JP2891461B2 - Toner image forming method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a toner image forming method capable of electrostatically recording an image and forming a toner image at any time.

[Conventional technology]

Conventionally, silver halide photography has been known as a high-sensitivity photographing technique. In this photographic method, a photographed image is recorded on a film or the like through a development process, and when an image is reproduced, a silver halide emulsion (such as photographic paper) is used, or a developed film is optically scanned and a cathode ray tube (hereinafter referred to as a cathode ray tube). (CRT).

In addition, an electrode is deposited on the photoconductive layer, the entire surface is charged by corona charging on the photoconductive layer in a dark place, and then the photoconductive layer exposed to strong light is exposed to light, and the photoconductive layer is made conductive. The latent electrostatic image is optically formed on the surface of the photoconductive layer by leaking and removing the toner, and a toner having a charge of the opposite polarity (or a charge of the same polarity) as the residual electrostatic charge is attached to the latent image for development. Electrophotography technology is mainly used for copying, but it cannot be used for photography because of low sensitivity in general.Because the electrostatic charge retention time is short, toner is used immediately after forming an electrostatic latent image. It is common to develop.

In TV shooting technology, images are taken with an image pickup tube, image information obtained using optical semiconductors is extracted as electrical signals, and
There are methods such as outputting to a CRT or video recording using magnetic recording or the like, and outputting an image on the CRT at an arbitrary time.

[Problems to be solved by the invention]

Silver halide photography is excellent as a means of preserving the subject image, but requires a development step to form a silver halide image,
Image reproduction requires complicated optical, electrical, or chemical treatments such as hard copy and soft copy (CRT output).

In electrophotography, visualization of the obtained electrostatic latent image is easier and faster than silver halide photography, or the latent image storage is extremely short,
The dissociation property and image quality of the developer are inferior to silver salts.

In the TV shooting technique, line-sequential scanning is required to extract and record an electric image signal obtained by an image pickup tube. Line-sequential scanning is performed by an electron beam in an image pickup tube, and a magnetic head is used in video recording. However, since the resolution depends on the number of scanning lines, the resolution is significantly deteriorated as compared with a planar analog recording such as a silver halide photograph.

A TV imaging system using a solid-state imaging device (CCD or the like), which has recently been developed, has essentially the same resolution.

The problems with these technologies are that image recording is of high quality,
If the resolution is high, the processing steps are complicated, and if the steps are simple, there is a lack of a storage function or a basic deterioration of image quality.

The present invention is to solve the above problems, high quality, high resolution, simple processing steps, long-term storage is possible, stored characters, line drawings, images, codes,
(1.0) It is an object of the present invention to provide a toner image forming method capable of forming a toner image at a point in time with a quality of information according to a purpose.

[Means for solving the problem]

FIG. 1 is a view for explaining a recording method in the electrostatic image recording / reproducing method of the present invention, wherein 1 is a photosensitive member, 3 is a charge holding medium, 5 is a photoconductive layer support, and 7 is a photosensitive member. Electrode, 9
Denotes a photoconductive layer, 11 denotes an insulating layer, 13 denotes a charge holding medium electrode, 15 denotes an insulating layer support, and 17 denotes a power supply.

FIG. 1 shows an embodiment in which exposure is performed from the photoreceptor 1 side. First, a transparent photoreceptor electrode 7 made of ITO having a thickness of 1000 mm is formed on a photoconductive layer support 5 made of 1 mm thick glass. The photoconductor 1 is formed by forming a photoconductive layer 9 of about 10 μm thereon. The charge holding medium 3 is arranged on the photoconductor 1 with a gap of about 10 μm. The charge holding medium 3 is placed on an insulating layer support 15 made of glass having a thickness of 1 mm.
An Al electrode 13 having a thickness of 0 mm is formed by evaporation, and
In this case, an insulating layer 11 having a thickness of 0 μm is formed.

First, as shown in FIG.
The charge holding medium 3 is set through a gap of about 10 μm,
As shown in FIG. 1 (b), a voltage is applied between the electrodes 7 and 13 by the power supply 17. In a dark place, since the photoconductive layer 9 is a high-resistance body, no change occurs between the electrodes. When light is incident from the photoreceptor 1 side, the photoconductive layer 9 in the portion where the light is incident shows conductivity, and a discharge occurs between the photoconductive layer 9 and the insulating layer 11.
The electric charge is accumulated.

When the exposure is completed, a voltage is applied as shown in FIG.
Turn off, and then take out the charge holding medium 3 as shown in FIG. 1 (d) to complete the formation of the electrostatic latent image.

The photoconductor 1 and the charge holding medium 3 may be of a contact type instead of a non-contact type as described above. In the case of the contact type, a positive or negative charge is applied to the exposed portion of the photoconductive layer 9 from the photoconductor electrode 7 side. Charges are injected, and the charges are drawn by the electrode 13 on the charge holding medium 3 side, pass through the photoconductive layer 9, and stop moving when reaching the surface of the insulating layer 11. Is done. Then, when the photoconductor 1 and the charge holding medium 3 are separated, the insulating layer
11 are separated while keeping the charge.

When this recording method is a planar analog recording, high resolution can be obtained in the same manner as the silver halide photography, and an insulating layer to be formed is formed.
Although the surface charge on 11 is exposed to the air environment, the air has a good insulating performance, so it is stored for a long time without discharging regardless of the light place and the dark place.

The charge storage period on the insulating layer 11 is determined by the properties of the insulator, and is affected by the charge trapping characteristics of the insulator in addition to the insulating properties of air. In the above description, charges are described as surface charges.Injected charges may simply accumulate on the surface, and microscopically penetrate into the vicinity of the insulator surface, and electrons or electrons enter the structure of the substance. Since the holes may be trapped, long-term storage is performed. In addition, the surface of the insulator 11 may be covered with an insulating film or the like and stored in order to prevent physical damage to the charge holding medium or discharge when the humidity is high.

Hereinafter, constituent materials of the photoreceptor and the charge holding medium used in the present invention will be described.

The material and thickness of the photoconductive layer support 5 are not particularly limited as long as the photoconductive layer support 5 has a certain strength capable of supporting the photoreceptor. For example, a flexible plastic film, metal foil, paper, or the like may be used. Alternatively, a rigid body such as a glass, a plastic sheet, or a metal plate (which can also serve as an electrode) is used. However, when used in a device that records information by irradiating light from the photoconductor side, it is naturally necessary to have the property of transmitting that light.For example, when using natural light as incident light and using it in a camera that enters from the photoconductor side Has a thickness of 1m
A transparent glass plate of about m or a plastic film or sheet is used.

