JPH02275960A - Charge holding medium and charge holding method - Google Patents

Abstract

PURPOSE:To allow the permanent holding of accumulated information charges by constituting a charge holding layer of a high-polymer material having >=1X10<14>OMEGA.cm specific resistance and specifying the glass transition temp. of the high-polymer material to the use environmental temp. or above or further specifying a moisture content to <=0.4wt.%. CONSTITUTION:The charge holding layer of the charge holding medium 3 laminated with an electrode layer 13 and the charge holding layer 11 is constituted of the insulating high-polymer material and the high-polymer material is so formed that the glass transition temp. thereof is the use environmental temp. or above or further the moisture content of the high-polymer material is <=0.4wt.%. More specifically, the charge holding layer 11 has the insulating characteristic of >=10<14>OMEGA.cm specific resistance in order to suppress the transfer of charges. This layer is so formed as to have 20 to 100 deg.C or higher glass transition temp. in the ordinary use environment. The moisture content of the above- mentioned layer is required to be lower by 0.4% in order to prevent the leakage by the accumulated information charges by the influence of humidity. The long-term preservation of the information charges is thus possible.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a charge-retaining medium in which information can be electrostatically recorded using an exposure method when a voltage is applied, etc., and information can be reproduced at any time. , I: Concerning a charge retention medium with excellent i-holding properties and a charge retention method.

[Conventional technology]

Conventionally, in electrophotography, a photoconductive layer is deposited on an electrode layer, the entire surface of the photoconductive layer is charged, and then imagewise exposed.
An electrostatic latent image is optically formed on the photoconductive layer by leaking the charge in the exposed area, and a l·ner having a charge of opposite polarity to the residual charge is deposited, It is known that the image is electrostatically transferred onto paper or the like and developed. This is mainly used for copying, but it shortens the retention period of the electrostatic charge that falls on the photoconductive layer as a recording medium, and the toner is developed directly after the electrostatic latent image is formed. For example, it cannot be used for photography due to its low sensitivity.

Furthermore, TV photographing technology requires line-sequential scanning in order to extract and record electrical image signals obtained by an image pickup tube. Line-sequential scanning is carried out using an electronic beam in the image pickup tube, and video recording is carried out using a magnetic hemisphere. However, since the resolution depends on the number of scanning lines, it is necessary to record a planar image like a silver halide photograph. The problem is that it deteriorates significantly compared to .

Furthermore, TV imaging systems that utilize solid-state imaging devices, which have been developing in recent years, are similar in terms of resolution, and the problems inherent in these technologies become more pronounced the higher the quality and resolution of image recording. The processing process is complicated, and if it is simple or simple, there will be a lack of the above-mentioned functions or a deterioration of the image quality.

In addition, a thermoplastic material layer having a selenium particle layer as a surface layer is provided on the transparent electrode, and after the entire surface is charged,
Each time the image is exposed and thermally developed, the exposure information becomes visible.
It is known that the image information is stored in the form of positional information of the selenium particle layer, and the surface charge is attenuated by thermal development at the same time as the development.

[Problem to be solved by the invention]

The present inventors first placed a photoreceptor made of a photoconductive layer with electrodes on the front surface and a charge retention medium made of a charge retention layer with electrodes on the rear surface facing each other, and both electrodes After image exposure with a voltage applied between them, the charge retention medium is separated,
It was discovered that information could be reproduced extremely clearly by amplifying the surface potential stored as image information on the surface of the charge retention layer and outputting the image reproduction, and filed an application for the charge retention medium (Japanese Patent Application No. 127555/1981).

The purpose of the present invention is to improve the charge retention properties thereof, and to provide a charge retention medium with excellent charge retention properties, and a charge image (
The challenge is to provide four methods.

[Failure to solve the problem]

For this purpose, the electric charge storage medium of the present invention is a charge storage medium in which an electrode layer and a charge storage layer are laminated, in which the charge storage layer is made of an insulating polymer + A rice grain, and the glass transition of the polymer material is It is characterized in that the temperature is higher than the operating environment temperature.

Further, in a charge retention medium in which an electrode layer and a '71 cargo holding Li layer are laminated, the charge retention layer is made of an insulating polymer material,
The polymer material is characterized in that the water content is 0.4% by weight or less.

Furthermore, in a charge retention medium in which an electrode layer and a charge retention layer are laminated, the charge retention layer is made of an insulating polymer material, and the temperature is higher than the glass transition temperature of the polymer material or the operating environment temperature,
Moreover, the water content is 0.4% by weight or less.

