JPH09203661A - Photosensor, information recorder and information recording/reproducing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain recording of a high quality image free from changes in image density, uneven sensitivity and noise on an information recording medium by providing an electrode modification thin film layer between an electrode of a photosensor and a photoconductive layer. SOLUTION: An electrode modification thin film layer 16 is provided between an electrode 13 of a photosensor and a photoconductive layer (electric load generation layer 14', electric load transportation layer 14"). The thin film layer 16 needs transparency when the electrode 13 is transparent. But when the electrode 13 is not transparent, the thin film layer can be either transparent or opaque. The material providing a specific resistance of below 10<6> Ω.cm stably, for example, gold, platinum, copper oxide or indium oxide is used and applied on the electrode 13 at a thickness of about 3-100nm or preferably about 10-50nm by vapor deposition or sputtering. The arrangement of the electrode modification thin film layer 16 can eliminate uneven contact between the electrode 13 and the electric load generation layer 14' to uniformize the injection of an electric carrier into the electric load generation layer 14 through the thin film layer 16 from the electrode 13 thereby reducing the unevenness and noises in the image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical sensor capable of recording optical information in the form of visible information or electrostatic information on an information recording medium, and more particularly to an optical sensor having a photoconductive layer laminated on a modification electrode. Further, the present invention relates to an information recording apparatus and an information recording / reproducing method comprising the optical sensor and an information recording medium, in particular, the information recording performance on the information recording medium is remarkably amplified to obtain a predetermined image density, and further image unevenness and image The present invention relates to an information recording device, an information recording method, and an information recording / reproducing method each including an optical sensor in which a photoconductive layer is laminated on a noise-free modified electrode.

[0002]

2. Description of the Related Art In order to record optical information on an information recording medium, a photosensor comprising a photoconductive layer having an electrode on the front surface and a charge holding layer having an electrode on the rear surface facing the photosensor. The information recording medium consisting of is arranged on the optical axis,
A method of exposing while applying a voltage between both electrode layers, recording an electrostatic charge on the charge holding layer in accordance with an incident optical image, and developing the electrostatic charge with a toner or reproducing with a potential reading device is, for example, a method described in Japanese Patent Application Laid-Open No. H11-163,873. It is described in Japanese Unexamined Patent Publication No. Hei 1-290366 and Japanese Unexamined Patent Publication No. Hei 1-289975. Further, the charge holding layer in the above method is a thermoplastic resin layer, the electrostatic charge is recorded on the surface of the thermoplastic resin layer, then heated, and the electrostatic charge recorded by forming a frost image on the surface of the thermoplastic resin layer. A method for visualizing is described in, for example, JP-A-3-19.
No. 2288.

Further, the present applicants have disclosed that the information recording layer in the information recording medium is a polymer dispersed liquid crystal layer, is exposed when a voltage is applied in the same manner as described above, and aligns the liquid crystal layer by an electric field formed by an optical sensor. An information recording and reproducing method for recording information and reproducing the recorded information as visible information using transmitted light or reflected light has been described in Japanese Patent Application Nos. 4-3394, 4-24722 and 4-24722. 5-
No. 266646. This information recording / reproducing method can visualize recorded information without using a polarizing plate. In such an information recording method, an optical sensor with higher sensitivity and higher image quality has been required. In addition, since the optical sensor of the present invention has features of high resolution and high sensitivity, a constant image density can be obtained at the time of imaging to form an image free from background contamination, and the injection current can be further stabilized. There has been a demand for an optical sensor having high sensitivity, non-uniform sensitivity, and no noise.

[0004]

DISCLOSURE OF THE INVENTION The present invention is an optical sensor used for forming information on an information recording medium, which has a remarkable problem of image density change and image density change which are significant problems in the optical sensor having both high resolution and high sensitivity. An object is to provide an optical sensor that can obtain a high-quality image without unevenness in sensitivity and noise, is excellent in information forming ability, and has improved information recording sensitivity, an information recording device including the optical sensor, and an information recording / reproducing method. .

[0005]

SUMMARY OF THE INVENTION The present invention is a photosensor having a photoconductive layer on an electrode and used for forming information on an information recording medium, which is semiconductive, and which has the photosensor electrode and the information. When voltage is applied between the electrodes of the recording medium and the exposed state, or when exposure is performed while the voltage is applied, information recording can be performed on the information recording medium with an intensity amplified more than the current caused by the exposure. In addition, in the photosensor having the action of continuing to record information on the information recording medium in a photosensor which exhibits a behavior that the conductivity gradually attenuates when the voltage is continuously applied even after the exposure is finished, It is an optical sensor having an electrode-modified thin film layer provided therebetween. In an optical sensor having a photoconductive layer on an electrode and used for forming information on an information recording medium, it faces an information recording medium in which an information recording layer capable of forming information by an electric field or a charge amount is laminated on the electrode. It is semi-conductive and is applied semi-conductingly.When a voltage is applied between the electrodes of the photosensor and the information recording medium in an exposed state, or when exposed with a voltage applied, the information recording medium is exposed. The applied electric field or the amount of electric charge is amplified, and when the voltage is continuously applied even after the exposure is finished, the conductivity gradually decreases, and the electric field or the amount of electric charge is continuously applied to the information recording medium. The optical sensor has an electrode modification thin film layer provided between the electrode and the photoconductive layer. When voltage is applied,
When an electric field strength of 10 ⁵ to 10 ⁶ V / cm is applied to the optical sensor, the passing current density at the unexposed portion is 10 ⁻⁴ to 10 ⁻⁷ A / c.
m is the optical sensor described above. The above-mentioned optical sensor, wherein the electrode-modified thin film layer is formed of a vapor-deposited thin film.
In the above optical sensor, the electrode-modified thin film layer is formed of an electropolymerized film. In the above optical sensor, the electrode-modified thin film layer is formed of a CVD thin film. In the above optical sensor, the electrode-modified thin film layer is formed of a sputtering thin film.

Further, in an information recording apparatus for recording optical information on an information recording medium by exposure, the optical sensor and the information recording medium having an information recording layer formed on an electrode are arranged facing each other on the optical axis with a gap provided therebetween. In addition, the information recording device is configured such that a voltage can be applied between the electrodes of the optical sensor and the electrodes of the information recording medium. In the above information recording device, the information recording layer comprises at least a liquid crystal phase and a resin phase. The information recording layer is made of a thermoplastic resin, and a charge corresponding to the information exposure is applied to the surface of the information recording layer and then heated, so that a frost image corresponding to the exposure is formed on the surface of the information recording layer. This is an information recording device. Whether the information recording layer is composed of a charge retaining layer, the charge corresponding to the exposure is applied to the surface of the information recording layer, and the charge corresponding to the exposure is formed on the surface of the information recording layer,
Alternatively, it is the above-mentioned information recording apparatus which develops the charges formed on the surface of the information recording layer with toner. The information recording device has the information recording layer having a memory property. When the electric field strength of 10 ⁵ to 10 ⁶ V / cm is applied to the optical sensor,
The passing current density in the unexposed area is 10 ⁻⁴ to 10 ⁻⁷ A / cm ²
And the specific resistance of the information recording medium is 10 ¹⁰ to 10 ¹³ Ω · c.
m is the above information recording device. In the information recording device in which the electrode-modified thin film layer, the photoconductive layer, the dielectric layer, the information recording layer, and the upper electrode are laminated in this order on the lower electrode, the optical sensor unit including the lower electrode, the electrode-modified thin film layer, and the photoconductive layer is An information recording device comprising the above-mentioned optical sensor, in which a voltage can be applied between a lower electrode and an upper electrode. In the above information recording device, the information recording layer in the information recording medium comprises at least a liquid crystal phase and a resin phase.