The photoreceptor electrode 7 is formed on the photoconductive layer support 5 except when a metal is used for the photoconductive layer support 5, and the material thereof is as long as the specific resistance value is 10 ⁶ Ω · cm or less. There is no limitation, and an inorganic metal conductive film, an inorganic metal oxide conductive film, or the like can be used.
Such a photoconductor 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 of the electrode must be changed depending on the electrical characteristics of the material constituting the photoreceptor electrode 7 and the applied voltage when recording information. For example, in the case of aluminum, the thickness is about 100 to 3000 °. Similarly to the photoconductive layer support 5, the photosensitive electrode 7 is required to have the above-mentioned optical characteristics when information light needs to be incident thereon. For example, when the information light is visible light (400 to 700
nm), a transparent electrode such as ITO (In ₂ O ₃ -SnO ₂ ), SnO _2, etc., which is formed by sputtering, vapor deposition, or inking and coating a fine powder thereof with a binder.
Translucent electrodes made of u, Al, Ag, Ni, Cr, etc. by evaporation or sputtering, tetracyanoquinodimethane (TCN
Q), an organic transparent electrode with a coating of polyacetylene or the like is used.

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

Further, when the information light is ultraviolet light (400 nm or less), the above-mentioned electrode materials can be basically used, but those in which the electrode substrate material absorbs ultraviolet light (organic polymer materials, soda glass, etc.) are not preferable. A material that transmits ultraviolet light, such as quartz glass, is preferable.

The photoconductive layer 9 is a conductive layer in which photocarriers (electrons and holes) are generated in the irradiated portion when light is irradiated, and the carriers can move in a layer width. In particular, an electric field exists. In this case, the effect is remarkable. The material is composed of an inorganic photoconductive material, an organic photoconductive material, an organic-inorganic hybrid type photoconductive material, or the like.

Hereinafter, a method for forming the photoconductive material and the photoconductive layer will be described.

(A) Inorganic Photoreceptor (Photoconductor) Examples of inorganic photoreceptor materials include amorphous silicon, amorphous selenium, cadmium sulfide, and zinc oxide.

(A) Amorphous silicon photoreceptor As an amorphous silicon photoreceptor, hydrogenated amorphous silicon (a-Si: H) fluorinated amorphous silicon (a-Si: F) ・ Those not doped with impurities, ・ B, Al , Ga, In, Tl, etc. are made P-type (hole transport type) by doping; and P, Ag, Sb, Bi, etc. are made N-type (electron transport type) by doping.

As a method of forming the photoreceptor layer, a silane gas and an impurity gas are introduced into a low vacuum together with a hydrogen gas (10 ^{-2 to 1} Torr).
r), a film is formed by pre-stacking on an electrode substrate heated or not heated by glow discharge, or a thermochemical reaction is formed on a heated electrode substrate, or a solid material is formed by vapor deposition and sputtering. Used as a film, a single layer or a laminate. The film thickness is 1 to 50 μm.

Further, a charge injection preventing layer can be provided on the surface of the photoreceptor electrode 7 in order to prevent charge from being injected from the transparent electrode 7 and being exposed as if it were not exposed. As the charge injection preventing layer, an a-SiN layer, an a-SiC layer or the like is formed on one or both of the electrode substrate and the photoconductor layer (surface layer) by glow discharge, vapor deposition, sputtering, or the like.
It is preferable to provide an insulating layer such as a layer, a SiO ₂ layer, and an Al ₂ O ₃ layer. If the insulating layer is too thick, no current will flow when exposed, so it must be at least 1000 ° or less, and preferably about 400-500 ° in consideration of ease of fabrication.

Further, as the charge injection preventing layer, it is preferable to provide a charge transporting layer having a charge transporting ability of a polarity opposite to the polarity of the electrode substrate on the electrode substrate by utilizing a rectifying effect. Is positive, an electron transport layer is provided. For example, a-Si: H in which boron is doped in Si
(N ⁺ ) enhances the hole transporting property, provides a rectifying effect, and functions as a charge injection preventing layer.

(B) Amorphous selenium photoconductor Amorphous selenium photoconductor includes amorphous selenium (a-Se) amorphous selenium tellurium (a-Se: Te) amorphous arsenic selenium compound (a-As ₂ Se ₃ ) amorphous arsenic selenium compound + Te .

This photoreceptor is prepared by vapor deposition and sputtering, and a SiO ₂ , Al ₂ O ₃ , SiC, SiN layer as a charge injection blocking layer is provided on the electrode substrate by vapor deposition, sputtering, glow discharge or the like. Further, the above-mentioned may be combined to form a laminated photoreceptor. The thickness of the photoconductor layer is the same as that of the alphas silicon photoconductor.

(C) Cadmium sulfide (CdS) This photoreceptor is prepared by coating, vapor deposition, and sputtering. In the case of vapor deposition, solid particles of CdS are placed on a tungsten board and deposited by resistance heating, or EB
(Electron beam) This is performed by vapor deposition. In the case of sputtering, deposition is performed on a substrate in argon plasma using a CdS target. In this case, CdS is usually deposited in an amorphous state, but a crystalline alignment film (oriented in the film thickness direction) can be obtained by selecting sputtering conditions.
You can also get In the case of coating, CdS particles (particle diameter: 1 to 100 μm) may be dispersed in a binder, and a solvent may be added to coat the substrate.

(D) Zinc oxide (Zn O) This photoreceptor is manufactured by a coating method or a CVD method. As the coating method, ZnS particles (particle size 1 to 100
μm) is dispersed in a binder, and a solvent is added thereto to perform coating on a substrate. In the CVD method, an organic metal such as diethyl zinc or dimethyl zinc and oxygen gas are mixed in a low vacuum (10 ^{-2 to 1} Torr), and a chemical reaction is performed on a heated electrode substrate (150 to 400 ° C.) to oxidize. Deposited as a zinc film. Also in this case, a film oriented in the film thickness direction can be obtained.

(B) Organic Photoreceptor The organic photoreceptor includes a single-layer type photoreceptor and a function-separated type photoreceptor.

(A) Single-layer photoconductor The single-layer photoconductor is composed of a mixture of a charge generating substance and a charge transport substance.

<Charge-generating substance type> It is a substance that easily absorbs light to generate an electric charge, and includes, for example, an azo pigment, a disazo pigment, a trisazo pigment, a phthalocyanine pigment, a perylene pigment, a pyrylium dye,
Cyanine dyes and methine dyes are used.

<Charge transporting substance type> It is a substance having good ionizing charge transporting properties, for example, hydrazone type, pyrazoline type, polyvinyl carbazole type, carbazole type, stilbene type, anthracene type,
There are naphthalene type, tridiphenylmethane type, azine type, amine type, aromatic amine type and the like.

Further, a charge transfer complex may be formed by forming a complex between the charge generation material and the charge transport material.

Normally, a photoreceptor has photosensitivity determined by the light absorption characteristics of a charge generating substance. However, if a charge generating substance and a charge transporting substance are mixed together to form a complex, the light absorption properties change. For example, polyvinyl carbazole (PVK) is an ultraviolet light. Only in the region, trinitrofluorenone (TNF) only feels around 400 nm wavelength, while the PVK-TNF complex feels up to 650 nm wavelength region.

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

(B) Function-separated type photoreceptor Although the charge generating material easily absorbs light, it has the property of trapping light, and the charge transporting material has good charge transporting properties.
Light absorption characteristics are not good. For this reason, the two are separated so that the characteristics of the two can be sufficiently exhibited, and the charge generation layer and the charge transport layer are stacked.