In addition, the charge retention method is characterized in that a charge retention medium in which a charge retention layer made of an insulating polymer material is laminated on the electrode layer is used at a temperature below the glass transition temperature of the insulating polymer material. It is something.

Hereinafter, the constituent materials of the charge retention medium of the present invention, the method for forming the same, the charge retention method, and the electrostatic image recording and reproducing method which is the method of using the charge retention medium will be explained.

FIG. 1 is a cross-sectional view showing each aspect of the charge retention medium 3 of the present invention, in which 3 is the charge retention medium, 11 is the charge retention layer,
13 is a charge retention medium electrode, 15 is a support, and 16 is an adhesive layer.

The charge retention layer 1] is made of a highly insulating polymer material in order to suppress the movement of charges, and has a specific resistance of 101'Ω・c.
It is required to have an insulation property of m or more.

In addition, it is necessary that the glass transition temperature of the polymer + aluminum constituting the charge retention layer is lower than 20 degrees Celsius in the usage environment.
A glass transition temperature of 1° C. or higher is desirable.

In addition, as the polymer +A Fl constituting the charge retention layer,
In order to prevent leakage of accumulated information charges due to humidity effects, the water absorption rate must be lower than 0.4%.

For such a polymer material, a thermoplastic resin, a thermosetting resin, an energy beam curing resin such as an ultraviolet curing resin, an electron beam curing resin, or an engineering plastic ζt can be used as the +Ai resin. .

Examples of thermoplastic resins include polyethylene, vinyl chloride resin, Polyp II pyrene, styrene resin, ABS resin, polyvinyl alcohol, acrylic resin, acrylonitrile-styrene resin, hnylidene chloride resin, and AAS.
(ASA) resin, ABS resin, cellulose derivative resin, thermoplastic bosourekun, polyvinyl butyral, poly-4
- Methylpentene-1, polyphthene-1, Ronne ester u1, and also fluororesins such as polytetrafluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and dispersions thereof. type, modified type (coating type), polyether ether ketone resin, polyparaxylylene shown by the following structural formula, (For D type, two of the sites other than the bonding site are substituted with chlorine. Polyester resins, epoxy resins, phenol resins, urea resins, melamine resins, diallyl chloride resins, silicone resins, etc. Furthermore, as energy ray curable resins such as ultraviolet ray curable resins and electron beam curable resins, radically polymerizable acrylate compounds are used. For example, ester compounds of acrylic acid or methacrylic acid or their derivatives have hydroxyl groups at both ends, specifically hydroxyethyl acrylate, hydroxyethyl acrylate,
Hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate,
Including (meth)acrylic acid ester compounds having one polymerizable unsaturated group such as hydroxybutyl methacrylate, 4-hydroxycyclohexyl acrylate, 5-hydroxycyclooctyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, etc. A compound having two polymerizable unsaturated groups represented by the formula % can be used.

Examples of the curable compound having two hydroxyl groups and one or more radically polymerizable unsaturated groups include glycerol methacrylate and the following formula % (where R and R' are methyl groups or hydrogen). Yes, R1
is a short chain diol residue such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, 16-hexanediol, etc. ) can be used.

Examples of engineering plastics that can be used include polycarbonate, polyamide, acetal resin, polyphenylene oxide, polybutylene ethylene chloride, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyimide resin, polysulfone, aromatic polyester, and polyacrylate.

Among the above-mentioned resins, the resin having a high water absorption rate can be used by lowering the water absorption rate by introducing atoms or substituents that can impart non-water absorbing properties. Alternatively, it can be used by mixing a resin with a low water absorption rate.

Note that even materials with a high water absorption rate such as polyether sulfone, polyimide, polyparabanic acid, etc. can be used by laminating a protective film made of a resin with a low water absorption rate.

As for the method of laminating the charge retention layer, first, in the case of the charge retention medium shown in FIG.

Coating by coating or by dissolving in a solvent,
Dino Pink can be layered.

Further, as the charge retention layer 11, silicone film, polyester film, polyimide film, fluorine-containing poly-7
-Film, polyethylene film, polypropylene film J5, polyparabanic acid film, polycarbonate I
- A layer may be formed by adhering a film, polyamide film J, etc. via an adhesive or the like. Alternatively, an electrode layer may be formed on one side of the film by vapor deposition, sputtering, coating, or the like. In this case, a protective layer may be provided to protect the electrode layer, and if further mechanical strength is required, a film or the like that provides higher mechanical strength may be laminated thereon.

