin and the like.

Further, in order to stably hold the electrostatic charge, elemental element fine particles can be added to the electrostatic charge recording medium. Elements include Group 1A (alkali metals), Group IB (copper group), Group IIA (alkaline earth metals), and IIB of the periodic table.
group (zinc group), mA group (aluminum group), [[B
Group (rare earths), Group B (titanium group), Group VB (vanadium group), Group VIB (chromium group), Group Group B (manganese group), Group II (iron group, platinum group), Also, the IVA group (
Carbon group) includes silicon, germanium, tin, lead, and VA
Group (nitrogen group) includes antimony, bismuth, VIA
As the group (oxygen group), sulfur, selenium, and tellurium are used in fine powder form. Further, among the above elements, metals can be used in the form of metal ions, fine powder alloys, organic metals, and complexes.

Furthermore, the above elements can be used in the form of oxides, phosphorus oxides, sulfides, and halides. These additives need only be added in a very small amount to the electrostatic charge recording material such as the resin or rubber mentioned above, and the amount added is 0.0% to the electrostatic charge recording material.
It may be about 1 to 10% by weight.

The insulating layer 11 formed in this way is shown in FIG.
It is preferable to provide a protective film 16 on the surface as shown in b). The protective film may be formed into a film of sticky rubber such as silicone rubber or resin such as polyterpene resin and adhered to the surface of the insulating layer 11, or a plastic film may be used with an adhesive such as silicone oil. It is best to stick the film with a specific resistance of 10'4 Ω·cm or more, and a film thickness of about 0°5 to 30 μm. In particular, when the information on the insulating layer 11 needs to have high resolution, the information is read from above the protective film, so the thinner the protective film is, the better.

Love! ! At the time of reading, information is reproduced from on this protective film, but the protective film may also be peeled off and information can be reproduced directly from the insulating layer. The information recording card 1 includes one in which information is already recorded on an electrostatic charge recording medium as shown in Fig. 1 (hereinafter referred to as ROM type), and a third type
Those that do not record information as shown in the figure or have some recordable areas (hereinafter referred to as DRAW type)
It can be done. In the case of the DRAW type, it is best to use the above-mentioned sticky plastic film as the protective film on the surface of the insulating layer, and when recording, the protective film is peeled off and recording can be performed on the unrecorded area. It is preferable that the surface of the insulating layer be coated again after recording.

4 and 5 are diagrams for explaining the electrostatic image recording method on an electrostatic charge recording medium of the present invention, in which 2 is a photoreceptor;
7 represents a photoconductive layer support, 7 represents a photoreceptor electrode, and 9 represents a photoconductive layer.

In order to record information on the electrostatic charge recording body 3 or the electrostatic charge recording card 1 produced as described above, as shown in FIGS.
This is carried out by exposing the photoconductor from the photoconductor electrode 7 side of the photoconductor while applying a voltage to the surface of the photoconductor layer 9 on the photoconductor 2.

Hereinafter, the structure of the photoreceptor 2 used in the present invention will be explained.

The photoconductive layer support 5 includes a photoreceptor electrode 7 and a photoconductive layer 9
It is made of the same material as the electrostatic charge recording medium support 15 described above. However, when used in a device that records information by entering light from the photoreceptor 2 side, it naturally requires a characteristic that allows the light to pass through.For example, it is used in a camera that uses natural light as incident light and enters from the photoreceptor side. In this case, 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 its material is limited as long as the specific resistance value is 106 Ω·cm or less. Instead, inorganic metal conductive films, inorganic metal oxide conductive films, etc. are used, and the lamination methods include vapor deposition, sputtering,
Laminated by CVD, coating, plating, dipping, electrolytic polymerization, etc. In addition, the film thickness of the photoreceptor electrode 7
It is necessary to change the electrical characteristics of the material constituting the material and the applied voltage when recording information, but for example, in the case of aluminum, the number is about 100 to 3000. If information light needs to be incident on this photoreceptor electrode 7,
The above-mentioned optical properties are required, for example, when information light is visible light (
400 to 700 nm), T TO (Inz0
Transparent electrodes coated with 3-5nOJ, S n O2, etc. by sputtering, vapor deposition, or by making ink with their fine powders together with a binder, and A u%A
A translucent electrode prepared by vapor deposition or sputtering of 1% Ag, Ni%Cr, etc., an organic transparent electrode coated with tetracyanoquinodimethane (TCNQ), polyacetylene, etc. are 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 in order to cant 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 conductive 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 the layer where the effect is noticeable in some cases. 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-5i: F
)・These are not doped with impurities, -B,, Al, Ga, In, TI, etc. are doped to make them P-type (hole transport type),・P% Ags S
B, B, etc. are made into 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), a film can be formed by depositing it on an electrode substrate that is heated or not heated by glow discharge, or 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 is formed into a film and used as a single layer or a stack. 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 can be provided on the surface of the photoreceptor electrode 7. As this charge injection prevention layer, an a-5iN layer, an a-5iN layer, an a-5
iC layer, 5iOJi.

It is preferable to provide an insulating layer such as an Altos layer. If this insulating layer is made too thick, no current will flow when exposed to light.
It is necessary to have a small number of people (both 1000 Å or less), and considering ease of production, etc., it is desirable to have about 400 to 500 people.

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 positive, an electron transport layer is provided. For example, a-3t in which Si is doped with poron
:H(n'') improves hole transport properties, provides a rectifying effect, and functions as a charge injection prevention layer.

(b) Amorphous selenium photoreceptor The amorphous selenium photoreceptor includes: ■Amorphous selenium (a-Se) ■Amorphous selenium telluride (a-5e-Te) ■Amorphous arsenic selenium compound (a-AszSet)■
There is an amorphous arsenic selenium compound +Te.

This photoreceptor was manufactured by vapor deposition and sputtering, and the charge injection blocking layer was made of SiO□, A 1103.5iC1
A SiN layer is provided on the electrode substrate by vapor deposition, sputtering, glow discharge method, or the like. Also, combine the above ■～■,
It may also be a laminated type photoreceptor. The thickness of the photoreceptor layer is similar to 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) vapor deposition. In the case of sputtering, a CdS target is used to deposit on the substrate in argon plasma. 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 μm) in a binder, add a solvent, and coat on a substrate. Also CVD
The method involves mixing organic metals such as diethylzinc and dimethylzinc with oxygen gas in a low vacuum (10-'' to I Torr) and causing a chemical reaction 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) only confuses people in the 400 nm wavelength range, but the PVK-TNF complex can be sensitive to wavelengths up to 650 nm.