<Charge Generating Layer> Examples of the material for forming the charge generating layer include azo-based materials,
There are disazo type, trisazo type, phthalocyanine type, acid xansen dye type, cyanine type, styryl dye type, pyrylium dye type, perylene type, methine type, a-Se, a-Si, azulenium salt type, squarium salt type and the like.

<Charge Transport Layer> Examples of the material forming the charge transport layer include hydrazone, pyrazoline, PVK, carbazole, oxazole, triazole, aromatic amine, amine, triphenylmethane, and polycyclic aromatic compounds. Group compounds.

As a method for producing a function-separated type photoreceptor, a charge generating substance is first dissolved in a solvent and applied on an electrode, and then the charge transport layer is dissolved in a solvent and applied to the charge transport layer.
It is preferable that the thickness of the charge transport layer be 0.1 to 10 μm and the thickness of the charge transport layer be 10 to 50 μm.

In addition, in any case of the single-layer type photoreceptor and the function separation type photoreceptor, as a binder, a silicone resin, a styrene-butadiene copolymer resin, an epoxy resin, an acrylic resin,
Saturated or unsaturated polyester resin, polycarbonate resin, polyvinyl acetal resin, phenol resin, polymethyl methacrylate (PMMA) resin, melamine resin,
0.1 to 10 parts of a polyimide resin or the like is added to 1 part of each of the charge generating material and the charge transport material so that the resin can be easily attached. As a coating method, a dipping method, an evaporation method, a sputtering method, or the like can be used.

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

The charge injection preventing layer is provided on at least one or both surfaces of the photoconductive layer 9 in a dark current (charge injection from an electrode) when a voltage is applied to the photoconductive layer 9, that is, even though the photoconductive layer 9 is not exposed. It can be provided to prevent development in which charges move in the photosensitive layer as if exposed.

The charge injection preventing layer includes two types, a layer using a so-called tunneling effect and a layer using a rectifying effect. First, in a device utilizing the so-called tunneling effect, current does not flow to the photoconductive layer or the insulating layer surface due to the charge injection preventing layer only by applying a voltage, but when light is incident, it corresponds to an incident portion. A high electric field is applied to the charge injection prevention layer due to the presence of one of the charges (electrons or holes) generated in the photoconductive layer, causing a tunnel effect and causing a current to flow through the charge injection prevention layer. is there. Such a charge injection prevention layer is formed of a single layer of an inorganic insulating film, an organic insulating polymer film, an insulating monomolecular film, or the like, or is formed by laminating them. As the inorganic insulating film, for example, As ₂ O _{3, B 2 O 3, Bi} 2 O 3, CdS, CaO, CeO 2, Cr 2 O 3, Co
_{O, GeO 2, HfO 2,} Fe 2 O 3, La 2 O 3, MgO, MnO 2, Nd 2 O 3, Nb 2
_{O 5, PbO, Sb 2 O} 3, SiO 2, SeO 2, Ta 2 O 5, TiO 2, WO 3, V
₂ O ₅ , Y ₂ O ₅ , Y ₂ O ₃ , ZrO ₂ , BaTiO ₃ , Al ₂ O ₃ , Bi ₂ TiO ₅ , CaO
_{-SrO, CaO-Y 2 O 3} , Cr-SiO, LiTaO 3, PbTiO 3, PbZr
_{O 3, ZrO 2 -CO, ZrO} 2 -SiO 2, AlN, BN, NbN, Si 3 N 4, Ta
N, TiN, VN, ZrN, SiC, TiC, WC, Al ₄ C _{3 and the} like are formed by glow discharge, vapor deposition, sputtering and the like. The thickness of this layer is determined for each material used in consideration of the insulating property for preventing charge injection and the tunnel effect.
Next, the current injection preventing layer using the rectifying effect is provided with a charge transporting layer having a charge transporting ability of a polarity opposite to the polarity of the electrode substrate using the rectifying effect. That is, such a charge injection preventing layer is formed of an inorganic photoconductive layer, an organic photoconductive layer, and an organic-inorganic hybrid type photoconductive layer, and has a thickness of about 0.1 to 10 μm.
Specifically, when the electrode is negative, B, Al, Ga, amorphous silicon photoconductive layer towed with In, etc., amorphous selenium, or oxadiazole, pyrazoline, polyvinylcarbazole, stilbene, anthracene, naphthalene, tridiphenylmethane, Organic photoconductive layer formed by dispersing triphenylmethane, azine, amine, aromatic amine and the like in a resin.
An amorphous silicon photoconductive layer doped with N, As, Sb, Bi, or the like, a ZnO photoconductive layer, or the like is formed by a method such as glow discharge, vapor deposition, sputtering, CVD, or coating.

Next, a charge holding medium material and a method for manufacturing the charge holding medium will be described.

The charge holding medium 3 is used together with the photoreceptor 1 to record information as a distribution of electrostatic charges on the surface of the insulating layer 11 constituting the charge holding medium 3 or inside thereof.
The charge holding medium itself is used as a recording medium. Therefore, the shape of the charge holding medium can take various shapes depending on the recorded information or the recording method. For example, when used for an electrostatic camera (filed on the same date by the same applicant), it takes the form of a general film (for single frame or continuous frame) or disk shape, and records digital information or analog information using a laser or the like. Takes a tape shape, a disk shape, or a card shape.

The insulating layer support 15 strongly supports the charge holding medium 3 as described above, but is basically made of the same material as the photoconductive layer support 5 and has the same light transmittance. May be required. Specifically, when the charge holding medium 3 takes the shape of a flexible film, tape, or disk, a flexible plastic film is used, and when strength is required, a rigid sheet, glass, or the like is used. An inorganic material or the like is used.

The charge storage medium electrode 13 may be basically the same as the photoreceptor electrode 7, and is formed on the insulating layer support 15 by the same forming method as the photoreceptor electrode 7 described above.

Since the insulating layer 11 records information on the surface or inside thereof as a distribution of static charges, high insulating properties are required to suppress the movement of charges, and the specific resistance is 10 ¹⁴ Ω ·
It is required to have insulation properties of not less than cm. Such an insulating layer 11 can be formed by dissolving a resin or rubber in a solvent and coating or dipping, or by vapor deposition or sputtering.

Here, examples of the resin and rubber include polyethylene, polypropylene, vinyl resin, styrene resin, acrylic resin, nylon 66, nylon 6, polycarbonate, acetal homopolymer, fluorine resin, cellulose resin, phenol resin, urea resin, and polyester resin. ,
Epoxy resin, flexible epoxy resin, melamine resin, silicone resin, phenoxy resin, aromatic polyamide, PP
O, polysulfone, etc., polyisoprene, polybutadiene, polychloroprene, isibutylene, extra-high nitrile,
Rubber alone such as polyacryl rubber, chlorosulfonated polyethylene, ethylene, propylene rubber, fluorine rubber, silicon rubber, polysulfide synthetic rubber, urethane rubber,
Or a mixture is used.

Further, a layer is formed by attaching a silicon 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 or the like to the charge holding medium electrode 13 via an adhesive or the like. Even if the layer is formed by coating or dipping a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, a curing agent necessary for a rubber or the like, a solvent, etc. Good.

As the insulating layer 11, a monomolecular film formed by a Langmuir-Blodgett method or a monomolecular cumulative film can be used.