In addition, photoconductive and electrically conductive fine particles may be present in these polymeric materials having absolute H properties for charge accumulation.

Examples of photoconductive particle materials include inorganic photoconductive materials such as amorphous silicon, crystalline silicon, amorphous selenium, crystalline selenium, sulfurized aluminum 11, and zinc oxide, as well as polyvinyl carbazole, lid I:1 cyanine, azo pigments, etc. Organic photoconductive materials are used.

Conductive materials include Group 1A (alkali metals) of the periodic table, Group IⅢ (copper group), Group ■∆ (alkaline earth metals), Group II B (zinc group), and Group 111A of the periodic table. Group (aluminum group), Group 1 [I B (rare earths), Group IVB (titanium group), Group VB (hanashiu J, group), Group VI
Group B (RIJM group), Vl group (manganese group), group II (iron group, platinum group), and group IVA (carbon group) include carbon, silicon, germanium, tin, lead, As the VA group (nitrogen group), antimony and hismuth are used, and as the VIA group (oxygen group), sulfur, selenium, and tellurium are used in fine powder form. In addition, the metals of the element -]- can also 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 saponified flies. In particular, carbon, gold, copper, aluminum, etc. are preferably used.

This fine particle layer &J is formed by depositing the forming material on the electrode or charge storage layer using a low-pressure evaporation device each time. The particle layer forming material is 10T.

rr ~ 1 (When evaporated under a low pressure of about 13 Torr, it aggregates and becomes ultrafine particles with a diameter of about 10 to 0.1 μm, and the fine particles are formed on the surface of the electrode or charge retention layer in the form of a jjI layer or a number of layers. In addition, when forming a charge retention layer by 1-ting, the fine particle material is dispersed in the charge retention layer forming material oblique solution, and each time the charge retention layer is formed by 1-ting. It can be formed by C.

The charge retention medium 3 records information in the charge retention layer 11 as a distribution of static charges. Therefore, the shape of this charge retention medium can take various shapes depending on the information to be recorded or the recording method.

For example, an electrostatic camera (patent application No. 63121 filed by the same applicant)
591), the general film (
For single frame or continuous frame), it is in the form of a 4-inch or disk shape, and when recording digital information or analog information using Rayleigh, etc., it can be in the form of a tape, a tape shape, or a number car shape. becomes.

The support 15 shown in FIG. 1(b) supports the charge retention medium 3 with strength, and the material may have a certain degree of strength that can support the charge retention (15 layers). , the thickness is 1, and there is no limit to Y. For example, a flexible plastic film, metal paper, or a rigid body such as glass, plastic sheet, or metal plate (which can also serve as an electrode) can be used. In some cases, the same characteristics are required.Specifically, when the charge retention medium is in the form of a solid film, tape, or disk, a flexible plastic film is used, and the strength is When this is required, rigid sheets, inorganic materials such as glass, etc. are used.

Electricity: Moisture holding medium 3 or F17; 1-Sible fill 11
, tape, and disk shapes will be explained below.

First, what is shown in FIG. 2(a) is a type in which the charge retention layer 11, which is a recording section, is continuous.

This is made by forming a charge retention layer on a support such as a plastic film provided with an electrode layer, leaving both sides of the support or the entire surface of the support. This charge retention medium is used to store at least one frame to be recorded (for example, one frame in the case of camera capture, two frames in the track "IJ" of digital information recording).
It has a length of 11 or more. Of course, it also includes a structure in which a plurality of charge-retaining media are joined in the longitudinal direction, and in this case, there may be a slit zone between adjacent charge-retaining layers, where the charge-retaining layer is missing.

In addition, as shown in FIG. 2(b), there is a case where the charge retention layer 1 is discontinuous in the longitudinal direction.

Dirt is formed by forming a charge retention layer discontinuously in the longitudinal direction on a support such as plastic or film, with or without leaving both sides of the support. is formed to have a size that includes a plurality of charge retention layers. The size of this charge retention layer depends on the image and the exposure method of the input device, but for example, when using a camera,
35 rn m x 35 rnm, and in the case of a sub-I input such as ant, Rayleigh 5-beam, etc., it is in the track of digital information recording.