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 dyes, cyanine, styryl dyes, pyrylium dyes, perylene, methine dyes, a-5e, a-5
i, azulenium salts, squalium bases, etc.

<Charge Transport Layer> Examples of substances forming the charge transport layer include hydrazone, pyrazoline, PVK, carbazole, oxazole, triazole, aromatic amine, amine, triphenylmethane, and polycyclic aromatic materials. There are group compounds, 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 μm, and the thickness of the charge transport layer is 10 to 50 μm.

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. Add 0.1 to 10 parts of acecool resin, phenol resin, polymethyl methacrylate (PMMA) resin, melamine resin, polyimide resin, etc. to 1 part of the charge generating material and charge transporting material name. Make it easy. 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 AS203, B2O3, etc. ,BizO,,CdS,,Ca
O, CeO,, CrzOz, CoO, GeO2, Hf
O,, FIBZO3, LazOt, MgO, Mn0z
, NdzOi , Nb2O2, PbO1Sb203, S
iO□, Sea□, Ta205, Ti0z, WO2,
V, O3, Y2O5, Y2O1, Zr0z, BaTiO
3, Al2O3, Bi, TiO3, CaO-5rO, C
a0-YzO*, Cr-5iO1LiTa03, PbT
i0:+, PbZr0z, Zr02-Co, ZrO
2-3i02, 8lN,,BNX NbN
,SiJ, ,TaN,TiNSVN,Z
rN.

S+C1T+C1WCs A14C, 1, etc. are formed 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 layer, an organic photoconductive layer, and an organic-inorganic composite photoconductive layer, and has a thickness of about 0.1 to 10 μm. Specifically, if the electrode is negative, B, AI, Ga
, an amorphous silicon photoconductive layer doped with In etc.
An organic photoconductive layer or electrode formed by dispersing amorphous selenium, oxadiazole, pyrazoline, polyvinylcarbazole, stilhene, anthracene, naphthalene, tridiphenylmethane, triphenylmethane, azine, amine, aromatic amine, etc. in a resin. In the case of a positive value, an amorphous silicon photoconductive layer doped with P, NSASS b % Bi, etc., a ZnO photoconductive layer, etc. are formed by methods such as glow discharge, vapor deposition, sputtering, CVD, and coating.

The photoreceptor and electrostatic charge recording member produced in this way may be produced by bringing the photoconductive layer surface of the photoreceptor into contact with the insulating layer surface of the electrostatic charge recording member, or by contacting them non-contact as shown in FIG. 4(a). In the case of non-contact, the photoreceptor and the electrostatic charge recording member may be placed opposite to each other with a spacer interposed between them at the opposing ends of the recording member. 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 photoreceptor surface and the electrostatic charge recording surface. In the case of non-contact, the distance between the photoreceptor and the electrostatic charge recording medium is 1 to 50 μm7! (as appropriate, and the spacer may be made of an organic material such as a plastic film.

In addition, the electrostatic charge recording material that can be used in the present invention is not limited to one in which an insulating layer is simply laminated on the electrostatic charge recording material electrode as described above, but also an insulating layer and a photoconductive layer on the electrostatic charge recording material electrode. It has an orientation perpendicular to the electrode surface, which can be obtained by sequentially laminating the photoconductive layer and etching the photoconductive layer pixel by pixel, or by selecting lamination conditions such as cadmium sulfide or zinc oxide as the photoconductive layer support material. The photoconductive layer is formed by using a photoconductive layer or by dispersing photoconductive particles such as cadmium sulfide or zinc oxide in a binder and applying it to the surface of the insulating layer, and information is stored in the insulating layer. It is also possible to use a type in which image exposure is performed through an electrode and information is stored in an insulating layer so as to prevent information charges from being diffused by the photoconductive layer.

Next, an electrostatic image recording method using the electrostatic charge recording member and photoreceptor produced in this manner will be described.

FIG. 4 is a diagram for explaining an electrostatic image recording method using the electrostatic charge recording medium of the present invention. 17 is a power source.

In FIG. 4, exposure is performed from the side of the photoreceptor 2. First, a transparent photoreceptor electrode 7 made of 1TO with a thickness of 1000 is formed on a photoconductive layer support 5 made of glass with an IB thickness. A photoconductive layer 9 having a thickness of about 10 μm is formed thereon to constitute the photoreceptor 2. For this photoreceptor 2, 10μ
The electrostatic charge recording body 3 is arranged with a spacer of about m in size interposed therebetween. The electrostatic charge recording body 3 is made by depositing a 1T electrode with a thickness of 1,000 on an electrostatic charge recording body support 15 made of glass with a thickness of 1 m.
An insulating film having a thickness of 10 μm was formed on this electrode.

First, as shown in FIG. 4(a), one
The electrostatic charge recording body 3 is set through a gap of about 0 μm,
As shown in FIG. 4(b), the electrode 7.13 is
A voltage is applied between them. In a dark place, since the photoconductive layer 9 is a high-resistance material, no change occurs between the electrodes. When light is incident on the photoreceptor l side, the portion of the photoconductive layer 9 where the light is incident exhibits conductivity, a discharge occurs between the photoconductive layer 9 and the insulating layer 11, and charges are accumulated in the insulating layer 11.

When the exposure is completed, turn off the voltage as shown in Figure 4 (c).
The formation of the electrostatic latent image is completed by setting the FF to FF and then taking out the electrostatic charge recording medium 3 as shown in FIG. 4(d).

Further, FIG. 5 is a diagram for explaining the electrostatic image recording method on the RAM type electrostatic charge recording card of the present invention. A voltage is applied between the section 14 and the photoreceptor electrode 7, and the RO
An electrostatic latent image is formed in the same manner as the electrostatic image recording method on an M-type electrostatic charge recording medium. In the case of electrostatic image recording on this RAM type electrostatic charge recording card, a protective film as shown in Figure 1 (B) is coated before recording, although not shown, and it is peeled off during recording. It is preferable to cover the insulating layer 11 again after recording is completed to protect the information charges on the insulating layer 11.