Further, in an information recording / reproducing method for recording optical information on an information recording medium by exposure, the above-mentioned optical sensor and an information recording medium having an information recording phase formed on an electrode are used, and an optical sensor or an information recording medium is used. At least one of the electrodes is a transparent electrode, and the optical sensor and the information recording medium are arranged facing each other on the optical axis with a gap, and a voltage is applied between both electrodes, or a voltage is applied. It is an information recording / reproducing method of performing information recording on an information recording medium by exposure in a state and reproducing optical information recorded on the information recording medium as visible information by transmitted light or reflected light. In an information recording method of recording optical information on an information recording medium by exposure, an information recording medium having an information recording layer made of a thermoplastic resin formed on the optical sensor and electrodes is used, and an electric charge is generated by exposure of the optical information. This is an information recording / reproducing method in which the optical information recorded on the information recording medium as visible information is reproduced by transmitting light or reflected light to form a frost image according to information exposure after heating on the recording layer. In an information recording method for recording optical information on an information recording medium by exposure, an information recording medium having an information recording layer formed of a charge holding layer on the above-mentioned optical sensor and an electrode is used, and an electric charge is recorded by exposing the optical information. This is an information recording / reproducing method in which the optical information recorded on the recording layer is read and reproduced by an electric potential sensor after the information is recorded on the recording layer.
In an information recording / reproducing method of recording optical information on an information recording medium by exposure, an information recording medium having an information recording layer composed of a charge holding layer on the above-mentioned optical sensor and electrodes is used, and charges are exposed by exposure of the optical information. This is an information recording / reproducing method of developing the recorded optical information with a toner after applying it on the information recording layer and reproducing the optical information as visible information by transmitted light or reflected light. In an information recording method for recording optical information on an information recording medium by exposure, the information recording medium has an electrode-modified thin film layer, a photoconductive layer, a dielectric layer, an information recording layer, and an upper electrode, which are sequentially laminated on a lower electrode, An optical sensor section composed of a lower electrode, an electrode-modified thin film layer, and a photoconductive layer is composed of the above-described optical sensor, and at least one of the lower electrode and the upper electrode is a transparent electrode and exposed between the lower electrode and the upper electrode. Information recording / reproduction in which information is recorded on the information recording medium by applying voltage with the voltage applied or by exposure while applying voltage, and reproducing optical information recorded on the information recording medium as visible information by transmitted light or reflected light. Is the way.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION An optical sensor in an information recording apparatus according to the present invention has a structure in which a photoconductive layer is laminated on an electrode, and this photoconductive layer has a configuration in which a charge generation layer and a charge transport layer are laminated. The photoconductive layer generally has a function of generating photo-induced charge carriers (electrons and holes) in the irradiated portion when light is irradiated, and these carriers can move in the layer width. The optical sensor of the invention uses the modified electrode described below, whereby the electric field or the amount of charge applied to the information recording medium at the time of irradiating light to the optical sensor is amplified over time with light irradiation, and after the light irradiation is finished. However, when the voltage is continuously applied, the increased conductivity continues while being gradually attenuated, so that the electric field or the amount of charge is continuously applied to the information recording medium. In addition, the photosensor of the present invention stably controls the injection of charge carriers between the electrode and the charge generation layer by using the modified electrode, and makes the photosensor semiconductive when it is not irradiated with light. It has the effect of reducing partial or local sensitivity unevenness of the optical sensor, which tends to occur during light irradiation, and noise that appears as white spots, black dots, etc. when an image is formed.

The photo-induced current amplifying action in the optical sensor of the present invention will be described. A 0.16 cm ² gold electrode is laminated on the photoconductive layer of the optical sensor for measuring amplification effect. A constant DC voltage is applied between the two electrodes with the ITO electrode as a positive electrode, and 0.5 seconds after the start of the voltage application, light is irradiated from the substrate side for 0.033 seconds, and the current value of the optical sensor during the measurement time is measured. At the start of light irradiation (t = 0)
Measure from. The irradiation light is a xenon lamp (L2274 manufactured by Hamamatsu Photonics) as a light source, and a green light obtained by a green filter (manufactured by Nippon Vacuum Optical Co., Ltd.)
Irradiation was performed at an intensity of 0 lux. The irradiation light intensity was measured with an illuminometer (manufactured by Minolta), and the characteristics of the filter used are shown in FIG. When light is irradiated with this light intensity, in consideration of the light transmittance of the transparent substrate, the ITO film, and the spectral characteristics of the filter, 4.2 × 10 ¹¹ photons / cm ² seconds are incident on the photoconductive layer. When all the incident photons are converted into photocarriers, theoretically, a current of 1.35 × 10 ⁻⁶ A / cm ² is generated as a photocurrent per unit area. Here, the ratio of the photo-induced current actually generated in the photosensor with respect to the theoretical photocurrent when measured by the measuring device, that is, the apparent quantum efficiency = (photo-induced current actually generated in the photosensor). Current value / theoretical photocurrent value) is defined as the apparent quantum efficiency of the photosensor. The light-induced current is a value obtained by subtracting a base current value, which is a current flowing in a portion not irradiated with light, from a current value of a light irradiation portion. The current that flows due to
This is different from a so-called photocurrent. The photo-induced current amplification action in the photo-sensor of the present invention is defined as such a behavior of the photo-induced current.

An optical sensor having a photo-induced current amplifying action and an optical sensor having no photo-induced current amplifying action (hereinafter referred to as a comparative sensor) according to the present invention will be described with reference to the measurement results of the measuring device. To do. First, an example of the measurement result of the comparative sensor is shown in FIG. In FIG. 5, line (m) indicates the theoretical value (1.35 × 10 ⁻⁶ A / c).
m ²⁾ with reference line indicating the performs light irradiation 0.033 seconds,
The state where voltage application is continued after light irradiation is shown. Line (n) is the measured line of the comparative sensor, and the increase in photocurrent during light irradiation is small, and its value does not exceed the theoretical value (1.35 × 10 ⁻⁶ A / cm ² ). The quantum efficiency does not reach 0.5 at the maximum. FIG. 6 shows a change in quantum efficiency during light irradiation.

On the other hand, in the photosensor of the present invention, as shown in FIG. 7 as an example, as shown in FIG. 7A, compared with FIG. As is clear from FIG. 8 showing the relationship with the quantum efficiency, the quantum efficiency exceeds 1 in about 0.01 seconds, and the quantum efficiency continues to increase thereafter. Further, in the comparative sensor, the photocurrent abruptly attenuates at the same time as the end of the light irradiation, so that even if a voltage is continuously applied after the light irradiation, an effective current as optical information cannot be obtained. On the other hand, in the photosensor of the present invention, by continuing the voltage application after the light irradiation, the photoinduced current continues to flow while being gradually attenuated, and the photoinduced current can be subsequently taken out. Can be continued. The relaxation-type damping behavior in the present invention is defined as such behavior of photo-induced current.

Although the detailed reason for this is not clear, in the photosensor of the present invention, all of the photo-induced charge carriers generated by the irradiation of the information light are applied in the layer width direction of the photoconductive layer in the voltage applied state. It does not move, but a part of the photo-induced charge carriers becomes trapped in a trap site existing in the photoconductive layer or at the interface between the modification electrode and the photoconductive layer. It is considered that in the state of being accumulated and applying a voltage, the injection current from the electrode induced by the trapped charges flows in addition to the photocurrent generated by exposure, and the apparent photoinduced current amount is amplified with time. . However, this phenomenon occurs when the injection of charge carriers from the electrode into the charge generation layer is appropriately performed, and when appropriate injection is not performed, that is, when injection is too small or injection is too large. There is almost no amplification effect. In the present invention,
By using the modified electrode as the electrode of the photosensor, the charge carriers are appropriately injected from the electrode into the charge generation layer, and the photoinduced current amplification effect can be effectively produced. When the exposure is terminated while maintaining the voltage applied state, the photocarriers generated by the exposure are immediately attenuated and disappear, but the decay of the trapped charges is slow, so that the trapped charges cause It is presumed that the induced injection current from the electrode attenuates but flows in a sufficient amount, resulting in relaxation-type attenuation. This photo-induced current is an effect of current amplification triggered by light in the optical sensor of the present invention, and a current larger than a photocurrent caused by incident light expected from a normal photoconductor flows. Optical information can be provided effectively to