Incidentally, in the case of digital information recording, the gap between charge retention layers and gaps formed between adjacent charge retention layers can be used as one racking zone when inputting and outputting information. Of course, this also includes a structure in which a plurality of charge retention 1) media are bonded in the longitudinal direction, and in this case, there may be a gap/band where the charge retention layer is missing between adjacent charge retention layers.

In addition, as shown in FIG. 2(C), if the charge retention layer is
There is a discontinuous type.

In this type, an electrode layer is provided on the plastic snack fill 1, and on the shade support, the electric current i: i protection 1, and Δ are applied in the I+1 direction, with or without leaving both sides of the support. It is formed continuously, and a plurality of band-shaped charge retention layers are formed on the support. IIJ of this charge retention layer is equal to or an integral multiple of the trunk I11 of digital information to be recorded, and the charge retention layer missing portion formed between adjacent charge retention layers is used for input/output of information Ye. This is used as the actual tracking band.

There is also a disc-shaped type, as shown in Figure 2 (()).

This type consists of a support such as a circular plastic film provided with an electrode layer and a charge retention layer on the entire surface, or an iJ!
It is formed by having continuous spiral-shaped charge retention layer missing portions. This charge retention medium may have a circular cutout for driving an input/output device. Further, in the case of a digital information recording section, the continuous spiral-shaped electron 6:j retention layer missing portion can be used as a tracking band when inputting and outputting information.

The electrode 13 is formed by interposing an adhesive layer on a support 6 or by a vapor deposition method, and the material thereof has a specific resistance value of 10.
There are no limitations as long as T is less than '.Ω.cm, and examples include non-metal conductive films, inorganic metal oxide conductive films, and organic conductive films such as quaternary ammonium salts. Is such a charge holding medium electrode on the support L? 'Arrival, sputtering, C
It is formed by methods such as V D , diluting, plating, dipping, and electrolytic polymerization. In addition, the film thickness needs to be changed depending on the electricity of 4, t1':I that constitutes the electrode, and the voltage applied during information recording. It is approximately 3,000 people, and is formed on the entire surface between the support and the charge retention layer, or in accordance with the formation pattern of the charge retention layer.

If light transparency is required, the antireflection effect can be improved by providing an antireflection film, adjusting the thickness of each electrode layer or charge retention layer, or by combining the two. It is better to let

In addition, the charge-retaining medium of the present invention has a charge-retaining layer forming rate as described above as a retaining AW film on the surface of the charge-retaining medium to prevent damage to the surface of the charge-retaining medium and attenuation of information charges after information is recorded. Use 7. Apply film 1 by adhering it or coating it with a solution.It is best to form a film with a thickness of several hundred to several tens of micrometers, and if the film is thick enough, it can be used as a protective film. is possible.

The protective film is made of styrene butaciengo J, a recycled rubber that has adhesive properties so that it can be peeled off and read when information is reproduced.
polyisoprene, Sotilco 11, Fu-j--N (butadiene/acrylic di-1-Rilcom), borihinyl ether (having an ethyl group or higher hydrocarbon group as an alcohol residue), polyacrylate ester One or more of the following hydrocarbon resins), silicone rubber, polyterpene resin, gum rosin, rosin ester, rosin derivative, oil-soluble phenol resin, coumaron-inten resin, and petroleum-based hydrocarbon resin Those formed by forming the mixture into a film having a thickness of several hundred to several tens of micrometers and pasting it on the surface of a charge-retention medium, and plastic films as double charge-retention layer forming materials. It may be pasted using a removable adhesive, and the adhesive has a specific resistance of 10"Ω・cm or more]L
silicone oil, dimethyl silicone oil, methylphenyl silicone oil, higher fatty acid modified silicone oil, methyl chlorinated phenyl silicone oil, alkyl modified silicone oil, methyl high-containing silicone oil, cyclic polycymethylsilicone oil, sirini-1-bolieral. It is preferable to use one kind or a mixture of two or more kinds of polymers, amino-modified silicone oils, epoxy-modified silicone oils, insulating oils, and the like.

Also, use the above polymer material as a solvent? 'J5! '+: L,
Dry 11! It may be formed by coating by a vapor deposition method, a spinner coating method, etc. so that the I'l thickness is several hundred to several tens of μm.

Next, an electrostatic image recording method, which is one method of using the charge retention medium of the present invention, will be explained.

FIG. 3 is a diagram for explaining the electrostatic image recording method, in which 1 is a photoreceptor, 5 is a photoelectric layer support, 7 is a photoreceptor electrode,
9 is a photoconductive layer, ] 7 is a power source.