When these recording methods are used for planar analog recording, high resolution can be obtained like silver halide photography, and the surface charge on the insulating film that is formed is exposed to the air environment, but air is a good insulator. Since it has high performance, it can be stored for a long time without discharging in bright or dark places.The storage period of charge on this insulating layer 11 is determined by the properties of the insulator, and it is It is influenced by the charge trapping properties of the body.In the above explanation, the charge is explained as a surface charge, but the injected charge is simply accumulated on the surface, or microscopically penetrates into the inside near the surface of the insulator. Long-term storage occurs because electrons or holes may be trapped within the material's structure.

In addition to the so-called free charge retention method in which surface charges are accumulated as described above, electrostatic charge retention methods include Niclet, which generates charge distribution and polarization inside an insulating medium.

FIG. 6 is a diagram showing an electrostatic charge holding method using a photoelectrode, and the same numbers as in FIG. 4 indicate the same contents. In addition, in the figure, 19 is a transparent electrode.

As shown in FIG. 6(A), an electrode 13 is formed on a support 15 such as a film, and ZnS, CdS, and ZnO are deposited on the electrode plate.
1 using vapor deposition sputtering, CVD, coating methods, etc.
Form a layer with a thickness of 1 to 5 μm. Then, when the transparent electrode 19 is placed on the surface of this photosensitive layer in contact or non-contact and is exposed to light while a voltage is applied (Fig. 6 (b)), charges are generated by the light in the exposed area and polarized by the electric field. Even if you remove it, it will remain trapped in that position (Figure 6 (c)). In this way, an electric left corresponding to the exposure amount is obtained. In this case, the electrostatic charge recording medium has the advantage that a separate photoreceptor is not required, compared to an electrostatic charge recording medium simply consisting of an insulating layer.

FIG. 7 is a diagram showing a method of holding an electrostatic charge using a thermosiliclet, and the same numbers as in FIG. 4 have the same contents.

Examples of thermal electret materials include polyvinylidene fluoride (PVDF), poly(VDF/trifluoroethylene), poly(VDF/tetrafluoroethylene), polyvinyl fluoride, and polyvinylidene chloride.

Polyacrylonitrile, poly-α-chloroacrylonitrile, poly(acrylonitrile/vinyl chloride), polyamide 11. Polyamide 3. Poly-m-phenylene isophthalamide, polycarbonate, poly(vinylidene cyanide vinyl acetate).

It consists of a PVDF/PZT composite etc., which is used as the electrode substrate 1.
A single layer with a thickness of 1 to 50 μm may be provided on No. 3, or two or more types may be laminated.

Then, before exposure, the medium is heated to a temperature above the glass transition of the medium material by resistance heating or the like, and in this state, voltage is applied and exposure is performed (FIG. 7(b)). At high temperatures, the mobility of ions increases, and a high electric field is applied to the insulating layer in the exposed area, and among the thermally activated ions, negative charges gather at the positive electrode, and positive charges gather at the negative electrode, causing them to flow into space. Forms a charge and causes polarization. Thereafter, when the medium is cooled, the generated charges are trapped in that position even when the electric field is removed, producing electrets corresponding to the exposure amount (FIG. 7(c)).

In the present invention, methods for inputting information to the electrostatic charge recording medium and electrostatic charge recording card include a method using a high-resolution electrostatic camera;
There is also a recording method using a laser. First, the high-resolution electrostatic camera used in the present invention uses a photoreceptor electrode 7 on the front instead of the photographic film used in ordinary cameras.
a photoreceptor 1 consisting of a photoconductive layer 9 provided with a photoreceptor 1; and an insulating layer 11 facing the photoreceptor 1 and provided with an electrostatic charge recording electrode 13 on its rear surface.
A recording member is constructed by applying a voltage to the picture electrode, and the photoconductive layer is made conductive according to the incident light, and charges are accumulated on the insulating layer according to the amount of incident light. An electrostatic latent optical image is formed on a charge storage medium, and a mechanical or electrical shutter may be used. Further, the electrostatic latent image can be retained for a long period of time regardless of whether it is in a bright place or a dark place. In addition, a prism separates the optical information into R, G, and B light components, and a color filter is used to extract them as parallel light, and one frame is formed with 3 cents of electrostatic charge recording material separated into R, G, and B, or Arrange RlG and B images on one plane
Color photography can also be done by setting the image to one frame.

In addition, as a recording method using a laser, the light source is an argon laser (514,488 rxm), a helium laser (514,488 rxm),
Neon laser (633nm), semiconductor laser (78nm)
0 nm, 810 nm, etc.), and a voltage is applied to the photoreceptor and the electrostatic charge recording member by bringing their surfaces into close contact with each other or facing each other at a fixed interval. In this case, it is preferable 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 images is performed by modulating the light intensity of the laser, and digital recording such as characters, codes, and line drawings is performed by ON-OFF control of the laser light. Also, in images where halftone dots are formed,
It is formed by applying focus 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, but only need to be sensitive to the wavelength of the laser light source.

Next, a method for reproducing a recorded electrostatic image will be explained.

FIG. 8 is a diagram showing an example of a potential reading method in the electrostatic image recording and reproducing method of the present invention, and the same numbers as in FIG. 4 indicate the same contents. In addition, 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.

When the potential reading unit 21 is opposed to the charge accumulation surface of the electrostatic charge recording body 3, the detection electrode 23 is exposed to the insulation N1 of the electrostatic charge recording body 3.
An electric field generated by the charges accumulated on the electrostatic charge recording member 1 acts, and an induced charge equivalent to the charge on the electrostatic charge recorder is generated on the surface of the detection electrode. 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 charge carrier is determined. You can ask for it. Then, by scanning the surface of the electrostatic charge recording medium with the potential reading section 21, the electrostatic latent image can be output as an electric signal. Note that if only the detection electrode 23 is used, an electric field (electric line of force) due to charges in a wider range than the area facing the detection electrode of the electrostatic charge recorder will act, reducing resolution, so a grounded guard electrode 25 is placed around the detection electrode. You may also do so.

As a result, the lines of electric force are oriented perpendicularly to the surface, so that the lines of electric force only act on the area facing the detection electrode 23, and the potential of the area approximately equal to the area of the detection electrode 23 is read. be able to. 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 charge recorder, so it is necessary to find and design optimal conditions according to the required performance.

FIG. 9 is a diagram showing another example of the potential reading method, which is the same as in FIG. 8 except that the detection electrode and the guard electrode are provided on the insulating protective film 31 and the potential is detected through the insulating protective film. It is similar to

According to this method, since detection can be performed by contacting the electrostatic charge recording medium, the distance between the detection electrode and the detection electrode can be made constant.