Next, the action of stabilizing the injection current in the optical sensor of the present invention will be described. The injection current stabilizing action has two effects, that is, an injection amount control action and an injection uniformization action. First, the first injection amount control action will be described. The optical sensor of the present invention is semi-conductive as a whole, and has a specific resistance in the dark of 10 ⁹ to 10 ¹³ Ω · c due to the flowing current density.
m is preferable. Especially, the specific resistance is 10 ¹⁰ to 10
^The amplification effect is remarkable in the range of ¹³ Ω · cm. With an optical sensor having a resistivity of more than 10 ¹³ Ω · cm, 10
^In the electric field intensity range of ⁵ to 10 ⁶ V / cm, no amplification action is exhibited unlike the optical sensor of the present invention. Also, the specific resistance is 10
An optical sensor of less than ⁹ Ω · cm is not preferable because a large amount of current flows and noise is generated by the current. By using a modified electrode as the electrode of the photosensor, the injection amount of charge carriers from the electrode to the charge generation layer can be controlled, and the conductivity of the photosensor as a whole device can be set to a desirable level, resulting in extremely high amplification. An optical sensor having good characteristics can be obtained. On the other hand, the photoconductor element used for general electrophotography has a dark resistivity of 10 ¹⁴ to 10 ^16.
Ω · cm is used, and the optical sensor of the present invention cannot achieve its purpose in electrophotography.
Further, a photosensor having a photoconductive layer having a large dark resistivity for general electrophotography cannot be used for the purpose of the present invention. Also, between the specific resistance ρ (Ω · cm) of the optical sensor and the current density J (A / cm ² ), the film thickness d of the optical sensor, the electrode area S, and the applied electric field intensity E (V / cm) Since the relational expression of ρ = (E · d / J · S) × (S / d) = E / J holds between them, it can be obtained from the applied electric field strength and the current density. In the example,
Expressed by current density.

Further, when the information recording layer in the information recording medium is a liquid crystal-polymer composite layer, it is necessary to set the sensitivity of the optical sensor in the operating voltage region of the liquid crystal. That is, the contrast voltage, which is the difference between the potential (bright potential) applied to the information recording medium in the exposed part and the potential (dark potential) applied to the information recording medium in the unexposed part, is the operating voltage of the liquid crystal in the information recording medium. It is necessary to have a predetermined size in the region. Therefore, for example, the dark potential applied to the information recording layer in the unexposed portion of the optical sensor needs to be set to about the operation start potential of the liquid crystal. Therefore, the resistivity of the information recording medium is 10 ¹⁰ to 10 ^{10 at} room temperature.
¹³ Ω · cm, 10 ⁵ to 10 ⁶ V / cm for optical sensor
10 ^-4 to 10 ^-7 A / cm ^{2 with} the electric field of
Is required to have such a conductivity that a base current is generated, and a range of 10 ⁻⁵ to 10 ⁻⁶ A / cm ² is preferable. In an optical sensor having a base current of less than 10 ^-7 A / cm ² , the information recording layer is not oriented even in an exposed state, and in an optical sensor having a base current of 10 ^-4 A / cm ² or more, the voltage is simultaneously applied even in an unexposed state. A large amount of current flows, the liquid crystal is oriented, and even when exposed, no difference in transmittance is obtained between the unexposed portion and the unexposed portion. Since the operating voltage and the range vary depending on the liquid crystal, it is necessary to consider the voltage distribution in the information recording medium when setting the applied voltage and the voltage application time.

Since the conductivity of the entire photosensor element can be controlled by using an electrode having a thin layer made of an electrode modification film as the electrode of the photosensor, it is suitable for the operating voltage and range of the liquid crystal recording medium. An optical sensor can be obtained. Therefore, the recording image density can be kept within a certain range, and stable recording of optical information can be performed. The detailed reason is unknown,
In the photosensor of the present invention, the injection current is large, and the injection amount of the charge carriers is considered to be more limited than the injection of the charge carriers from the electrode to the charge generation layer. is important. In the optical sensor of the present invention, by using an electrode having an electrode-modified thin film layer as an electrode of the optical sensor, the injection amount of charge carriers from the electrode to the charge generation layer via the electrode-modified thin film layer can be controlled, and the optical sensor element It is considered that the overall conductivity can be set to a predetermined size.

Next, an explanation will be given of the injection uniformizing action which is the second action of the injection current stabilizing action in the optical sensor of the present invention. Since the optical sensor of the present invention has high resolution and high sensitivity, sensitivity unevenness and noise, which are not problems with ordinary photoconductors, are remarkably recorded on the information recording medium,
This is a big problem in the quality of recorded images. In the present invention, by using the modified electrode as the electrode of the optical sensor,
It is possible to reduce image unevenness and image noise. The detailed reason for this is unknown, but if the electrode is not modified and the charge generation layer is laminated on the charge generation layer, the contact state between the electrode and the charge generation layer will be partially or locally nonuniform for some reason. It is thought that the non-uniformity is reflected in image unevenness and image noise in the final image, but by providing an electrode-modified thin film layer between the electrode and the charge generation layer, the non-uniformity between the electrode and the charge generation layer It is considered that such a contact state is eliminated, and as a result, charge carriers are uniformly injected from the electrode to the charge generation layer through the electrode-modified thin film layer, and image unevenness and image noise can be greatly reduced.

Next, the optical sensor of the present invention will be described. FIG. 1 is a cross-sectional view for explaining an optical sensor of the present invention, in which 13 is an electrode of the optical sensor, 16 is an electrode-modified thin film layer, 14 'is a charge generation layer, 14 "is a charge transport layer, and 1".
5 is a substrate. As shown in the figure, the photosensor is formed by sequentially stacking a charge generation layer and a charge transport layer on a modified electrode, and the photoconductive layer includes an inorganic material and an organic material. The charge generation layer 14 ′ made of an inorganic material is formed by depositing Se—Te, Si doped with sulfur, oxygen, or the like on the electrode to a thickness of 0.05 to 1 μm by vapor deposition, sputtering, CVD, or the like.

The charge generating layer 14 'made of an organic material is composed of a charge generating substance and a binder. Examples of the charge-generating substance include pyrylium-based dyes, thiapyrylium-based dyes, azurenium-based dyes, cyanine-based dyes, kaolin-based dyes such as azurenium-based dyes, squarylium-salt-based dyes, phthalocyanine-based pigments, perylene-based pigments, and pyranthrone-based pigments. Polycyclic quinone pigment, indigo pigment,
Pigments such as quinacridone type pigments, pyrrole type pigments, azo type pigments and the like can be used alone or in combination of two or more. As the binder, for example, silicone resin, polycarbonate resin, vinyl formal resin, vinyl acetal resin, vinyl butyral resin, styrene resin, styrene-butadiene copolymer resin, epoxy resin, acrylic resin, saturated or unsaturated polyester resin, methacrylic resin, Examples thereof include vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin and the like, and binder resins can be used alone or in combination of two or more. The mixing ratio of the charge generating agent and the binder is 0.1 to 10 parts by weight, and preferably 0.2 to 1 part by weight of the binder.
It is preferable to use it in a ratio of 1 part by weight. The film thickness of the charge generation layer after drying is 0.01 to 2 μm, preferably 0.1 to 0.5 μm, and such a film thickness shows good sensitivity and image quality. Further, among the above-mentioned charge-generating substances, those that can be formed into a film by the vapor deposition method can be formed into a film alone without using a binder.

The charge-transporting layer 14 "comprises a charge-transporting substance and a binder. The charge-transporting substance is a substance having a good property of transporting the charges generated in the charge-generating layer, and is, for example, oxadiazole-based or oxazole-based. , Triazole, thiazole, triphenylmethane, styryl, pyrazoline, hydrazone, aromatic amine, carbazole, polyvinylcarbazole, stilbene, enamine, azine, triphenylamine, butadiene, There is a polycyclic aromatic compound type, a stilbene double type, a biphenyl type, etc., and it is necessary to use a substance having a good hole transport property. Resins and phenoxy resins can be used, but styrene resins and Down -. Butadiene copolymer resin, a polycarbonate resin binder from 0.1 to 10 parts by weight of the charge-transporting material 1 part by weight, preferably 0.
It is desirable to use it in a ratio of 1 to 1 part by weight. The thickness of the charge transport layer after drying is 1 to 50 μm, and preferably 3 to 20 μm. With such a thickness, good sensitivity and image quality can be obtained. Further, the above-described charge transporting substance that can be formed into a film by the vapor deposition method can be formed into a film without using a binder.