First, a transparent photoreceptor electrode 7 made of ITO with a thickness of 1,000 layers is formed on a photoconductive layer support 5 made of glass with a thickness of 1 m11, and a photoconductive layer 9 of about 10 Iim is formed on this to form a photoreceptor 1. I have configured it. As shown in FIG. 2(a), a charge holding medium 3 is placed with respect to this photoreceptor (2) with a gap of about 10 μrn in between.

Then, as shown in FIG. 7(b), the electrodes 7,
A voltage is applied between 13. Since the photoconductive layer 9 is a high resistor in the dark, no change occurs between the electrodes as long as the voltage applied to the gap is equal to or higher than the discharge starting voltage according to Paschen's law. Further, when a voltage equal to or higher than the discharge starting voltage is applied to the gap by an external power source, a discharge occurs, charge is accumulated on the surface of the charge holding medium, and this state continues until the voltage drops to the discharge starting voltage, resulting in fogging charge. Light 18 from the photoreceptor 1 side
When the light is incident, the photosensitive layer 9 in the area where the light is incident exhibits conductivity and discharge occurs, and charges 7;;;■ are accumulated on the surface of the charge holding medium. Also, even if there is a uniform fog charge in advance,
Further charge is accumulated in the area where the light is incident. Next, the power supply 17 is turned off and the charge holding medium 3 is peeled off from the photoreceptor 1, thereby completing the formation of the electrostatic latent image.

When this electrostatic image recording method is used for side-plane analog recording, high resolution can be obtained as in silver halide photography, and the information charges are protected in the charge retention layer and can be stored for a long time without discharging. Ru.

Information on the charge retention medium of the present invention (Manual methods include a method using a high-resolution electrostatic camera and a recording method using a Rayleigh.First, a high-resolution electrostatic camera uses photographic film used in ordinary cameras. Instead, a photoreceptor 1 consists of a photoconductive layer 9 with a photoreceptor electrode 7 on the front surface, and a charge retention layer 11 with a charge retention medium electrode 13 on the rear surface facing the photoreceptor 1. A recording section is formed by the medium, and a voltage is applied to the picture electrode, and the photoconductive layer is made conductive according to the incident light, and charges are accumulated on the charge retention layer according to the amount of incident light U = 1. An electrostatic latent image of an incident optical image is formed in a fine particle, and a mechanical shutter or an electric shutter can also be used. It is possible to retain the optical information for a long time regardless of the location.In addition, the prism allows optical information to be stored in R,
Using a color filter that separates G and B light components and extracts them as parallel light, R, C, 13 minutes 5N7. 1. Set of 3 charge retention media. : Color photography can also be done by forming a J frame or by making one frame of RlG and B images parallel to each other on one plane.

In addition, for the recording method using laser beams, an alkaline laser (514,488nrn), a helium-neon laser (633nm), a semiconductor laser (780nm, 810nm, etc.) can be used as a light source, and the photoreceptor and charge retention Make the media's planar ′ζ surfaces come into close contact with each other, or -・
They are placed facing each other at a certain interval and a voltage is applied. In this case, it is preferable to center the photoreceptor electrode in the same polarity as the carrier of the photoreceptor. Laser exposure corresponding to this state - ζ image signal, character signal, coat signal, and line drawing signal is performed by scanning. Analog recording such as images is done by modulating the light intensity of the laser, and it records letters, codes, etc.
Digital records such as line drawings are created using 0N-O laser light.
This is done by FF control. In addition, in images where halftone dots are formed, laser light is
○It is formed using FF control. Incidentally, the spectral characteristics of the photoconductive layer in the photoreceptor do not need to be punctuated 1:I, but only need to be sensitive to the wavelength of the laser light source.

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

FIG. 4 is a diagram showing an example of a potential reading method in the electrostatic image recording and reproducing method, and the same numbers as in FIG. 1 indicate the same contents. In the figure, 21 is a potential reading section, 23 is a detection electrode, 25 is a guard electrode, 27 is a capacitor, and 29 is a voltmeter.