FIG. 10 is a diagram showing another example of the potential reading method, in which the needle-like electrode 33 is brought into direct contact with the electrostatic charge recording medium and the potential of that portion is detected, and the detection area can be made small. High resolution can be obtained. Note that if a plurality of needle-like electrodes are provided for detection, the reading speed can be improved.

The above is a direct current amplification type that detects a direct current signal with or without contact, but an example of an alternating current amplification type will be explained next.

Figure 11 is a diagram showing the method of reading the potential of the vibrating electrode type.
2 is a detection electrode, 24 is an amplifier, and 26 is a meter.

The detection electrode 22 is driven to vibrate and change its distance with respect to the charged surface of the electrostatic charge recording body 3 over time. As a result, the potential at the detection electrode 22 changes depending on the electrostatic potential of the charged surface. The amplitude changes over time. This temporal potential change is taken out as a voltage change across the impedance Z, and the AC bone is amplified by the amplifier 24 through the capacitor C.
By reading with the meter 26, the electrostatic potential of the charged surface can be measured.

FIG. 12 shows an example of a rotating type detector, and 28 in the figure is a rotating blade.

A conductive rotary blade 28 is provided between the electrode 22 and the charging surface of the electrostatic charge recording medium 3 and is rotationally driven by a driving means (not shown). As a result, the detection electrode 22 and the electrostatic charge recording body 3 are electrically shielded periodically. Therefore,
A potential signal whose amplitude changes periodically according to the electrostatic potential of the charged surface is detected by the detection electrode 22, and this alternating current component is amplified by the amplifier 24 and read.

FIG. 13 shows an example of a vibration capacitance type detector, where 28 is a drive circuit and 30 is a vibrating piece.

The vibrating piece 30 of one electrode forming the capacitor is vibrated by the drive circuit 28 to change the capacitor capacity. As a result, the DC potential signal detected by the detection electrode 22 is modulated, and this AC component is amplified and detected. This detector converts direct current to alternating current and can measure potential with high sensitivity and stability.

FIG. 14 is a diagram showing another example of a potential reading method, in which a long and thin detection electrode is used to detect the potential using CT (computed tomography).

When the detection electrodes 35 are placed opposite each other across the charge storage surface, the data obtained is a value obtained by line integration along the detection electrodes, that is, data corresponding to projection data in CT. Therefore, by scanning this detection electrode over the entire surface as shown by the arrow in Fig. 14 (b), and then changing the angle θ and scanning in the same manner, the necessary data can be collected. By performing arithmetic processing using the CT algorithm, the potential distribution state on the charge carrier can be determined.

Note that by arranging a plurality of detection electrodes as shown in FIG. 15, the data collection speed can be increased, and the overall processing speed can be improved.

FIG. 16 shows an example of a current collector type detector, in which 32 is a grounded metal cylinder, 34 is an insulator, and 36 is a current collector.

The current collector 36 has a built-in radioactive substance, from which alpha rays are emitted. Therefore, the air inside the metal cylinder is ionized to form positive and negative ion pairs. In their natural state, these ions disappear through recombination and diffusion and maintain an equilibrium state, but in the presence of an electric field, they statistically move in the direction of the electric field while repeatedly colliding with air molecules due to thermal motion. It plays a role in transporting electric charges.

That is, the air becomes conductive due to the ions, and it can be considered that an equivalent electrical resistance path exists between the surrounding objects including the current collector 36.

Therefore, the charging surface of the electrostatic charge recording body 3 and the grounded metal cylinder 32,
If the resistances between the charged body and the current collector 36 and between the current collector 36 and the grounded metal cylinder 32 are respectively Ro, R1, and RZ,
When the potential of the charged body is Vl, the potential V2 of the current collector 3G is Vz = Rz V+ / (R+ +
Rz). As a result, the potential of the electrostatic charge recording body 3 can be determined by reading the potential of the current collector 36.

FIG. 17 is a diagram showing an example of an electron beam type potential reading device, where 37 is an electron gun, 38 is an electron beam, 39 is a first dynode, and 40 is a secondary electron multiplier.

Electrons emitted from the electron gun 37 are deflected by an electrostatic deflector or an electromagnetic deflector (not shown) to scan the charged surface. A portion of the scanning electron beam combines with the charges on the charged surface, causing a charging current to flow, and the potential on the charged surface decreases to the equilibrium potential by that amount.

The remaining modulated electron beam returns to the electron gun 37 and collides with the first dynode 39, and its secondary electrons are amplified by the secondary electron multiplier 40 and taken out from the anode as a signal output. Reflected electrons or secondary electrons are used as the returning electron beam.

In the case of the electron beam type, a uniform charge is formed on the medium after scanning, but a current corresponding to a latent image is detected during scanning. If the latent image has a negative charge, there is less charge accumulated by electrons in the area with more charge (exposed area),
Although the charging current is small, for example, the maximum charging current flows in a portion where no charge exists. In the case of a positive charge, the opposite is true; it becomes a negative type.

FIG. 18 is a diagram showing another example of the potential reading method, in which the electrostatic charge recording material 3 on which the electrostatic latent image is formed is developed with toner, the colored surface is irradiated with a light beam and scanned, and the reflected light is is converted into an electrical signal by a photoelectric converter 41. High resolution can be achieved by reducing the diameter of the light beam, and electrostatic potential can be detected optically.

FIG. 19 is a diagram showing another example of the potential reading method,
R formed by a fine color filter as described later
, G, 8 separated images are developed with toner, the colored surface is irradiated with a light beam, and Y, M, and C signals are obtained from the reflected light. In the figure, 43 is a scanning signal generator, 45 is a laser, 47 is a reflecting mirror, 49 is a half mirror, 151 is a photoelectric converter, and 53, 55, and 57 are gate circuits.

A laser beam from a laser 45 is applied to the colored surface via a reflecting mirror 47 and a half mirror 49 and scanned by a scanning signal from a scanning signal generator 43. The reflected light from the colored surface is made incident on a photoelectric converter 51 via a half mirror 49 and converted into an electrical signal. If the opening/closing of the gate circuits 53, 55, 57 is controlled in synchronization with the signal from the scanning signal generator 43, the gate circuits 53, 55,
．． 57 is controlled to open and close, it is possible to obtain Y, M, and C signals without having to color Y, M, and C. Note that even if the color image is divided into three planes as described later, Y, M, and C signals can be obtained in exactly the same way, and in this case as well, Y, M, and C may be colored. Good things are similar.