The electrodes 13, it is necessary to have a transparency if opaque information recording medium to be described later, transparent if the information recording medium has a transparency may be either opaque, 10 ⁶ Omega · A material that stably gives a specific resistance of not more than cm, for example, a metal thin film conductive film of gold, platinum, zinc, titanium, copper, iron, tin, tin oxide, indium oxide, zinc oxide,
A metal oxide conductive film such as titanium oxide, tungsten oxide or vanadium oxide, an organic conductive film such as a quaternary ammonium-containing substance or the like can be used alone or as a composite material of two or more kinds. Of these, oxide conductors are preferable, and indium tin oxide (ITO) is particularly preferable. The electrode is formed by a method such as vapor deposition, sputtering, CVD, coating, plating, dipping, and electrolytic polymerization, and is formed on the front surface between the electrode and the information recording layer or according to an arbitrary pattern. Further, two or more kinds of materials can be stacked and used.

The substrate 15 is required to have transparency if the information recording medium described later is opaque. If the information recording medium has transparency, it may be transparent or opaque, and may be a card, a film, It has the shape of a tape, disk, etc., and strongly supports the optical sensor. If the optical sensor itself has a supporting property, it is not necessary to provide it. However, the material and thickness are not particularly limited as long as the optical sensor has a certain strength capable of supporting the optical sensor.
For example, a flexible plastic film, or a plastic sheet or card of glass, polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polymethyl acrylate, polyester, polycarbonate or the like is used. In addition, if the electrode 13 is transparent, a layer having an antireflection effect is laminated on the other surface of the substrate on which the electrode 13 is provided, or a layer having an antireflection effect is formed, if necessary. It is preferable to provide an antireflection property by adjusting a transparent substrate or by combining the two.

An electron-accepting substance, a sensitizing dye, an antioxidant, an ultraviolet absorber, a light stabilizer and the like may be added to the charge generation layer and the charge transport layer. The electron-accepting substance and the sensitizing dye have effects such as adjustment of base current, stabilization of base current, and sensitization. Examples of the electron-accepting substance include compounds listed as nitro-substituted benzenes, amino-substituted benzenes, halogen-substituted benzenes, substituted naphthalenes, benzoquinones, nitro-substituted fluorenones, chloranyls, and charge-transporting substances. Examples of the sensitizing dye include a triphenylmethane dye, a pyrylium salt dye, a xanthene dye, and a leuco dye. As the antioxidant, a phenolic antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and as the ultraviolet absorber, a salicylic acid-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, Examples of the cyanoacrylate-based ultraviolet absorber as a light stabilizer include an ultraviolet stabilizer and a hindered amine-based light stabilizer. The electron-accepting substance and the sensitizing dye are used in an amount of 0.001 to 10 parts by weight, preferably 0.01 part by weight, per part by weight of the charge-generating substance or the charge-transporting substance.
It is added in a ratio of 1 to 1 part by weight. When the amount is less than 0.001 part by weight, no action is exhibited. When the amount is more than 10 parts by weight, the image quality is adversely affected.

The antioxidant, the ultraviolet absorber and the light stabilizer may be used alone or in combination of 0.001 to 1 part by weight of the charge generating substance or the charge transporting substance.
10 to 10 parts by weight, preferably 0.01 to 1 part by weight. If the amount is less than 0.001 part by weight, the effect of adding these substances cannot be obtained. If the amount is more than 10 parts by weight, the image quality is adversely affected. The same amount can be added to the charge generation layer and the charge transport layer. Preferably, these substances are added to the charge generation layer.

Next, the electrode modification thin film layer 16 of the optical sensor will be described. Electrode modified thin layer, it is necessary that the electrodes having transparency be transparent, if the electrodes are opaque transparent may be either opaque, 10 ⁶ Omega
-It is necessary to stably provide a specific resistance of cm or less, and workability as a thin film is also required. The thickness of the electrode-modified thin film layer is 3 to 100 nm, preferably 10 to 50 nm, and the vapor deposition method, multi-source vapor deposition method, sputtering method, ion plating method, plasma CVD method, CVD method, LB
Method, electrolytic polymerization method or the like. 300 nm
If it is thicker than 3 nm, its function is not fulfilled, and if it is thinner than 3 nm, it causes image noise.

As a material for forming the electrode-modified thin film layer,
When the vapor deposition method is used, for example, a metal thin film conductive film of gold, platinum, copper, tin or the like can be used. When the sputtering method is used, for example, a metal oxide conductive film of tin oxide, indium oxide, zinc oxide, titanium oxide, tungsten oxide, vanadium oxide, or the like can be given. When the CVD method is used, an organic conductive film such as a quaternary ammonium salt can be used. When using the LB method, for example, a tetraphenylporphyrin derivative and the like can be mentioned. When the electrolytic polymerization method is used, examples thereof include a pyrrole derivative and a thiophene derivative. Each of these can be used alone or as a composite material of two or more kinds. Further, since the film thickness is extremely thin, a material that is not suitable for thick film processing can be used.

The information recording medium 2 will be described. First,
Examples of the information recording medium in the present invention include a case where the information recording layer is a liquid crystal polymer composite (hereinafter, also referred to as LCPC). LCPC has a structure in which resin particles are dispersed in a liquid crystal phase, and as a liquid crystal material, a smectic liquid crystal, a nematic liquid crystal, a cholesteric liquid crystal, or a mixture thereof can be used. As a liquid crystal,
It is preferable to use a smectic liquid crystal from the viewpoint of so-called memory property in which the orientation is maintained and information is maintained permanently. As the smectic liquid crystal, a liquid crystal material exhibiting a smectic A phase such as a cyanobiphenyl-based, cyanoterphenyl-based, phenylester-based, or fluorine-based liquid crystal material having a long terminal carbon group of a liquid crystalline material, and a ferroelectric liquid crystal. A liquid crystal material exhibiting a smectic C phase or a liquid crystal material exhibiting smectic H, G, E, F or the like is used.

The material for forming the resin particles is, for example, an ultraviolet curable resin that is compatible with the liquid crystal material in the monomer or oligomer state, or a solvent common to the liquid crystal material in the monomer or oligomer state. Those having compatibility with can be preferably used. Examples of such an ultraviolet-curable resin include acrylic acid esters and methacrylic acid esters. In addition, a solvent-soluble thermosetting resin having compatibility with a liquid crystal material and a common solvent, such as an acrylic resin, a methacrylic resin, a polyester resin, a polystyrene resin, and a copolymer based on these, an epoxy resin, a silicone resin Etc. may be used.

The ratio of the liquid crystal material to the resin used is such that the liquid crystal content is 10% by weight to 90% by weight, preferably 40% by weight.
When the content is less than 10% by weight, the light transmittance is low even if the liquid crystal phase is oriented by information recording, and when it exceeds 90% by weight, phenomena such as exudation of the liquid crystal occur. This is not preferable because image unevenness occurs. Since the film thickness of the information recording phase gives a liquid crystal to the resolution, the film thickness after drying should be 0.1 μm to 10 μm, preferably 3 μm to 8 μm, and the operating voltage should be reduced while maintaining high resolution. Can be. If the film thickness is too thin, the contrast of the information recording section is low, and if it is too thick, the operating voltage is undesirably high. As shown in FIG. 2, this information recording medium is opposed to the above-described optical sensor via a spacer 19 made of an insulating resin film such as polyimide, and both electrodes 1
3 and 13 'are connected via a voltage source to form a first information recording device. One or both of the electrodes 13 and 13 'in this device may be transparent.