In addition, a charge retention enhancing layer can be provided between the insulating layer 11 and the electrode surface or on the insulating layer 11. The charge retention enhancing layer refers to a layer into which electric charge is injected when a strong electric field (10 ⁴ V / cm or more) is applied, but which is not injected at a low electric field (10 ⁴ V / cm or less). As the charge retention enhancing layer, for example, SiO ₂ , Al ₂ O ₃ , SiC, SiN or the like can be used, and as the organic substance, for example, a polyethylene deposited film or a polyparaxylene deposited film can be used.

In order to more stably hold the electrostatic charge, the insulating layer 11
In addition, a substance having an electron-donating property (donor material) or a substance having an electron-accepting property (acceptor material) may be added. Donor materials include styrene, pyrene,
Naphthalene, anthracene, pyridine and azine compounds, specifically tetrathiofulvalene (TT
F), polyvinyl pyridine, polyvinyl naphthalene, polyvinyl anthracene, polyazine, polyvinyl pyrene, polystyrene and the like are used, and one kind or a mixture is used. As the acceptor material, there are a halogen compound, a cyan compound, a nitro compound and the like, and specifically, tetracyanoquinodimethane (TCNQ) trinitrofluorenone (TNF) and the like are used, and one kind or a mixture is used. The donor material and the acceptor material are used by adding about 0.001 to 10% to the resin or the like.

Further, in order to stably hold the charge, elemental element fine particles can be added to the charge holding medium. Elemental elements include the following elements in the periodic table: Group IA (alkali metal), Group IB (copper group), Group IIA (alkaline earth metal), Group IIB (zinc group), Group IIIA (aluminum group), Group IIIB (rare earth), Group IVB (Titanium), Group VB (Vanadium), Group VIB (Chromium), Group VIIB (Manganese), Group VIII (Iron, Platinum), and Silicon, germanium, tin, and lead are used as the IVA group (carbon group), antimony and bismuth as the VA mounting (nitrogen group), and sulfur, selenium, and tellurium are used as fine powders as the V1A group (oxygen group). You. Metals among the above elemental elements can be used in the form of metal ions, fine powdery alloys, organic metals, and complexes. Further, the above element simple substance can be used in the form of an oxide, a phosphate, a sulfate, or a halide.
These additives may be added to the charge holding medium such as the above-mentioned resins and rubbers in a very small amount, and may be added in an amount of about 0.01 to 10% by weight based on the charge holding medium. The insulating layer 11 needs to have a thickness of at least 1000 ° (0.1 μm) from the viewpoint of insulating properties, and preferably 100 μm or less from the viewpoint of flexibilizing properties.

The insulating layer 11 thus formed can be provided with a protective film on its surface in order to prevent damage or discharge of information charges on its surface. As the protective film, a rubber such as silicone rubber having adhesiveness, a resin such as polyterpene resin or the like may be attached to the surface of the insulating layer 11 in the form of a film, or a plastic film may be adhered with an adhesive such as silicone oil. It is good if the specific resistance is 10 ¹⁴ Ωcm or more, the film thickness is about 0.5 to 30 μm,
When the information of the insulating layer 11 needs to have high resolution, the thinner the protective film, the better. This protective layer may reproduce information from above the protective film at the time of reproducing information, or may reproduce the information of the insulating layer by peeling off the protective film.

As an electrostatic charge holding method, there is an electret that causes distribution and polarization of charges inside an insulating medium, other than the so-called free charge holding method of accumulating surface charges as described above.

FIG. 2 is a diagram showing a method for holding electrostatic charges using an optical electret, and the same numbers as those in FIG. 1 indicate the same contents.
In the figure, reference numeral 19 denotes a transparent electrode.

As shown in FIG. 2 (a), an electrode 13 is formed on a support 15 such as a film, and ZnS, CdS, and ZnO are formed on the electrode plate in a thickness of 1 to 5 μm by vapor deposition sputtering, CVD, coating method, or the like. I do. Then, when a transparent electrode 19 is superposed on the surface of the photosensitive layer in a contact or non-contact manner, and exposed under a voltage applied state (FIG. 2 (b)), charges are generated by light in the exposed portion and polarized by an electric field. Is trapped at that position (FIG. 2 (c)). Thus, an electret corresponding to the exposure amount is obtained. In the case of the charge holding medium shown in FIG. 2, there is an advantage that a separate photoconductor is not required.

FIG. 3 is a diagram showing a method for retaining electrostatic charges using a thermal electret, and the same reference numerals as those in FIG. 1 denote the same contents.

Examples of the heat electret material include polyvinylidene fluoride (PVDF), poly (VDF / ethylene trifluoride), poly (VDF / ethylene tetrafluoride), polyvinyl fluoride, polyvinylidene chloride, polyacrylonitrile, and poly-α-. The electrode substrate 13 is made of chloroacrylonitrile, poly (acrylonitrile / vinyl chloride), polyamide 11, polyamide 3, poly-m-phenylene isophthalamide, polycarbonate, poly (vinylidene cyanide vinyl acetate), PVDF / PZT composite, etc. A single layer of 1 to 50 μm is provided thereon, or two or more layers are laminated.

Then, before exposure, the medium is heated to a temperature higher than the glass transition of the medium material by resistance heat or the like, and voltage application exposure is performed in that state (FIG. 3 (b)). At high temperatures, the mobility of ions increases, and in the exposed area, a high electric field is applied to the insulating layer.
Of the thermally activated ions, the negative charge collects on the positive electrode and the positive electrode collects on the negative electrode to form a space charge, causing polarization. Thereafter, when the medium is cooled, the generated charges are trapped at the position even when the electric field is removed, and an electret is generated according to the exposure amount (FIG. 3 (c)).

Next, as a method for inputting information to the insulating layer 11, a method using a high-resolution electrostatic camera is used. There is also a recording method using a laser. First, the high-resolution electrostatic camera used in the present invention comprises a photoconductor 1 comprising a photoconductive layer 9 provided with a photoconductor electrode 7 on the front, instead of a photographic film used in a normal camera, A recording member is constituted by a charge holding medium comprising an insulating layer 11 having a charge holding medium electrode 13 provided on the rear surface thereof, and a voltage is applied to both electrodes so that the photoconductive layer becomes conductive according to incident light. An electrostatic latent image of an incident optical image is formed on a charge storage medium by accumulating electric charges on an insulating layer in accordance with the amount of incident light, and a mechanical shutter can be used. It can be used, and the electrostatic latent image can be held for a long period of time irrespective of a bright place or a dark place. Further, a color filter that separates optical information into R, G, and B light components by a prism and takes out as parallel light is used. By arranging the R, G, and B images on one plane to form one frame in one set, color photographing can also be performed.

As a recording method using a laser, an argon laser (514.488 nm), a helium-neon laser (633 nm), a semiconductor laser (780 nm, 810 nm, etc.) are used as a light source.
A voltage is applied by bringing the photoreceptor and the charge holding medium into a planar shape and bringing the surfaces into close contact or facing each other at a certain interval. In this case, the photoconductor electrode may be set to the same polarity as the carrier of the photoconductor. In this state, laser exposure corresponding to the image signal, character signal, code signal, and line drawing signal is performed by scanning. Analog recording such as images is performed by modulating the laser light intensity, and digital recording such as characters, codes, and line drawings is performed by ON-OFF control of laser light. In the case where dots are formed in an image, the 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 need not be panchromatic, but may be any as long as they have sensitivity to the wavelength of the laser light source.