In the electrostatic potential detection method shown in FIGS. 18 and 19, it is necessary that the toner image has a γ characteristic corresponding to the amount of charge of the electrostatic latent image, and therefore, the amount of charge changes in an analog manner. It is necessary to avoid having a threshold for . As long as the correspondence is established, T may be corrected by electrical processing even if the γ characteristics do not match.

FIG. 20 is a diagram showing a schematic configuration of the electrostatic image reproducing method of the present invention, in which 61 is a potential reading device, 63 is an amplifier,
65 is a CRT, and 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.

Fig. 21 is a diagram showing a color separation optical system using a prism. In the figure, 71.73.75 is a prism block, 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.
．． A G color light component and an R color light component are extracted from 81. 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 such a filter 91 in front of the photoreceptor 1 as shown in FIG.
Either three sets of electrostatic charge recording bodies separated into R, G, and B form one frame as shown in (b), or R, G are separated on one plane as shown in FIG. 22 (c).

They can also be lined up as B images and one set can be one frame.

FIG. 23 is a diagram showing an example of a fine color filter. For example, a film coated with resist is exposed with a mask pattern to form an R, G, B stripe pattern,
A method of forming by staining each with R, G, and B,
Alternatively, R, G, and B interference fringes produced by passing the color-separated light as shown in Figure 21 through narrow slits can be formed by recording them on a hologram recording medium, or by using a mask on a photoconductor. It is formed by a method in which R, G, B stripe pattern is formed by an electrostatic latent image by closely exposing it to light, and this is developed with toner and transferred three times to combine the colors and form toner stripes. do. R of the filter formed by such a method,
A pair of G and B forms one pixel, and each pixel is made as fine as about 10 μm. By using this filter as filter 91 in FIG. 22, a color electrostatic latent image can be formed. In this case, the filter may be placed separately from the photoreceptor or may be formed integrally with the photoreceptor.

Figure 24 is a diagram showing an example of a combination of a fine color filter and a Fresnel lens.
, B patterns can be reduced and recorded, and the lens can be designed to be thinner and more compact than a normal lens.

Figure 25 shows ND (Neutral Density)
) This is a diagram showing an example of three-sided division using filters 81, 83 and R, G, and B filters, in which the incident light is divided into 3 by ND filters 81, 83 and reflection mirror 85, and R filter 8 is used for each.
7. By passing through the G filter 89 and the B filter 91, the R, G, and B lights can be extracted as parallel lights.

[Effect]

The electrostatic charge recording medium in the present invention is formed by laminating an insulating layer on an electrode substrate, and the insulating layer is placed facing the photoconductive layer surface on the electrode substrate, and information light is emitted from the photoreceptor side while a voltage is applied between both electrodes. When the information light is irradiated, charges move toward the electrode on the electrostatic charge recording body side in the portion of the photoconductive layer irradiated with the information light.

The moving charges are accumulated as information charges on the surface of the electrostatic charge recording material by discharge or charge injection, or penetrate into the inside of the insulating layer to form a permanent electrostatic charge recording material. By covering the surface of the insulating layer with a protective film such as a plastic film, the charge once accumulated in the insulating layer can be retained for an extremely long period of time, and this electrostatic charge recording material can be embedded into the card base material. , or by pasting it, it can be used for cards.

In addition to simply turning information recorded into cards, by turning unrecorded electrostatic charge recording materials into cards and using adhesive plastic film as a protective film to make it removable, Users can also peel off the protective film and record information at any time. In particular, as an electrostatic charge recording card, by recording digital information such as (0/1) information through a scanning operation using beam irradiation, the recorded charge can be stored as is or by developing it with toner. It is possible to easily output the data to a CRT or a printer using a potential reading means and a reproducing means, and the reading means used in an optical card can also be used as the reading means.

Examples will be described below.

[Example 1]...Production method of electrostatic charge recording material 10 g of methylphenyl silicone resin 1 xylene-butanol 1: [
1% by weight (0.2 g) of a hardening agent (metal catalyst) (trade name: CR-15) was added to the mixed solution having the composition of the solvent Log, and the mixture was stirred well. A coating was applied on top using a doctor blade 4 mil. Thereafter, drying was performed at 150° C. for 1 hour to obtain an electrostatic charge recording material (a) having a film thickness of 10 μm.

In addition, 100μ of the above mixed solution was deposited with A1 by 1000 people.
It was coated on a polyester film in the same manner and then dried to obtain a film-like electrostatic charge recording material (b).

Furthermore, 0.1 g of zinc stearate was added to the above mixed solution, and A1 was similarly coated on a polyester film of 100 μm H'AK deposited by 1000 people, dried, and an electrostatic charge recording material having a film thickness of 10 μm ( c) was obtained.

[Example 2] A mixed solution having a composition of polyimide resin Log and 10 g of N-methylpyrrolidone was spinner coated (1000 rpm
, 20 seconds) at 150 °C for 30 seconds to dry the solvent.
After pre-drying for 2 minutes, heat at 350°C for 2 minutes to harden.
heated for an hour.

A uniform film with a film thickness of 8 μm was formed.

[Example 3]...Single layer organic photoreceptor (PVK-TN
F') Preparation method Poly-N-vinylcarbazole 10g (Anan Fragrance Co., Ltd.)
(manufactured by Toyobo Co., Ltd.), 2.4.7-) 10 g of linitrofluorenone, 2 g of polyester resin (binder: Byron 200 manufactured by Toyobo Co., Ltd.), 90 g of tetrahydrofuran (THF)
A mixed solution having the composition was prepared in a dark place, and InzOs-5
Sputtered nOz to a film thickness of about 1000 mm was applied to a glass substrate (1 layer thick) using a doctor blade.
The mixture was dried with ventilation at 0° C. for about 1 hour to obtain a photosensitive layer having a photoconductive layer with a thickness of about 10 μm. In addition, in order to completely dry the sample, it was further air-dried for one day before use.

[Example 4]...Amorphous silicon a Si
: H Inorganic photoreceptor manufacturing method ■Substrate cleaning Corning 7059 glass (23XI6XO, 9t, optically polished) with a 5nOz thin film photoreceptor electrode layer on one surface was placed in trichloroethane, acetone, and ethanol in this order. Ultrasonic cleaning for 10 minutes each.