Next, the second information recording device will be described. FIG. 3 is a sectional view showing the second information recording apparatus of the present invention, in which 20 is a dielectric layer, and the same reference numerals as those in FIG. 2 indicate the same contents. The second information recording device is a device in which the optical sensor and the information recording medium in the first information recording device are arranged so as to face each other with the dielectric layer 20 in between and are directly laminated. The second information recording device is particularly suitable when the photoconductive layer in the photosensor is formed by coating using a solvent, and when the information recording layer is directly formed by coating on the photoconductive layer, the interaction between them causes The liquid crystal in the information recording layer is eluted, and the photoconductive material is eluted by the solvent for forming the information recording layer to prevent image unevenness, and the optical sensor and the information recording medium can be integrated. It is what

In forming the dielectric layer 20, it is necessary that it has no solubility in the photoconductive layer-forming material and the information recording layer-forming material, and that it does not have conductivity. Is. In the case of having conductivity, the space charge is diffused and the resolution is deteriorated, so that the insulating property is required. In addition, since the dielectric layer reduces the distribution voltage applied to the liquid crystal layer or deteriorates the resolution, it is preferable that the film thickness is small, and it is preferable that the film thickness be 2 μm or less. Not only the generation of image noise due to the interaction with time, but also the problem of permeation due to defects such as pinholes at the time of laminating coating occurs. The penetrability due to defects such as pinholes depends on the solid content ratio of the material to be laminated and coated, the type of solvent, and the viscosity, so the thickness of the laminated coating is set appropriately, but at least 10 μm.
The film thickness should be less than m, preferably 0.1 to 3 μm.
It is good to Further, in consideration of voltage distribution applied to each layer, it is preferable to use a material having a high dielectric constant as well as a thin film.

Inorganic materials such as SiO ₂ , TiO ₂ , CeO ₂ , Al ₂ O ₃ and Ge are used as materials for forming the dielectric layer.
O ₂ , Si ₃ N ₄ , AlN, TiN, MgF ₂ , ZnS,
It is preferable to use a combination of silicon dioxide and titanium dioxide, a combination of zinc sulfide and magnesium fluoride, a combination of aluminum oxide and germanium, or the like, and form a layer by an evaporation method, a sputtering method, a CVD method, or the like. Further, a water-soluble resin having low compatibility with an organic solvent, for example, polyvinyl alcohol, water-based polyurethane,
Using an aqueous solution such as water glass, the layers may be laminated by a spin coating method, a blade coating method, a roll coating method, or the like.
Further, a coatable fluororesin may be used, and in this case, it is dissolved in a fluorine-based solvent or the like and coated by a spin coating method, or a blade coating method, a roll coating method, a bead coating method, a slide coating method. You may laminate | stack by the etc. As the applicable fluororesin, for example, a fluororesin disclosed in JP-A-4-24722 and the like,
Further, an organic material such as polyparaxylylene which is formed into a film in a vacuum system can be preferably used.

Next, an information recording method in the first and second information recording devices of the present invention will be described. FIG.
FIG. 4 is a diagram for explaining an information recording method in the first information recording device of the present invention. The same applies to the second information recording device. In the figure, 11 is an information recording layer, 13 is an electrode of an optical sensor, 13 'is an electrode of an information recording medium, 14' is a charge generation layer, 14 "is a charge transport layer, 16 is an electrode modified thin film layer, 21 is a light source, 22 Is a shutter having a driving mechanism,
Reference numeral 23 denotes a pulse generator serving as a power supply, and reference numeral 24 denotes a dark box. Pulse generator 2 between electrodes 13 and 13 '
When the information light is incident from the light source 21 while applying an appropriate voltage according to 3, the charge generation layer 14 'at the portion where the light is incident
The photocarriers generated in the step move to the interface on the information recording layer 11 side by the electric field formed by the two electrodes, redistribution of the voltage is performed, the liquid crystal layer in the information recording layer 11 is oriented, and according to the pattern of the information light. Recording is performed. In the information recording method of the present invention, planar analog recording is possible, and recording at a liquid crystal level is obtained, so that high-resolution recording is achieved, and the exposure pattern is visualized and retained by the orientation of the liquid crystal phase. Is done.

As a form of the information recording apparatus, there are a method using a camera and a recording method using a laser. As a method using a camera, an information recording medium is used in place of a photographic film used in a normal camera, and a recording member is used. An optical shutter may be used. It can be used. For example, a film of an imaging camera (RB67 manufactured by Mamiya Co., Ltd.) is replaced with this laminated body, and a direct voltage of 700 V is applied for 0.04 seconds between both electrodes of the optical sensor and the information recording medium, and at the same time, a gray scale is displayed. By performing projection exposure from the side of the optical sensor for 1/30 seconds, a recording portion including a light transmitting portion corresponding to a gray scale is formed on the information recording layer of the information recording medium, and information recording can be performed. In addition, the optical information can be read by a prism, color filter, etc.
G and B light components are separated and extracted as parallel light R, G,
One frame is formed by three information recording media for each color of B, or R, G,
It is also possible to perform color photography by recording each image of B and forming one frame.

The laser recording method is as follows:
The light source is an argon laser (514.488n)
m), a helium-neon laser (633 nm), a semiconductor laser (780 nm, 810 nm, etc.) can be used,
The 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 light intensity of the laser,
Digital recording such as characters, codes, and line drawings is performed by ON-OFF control of a laser beam. In a case where a halftone dot is formed in an image, a laser beam is formed by ON-OFF control of a dot generator. Note that the spectral characteristics of the photoconductive layer in the optical sensor need not be panchromatic, as long as they have sensitivity to the wavelength of the laser light source.

The exposure information recorded on the information recording medium is separated from the information recording medium in the case of the first information recording apparatus as shown in FIG. 10, and in the case of the second information recording apparatus. When the information is reproduced as it is by the transmitted light, the liquid crystal is oriented in the direction of the electric field in the information recording portion, so that the light A is transmitted while the light B is transmitted at the portion where the information is not recorded.
Are scattered and a contrast with the information recording section can be obtained. Further, it may be read by reflected light through the light reflecting layer.
Next, the information recorded on the information recording medium is read by the information output device shown in FIG. 11 by an image scanner having a CCD line sensor, and the information is read by a sublimation transfer printer (for example, SP manufactured by Victor Company of Japan). It is possible to obtain a good printed matter corresponding to a gray scale by outputting information by using (-5500). The information recorded by the orientation of the liquid crystal is
Although it is visible information that can be visually read, it can be read by enlarging it with a projector, and information can be read with high accuracy by laser scanning or using a CCD. Note that scattered light can be prevented by using a schlieren optical system as needed.

In the above method, as the information recording medium, the recording by the information exposure is visualized by the crystal orientation. However, the information visualized once by selecting the combination of the liquid crystal and the resin is obtained. A memory property can be imparted without erasing. Further, by heating to a high temperature near the isotropic phase transition, the memory property can be erased, so that it can be used for recording information again.

As the information recording medium in the information recording system, for example, JP-A-3-7942 and JP-A-5-10 are available.
7775, JP-A-5-107776, JP-A5-1
No. 07777, JP-A-4-70842, etc., an electrostatic information recording medium having a charge holding layer as an information recording layer may be used. In this case, information is stored in the information recording medium by electrostatic charge. Therefore, the electrostatic charge can be developed by toner, or the electrostatic charge can be reproduced by a potential reading device as described in, for example, JP-A-1-290366. Further, an information recording medium having a thermoplastic resin layer as an information recording layer described in JP-A-4-46347 may be used. In this case, the information is transferred in the form of an electrostatic charge to the surface in the same manner as described above. Then, by heating the thermoplastic resin layer, the information is accumulated as a frost layer, and the information can be reproduced as visible information.

The optical sensor used for recording optical information on the information recording medium of the present invention has a photoconductive layer laminated on electrodes, is semiconductive, and is exposed to information with the information recording medium. When a voltage is applied in a state or information exposure is performed with a voltage applied, the electric field or charge amount applied to the information recording medium is amplified. Has a function of continuously applying an electric field or electric charge to the information recording medium, and since the electrode of the photosensor is modified with the electrode-modifying thin film layer, it has high sensitivity and causes uneven sensitivity and noise. No information can be recorded.

[0039]

【Example】

(Production of Laminated Photosensor) Example 1 Sheet resistance 8 formed on a glass substrate having a thickness of 1.1 mm
An ITO film having a thickness of 100 nm and a thickness of 0Ω / □ was sufficiently washed and dried. On this electrode, under a vacuum of 5 × 10 ⁻⁶ torr,
Gold vaporized by resistance heating and vacuum deposited to a film thickness of 30n
m electrode modified thin film layer was formed. On this electrode-modified thin film layer, 1, 4 parts by weight of a disazo pigment having the following structure as a charge generating substance and 3 parts by weight of a polyvinyl acetate resin were added.
-85 parts by weight of dioxane and 85 parts by weight of cyclohexanone were mixed and sufficiently kneaded with a paint shaker to obtain a dispersion coating solution, which was coated with a blade coater, air-dried and then dried at 100 ° C for 1 hour to give a film thickness of 0. Three
A charge generation layer of μm was laminated. Next, on the charge generation layer, the following structure was formed as a charge transporting substance.