FIG. 4 is a view for explaining the toner image forming method of the present invention. In the figure, reference numerals 21 and 23 denote a charger, 25 a transfer film, and 27 a transfer film.
Is an infrared lamp.

There are two types of toner, dry toner and wet toner.They are composed of dyes, pigments, and colored fine powders obtained by adding resins to them.The former is charged by iron powder, glass beads or triboelectric charging of itself. The latter is charged by adsorption of ions and dispersed in an insulating solvent.

The development is carried out by bringing the toner into contact with the charge holding medium 3 on which the electrostatic latent image has been formed by the method shown in FIGS. 1 to 3, but the charge has a polarity opposite to that of the charge of the electrostatic latent image. When toner is used, a toner image corresponding to the electrostatic latent image is obtained,
When toners of the same polarity are used, an inverted image of the electrostatic latent image can be obtained as a toner image. The black circles in the figure indicate (-) charged toner and the white circles (+) charged toner.

When the toner image is formed, the toner transfer is performed next. This involves pressing the transfer film 25 against the charge holding medium 3 and charging
In step 21, the toner particles are corona-charged with the opposite polarity, or a bias voltage having a polarity that attracts the toner particles is applied.

When the transfer is performed in this manner, thermal fixing is performed by the infrared lamp 27 or a heat oar (not shown), and the image conversion is completed.

Since the charge holding medium of the present invention can store electric charges for a long period of time, it is not necessary to develop the toner immediately after forming an electrostatic latent image by cooperative light as in the electrophotographic method used in a copying machine, The toner development may be performed at any time.

Next, a color filter used for forming a color image will be described.

FIG. 5 is a view showing a color separation optical system using a prism. In the drawing, 31, 33, and 35 are prism blocks, 37, 39, and 41 are filters, and 43 and 45 are reflection mirrors.

The color separation optical system is composed of three prism blocks. Light information incident from the a surface of the prism block 31 is partially reflected and reflected on the b surface, further reflected on the a surface, and the b color light component is extracted from the filter 37. It is. The remaining light information is incident on the prism block 33, proceeds to the c-plane, and is partially reflected and reflected, and the other goes straight to extract the G color light component and the R color light component from the filters 39 and 41, respectively. And G,
By reflecting the B color light component with the reflecting mirrors 43 and 45,
R, G, B light can be extracted as parallel light.

By arranging such a filter 51 on the front surface of the photoreceptor 1 as shown in FIG. 6 for recording, the filter 51 shown in FIG.
1 set for 3 sets of charge-retaining medium that has been decomposed into R, G, and B
Frames may be formed or, as shown in FIG. 6 (c), R, G and B images may be arranged on one plane to form one frame in one set.

FIG. 7 is a diagram showing an example of a fine color filter. For example, a resist-coated film is exposed by a mask pattern to form an R, G, B stripe pattern, and formed by R, G, B dyeing, respectively. 5, a method in which R, B, and G interference fringes generated by passing the color-separated light by the method shown in FIG. 5 through a narrow slit are recorded on a hologram recording medium; A method in which an R, G, B stripe pattern based on an electrostatic latent image is formed by exposing a mask to a conductor in close contact with the conductor, developed with toner, and transferred three times to form a color stripe to form a toner stripe. And the like. One pixel is formed by one set of R, G, and B of the filter formed by such a method, and one pixel is made as fine as about 10 μm. By using this filter as the filter 61 in FIG. 6, a color electrostatic latent image can be formed. In this case, the filter may be arranged separately from the photoconductor, or may be formed integrally with the photoconductor.

FIG. 8 is a diagram showing an example in which a fine color filter and a Fresnel lens are combined.
The pattern can be recorded in a reduced size, and a thin and compact lens can be designed as compared with a normal lens.

FIG. 9 shows a case where color synthesis is performed from a toner-developed charge holding medium to an electrostatic latent image divided into R, G, and B planes as shown in FIG. 6 (c), and the charge holding medium 3 is transferred. the film
The transfer roll 61 is attached to the transfer roll 61 to which 63 is attached. Transfer roll
Assuming that the circumference of 61 is equal to the length of each color, a color image is formed by rotating the roll three times. Alternatively, the color may be synthesized by moving the transfer film for each color. In addition, as shown in FIG. 6 (b), when the R, G, and B charge holding media are independent, color synthesis can be similarly performed.

In the above description, the case where the toner development, transfer, and fixing are performed to form the final image by itself has been described. However, the final image may not be formed.

For example, when the charge holding medium 3 is transparent, the medium developed with toner can be irradiated with light, projected and viewed as an enlarged image, and when the charge holding medium 3 is not transparent,
The reflected image can be magnified and projected as a reflected image by utilizing the light reflection reduction by the toner. In this case, in the case of monochrome, the projection may be simply performed. In the case of the color, the transmission image or the reflection image of the three-plane split image may be synthesized on the projection surface. The filter itself has a filter effect on a transmission image, and in the case of non-transmission, a color filter may be arranged in front of the projection surface.

FIG. 10 is a view showing an embodiment for obtaining a video signal from a toner image, and shows a charge holding medium 3 on which a toner image is formed.
Is scanned by irradiating the colored surface with a light beam, and the reflected light is converted into an electric signal by the photoelectric converter 61. By reducing the diameter of the light beam, high resolution can be achieved.

FIG. 11 is a diagram showing an embodiment in which a video signal is obtained from a color toner image.The R, G, B separation image formed by the fine color filter is developed with toner, the colored surface is irradiated with a light beam, and the reflected light is reflected. An example in which Y, M, and C signals are obtained by light is shown. In FIG. 6, 63 is a scanning signal generator, 65 is a laser, 67 is a reflecting mirror, 69 is a half mirror, 71 is a photoelectric converter, and 73, 75, and 77 are gate circuits.

The scanning signal generator 63 scans the laser light from the laser 65 with a scanning signal by irradiating the colored surface via the reflecting mirror 67 and the half mirror 69. Half mirror for reflected light from colored surface
The light enters the photoelectric converter 71 via 69 and is converted into an electric signal. Gate circuit in synchronization with the signal from the scanning signal generator 63
By controlling the opening and closing of 73, 75, and 77, the gate circuits 73, 75, and 77 are controlled to be opened and closed in synchronization with the pattern of the fine filter, so that Y, M, and C do not need to be colored Y, M, and C. The signal of C can be obtained.

In the case where the color image is divided into three planes, Y, M, and C signals can be obtained in exactly the same manner.
It is the same that M and C need not be colored.

In the method shown in FIGS. 10 and 11, it is necessary that the toner image has a γ characteristic corresponding to the charge amount of the electrostatic latent image. It is necessary not to have a threshold value, but if the measures are taken, even if the γ characteristics do not match, γ
May be corrected.