■ After setting the cleaned substrate on the anode 106 in the reaction chamber 104 in FIG. 26 to ensure sufficient heat conduction,
The temperature inside the reaction chamber was increased to 10-' Torr.

The reaction vessel and gas pipe are baked out at 150'C to 350'C for about 1 hour, and the apparatus is cooled after baking out.

■a-3i: Deposit H(n・) Set the heater to 108°C so that the temperature of the glass substrate is 350'C.
The internal pressure of the reaction chamber 104 was brought to 200 mT by controlling the needle valve and the rotation speed of the PMB.

After the flow internal pressure becomes constant so as to become rr, Mat
40W Rf through Ching Box 103
Power 102 (13,56 KHz) is applied to form a plasma between the power '/-)' and the anode. Deposition is performed for 4 minutes, then Rf input is stopped and the needle valve is closed.

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

■a-5t: Deposition of H 5fH4 100% gas in the same way as ■ until the internal pressure is 200
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 valve is closed. After Heater 1080ff, the board is cold, so take it out.

As a result, a film of approximately 18.8 μm is a-3i:H(n゛)
deposited on the membrane.

In this way, a photoreceptor with a SnO2/a-3i:H(n') blocking layer/a-3i:H (non-dope) of 20 μm was fabricated.

CX Example 5)...Production method of amorphous selenium-tellurium inorganic photoreceptor Using the same equipment as in Example 4, tellurium (Te) was mixed with selenium (Se) at a ratio of 13% by weight. Using metal particles, an a-5e-Te thin film is deposited at a vacuum degree of 1 using a vapor deposition method.
It was deposited on an ITO glass substrate using a resistance heating method at 0-'Torr. The film thickness was 1 μm. Furthermore, while maintaining the degree of vacuum, only Se was evaporated using the same resistance heating method.
A 10 μma-Se layer was laminated on the 5e-Te layer.

[Example 6] 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 m/volume stainless steel container, and Glass Peas NO3, 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, Niepiron E-2000 (Mitsubishi Gas Chemical) was added and stirred for about 4 hours. This solution was applied to a glass substrate (In thickness) spun with about 1000 InzOs-Snow using a doctor blade to obtain a charge generation layer with a thickness of about 1 μm. Drying was carried out at room temperature for one day.

[Method for forming charge transport layer]

4-Dibenzylamino-2-methylbenzaldehyde-
1,1'-diphenylhydrazone 0.1 g, polycarbonate (Nipilon 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 to form a layer of about 10 μm.
A charge transport layer of m was obtained. Drying was performed at 60°C for 2 hours.

[Example 7] (Formation method of charge generation layer) Butyral resin (Building Chemical, 5LE) was added to butyl acetate Log.
C) 0.25g, azulenium C having the following structural formula
Mix 0.5 g of f104 salt and 133 g of Glass Peas No., stir with a touch mixer for 1 day, disperse well, apply with a doctor blade or applicator on ITO layered on a glass plate, and heat at 60°C. , dried for more than 2 hours. The film thickness after drying is 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., CTCI
91) was mixed with 0.5 g, 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.

[Example 8] (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 fucrocyanine.
5g, 4.10-dibromoanthrone 0.25g
, Glass Peas No. 1, 33g, 1 with a touch mixer
The mixture was stirred for several days to be well dispersed, and then applied using a doctor blade or applicator onto ITO laminated on a glass plate, and dried at 60° C. for 2 hours or more. The film after drying had a thickness of 1 μm or less.

(Method for Preparing Charge Transport Layer) To 9.5 g of dichloroethane, 0.5 g of polycarbonate (Mitsubishi Gas Chemical, Nipiron E2000), 0.5 g of the above hydrazone derivative (CTCI91, Anan Perfumery). sg) and coated on the charge generation layer with a doctor blade,
It was dried at 60°C for 2 hours or more. The film thickness was 10 μm or more.

[Example 9]... 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., Fl-175SVLO) was applied to a thickness of 0.5 to 1 μm 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, azulenium C10 as described above, salt 0.
5 g and 133 g of Glass Peas N01 were mixed, stirred for 1 day using a touch mixer, dispersed well, and applied onto the charge injection prevention layer using a doctor blade or applicator, and dried at 60° C. for 12 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, Nipiron E2000), and 0.5 g of the above-mentioned hydrazone derivative Kuanan Kaori, CTC191).
was dissolved and applied onto the charge generation layer using a doctor blade, and dried at 60° C. for 2 hours or more. Film thickness 10μm
It was below.

[Example 10] (Method for forming charge injection prevention layer) Soluble polyamide (
Toagosei Chemical Co., Ltd., FS-175SV10) was applied to a thickness of 0.5 to 1 μm using a spin coater and 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
, 33g of glass peas NO61, 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 charge 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 Kaori, cTc191) 0.
5 g was dissolved and applied onto the charge generation layer using a doctor blade, and dried at 60° C. for 2 hours or more. Film thickness is 10μ
It was more than m.

[Example 11] (Method for forming photoconductor 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. The 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 12] Electrostatic charge recording method Fig. 4 is a diagram for explaining the electrostatic charge recording method in a ROM type electrostatic charge recording card, and Fig. 5 shows the electrostatic charge recording method in a DRAWROM type electrostatic charge recording card. It is a figure for explaining.

1 is an electrostatic charge recording card, 2 is a photoreceptor, 3 is an electrostatic charge recording member, 4 is a card base material, 5 is a photoconductive layer support, 7 is a photoconductor electrode, 9 is a photoconductive layer, 11 is an insulating layer, 13 is an electrostatic charge recording member electrode, 14 is an exposed electrode portion, 15 is an electrostatic charge recording member support,
16 is a protective film, 17 is a power supply, and 18 is a switch.

As shown in FIG. 4(A), first, the electrostatic charge recording body 3 produced in Example 1 was inserted into an insulating N11
Place the surface facing the photoconductor N9 of the photoreceptor prepared in Example 3, and then as shown in FIG.
13, set the photoconductor side as negative and the insulating layer side as positive, and set -700.
A DC voltage of V is applied. In a dark place, since the photoconductive layer 9 is a high-resistance material, no change occurs between the electrodes. In this state, exposure was performed for 1 second from the back surface of the photoreceptor using a halogen lamp with an illuminance of 1000 lux as a light source, and after the exposure was completed, the voltage was turned off as shown in FIG. The photoconductive layer 9 in the part where the light is incident exhibits conductivity, and the insulating layer 1
1, and electric charges are accumulated in the insulating layer 11. Next, as shown in FIG. 4(d), the electrostatic charge recording medium 3 is taken out, thereby completing the formation of the electrostatic latent image. As a result, a surface potential of 1100 cm was measured on the electrostatic charge recording medium using a surface electrometer, while the surface potential in the unexposed area was Ov. After that, it was laminated with an insulating film, and the potential was read from the top of the laminated film.
A surface potential of 0v was measured by a surface electrometer.