[0040]

Embedded image

3 parts by weight of the disazo pigment and 2 parts by weight of a polyvinyl acetate resin were mixed with 85 parts by weight of 1,4-dioxane and 85 parts by weight of cyclohexanone, and sufficiently kneaded with a paint shaker to obtain a dispersion coating solution. , Coat with a blade coater, air dry, then 100 ℃, 1
After drying for an hour, a charge generation layer having a thickness of 0.3 μm was laminated. Next, on the charge generation layer, the following structure was formed as a charge transporting substance.

[0042]

Embedded image

5 parts by weight of a butadiene derivative having a polycarbonate resin (Iupilon Z manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.)
200) 1 part by weight and 24 parts by weight of dichloroethane are uniformly dissolved to obtain a coating solution, which is then spun at 500 rpm at 0.
It is applied for 4 seconds and left to stand in the absence of wind for leveling drying until a film is formed on the surface of the coating film and the surface of the coating film does not adhere, then it is dried at 80 ° C. for 2 hours and then the charge transport layer. Were laminated to prepare an optical sensor of the present invention having a film thickness of 10 μm.

(Electrical Characteristics of Optical Sensor) In order to measure the electrical characteristics of the obtained optical sensor, a gold electrode having 0.16 cm ² , a thickness of 10 nm and a surface resistance of 1 kΩ / □ was formed on the charge transport layer of the optical sensor. Was vapor-deposited as an electrode to prepare a measurement sample, and a current measuring device as shown in FIG. 12 was constructed.
In the figure, 15 is the substrate of the optical sensor, 13 is the electrode of the optical sensor, 16 is the electrode modified thin film layer, 14 ″ is the charge generation layer, 1
4'is a charge transport layer, 30 is a gold electrode, 31 is a light source, 32 is a shutter (No. 0 electromagnetic shutter manufactured by Copal), 33 is a shutter drive mechanism, and 43 is a pulse generator (Yokogawa Hewlett Packard). , 35 are oscilloscopes. In this current measuring device, a DC voltage of 150 V is applied between both electrodes with the electrode 13 of the photosensor being positive and the gold electrode being negative, and 0.533 seconds after the start of voltage application, 0.033 seconds from the glass substrate side. Light irradiation was performed, and the light irradiation start time was set to t = 0, and the current flowing through the photosensor was measured. Irradiation light is a xenon lamp (L2274 manufactured by Hamamatsu Photonics) as a light source, and 20 green light obtained by a green filter (manufactured by Nippon Vacuum Optical Co., Ltd.).
Irradiation was performed at a lux intensity. The irradiation light intensity was measured with an illuminometer (manufactured by Minolta), and the characteristics of the filter used are shown in FIG. The voltage application was continued even after the end of the light irradiation, and the voltage application was continued for 0.15 seconds from the light irradiation start time. The time change of the current during that time was measured by an oscilloscope, and the measurement result is shown by line A in FIG. The horizontal axis represents voltage application time (seconds), and the vertical axis represents current density (A / cm ² ). Also,
The value of the base current density of this optical sensor is 3.0 × 10 ^-6
It was A / cm ² .

(Production of Information Recording Medium) An ITO film having a thickness of 100 nm was formed by sputtering on a glass substrate having a thickness of 1.1 mm to obtain an electrode, and then the surface was washed. On this electrode, a polyfunctional monomer (dipentaerythritol hexaacrylate, manufactured by Toagosei Kagaku Kogyo M-
400) 40 parts by weight, photocuring initiator (2-hydroxy-
2-Methyl-1-phenylpropan-1-one, 2 parts by weight of Ciba-Geigy, Darocure 1173, 90% of liquid crystal (smectic liquid crystal (Merck S-6), nematic liquid crystal (Merck E31V)) Contains 10%) 5
A coating solution obtained by uniformly dissolving 0 part by weight and 3 parts by weight of a surfactant (Sumitomo 3M Co., Ltd., Florard FC-430) in 96 parts by weight of xylene was prepared using a blade coater with an interval of 50 μm. After coating, it was dried at 47 ° C. for 3 minutes, and then dried under reduced pressure at 47 ° C. for 2 minutes, and the coating film was immediately cured by irradiation with 0.3 J / cm ² of ultraviolet light, and an information recording layer having a thickness of 6 μm was recorded. A recording medium was obtained. After extracting the liquid crystal from the information recording layer surface using hot methanol and drying it, a scanning electron microscope (manufactured by Hitachi Ltd.,
When the internal structure was observed 1000 times with S-800), the surface of the layer was covered with a UV-curable resin having a thickness of 0.6 μm, and the inside of the layer had a particle size of 0.1 μm in the liquid crystal phase forming a continuous layer.
It had a structure filled with the resin particle phase.

(Information recording method and recording characteristics) The obtained optical sensor and the information recording medium are laminated so as to face each other with an air layer provided via a spacer of a polyimide film having a thickness of 10 μm as shown in FIG. did. This stack is shown in FIG.
As shown in the figure, the photographic film was changed and mounted on an imaging camera (RB67 manufactured by Mamiya), and a direct voltage of 700 V was applied between both electrodes of the optical sensor and the information recording medium for 0.04 seconds, and at the same time, gray scale exposure was performed. Projection exposure was performed from the optical sensor side for 1/30 second at an amount of 0.2 to 200 lux. After the exposure, the information recording medium was taken out. When the information recording medium was observed with transmitted light, a recording portion composed of a light transmitting portion corresponding to gray scale was observed in the information recording layer. Then, the information recording on the information recording medium was reproduced by the information output device shown in FIG. In the figure, 41 is an information recording medium scanner, 42 is a personal computer, and 43 is a printer. The recording information is read from the information recording medium by an image scanner using a CCD line sensor, and the information is transferred to a sublimation transfer printer (SP-550 manufactured by Victor Company of Japan, Ltd.).
As a result of outputting the information using 0), a good printed matter having a gradation property corresponding to a gray scale was obtained. When the color image was similarly recorded after being separated into three colors of R, G, and B by the prism and the color filter, the recorded image was good. , Good printed matter was obtained.

Comparative Example 1 An optical sensor manufactured in the same manner as in Example 1 except that the electrode-modified thin film layer was not formed.
Similarly, the electric characteristics were measured, and the result is shown by line B in FIG. The value of the base current density of this optical sensor is 2.3 ×
It was 10 ⁻⁸ A / cm ² , and a sufficient function as an optical sensor could not be obtained. In addition, information recording was tried in the same manner as in Example 1, but information recording could not be performed.

Example 2 (Production of laminated optical sensor) Area resistance 80 Ω / □ and film thickness 100 nm formed on a glass substrate having a thickness of 1.1 mm.
The ITO film of was thoroughly washed and dried. This electrode was used as an anode, a platinum electrode was used as a cathode, acetonitrile was used as a solvent, and the potential of the anode was set to 1.2 V with respect to the saturated sweet potato electrode to carry out electrolytic polymerization to form a film having a thickness of about 30 nm on the anode. An electrode-modified thin film layer made of polypyrrole was formed. On this electrode-modified thin film, 3 parts by weight of the same disazo pigment as used in Example 1 as a charge-generating substance and 2 parts by weight of polyvinyl chloride resin were mixed with 170 parts by weight of tetrahydrofuran, and sufficiently kneaded with a paint shaker. To prepare a dispersion coating solution, which is coated with a blade coater, air-dried, and then 10
After drying at 0 ° C. for 1 hour, a charge generation layer having a film thickness of 0.3 μm was laminated. Next, 5 parts by weight of the same butadiene derivative as that used in Example 1 as a charge transporting material, 1 part by weight of a polycarbonate resin (Iupilon Z200 manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.) and 24 parts by weight of dichloroethane were uniformly formed on the charge generation layer. Dissolve in to form a coating solution and spinner to 500
After coating at rpm for 0.4 seconds, the coating film is left on the surface of the coating film without wind until the coating film surface does not adhere, and after leveling and drying, 80 ° C. for 2 hours After drying, a charge transport layer was laminated to produce an optical sensor of the present invention having a film thickness of 10 μm.