To reproduce information from a charge retention medium that has accumulated information charges, first, the potential reading section 21 is placed opposite to the surface of the charge retention medium, and the detection electrode 23 detects the electric GI accumulated in the fine particle layer.
The electric field generated by this acts, and an induced charge equivalent to the charge on the charge retention medium is generated on the detection electrode surface. 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 Ninondenser, and by reading this value with the voltage indicator 29, the potential of the information charge is determined. be able to. Then, by scanning the surface of the charge holding medium with the potential reading section 21, the electrostatic latent image can be output as an electrical signal. Note that the detection electrode 23 is affected by an electric field (electric line of force) caused by charges in a wider range than the portion of the charge holding medium that faces the detection electrode, reducing the resolution, so a grounded guard electrode 25 is placed around the detection electrode. You can do it like this. As a result, the lines of electric force are oriented perpendicularly to the surface, so that only the lines of electric force 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. I can do it. The accuracy and resolution of potential reading vary greatly depending on the shape and size of the detection electrode and Kerr 1 electrode, and the distance between them and the charge retention medium, so it is necessary to find and design optimal conditions according to the required performance.

FIG. 5 is a diagram showing a schematic configuration of an electrostatic image reproduction method, in which 6" is a potential reading device, 63 is an amplifier, and 65 is a CR.
T, 67 is a printer.

In the figure, a potential reading device 61 detects the charge potential, the detected output is amplified by an amplifier 63 and displayed as CR1 65, and can be printed out by a printer 67. In this case, you can select the part you want to read at any time.
It is possible to output the output by selecting Q, and it is also possible to play it repeatedly.

It is also possible to read optically using a material whose optical properties change depending on an electric field, such as an electro-optic crystal. Furthermore, since the electrostatic latent image is obtained as an electric signal, it can also be used for recording on other recording media, etc., if necessary.

[Effect]

The charge retention layer 11 in the charge retention medium must be made of a highly insulating polymer in order to suppress the movement of charges, and is required to have an insulating property with a specific resistance of 1014 Ω·cm or less. . Further, it is necessary that the temperature of the polymer constituting the charge retention layer is equal to its glass transition temperature or the temperature of the environment in which it is used. The glass transition temperature is the temperature at which the slope of the decrease in specific volume when a molten polymer is cooled shows a discontinuous change, or in general, polymeric materials have a glass transition temperature that is unique to the substance. Below the glass transition point, thermal energy is so small that one segment of the molecular chain cannot move as a whole.On the other hand, above the glass transition point, the thermal energy increases and the number of atoms making up the molecular chain [ It is believed that this makes it possible for atoms of llI or more to move as a whole, which greatly changes specific heat, specific volume, toughness, embrittlement temperature, etc. The inventors of the present invention came up with an unprecedented idea in using an insulating material as a charge retention medium. The inventors have discovered that it is necessary to use the glass transition temperature below this glass transition temperature in order to improve the compatibility.

In addition, in order to prevent leakage of the information charge i:j accumulated as a polymer material forming the charge retention layer, it is necessary that the water absorption rate of the polymer +, (Fl is low, !-).

If the water absorption rate is higher than 0.4% by weight, the resistivity decreases due to the influence of water adsorbed in the fat and the insulation deteriorates,
Charge retention due to charge diffusion in the volume direction and surface area direction
The present invention was developed based on the discovery that the performance deteriorates.

Charge retention media formed using such polymeric materials have extremely high charge retention performance, and can be used, for example, in electrostatic recording using /I- to electrode needle heads or ion streams, or Rayleigh printers. ) It can be used in optical printers, etc., but it is preferable to place 11- in opposition to a photoreceptor and use it in an information recording and reproducing method using exposure when a voltage is applied. When this photoconductor is used in an electrostatic image recording medium, the surface of the charge retention medium is brought into contact with the photoconductive layer surface of the photoconductor, or the surface of the charge retention medium is placed opposite to the J1 contact, and a voltage is applied between both electrodes. By imagewise exposure in this state, information charges are accumulated in the charge retention performance table 1m. The charge retention I) medium of the present invention has good charge retention performance, and the accumulated information charge is stored inside the charge retention layer, so it is extremely stable, and when reproducing 1111 information, the potential difference between the electrode and the surface potential The potential difference can be easily detected by measuring the high quality,
This can be easily reproduced as information with high M'' resolution.

Examples will be described below.

[Example 1] 1mm thick glass substrate. 2. Vacuum thin bonding (10-'T.

Aβ electrodes are laminated to a thickness of 1,000 layers using the rr) method. Glass transition temperature 67°C1 resistivity 7×1 on the If electrode
After dissolving a 0'7 Ω cm polyester resin (Toyobo Co., Ltd., trade name Byron 200) in a mixed solvent of 37.5 parts by weight of methyl ethyl getone and 37.5 parts by weight of 1 toluene, it was coated with a plate coater. It was dried to obtain a charge retention medium with a polyester resin layer having a thickness of about 10 μm.