FIG. 12 is a view showing a method for obtaining a transmitted image of the toner image formed on the charge holding medium 3, in which 80 is a light source, 81 is a lens, 83 is a filter, and 85 is a screen.

The charge holding medium 3 is composed of a transparent insulating layer 11, a transparent electrode 13, and a transparent support 15. Light is irradiated from the transparent support side 15 by a light source 80, and a transmitted image of a toner image is formed on a lens 85 through a lens 81 and a filter 83. Projected onto In this case, a black-and-white image can be projected by using a black-and-white toner, and a color projection image can be obtained by combining a color toner and a filter on a screen 85.

FIG. 13 is a view for explaining a method of obtaining a reflection image of the toner image formed on the charge holding medium.

In this case, the electrode 13 forms a light reflecting layer and the light source 80
The projected image of the toner image by reflecting light from the screen 85
Formed on top. Also in this case, a monochrome image or a color projection image can be obtained.

[Action]

The toner image forming method of the present invention is to form an electrostatic latent image as an analog amount on a surface of a charge holding medium in the form of an analog, develop this with charged particles and convert the latent image into a visible image, With high quality and high resolution, the processing process is simple,
Long-term storage is possible, and a stored toner image can be formed at any time based on the stored image information.

〔Example〕

 Hereinafter, examples will be described.

Example 1 Method for Producing a Charge Retaining Medium To a mixed solution having a composition of 10 g of methylphenylsilicone resin and 10 g of xylene-butanol 1: 1 solvent, 1% by weight of a curing agent (metal catalyst): trade name CR-15 (0.2 g), and the mixture was stirred well, and coating was performed on a glass substrate on which Al was deposited at 1000 ° using a doctor blade 4 mil. Then 15
Dry at 0 ° C for 1 hour. A charge holding medium (a) having a film pressure of 10 μm was obtained.

In addition, the above mixed solution was coated on a 100 μm polyester film on which Al was deposited at 1000 ° in the same manner, and then dried to obtain a film-shaped charge holding medium (b).

The above mixed solution was spin-coated on a 4-inch disk-shaped acrylic (1 mm thick) substrate on which Al was vapor-deposited at 1000 °
And dried at 50 ° C. for 3 hours to obtain a disk-shaped charge holding medium (c) having a thickness of 7 μm.

Further, 0.1 g of zinc stearate was further added to the above mixed solution, and the same coating and drying were performed to obtain a charge retaining medium (d) having a film thickness of 10 μm.

Example 2 A mixed solution having a composition of 10 g of a polyimide resin and 10 g of N-methylpyrrolidone was spin-coated (1000 rpm, 20 seconds) on a glass substrate on which Al was deposited at 1000 °. After pre-drying at 150 ° C for 30 minutes to dry the solvent,
It was heated at 350 ° C. for 2 hours for curing. A uniform coating having a thickness of 8 μm was formed.

Example 3 Method for producing single-layer organic photoreceptor (PVK-TNF) 10 g of poly-N-vinyl carbazole (Anan Kofu Co., Ltd.)
Manufactured), 2,4,7-trinitrofluorenone 10 g, polyester resin 2 g (binder: Byron 200 Toyobo Co., Ltd.)
A mixed solution having a composition of 90 g of tetrahydrofuran (THF) was prepared in a dark place, and a doctor blade was applied to a glass substrate (1 mm thick) on which In ₂ O ₃ -SnO ₂ was sputtered to a thickness of about 1000 mm. It was then applied and dried by ventilation at 60 ° C. for about 1 hour to obtain a photosensitive layer having a photoconductive layer having a thickness of about 10 μm. In order to dry completely, it was further dried naturally for one day before use.

Example 4 A method for producing an amorphous silicon aSi: H inorganic photoreceptor.

Substrate cleaning SnO ₂ thin film transparent electrode layer one surface provided with Corning 7059 glass (23 × 16 × 0.9t, optical polished) the Toriuroroetan, acetone, ethanol each liquid, ten minutes each in this order super Sonic clean.

Preparation of Apparatus The cleaned substrate is placed in the anode 2 in the reaction chamber 204 shown in FIG.
After setting it on the 06 so that heat conduction is sufficient, the reaction chamber is evacuated to 10 ^-5 Torr level by D and P, and the reaction vessel and gas pipe are baked out at 150-350 ° C. for about 1 hour. After the baking out, cool the device.

a. Deposition of Si: H (n ⁺ ) Adjust the heater 208 so that the temperature of the glass substrate is 350 ° C.
PH ₃ / SiH ₄ preheated and mixed in tank 201 =
After controlling the rotation of the needle valve and PMB so that the internal pressure of the reaction chamber 204 becomes 200 mTorr and the internal pressure becomes constant, a 40 W R f Power 202 (13.56 KHz) is passed through the matching box 203. And plasma is formed between the cathode and the anode. The deposition is performed for 4 minutes, the supply of Rf is stopped, and the needle valve is closed.

As a result, about 0.2 μm
-A Si: H (n ⁺ ) film was deposited on the substrate.

a. Deposition of Si: H SiH ₄ 100% gas was flowed in the same manner as in the above to keep the internal pressure at 200 mTorr, and when the internal pressure became constant, Matching
A 40 W R f power 202 (13.56 KHz) is supplied through Box 203, and the plasma is converted and maintained for 70 minutes. End of deposition
Stop charging Rf and close the needle valve. Heater208
After Off, take out the board because it is cold.

As a result, a film of about 18.8 μm was deposited on the a.Si:H(n ⁺ ) film.

Thus, SnO ₂ / a · Si: H (n ⁺ ) blocking layer / a · Si: H
A (non / dope) 20 μm photoconductor was able to be produced.

Example 5 Method for Preparing Amorphous Selenium-Tellurium Inorganic Photoreceptor Using metal particles in which selenium (Se) and 13% by weight of tellurium (Te) were mixed, a-Se-Te was formed by vapor deposition. The thin film was deposited on an ITO glass substrate by a resistance heating method at a degree of vacuum of 10 ^-5 Torr. The film pressure was 1 μm. Further, while maintaining the degree of vacuum, vapor deposition of only Se was performed by the same resistance heating method, and a-
A 10 μma-Se layer was laminated on the Se-Te layer.

Example 6 Method for Producing a Function-separated Photoreceptor (Method for Forming Charge Generation Layer) A mixed solution having a composition of 0.4 g of chlorodian blue and 40 g of dichloroethane was placed in a 250 ml stainless steel container,
Further, 180 ml of glass beads No. 3 is added, and crushed for about 4 hours by a vibration mill (KED9-4, Yaskawa Electric Seisakusho) to obtain chlorocyan blue having a particle size of ~ 5 µm. After filtering the glass beads, 0.4 g of polycarbonate and Iupilone E-2000 (Mitsubishi Gas Chemical) is added and stirred for about 4 hours. In this solution
₂ O ₃ -SnO ₂ to about 1000Å sputtered glass substrate (1mm
Thickness) using a doctor blade to a thickness of about 1 μm
Was obtained. Drying was performed at room temperature for one day.