In addition, after performing similar exposure with the resolution pattern film in close contact with the back surface of the photoreceptor during exposure, the electrostatic charge recording material was
XY-axis scanning was performed on the small area surface potential measurement probe surface of 50 μm, and the potential data at 50 μm position was processed and enlarged and displayed on the CRT using potential-luminance conversion. As a result, a resolution pattern of up to 100 μm was confirmed on the CRT. .

After exposure, the electrostatic charge recording medium was heated at room temperature of 25℃ and 35℃ for 3
After being left for several months, a similar potential scanning reading was performed, and as a result, a resolution pattern display with no change at all from immediately after exposure was obtained. After exposure to the resolution pattern, a polyester film was used as a protective film to cover the film, and a resolution of 10 (lumens) was obtained by reading the potential on the film on the CRT.

Also, as an exposure method, using a normal camera, -700
A copy was made outdoors during the daytime (closest shadow) with a voltage of V applied, exposure f=1.4, and shutter speed 1/60 seconds.

After exposure, the electrostatic charge recording medium was scanned in the XY axes with a surface potential measuring probe surface of a micro area of 50 x 50 μm, and
As a result of processing potential data in μm units and enlarging and displaying it on a CRT by potential-luminance conversion, an image with gradation was formed. When this electrostatic recording medium was laminated in the same manner as described above and measurements were made from the top of the laminate, an image was formed with the same gradation as in the case without lamination.

Next, as the exposure means in FIG. 4, a laser irradiation means is used to form an electrostatic latent image, which is made visible with toner, and an optical card reading device is used to scan the card surface to determine the presence or absence of potential charges. Alternatively, the potential difference could be read as rOJ, a "1" signal.

In addition, analog information charges are accumulated in the insulating layer by surface exposure,
By scanning with laser light, it was possible to read analog (5II) and digital (0,1) signals.

[Example 13] Color images were taken using the following method.

■ Prism-type three-plane division method As shown in FIG. 21, RlG and B filters are arranged on three sides of a prism, and the same medium used in Example 12 above is set on each side, and f=1. 4. Shutter
The subject was photographed at a speed of 1/30 seconds.

■Color CRT display method Each of the R, G, and B latent images is scanned and read in the same manner as in Example 12, and fluorescent colors corresponding to the R, G, and B latent images are formed on the CRT, and three-color separation is performed. A color image was obtained by combining the images on a CRT.

[Example 14] FIG. 27 is a diagram showing the charge retention characteristics of the electrostatic recording material of Example 1 (a), and shows the results of measuring the surface potential over time.

Line A was measured after being left at a temperature of 25° C. and a humidity of 30%, and the surface charge on the electrostatic charge recording material did not attenuate even after 3 months. The B line was measured after being left at a temperature of 40° C. and a humidity of 75%, and it was only attenuated by about 25% after one week had passed.

[Example 15]...Method for producing electrostatic charge recording material by thermal electroleft vacuum evaporation (1
A 1,000-person vacuum-deposited layer of A2 was used as an electrostatic charge recording medium using a resistive heating method (0-6 Torr, resistance heating method), and an electrostatic latent image was formed together with the photoconductive photoreceptor of the functionally separated photoreceptor.

First, from the Ad substrate side of the electrostatic charge recording medium, the hot plate (3
x 3 cm) and heat the medium to 180°C. Immediately after heating, the photoreceptor was placed so that its surfaces faced each other with an air gap of 10 .mu.m, and a voltage of -550 V was applied between the electrodes (with the photoreceptor electrode being negative) to expose the photoreceptor to light. Exposure was carried out at 10 lux using a halogen lamp as a light source for 1 second from the back surface of the photoreceptor through the character pattern document.

After this, the film was naturally cooled, and as a result, the exposed areas (characters)
A potential of -150 V was measured in the area, and no potential was measured in the unexposed area. Water droplets were dropped onto the film on which the charged pattern was formed, and after being collected, the potential was measured. As a result, the potential of -150 V was measured in the exposed area, which was the same as before.

On the other hand, after forcibly forming a charge of -150V on the surface of the electrostatic charge recording medium by corona discharge, water droplets were dropped and collected. Disappeared. Therefore, it was found that charge formation under heating is caused by polarization inside polyvinylidene fluoride, resulting in electroleft formation.

The thermoelectric node thus formed was capable of reading the potential as described above as an electrostatic charge recording medium.

[Example 16]...Method for producing photoelectret 1,
A1 was laminated on a 1 mm thick glass support by about 1000 sputtering method to form a substrate, and zinc sulfide was evaporated onto the AP layer to a thickness of about 1.5 μm (10-'T
orr, resistance heating). The surface of this zinc sulfide layer is opposed to the surface of ITO laminated on glass with an air gap of 10 μm, and a voltage of +700V is applied between both electrodes (A7!
Exposure was performed from the ITO substrate side with the electrode side set negative.

Exposure was performed in the same manner as in Example 11. As a result, a potential of +80 V was measured in the exposed area, and no potential was measured in the unexposed area. In this case as well, a water droplet experiment similar to that in Example 11 was conducted, but there was no change in the potential after recovery, and an electret with charge accumulated inside was formed.

The photoelectric left thus formed could be used as an electrostatic charge recording medium to read the potential in the same way as described above.

[Example 17]...Production method of ROM type electrostatic charge recording card As shown in Figure 1, a vinyl chloride sheet (85 x 55 mm) with a film thickness of 0.8 mm was used as the card base material, and a A rectangular electrostatic charge recording body 3 is molded into a shape having a storage hole, and then an adhesive is applied to the back side of the electrostatic charge recording body 3 on which information has been recorded by the above-mentioned electrostatic charge recording method, and the card base material 4 is stored. The surface of the insulating layer 11 was exposed and embedded in the hole, and the insulating layer 11 was integrated by pressure bonding. Next, the surface of the electrostatic charge recording card was coated with a polyester film as a protective film 16.