The charge retention medium obtained above was charged by corona charging to a surface potential of +100 V or -100 V, and its charge retention performance was measured.

The surface potential measured after being left at room temperature and pressure for 30 days was maintained at 80V for both sides, and as an accelerated test at 80°C and 20% 11.
11. When exposed to an environment of

Similarly, polyesters with different glass transition temperatures
50, GK103 (each glass transition temperature 4°C
A charge retention medium was prepared in the same manner as above using 126°C (147'C) as the charge retention layer, and the relationship between the glass transition temperature and surface potential after being left at 40°C and 310°C was determined.

The results are shown in FIG. 6, where the Δ symbol indicates the charge retention rate for each double glass transition temperature.

[Example 2] Vacuum deposition (10-5T) on a 1 mm thick glass substrate.

rr) method to stack ae electrodes to a thickness of 1,000 layers. Polyparaxylylene (Tomoe Kogyo 0 grade, manufactured by Union Carbide Co., Ltd., trade name Parylene, glass transition temperature 80-100°C, specific resistance 9 x 10''Ω・Cm, water absorption 0.01%) was placed on the Aβ electrode. It was deposited by vacuum evaporation (10"l'orr) method to obtain a charge retention medium with a film Ty of about 10 μm.

The charge retention medium obtained in the above manner was charged to a surface potential of +100 V by 1-2 charging, and its charge retention performance was measured.

30I at room temperature and normal pressure] The surface potential measured after being left is 80V.
Met. In addition, as an accelerated test, 60°C 820% 11.
11. When exposed to this environment, the surface potential measured after being left for 30 days was 60V. Also 45°C195%R, 11
, (left for 30 days), the surface potential remained at 60 V, indicating that it was an excellent charge retention medium.

[Example 3] Polyester resin (PET) film (lIs[+2
tr m, manufactured by Toshi ■, product name Lumirror S, glass transition temperature 69°C, water absorption 0.4%, specific resistance 1 x 108 Ω-c
After laminating the Δp electrode to a thickness of 1,000 layers using a vacuum evaporation method (10-' Torr) on the 1-mm-thick glass substrate, lamination was performed using double-sided adhesive bonding (N=1) on a 1-mm-thick glass substrate. A charge storage medium was prepared.

The charge retention medium obtained above was charged by corona charging to a surface potential of +400 V and -10011, and its electric charge f and storage performance were measured.

The surface potentials measured after being left at room temperature and pressure for 30 minutes were 50V for both.

[Example 4] Polyenalene naphthalene 1-(PEN) film (film j
Zol 2p m, Music University (pillow type, product name Q) I) I/J1
, glass transition temperature 113° (:, water absorption q:;o, 4%)
A charge retention medium was prepared by laminating a C electrode to a thickness of 1000 nm using the IQ-'Torr method.

As described above, the charged charge retention medium was charged to a surface potential of →100ν and -100ν by electrification, and its 'tK (iJ retention performance) was measured.

The surface potentials measured after being left at room temperature and pressure for 30 minutes were 80 VC for both sides. In addition, as an accelerated test, 60℃, 20%
R, I1. The surface potential measured after 30 minutes of exposure to this environment was 80V.

[Reference Example 1] 11-layer organic photoreceptor (PVX-T
NF) Preparation method Poly N-hinyl carhasol Log (manufactured by Ai Fragrance Co., Ltd.), 10 g of 2,4,7-dolinitocinone, 2 g of polyester resin (binder: Vylon 200 manufactured by Toyobo Co., Ltd.), tetrahydrofuran ('r''II do)
A liquid mixture having a composition of 90 g was prepared in the dark, and about 1 (
] Glass sputtered with a film thickness of 0! . (Board (
1 dragon thickness) using doctor spray 1.
Dry with ventilation for about 1 hour at ゛C, and the thickness of 11mm is about 101mm! A photosensitive layer having a photoconductive layer of m was obtained. In addition, in order to completely dry the product, it was further subjected to natural drying in step 1).

[Example 4] Electrostatic image recording and reproducing method As shown in Fig. 6, the monolayer organic photoreceptor (PVX
- TNF) I and the charge retention medium prepared in Example 1 were placed so that the surface of the charge retention medium was opposed to the photoconductive layer surface of the photoreceptor, using a polyvarnish wool film J with a film thickness of 0 μm as a spacer. It landed on the ground.