(Method of forming charge transport layer)

A mixture having a composition of 0.1 g of 4-dibenzylamino-2-methylbenzaldenide-1,1'-diphenylhydrazone, 0.1 g of polycarbonate (Iupilone E-2000) and 2.0 g of dichloroethane was charged with a doctor blade using the above-mentioned electric charge. It was applied on the generating layer to obtain a charge transport layer of about 10 μm. Drying was performed at 60 ° C. for 2 hours.

[Example 7] (Method of forming charge generation layer) Butyral resin (Sekisui Chemical, SLEC) in 10 g of butyl acetate
0.25 g, azulhenium ClO ₄ salt having the following structural formula, 0.5 g, glass beads No., 133 g were mixed, stirred for 1 day with a touch mixer, well dispersed and then laminated on a glass plate with a doctor blade or applicator.
It was applied on O and dried at 60 ° C. for 2 hours or more. The film thickness after drying is 1 μm or less.

(Method of forming the charge transport layer) 0.5 g of polycarbonate (Mitsubishi Gas Chemical, Iupilon E2000) in 9.5 g of tetrahydrofuran and a hydrazone derivative represented by the following structural formula (Anan perfume, CTC191) Then, the mixture was mixed with 0.5 g and applied on the charge generating layer with a doctor blade, and dried at 60 ° C. for 2 hours or more. 10 μm thick
It was below.

[Example 8] (Method of forming charge generation layer) In 20 g of tetrahydrofuran, 0.5 g of butyral resin (Sekisui Chemical, SLEC), 0.25 g of titanyl phthalocyanine, 4.10
-0.25 g of dibromoanthranthrone, glass beads No. 1
Was stirred for 1 day with a touch mixer, and the well-dispersed mixture was applied to ITO laminated on a glass plate with a doctor blade or an applicator and dried at 60 ° C. for 2 hours or more. The dried film had a thickness of 1 μm or less.

(Preparation method of charge transport layer) In 9.5 g of dichloroethane, 0.5 g of polycarbonate (Mitsubishi Gas Chemical, Iupilon E2000) and 0.5 g of the above hydrazone derivative (Anan fragrance, CTC191) were dissolved, and the above-mentioned charge generation layer was placed on the charge generation layer with a doctor blade. The coating was performed and dried at 60 ° C. for 2 hours or more. The film thickness was 10 μm or more.

[Example 9] ... Method of producing a function-separated type photoreceptor provided with a charge injection preventing layer (Method of forming charge injection preventing layer) Soluble polyamide (Toa Gosei Chemical, FS-175SV10) on ITO laminated on a glass plate 0.5 by spin coater
１1 μm coating, dried at 60 ° C. for 2 hours or more.

(Formation method of charge generation layer) Butyral resin (Sekisui Chemical, SLEC) in 10 g of butyl acetate
0.25 g, the above-mentioned azulhenium ClO ₄ salt 0.5 g, glass beads No., 133 g were mixed, stirred for 1 day with a touch mixer, and well dispersed and applied on the above-mentioned charge injection preventing layer with a doctor blade or an applicator. And 60 ° C,
Dry for at least 2 hours. The dried film had a thickness of 1 μm or less.

(Method of forming charge transport layer) In 9.5 g of tetrahydrofuran, 0.5 g of polycarbonate (Mitsubishi Gas Chemical, Iupilon E2000) and 0.5 g of the above-mentioned hydrazone derivative (Anan Perfume, CTC191) are dissolved, and the above-mentioned charge generation layer is placed on the charge generation layer with a doctor blade. It was applied and dried at 60 ° C. for 2 hours or more. The film thickness was 10 μm or less.

Example 10 (Method for Forming Charge Injection Prevention Layer) Soluble polyamide (Toa Gosei Chemical Co., FS-175SV10) was applied on ITO laminated on a glass plate by a spin coater for 0.5 minute.
１1 μm coating, dried at 60 ° C. for 2 hours or more.

(Method of forming charge generation layer) 0.5 g of butyral resin (Sekisui Chemical, SLEC), 0.25 g of titanyl phthalocyanine, 4.10 in 20 g of tetrahydrofuran
-0.25 g of dibromoanthranthrone, glass beads No. 1
Was stirred for 1 day with a touch mixer, and the resulting mixture was well dispersed and applied to the above-mentioned charge injection preventing layer with a doctor blade or an applicator, and dried at 60 ° C. for 2 hours or more. The dried film had a thickness of 1 μm or less.

(Method of forming charge transport layer) In 9.5 g of dichloroethane as a solvent, 0.5 g of polycarbonate (Mitsubishi Gas Chemical, Iupilon E2000) and 0.5 g of the above-mentioned hydrazone derivative (Anan Perfume, CTC191) were dissolved, and the above-mentioned electric charge was dissolved with a doctor blade. The coating was applied on the generating layer and dried at 60 ° C. for 2 hours or more. The film thickness was 10 μm or less.

Example 11 (Method of forming photoconductor electrode layer) Indium tin oxide (ITO, specific resistance 100
Ω · cm ² ) was deposited by a sputtering method.

 In addition, vapor deposition can be similarly performed by the EB method.

(Method of Forming Charge Injection Prevention Layer) On the photoreceptor electrode layer, silicon dioxide was deposited by a sputtering method.

The film thickness can be 100 to 3000 °, aluminum oxide may be used instead of silicon dioxide, and vapor deposition can be similarly performed by EB instead of sputtering.

(Method of forming charge generation layer) Selenium-tellurium (tellurium content: 13% by weight) was deposited on the charge injection preventing layer by resistance heating. The film thickness is 2
μm or less.

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

[Example 12] ... Method for preparing thermal electret Vacuum evaporation (10 μm) on a 20 μm polyvinylidene fluoride film
^An electrostatic latent image is formed together with the photoconductive photoreceptor of the function-separated type photoreceptor by using a charge-retention medium that has been formed by depositing Al at 1000 ° C. by ^-6 Torr (resistance heating method).

First, a hot plate (3
× 3 cm) and heat the medium to 180 ° C. Immediately after heating, the photoreceptor was exposed to the charge holding medium by applying a voltage of -550 V between the electrodes (the photoreceptor electrode was made negative) with the surfaces facing each other with an air gap of 10 μm. Exposure was performed for 1 second from the back of the photoreceptor through a character pattern original at 10 lux using a halogen lamp as a light source.

Thereafter, the film was naturally cooled. As a result, a potential of -150 V was measured in the exposed portion (character portion), and no potential was measured in the unexposed portion. After a water drop was dropped on the film on which the charged pattern was formed and collected, the potential was measured. As a result, a potential of -150 V was measured in the exposed portion as before. On the other hand, after forcibly forming a charge of -150 V on the surface by corona discharge in the same charge holding medium, a water drop was dropped,
Upon recovery, the exposed portion which initially showed -150 V was 0 V and the charge was completely lost. Therefore, it was found that polarization was generated inside the polyvinylidene fluoride during electrification under heating, and the film was electretized.