[Example 18]...Production method of DRAW type electrostatic charge recording card As shown in Fig. 3, a vinyl chloride sheet (85 x 55 mm) is used as the card base material 4, and a rectangular electrostatic charge recording body 3 is placed on the top surface of the vinyl chloride sheet (85 x 55 mm). A through hole to the back surface is formed in the storage hole and a part of the bottom of the storage hole.

On the other hand, the exposed electrode part 14 is integrally molded on the back surface of the electrostatic charge recording body electrode 13 in the electrostatic charge recording body 3, and the insulating layer 11 is laminated on the electrostatic charge recording body electrode 13, and the insulating layer 11 is formed without recording information. The lead-out electrode part 14 is exposed from the exposure hole of the card base material 4 and stored in the storage hole, and is crimped and integrated. As in Example 17, a silicone rubber film was adhered to the surface of the electrostatic charge recording material as a protective film (not shown).

To record on this DRAW type electrostatic charge recording card, first, the protective film is peeled off, and as shown in FIG. 5(a), the picture electrode 7.
Information was recorded on the surface of the insulating layer by exposing it to light for 1 second using a 1000 lux halogen lamp while applying a voltage of 700 .mu. during 13 hours, and the protective film was again adhered to the surface of the electrostatic charge recording material.

When we read the surface potential on this film, we found that
The information charge was suitably retained, and the image information charge did not attenuate at all even after three months.

〔Effect of the invention〕

The electrostatic charge recording material in the present invention includes characters, line drawings, images, (
0,1) Since it stores analog information such as information and digital information in the form of electrostatic charge, it can store high quality and high resolution information and can be stored for a long time as an electrostatic latent image. That is. In addition, the accumulated information is
The local potential of an electrostatic latent image can be read and output at any scanning density at any time, and a high-quality original image can be output at any time. Furthermore, by using this electrostatic charge recording medium, direct potential detection eliminates the need for physical or chemical means such as developing means, making it possible to create an inexpensive and simple recording/reproducing system. . The electrostatic charge recording card of the present invention is made into a card by arranging this electrostatic charge recording body on a card base material, and has a simple means for storing information, and can record and retain information permanently. It also makes it possible to re-record data once it has been converted into a card. Furthermore, by developing the information charge with toner, it can be used as an optical card. Further, the information on the electrostatic charge state or the information on the toner development can be easily and quickly reproduced by a surface electrometer or an optical card reader.
It can be suitable as a recording card such as a cash card or a credit card.

[Brief explanation of the drawing]

FIG. 1(A) is a perspective view of a ROM type electrostatic charge recording card of the present invention, and FIG. 1(B) is a line A-A in FIG. A cross-sectional view at
Figure 2 is a sectional view of the electrostatic charge recording body in the present invention, and Figure 3 (
A) is a perspective view of a DRAWROM type electrostatic charge recording card (B)
is a cross-sectional view taken along line B-B in Figure (A), Figure 4 is a diagram explaining the electrostatic charge recording method in a ROM type electrostatic charge recording card, and Figure 5 is a diagram explaining the electrostatic charge recording method in a DRAWROM type electrostatic charge recording card. Figure 6 is a diagram to explain the principle of the electrostatic image recording and reproducing method using a photoelectret, and Figure 7 is a diagram explaining the principle of the electrostatic image recording and reproducing method using a thermal electret. Diagrams for explaining, Figures 8 and 9,
Figure 10 is a diagram showing an example of a DC amplification type potential reading method, Figures 11, 12, and 13 are diagrams showing an example of an AC amplification type potential reading method, and Figures 14 and 15 are diagrams showing an example of a potential reading method of an AC amplification type. Figure 16 showing an example of a potential reading method using the CT scan method
The figure shows an example of a current collector type potential reading method, Figure 17 shows an example of an electron beam type potential reading method, and Figure 1 shows an example of an electron beam type potential reading method.
Figures 8 and 19 are diagrams for explaining a potential reading method using toner coloring, Figure 20 is a diagram showing a schematic configuration of electrostatic image reproduction according to the present invention, and Figure 21 is a diagram showing the configuration of a color separation optical system. FIG. 22 is an explanatory diagram for forming a color electrostatic latent image, FIG. 23 is a diagram showing an example of a fine color filter,
Figure 24 shows an example of a combination of a fine color filter and a Fresnel lens, and Figure 25 shows an ND filter and R, G
, a diagram showing three-plane division using a B filter in combination, FIG. 26 is a diagram for explaining the method for manufacturing an a-Si:H photoreceptor,
FIG. 27 is a diagram showing the charge retention characteristics of the electrostatic charge recording medium. 1 is an electrostatic charge recording card, 2 is a photoreceptor, 3 is an electrostatic charge recording member, 4 is a card base material, 5 is a photoconductive layer support, 7 is a photoconductor electrode, 9 is a photoconductive layer, 11 is an insulating layer, 13 is an electrostatic charge recording member electrode, 14 is an exposed electrode portion, 15 is an electrostatic charge recording member support,
16 is a protective film, 17 is a power supply, 18 is a switch, 21...
・Potential reading section, 23...Detection electrode, 25...Guard electrode, 27...Capacitor, Applicant Dai Nippon Printing Co., Ltd. Agent Patent attorney (1) Nobuhiko (4 others) Figure 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 8 Fig. 9 Fig. 10 Fig. 11 Fig. 7, 24 Fig. 12 Fig. 2 M Fig. 14 Fig. 15 Fig. 16 Fig. 17 Fig. 20 Figure 21 Figure 22 Figure 23 Figure 24 Figure 25

Claims (5)

[Claims] (1) An electrostatic charge recording card in which an electrostatic charge recording medium in which an insulating layer is laminated on an electrode is laminated on a card base material with the insulating layer facing upward. (2) The electrostatic charge recording material according to claim 1, wherein the electrostatic charge recording body is embedded in the card base material with the surface of the insulating layer exposed, or is laminated by being stuck on the card base material with the insulating layer facing upward. Electrostatic charge recording card. (3) Claim 1, wherein the electrostatic charge recording body is laminated in a state in which information is recorded or in a state in which information is not recorded.
Or the electrostatic charge recording card described in 2. (4) The electrostatic charge recording card according to claim 3, wherein the recording form on the electrostatic charge recording medium is charge or toner developed with toner. (5) The electrostatic charge recording card according to claim 1, 2, 3, or 4, wherein the electrodes are partially exposed at appropriate locations on the card base material.