(Electrical characteristics of optical sensor and information recording characteristics) When the electric characteristics were measured in the same manner as in Example 1,
It showed good characteristics. The results are shown in Fig. 14. The base current density value of this optical sensor is 4.7 × 10 ⁻⁶ A / cm ^2.
Met. Further, when information recording was performed in the same manner as in Example 1, a recording portion composed of a light transmitting portion corresponding to gray scale was observed in the information recording layer, and as a result of information output, gradation characteristics corresponding to gray scale were obtained. A good printed matter having Also, when a color image was recorded in the same manner by separating it into three colors of R, G, and B by a prism and a color filter, the recorded image was good, and the recorded information of the color image was read in the same way and the information was output. A good printed matter was obtained.

Comparative Example 2 An optical sensor manufactured in the same manner as in Example 2 except that the electrode modified thin film layer was not formed.
As a result of measuring the electric characteristics in the same manner as above, the value of the base current density of this optical sensor is 8.1 × 10 ⁻⁴ A / cm ² ,
It was not possible to obtain a sufficient function as an optical sensor. Further, when the information recording was tried in the same manner as in Example 1 and the information recording was changed, the information recording could be performed, but the image was not good because the image noise was generated.

Example 3 (Fabrication of laminated optical sensor) After washing the electrode in the same manner as in Example 2, an electrode-modified thin film layer made of polyphenylacetylene was formed on the electrode by the CVD method using acetylene as a source gas. Then, a photoconductive layer was laminated on the obtained electrode-modified thin film layer in the same manner as in Example 2 to prepare an optical sensor. (Electrical Characteristics and Information Recording Characteristics of Optical Sensor) Example 1
When the electrical characteristics were measured in the same manner as, the favorable characteristics were shown. The results are shown in Fig. 15. The value of the base current density of this optical sensor was 1.1 × 10 ⁻⁶ A / cm ² , and when information recording was carried out in the same manner as in Example 1, the information recording layer showed gray scale. The recording portion composed of the light transmitting portion was observed, and as a result of information output, a good printed matter having gradation corresponding to the gray scale was obtained. Also,
When a color image was recorded in the same manner by separating it into three colors of R, G, and B with a prism and a color filter, the recorded image was good, and the recorded information of the color image was read in the same way and the information was output. A printed matter was obtained.

Example 4 (Fabrication of Laminated Photosensor) After washing the electrodes in the same manner as in Example 1, the electrode substrate was placed in a sputtering apparatus and the inside of the apparatus was evacuated to about 5 × 10 ⁻⁶ torr. Next, oxygen was vented to about 2.5 × 10 ⁻⁵ torr, and argon was ventilated to about 1 × 10 ⁻³ torr. In this state, sputtering was performed using zinc as a target with an input power of 1.3 kW for 3 minutes, and an electrode-modified thin film layer made of zinc oxide was formed on the electrode by a sputtering method. A photoconductive layer was laminated in the same manner as in 1 to manufacture an optical sensor. (Electrical Characteristics and Information Recording Characteristics of Optical Sensor) Example 1
When the electrical characteristics were measured in the same manner as, the favorable characteristics were shown. The results are shown in Fig. 16. The value of the base current density of this optical sensor was 3.4 × 10 ⁻⁶ A / cm ² , and when information recording was carried out in the same manner as in Example 1, the information recording layer showed gray scale. As a result of observing the recording portion composed of the light transmitting portion and outputting information, a good printed matter having gradation corresponding to the gray scale was obtained. Also, when a color image was recorded in the same manner by separating it into three colors of R, G, and B by a prism and a color filter, the recorded image was good, and the recorded information of the color image was read in the same way and the information was output. A good printed matter was obtained.

Example 5 On the photoconductive layer of the optical sensor prepared in Example 1,
Polyvinyl alcohol 5 parts by weight (Nippon Gosei Kagaku, AH
-26, saponification degree 97-99%) was dissolved in 95 parts by weight of water, and this was applied by a spinner to form a dielectric layer having a film thickness of 1 μm. Then, an information recording layer is formed on this dielectric layer in the same manner as in the method of forming the information recording layer shown in Example 1, and ITO is formed on the information recording layer by sputtering to a thickness of 20 nm. By laminating the conductive layers with each other, an information recording medium was produced. A 700 V DC voltage was applied between both electrodes of this information recording medium, and at the same time, the gray scale was changed to 1/30 as in Example 1.
Projection exposure was performed from the photosensor side for 2 seconds. The voltage application time was 0.05 seconds. After the exposure, the information recording medium was taken out and read and output by the same information output device as in Example 1, and good printed matter was obtained.

Example 6 (Production of Information Recording Medium) Tin oxide was vapor-deposited to a thickness of 100 nm on a sufficiently washed glass substrate to prepare an electrode, and then the electrode was subjected to the same cleaning treatment as in Example 1. Β-on this electrode
A coating solution obtained by uniformly mixing 16 parts by weight of a pinene polymer (Crystalex 3100 manufactured by Rika Hercules Co., Ltd.) and 80 parts by weight of xylene was applied with a spinner at 2000 rpm for 5 seconds, and then at room temperature. It was left for 30 minutes to obtain an information recording medium having a film thickness of 0.7 μm. (Information recording method) Using the obtained information recording medium and the optical sensor manufactured in Example 1, an information recording apparatus similar to that in Example 1 was manufactured, and a direct current voltage of 800 V was applied between both electrodes. The grayscale was projected and exposed from the photosensor side for 0.1 seconds. The voltage application time was 0.5 seconds. After the exposure, the information recording medium was taken out and heated at 80 ° C. for 30 seconds for development, whereby a frosted image on a gray scale was formed. The frost image on this information recording medium could be read by the same information output device as in Example 1, and a good image was obtained.

Example 7 (Production of Information Recording Medium) An ITO film having a film thickness of 100 nm was formed by a sputtering method on a sufficiently washed glass substrate having a thickness of 1.1 mm to obtain an electrode. The same cleaning process as in No. 1 was performed. On the electrode, a 7% fluorine-based solvent solution of fluororesin (manufactured by Asahi Glass Co., Ltd., Cytop, glass transition temperature 100 ° C., water absorption 0.01%, specific resistance 1 × 10 ¹⁸ Ω · cm) was spun at 1500 rpm, 20
After being applied for 2 seconds and dried at room temperature for 3 hours, an information recording medium having an information recording layer with a film thickness of 3 μm was obtained.

(Information Recording Method) Using this information recording medium and the optical sensor manufactured in Example 1, an information recording apparatus similar to that in Example 1 was manufactured, and a DC voltage of 950 V was applied between both electrodes at the same time. The grayscale was projected and exposed from the photosensor side for 1/30 seconds. The voltage application time was 0.1 seconds. The electrostatic information on the resin surface of the information recording medium could be read using a vibration capacitance type surface electrometer (Model 344, manufactured by Trek).

[0057]

The optical sensor and the information recording medium are arranged so as to face each other, and the information is exposed while applying a voltage, so that the liquid crystal in the information recording medium is aligned and is made light transmissive according to the information exposure, and is not exposed. The electric field or the amount of electric charge applied to the information recording medium that records information by the contrast with the area is amplified as the light is irradiated, and even after the light irradiation is completed, the conductivity is maintained when the voltage is continuously applied, and the electric field continues. Alternatively, in an optical sensor used for forming information on an information recording medium having a function of continuously imparting a charge amount to the information recording medium, since an electrode having a modified thin film layer formed on the surface is used,
An image having no image noise or unevenness can be recorded on the information recording medium, and the information recording characteristic on the information recording medium can be improved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating an optical sensor according to the present invention.

FIG. 2 is a diagram illustrating an example of an information recording device according to the present invention.

FIG. 3 is a diagram illustrating another example of the information recording apparatus of the present invention.

FIG. 4 is a diagram illustrating characteristics of a filter used in the present invention.