[Example 13] ... Method of producing optical ejectlet Al was laminated on a glass support having a thickness of 1.1 mm by a sputtering method of about 1000 ° to form a substrate, and zinc sulfide was deposited on the Al layer to a thickness of about 1.5 μm. (10 ^-5 Torr, resistance heating). An ITO surface laminated on glass was opposed to this zinc sulfide layer surface with an air gap of 10 μm, and a +70
While applying 0V voltage (negative on the Al electrode side),
Exposure was performed from the O substrate side. Exposure was performed in the same manner as in Example 11. As a result, a potential of +80 V was measured in the exposed portion, and no potential was measured in the unexposed portion. In this case as well, a water droplet experiment similar to that of Example 11 was performed, but there was no change in the potential after the collection, and an electret in which charges were accumulated was formed inside.

Example 14 Single-Layer Organic Photoconductor (PVK-TNF) of Example 3, Example 1
(A) The charge holding medium and the glass substrate are used, and they are stacked with the electrode side facing out and set in a camera. At this time, since a gap is provided between the photoconductor 1 and the charge holding medium 3,
As shown in FIG. 15, a 10 μm polyester film is disposed as a spacer 2 around the area other than the exposed surface.

The voltage is set with the photoconductor electrode side negative and the charge holding medium side positive.
700V is applied, and in that state, the optical shutter is released at an exposure f = 1.4 and a shutter speed of 1/60 second, or the exposure f
= 1.4, apply voltage for 1/60 seconds with the jitter open,
The subject was photographed outdoors during the daytime.

After the exposure is turned off and the voltage is turned off, place the charge holding medium in a bright place,
Alternatively, it was taken out in a dark place, and a CRT image was formed by a micro area potential reading method, and an image was formed by toner development.

Then, a 100 × 100 μm micro area surface potential measurement probe was scanned in the XY axis, potential data in 100 μm units was processed, and an image was formed on a CRT by potential-luminance conversion. An analog potential latent image from the highest exposed portion potential of 200 V to the unexposed portion 0 V was formed on the charge holding medium, and the latent image could be visualized on a CRT with a resolution of 100 μm.

In Example 1, the positive charge image was obtained by immersing the removed charge holding medium in a negatively charged wet toner (black) for 10 seconds. The resolution of the obtained toner image was a high resolution of 1 μm.

 The photographing of the color image was performed by the following method.

Prism-type three-plane splitting method As shown in FIG. 5, R, G, and B filters are arranged on three surfaces of a prism, and the above medium is set on each surface.
1.4, the subject was shot at a shutter speed of 1/30 second.

Color CRT display method Each of the R, G, B latent images is scanned and read in the same manner, and a fluorescent color corresponding to the R, G, B latent image is formed on the CRT,
A color image was obtained by synthesizing the three-color separated image on a CRT.

Toner Development Method The charge-holding medium subjected to the separation exposure is developed with negatively charged C (cyan), M (magenta), and Y (yellow) toners for the R, G, and B latent images to form toner images. Before the toner dries, plain paper is overlaid on the medium on which the cyan toner image is formed, and positive corona charging is performed on the paper. Thereafter, when peeling was performed, the toner image was transferred to plain paper. Further, when the positions of the images were matched by the same method and the magenta toner and the yellow toner were sequentially transferred and synthesized at the same location, a color image was formed on plain paper.

〔The invention's effect〕

As described above, according to the present invention, an electrostatic latent image is recorded on a plane in an analog manner, and can be stored for a long time regardless of a light place or a dark place. The image can be visualized, high quality and high resolution can be obtained, and the processing steps can be simplified. Also, instead of using the toner image itself as the final image, the transmitted image or the reflected image can be projected and magnified, and the slide image, OH
It can be used for P images, microfilm images, etc.

After exposing the charge holding medium according to the present invention, room temperature 25 ° C., humidity
After standing for 3 months at 35%, the image was developed with a (+) charged wet toner. As a result, an image was formed which was completely the same as when the toner was developed immediately after the latent image was formed.

Further, after exposing the charge holding medium, the medium was allowed to stand at room temperature of 40 ° C. and humidity of 75% for 3 days, and the same development was performed. As a result, the same quality image was obtained.

After exposure of the charge holding medium, the latent image was left at room temperature of 40 ° C and humidity of 75% for 10 days.
The density was reduced to 70 V, and the density due to the toner phenomenon was reduced from 1.5 to 1.3 with a Macbeth reflection densitometer, but the resolution of the image itself did not change.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining the principle of toner image formation of the present invention, FIG. 2 is a diagram for explaining the principle of a toner image format using an optical electret, and FIG. 3 is a toner using a thermal electret. Diagram for explaining the principle of image formation,
FIG. 4 is a view for explaining a toner image forming method of the present invention, FIG. 5 is a view showing a configuration of a color separation optical system, FIG. 6 is an explanatory view for forming a color electrostatic latent image, 7 is a diagram showing an example of a fine color filter, FIG. 8 is a diagram showing an example in which a fine color filter and a Fresnel lens are combined, FIG. 9 is a diagram for explaining a color synthesizing method, FIG. 10, FIG. FIG. 12 is a diagram for explaining an example of obtaining a video signal from a toner image. FIG. 12 is a diagram for explaining a transmission image forming method.
FIG. 14 is a diagram for explaining a reflection image forming method, and FIG.
FIG. 15 is a diagram for explaining a method for manufacturing a Si: H photoconductor, and FIG. 15 is a diagram for explaining an example of photographing by an electrostatic camera to which the present invention is applied. DESCRIPTION OF SYMBOLS 1 ... Photoreceptor, 3 ... Charge holding medium, 5 ... Transparent support, 7 ...
Transparent electrode, 9 photoconductive layer, 11 insulating layer, 13 electrode, 15
Support, 17 ... Power supply, 21, 23 ... Charger, 25 ... Transfer film, 27 ... Infrared lamp.

Continuation of front page (56) References JP-A-56-156840 (JP, A) JP-A-56-126856 (JP, A) JP-A-55-130543 (JP, A) JP-A-57-67948 (JP) JP-A-56-48655 (JP, A) JP-A-62-291845 (JP, A) JP-B-57-55140 (JP, B2) JP-B-51-2248 (JP, B1) (58) Field surveyed (Int.Cl. ⁶ , DB name) G03G 13/05 G03G 15/05

Claims (5)

(57) [Claims] 1. A photoconductor in which electrodes and a photoconductive layer are laminated on a substrate, and a charge holding medium in which electrodes and an insulating layer having a specific resistance of 10 ¹⁴ Ω · cm or more are laminated on the substrate are disposed so as to face each other. After image exposure from the photoreceptor side or the charge holding medium side with a voltage applied between both electrodes, the charge holding medium is separated, and the separated charge holding medium is developed with toner at any point during the period in which the charge is held. Forming a toner image by forming the toner image. 2. The toner image forming method according to claim 1, wherein the charge holding medium has a charge holding enhancement layer into which charges are injected when an electric field of 10 ⁴ V / cm or more is applied. 3. The toner image forming method according to claim 1, wherein said charge holding medium has an insulating layer to which a donor material having an electron donating property or an acceptor material having an electron accepting property is added. 4. The charge-holding medium according to claim 1, wherein the element-containing fine particles are:
2. The toner image forming method according to claim 1, wherein 0.01 to 10% by weight is added to the charge holding medium. 5. The toner image forming method according to claim 1, wherein said charge holding medium has a protective layer formed on an insulating layer surface.