Next, a DC voltage of 7ζ and 100 V was applied between both electrodes (positive on the emitter side and negative on the resin layer side).

With the voltage applied, exposure is performed from the photoconductor side for 1 second using a Haloken lamp with an illuminance of 1000 lux as a light source, and the formation of the electrostatic image is completed.

Subsequently, the surface potential was measured, and as a result, a surface potential of 100 cm was measured on the surface of the medium using a surface potentiometer, and the surface potential in the unexposed area was QV.

[Comparative example]

Vacuum evaporation (10-5T
.

If the main electrode is laminated to a thickness of 1000 using the rr) method. Glass transition temperature -70'C, water absorption rate 0,
3%, styrene buxene rubber with specific resistance IXIO”Ω・(,n) (manufactured by Shell, trade name: Califlex TR41)
13) was dissolved in a mixed solvent of 375 parts by weight of methyl ethyl ketone and 37.5 parts by weight of Torcorn, coated with a solade coater and dried to obtain a charge retention medium with a film thickness of about 10 μm.

The charge retention medium obtained above was charged to a surface potential of -1 to 400 V or -0011, and its charge retention performance was measured.

The surface potential measured after being left at room temperature and pressure for 30 minutes was 0. +1. 1 when exposed to the environment of
The surface potential measured after being left in the sun was also 0.

〔Effect of the invention〕

The charge retention medium of the present invention has a charge retention layer or a specific resistance IXIO.
``It is made of a polymeric material with a diameter of Ωcm or more, and the glass transition temperature of the polymeric material or the operating environment temperature plate -1-, or the moisture content is 0.4 double star% or less, The accumulated information charge can be retained permanently, and the surface potential generated by the electric field formed by the accumulated charge can be easily detected by the potential @ sampling method that measures the potential difference with the electrode. , further outputs an electrical signal corresponding to the electrostatic latent image (which can be displayed on an RT display or printed out using a printer. Also, since the information storage means is a unit of electrostatic charge, the charge retention medium The information stored in the 4J is of high quality and high resolution, the processing process is simple, it can be stored for a long time, and the stored information can be repeatedly played back at any desired image quality according to the purpose. It is something that can be done.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing each aspect of the charge-holding medium of the present invention, FIG. 2 is a perspective view showing various flexible charge-holding media, and FIG. 3 is electrostatic image recording on the charge-holding medium of the present invention. A diagram for explaining the method, FIG. 4 is a diagram showing an example of the DC amplification type potential reading horn method, and FIG. The figure shown in FIG. 6 is a diagram showing the glass transition temperature and charge retention rate of each polymer material constituting the electric Gj retention layer in relation to the operating temperature. 1 is a photoreceptor, 3 is a charge retention medium, 5 is a photosensitive layer support,
7 is a photoreceptor electrode, 9 is a photoconductive layer, 11 is a charge retention layer, 1
2 is a missing portion of the charge storage 14 layer, 13 is a charge storage medium electrode, 1
5 is a charge retention layer support, 1G is an adhesive layer, 17 is a power source, 1
8 is a pattern exposure light, 21 is a potential reading section, 23 is a detection electrode, 25 is a guard electrode, and 27 is a capacitor. Applicant Dainichi Printing Co., Ltd. Agent TR Physician (1) Nobuhiko (5 others) G (a) (b) Figure 2 (C) (d) Figure 3 (C) (D) Figure 5 figure

Claims (4)

[Claims] (1) A charge retention medium in which an electrode layer and a charge retention layer are laminated, characterized in that the charge retention layer is made of an insulating polymer material, and the glass transition temperature of the polymer material is higher than the operating environment temperature. Charge retention medium. (2) A charge-holding medium in which an electrode layer and a charge-holding layer are laminated, characterized in that the charge-holding layer is made of an insulating polymeric material, and the water absorption rate of the polymeric material is 0.4% by weight or less. charge retention medium. (3) In a charge retention medium in which an electrode layer and a charge retention layer are laminated, the charge retention layer is made of an insulating polymeric material, and the glass transition temperature of the polymeric material is equal to or higher than the operating environment temperature;
A charge retention medium characterized in that the water content is 0.4% by weight or less. (4) A charge retention method comprising using a charge retention medium in which a charge retention layer made of an insulating polymer material is laminated on an electrode layer at a temperature below the glass transition temperature of the insulating polymer material.