FIG. 5 is a diagram illustrating a change in current density of an optical sensor having no photo-induced current amplification effect.

FIG. 6 is a diagram illustrating a change in quantum efficiency of an optical sensor having no photo-induced current amplification effect.

FIG. 7 is a diagram illustrating a change in current density of the optical sensor of the present invention.

FIG. 8 is a diagram illustrating a change in quantum efficiency of the optical sensor of the present invention.

FIG. 9 is a diagram illustrating an information recording method in the information recording apparatus of the present invention.

FIG. 10 is a diagram illustrating a method of reproducing information in the information recording device of the present invention.

FIG. 11 is a diagram illustrating an information output device.

FIG. 12 is a diagram illustrating a current measuring device.

FIG. 13 is a diagram illustrating the electrical characteristics of the optical sensor of the example of the present invention and the optical sensor of the comparative example.

FIG. 14 is a diagram illustrating electrical characteristics of an optical sensor according to another example of the present invention.

FIG. 15 is a diagram illustrating electrical characteristics of a photosensor according to another embodiment of the present invention.

FIG. 16 is a diagram illustrating electrical characteristics of an optical sensor according to another example of the present invention.

[Explanation of symbols]

11 ... information recording layer, 13 ... electrode, 13 '... electrode of information recording medium, 14' ... charge generation layer, 14 "... charge transport layer, 1
5 ... Substrate, 16 ... Electrode-modified thin film layer, 19 ... Spacer,
20 ... Dielectric layer, 21 ... Light source, 22 ... Shutter having drive mechanism, 23 ... Pulse generator, 24 ... Dark box, 30 ... Gold electrode, 31 ... Light source, 32 ... Shutter, 3
3 ... Shutter drive mechanism, 43 ... Pulse generator, 35 ... Oscilloscope, 41 ... Information recording medium scanner, 42 ... Personal computer, 43 ... Printer

Claims (17)

[Claims] 1. An optical sensor having a photoconductive layer on an electrode, which is used for forming information on an information recording medium, is semiconductive, and is exposed between the electrode of the optical sensor and the electrode of the information recording medium. If voltage is applied while the voltage is applied, or if exposure is performed while voltage is applied, information can be recorded on the information recording medium with an intensity amplified above the current caused by the exposure. Also shows a behavior in which the conductivity gradually decreases when a voltage is continuously applied, and in an optical sensor having a function of continuing to record information on an information recording medium, an electrode-modified thin film layer is provided between the electrode and the photoconductive layer. An optical sensor characterized by that. 2. An optical sensor having a photoconductive layer on an electrode and used for forming information on an information recording medium, wherein information is formed by laminating an information recording layer on the electrode capable of forming information by an electric field or an electric charge amount. Used by being placed facing the recording medium,
It is semi-conductive, and the amount of electric field or charge applied to the information recording medium when a voltage is applied between the electrodes of the photosensor and the information recording medium in an exposed state, or when a voltage is applied and exposed. Is amplified, and exhibits a behavior in which the conductivity gradually attenuates even when the voltage is continuously applied even after the exposure is finished, and in the photosensor having the action of continuously applying the electric field or the electric charge to the information recording medium, An optical sensor comprising an electrode-modified thin film layer provided between the photoconductive layer and the photoconductive layer. 3. When a voltage is applied to the optical sensor, 10
The optical sensor according to claim 1 or 2, wherein a passing current density in an unexposed portion is 10 ^-4 to 10 ^-7 A / cm when an electric field strength of ⁵ to 10 ⁶ V / cm is applied. 4. An electrode-modified thin film layer is deposited, electrolytically polymerized, CV
The photosensor according to claim 1, wherein the photosensor is a thin film formed by either D or sputtering. 5. An information recording apparatus for recording optical information on an information recording medium by exposure, wherein an optical sensor according to any one of claims 1 to 4 and an information recording medium having an information recording layer formed on an electrode are provided with a gap. An information recording apparatus, which is arranged so as to face each other on an optical axis and is connected so that a voltage can be applied between an electrode of an optical sensor and an electrode of an information recording medium. 6. The information recording apparatus according to claim 5, wherein the information recording layer comprises at least a liquid crystal phase and a resin phase. 7. The information recording layer is made of a thermoplastic resin, and after charges according to information exposure are applied to the surface of the information recording layer,
8. The information recording apparatus according to claim 7, wherein a frosted image is formed on the surface of the information recording layer by being heated and exposed to light. 8. The information recording layer comprises a charge retaining layer, the charge according to exposure is applied to the surface of the information recording layer, and the charge according to exposure is formed on the surface of the information recording layer. 6. The information recording apparatus according to claim 5, wherein the charge formed on the surface of the recording layer is developed with toner. 9. The information recording apparatus according to claim 5, wherein the information recording layer has a memory property. 10. Optical sensor to 10 ⁵ to 10 ⁶ V / cm
When applying the electric field strength of, the passing current density in the unexposed area is 1
7. The information recording apparatus according to claim 5, wherein the information recording medium has a specific resistance of 0 ⁻¹⁰ to 10 ⁻⁷ A / cm ² and a specific resistance of 10 ¹⁰ to 10 ¹³ Ω · cm. 11. An information recording device comprising an electrode-modified thin film layer, a photoconductive layer, a dielectric layer, an information recording layer, and an upper electrode, which are stacked in this order on a lower electrode. The information recording device comprises a lower electrode, an electrode-modified thin film layer, and a photoconductive layer. The optical sensor unit comprises the optical sensor according to any one of claims 1 to 4, and an information recording device characterized in that a wire is connected between the lower electrode and the upper electrode so that a voltage can be applied. 12. The information recording layer of the information recording medium,
The information recording device according to claim 11, wherein the information recording device comprises at least a liquid crystal phase and a resin phase. 13. An information recording / reproducing method for recording optical information on an information recording medium by exposure, using the optical sensor according to any one of claims 1 to 4 and an information recording medium having an information recording phase formed on an electrode. At least one of the electrodes of the sensor and the information recording medium is a transparent electrode, and the optical sensor and the information recording medium are arranged facing each other on the optical axis with a gap, and a voltage is applied between both electrodes in an exposed state. , Or information is recorded on the information recording medium by exposure with a voltage applied, and the optical information recorded on the information recording medium as visible information is reproduced by transmitted light or reflected light. Method. 14. An information recording method for recording optical information on an information recording medium by exposure, comprising the optical sensor according to claim 1 and an information recording medium having an information recording layer made of a thermoplastic resin formed on an electrode. Optical information recorded on the information recording medium as visible information by using, heating after forming electric charges on the information recording layer by exposure of optical information, and forming a frost image according to the information exposure. An information recording / reproducing method, characterized in that the information is reproduced. 15. An information recording method for recording optical information on an information recording medium by exposure, comprising: the optical sensor according to any one of claims 1 to 4, and an information recording medium having an information recording layer formed of a charge retaining layer on an electrode. An information recording / reproducing method, which comprises using an electric charge on an information recording layer by exposure of optical information, and then reading and reproducing the recorded optical information with a potential sensor. 16. An information recording / reproducing method for recording optical information on an information recording medium by exposure, the information recording medium comprising an optical sensor according to any one of claims 1 to 4 and an information recording layer formed of a charge retaining layer on an electrode. Is used to apply a charge on the information recording layer by exposure of optical information, the recorded optical information is developed with a toner, and the optical information is reproduced as visible information by transmitted light or reflected light. Information recording / playback method. 17. An information recording method for recording optical information on an information recording medium by exposure, the information recording medium comprising an electrode-modified thin film layer, a photoconductive layer, a dielectric layer, an information recording layer and an upper electrode on a lower electrode in this order. The optical sensor unit, which is laminated and includes a lower electrode, an electrode-modified thin film layer, and a photoconductive layer, is defined by claim 1.
4. The optical sensor according to 4, wherein at least one of the lower electrode and the upper electrode is a transparent electrode, and a voltage is applied between the lower electrode and the upper electrode in an exposed state, or by exposure while applying a voltage. An information recording / reproducing method characterized in that information is recorded on an information recording medium, and optical information recorded on the information recording medium as visible information is reproduced by transmitted light or reflected light.